TW200837499A - Photosensitive resin composition, photosensitive resin transfer film, method of manufacturing photospacer and support for liquid crystal display device, and liquid crystal display device - Google Patents

Abstract

To provide a photosensitive resin composition that exhibits excellent image quality after it is irradiated with light in a case where the composition is used for a color filter for forming a part of a display device. A photosensitive resin composition containing therein a polymerization compound, a cross-linking binder, and a photopolymerization initiator represented by the following general formula (I), wherein the content of the photopolymerization initiator with respect to the monomer is within a range of 4 wt. % to 12 wt. %. (wherein R1 and R2 each independently represent a hydrogen atom, an alkyl group, an aryl group or a group expressed by the following general formulae (I-A) or (I-B); R3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group; W represents a halogen atom; X and Y each independently represent Cl or Br; and m, n each independently represent 0,1 or 2). (wherein R5 to R7 each independently represent an alkyl group or an aryl group).

Description

[Technical Field] The present invention relates to a photosensitive resin composition suitable for a color filter, a spacer, or the like constituting a display device, and particularly relates to a display device (which constitutes a liquid crystal cell) The photosensitive resin composition produced by the gap of the cell thickness is likely to be a gap*, the photosensitive resin transfer film and the optical spacer are produced, and the optical spacer produced by the method is provided. A substrate for a liquid crystal display device and a liquid crystal display device. ^ [Prior Art] Currently, liquid crystal display devices are widely used in display devices that display high-quality images. In a liquid crystal display device, a liquid crystal layer capable of displaying an image via a predetermined alignment is disposed between a pair of substrates, and the substrate interval is uniformly maintained, that is, the thickness of the liquid crystal layer is one of the elements for determining image quality. The thickness of the liquid crystal layer is kept constant, and a spacer is provided. The thickness between the substrates is generally referred to as "cell thickness", and the cell thickness is usually the thickness of the liquid crystal layer, in other words, the distance between the two electrodes, which is used to apply an electric field to the display region. The liquid crystal has been formed by the scattering of beads in the past, but in recent years, a photosensitive composition has been used to form a spacer having high positional precision by lithography. The gap formed by using such a photosensitive composition is used. The optical spacer is formed by patterning, alkali development, and baking using a photosensitive composition, and the compression strength at the interval is weak, and the plasticity at the time of panel formation is changed. In the high-quality image display, there is no problem that the thickness of the liquid crystal layer is smaller than the design 而, and the uniformity cannot be maintained, or no image unevenness occurs. In addition, in the point of high precision of the liquid crystal display device, it is also important that the alkali image developing residue of the photosensitive composition does not occur. In connection with the above, the thickness of the liquid crystal layer is used. (The cell thickness is a technique for forming a spacer which is fixed, and a resin having an allyl group for forming a spacer is disclosed (for example, see Patent Document 1). Further, there is a light spacer which is excellent in storage stability and which is easy to manufacture. A photosensitive composition to be used (for example, see Patent Document 2). Further, a composition excellent in cold and heat resistance and a composition in which a spacer is formed on a black matrix provided on a transparent substrate are disclosed (for example, refer to the patent document) 3, 4) [Patent Document 1] JP-A-2002-207787 (Patent Document 3) JP-A-200-62620 [Patent Document 3] JP-A-2002-2 873 54 (Patent Document 4) SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The subject of the present invention is to provide a good photosensitive image shape after light irradiation when used as a color filter constituting a display device. The resin composition is particularly useful as a photosensitive resin composition having a favorable tapered shape when used as a photonic spacer. Further, the object of the present invention is to provide the use of the aforementioned photosensitivity. A photosensitive resin transfer film of a resin composition. The object of the present invention is to provide a photosensitive resin composition and a method for producing a photoclear using the photosensitive resin transfer film, and to provide a method for producing the optical spacer. A substrate for a liquid crystal display device having a light gap, and a liquid crystal display device including the substrate. In view of the above-mentioned actual circumstances, the present inventors conducted intensive studies and found that when the above specific photopolymerization initiator is used The present invention can be achieved by solving the above problems. f' " That is, the present invention is achieved by the following means: < 1 > A photosensitive resin composition characterized by comprising a polymerizable compound and crosslinkability The photopolymerization initiator represented by the following formula (I) contains the photopolymerization initiator in an amount of 4% by mass or more and 12% by mass or less based on the polymerizable compound, and the formula (1)

(In the formula (I), R1 and R2 each independently represent a hydrogen atom, an alkyl group, an aryl group, a group represented by the following formula (Ι-A) or (IB); and R1 and R2 may be bonded to each other. The bonded nitrogen atoms together form a heterocyclic ring formed by a non-metal atom; R3 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group; W represents a halogen atom; and X and Y each independently represent a chlorine atom or a bromine atom. ;m, η each independently represent 0, 1 or 2), 200837499 Formula (IA) R-〇Xch2- General formula (Ι·Β)

(In the formula (Ι-Α) and (Ι-Β), R5, R6 and R7 each independently represent an alkyl group or an aryl group). The photosensitive resin composition of the above-mentioned <1>, wherein the photosensitive resin composition is formed into a spacer. The photosensitive resin composition of the above-mentioned <1> or <2>, wherein the photopolymerization initiator represented by the above formula (1), the above formula (1) R3 is a hydrogen atom, m and n are both oxime, X and γ are all chlorine atoms, R1 and R2 both represent a general formula (Ι-Α), and R5 is an alkyl group. &lt; 4 &gt; A photosensitive resin transfer film characterized by being a photosensitive resin transfer film having at least a photosensitive resin layer on a temporary support, wherein the photosensitive resin layer is the above &lt;1 &gt; The photosensitive resin composition according to any one of the above-mentioned items, wherein the photosensitive resin composition is formed. &lt;5&gt; A method for producing a photosensitive spacer, which is characterized in that the photosensitive resin composition according to any one of the above-mentioned items <1> to <3> is applied to a support by coating. A step of forming a photosensitive resin layer. &lt;6&gt; The method for producing a photo-gap, characterized in that the photosensitive resin transfer film according to the above &lt;4&gt; is heated on the support by heating, pressurization, or heating and pressurization. A step of printing a photosensitive resin layer. &lt;7&gt; The substrate for a liquid crystal display device comprising the optical spacer manufactured by the method of producing the optical spacer described in the above &lt;5&gt; or &lt;6&gt;. -9-200837499 A liquid crystal display device comprising the substrate for a liquid crystal display device described in the above &lt;7&gt;. Advantageous Effects of Invention According to the present invention, it is possible to provide a photosensitive resin composition having a good image shape after light irradiation when used as a color filter constituting a display device, and particularly for use as a photo spacer. At this time, a suitable photosensitive resin composition having a good tapered shape can be obtained. Moreover, according to the present invention, a photosensitive resin transfer film using the photosensitive resin group 1 can be provided. Furthermore, according to the present invention, the photosensitive resin composition and the optical spacer using the photosensitive resin transfer film can be provided, and the substrate for liquid crystal display device having the optical spacer manufactured by the method can be provided and A liquid crystal display device of a substrate. [Embodiment] The best mode of the invention is that the photosensitive resin composition of the present invention contains at least a crosslinkable binder (hereinafter also referred to as "a polymer compound having a crosslinkable group (A)) "It is also called "resin (A)"), a polymerizable compound (B) (hereinafter also referred to as "monomer"), and a photopolymerization initiator (C) (hereinafter also referred to as "specific initiator"). Further, if necessary, other components such as a coloring agent or a surfactant may be used. The photosensitive resin composition is particularly preferably used for optical spacers. Hereinafter, the photosensitive resin composition ' is described mainly by a light spacer, but it can also be used for a color filter used in a display device, a black moment 10-200837499 array, or the like. - Photopolymerization Initiator - The photopolymerization initiator of the present invention contains at least one kind of photopolymerization initiator (specific initiator) represented by the following formula (I) from the viewpoint of good photocuring performance. ). Further, other photopolymerization initiators may be contained within a range not inhibiting the effects of the present invention. Hereinafter, the photopolymerization initiator represented by the formula (1) will be described. General formula (I) pHmX3-m

In the formula (I), R1 and R2 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a group represented by the following formula (I_A) or (I-B). R3 represents a hydrogen atom, a halogen atom, a hospital base, or a hospitaloxy group. W represents a halogen atom. χ and γ each independently represent a chlorine atom or a bromine atom. m, η each independently represent 〇' 1 or 2. In the above formula (I), the alkyl group is preferably a carbon number of from 1 to 20, more preferably a carbon number of from 2 to 10, particularly preferably a carbon number of from 3 to 5. The above aryl group is preferably a carbon number of 6 to 20, more preferably a carbon number of 6 to 15, and particularly preferably a carbon number of 6 to 10. The alkoxy group is preferably a carbon number of 1 to 20, more preferably a carbon number of 2 to 10, particularly preferably a carbon number of 3 to 5. In the above formula (I), the alkyl group, the aryl group and the alkoxy group may further have a substituent of 200837499, and examples of the substituent which may be introduced include an aryl group such as a phenyl group, a halogen atom, an alkoxy group, and the like. An alkoxycarbonyl group, an aryloxycarbonyl group, a decyl group, a nitro group, a dialkylamino group, a sulfonyl derivative, and the like. General formula (I-B)

General formula (Ι·Α) Ο R5— Ο - G~CH2 In the formulae (Ι-A) and (I-B), R5, R6 and R7 each independently represent a hospital group or an aryl group. In the formula (I), R1 and R2 may form a hetero ring formed of a non-metal atom together with the nitrogen atom to which they are bonded. In this case, examples of the hetero ring include the following. .

Cxy-cv is a specific example of a specific initiator represented by the formula (I), $ _ $ 2,4-bis(trichloromethyl)_6-[4,_(叱1 bisethoxycarbonylmethyl)amine Base_3,_ desert phenyl]-homo-trimium, 4-[m-chloro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl b 2,6-bis(trichloromethyl)- Uniform triple trap, 4-[m-fluoro-p-indole 1 bis(ethoxyxomethyl)aminophenyl]-2,6-bis(trichloromethyl)-homogeneous trap, 4_[o N,N-bis(ethoxycarbonylmethyl)aminophenyl]_2,6-bis(trichloromethyl)_-tris-trimium, 4-[o-chloro-p-m-bis(ethoxycarbonylmethyl) Aminophenyl 2,6-bis(trichloromethyl)-homoindene, 4-[o-fluoro-encapsulated N,N-bis(ethoxylatylmethyl)aminophenyl]-2,6 - bis(trichloromethyl)_-homo-trap, 4-[o-bromo-p-quinone 1 bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)·semi-trap, 4-[o-chloro.p.11 pairs (200837499 chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-allotriazole, 4-[o-fluoro-p-N,N-double ( Chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-homogeneous triple trap, 4-[m-bromo-p-N,N-bis(chloroethyl)aminophenyl]-2 , 6_ double Trichloromethyl)·mean trap, 4-[m-chloro-p-purine, fluorenyl-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-allotriazole, 4 -[m-fluoro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-homogeneous, 4-(m-bromo-p-N-ethoxycarbonyl) Methylaminophenyl)-2,6-bis(trichloromethyl)-homogeneous, 4-(m-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6- Γ' ~ bis(trichloromethyl)-homogeneous trap, 4-(m-fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-all three tillage, 4 -(o-bromo-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-homo-trim, 4-(o-chloro-p-N-ethoxycarbonylmethylamine Phenyl)-2,6-bis(trichloromethyl)-homogeneous triad, 4-(o-fluoro-p-N-ethoxycarbonylmethylaminophenyl)_ 2,6-bis(trichloromethane) Base)-mean triple trap, 4-(m-bromo-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-all three tillage, 4-(m-chloro-p-N- Chloroethylaminophenyl)-2,6-bis(trichloromethyl)-homogeneous, 4-(m-fluoro-p-N-chloroethylamino V^phenyl)-2,6-di (trichloromethyl)-all three tillage, 4-(o-bromo- N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-homo-trimium, 4-(o-chloro-p-N-chloroethylaminophenyl)-2,6-bis ( Trichloromethyl)--monotrimium, 4-(o-fluorenyl-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)·meanstrap, etc., and in the phenyl moiety Three kinds of halogen atoms and the like are introduced. These specific initiators are, for example, those having a radical generating moiety and a triterpene skeleton in the molecule, and preferably having a halogen atom in the central position of the phenyl ring or having a bromine atom. -13- 200837499 The specific initiator may be used alone or in combination of two or more. The content of the specific initiator in the photosensitive resin composition is preferably in the range of 0.1 to 15.0% by mass, and more preferably in the range of 〇·5 to 10.0% by mass, in terms of solid content. The polymerization reaction can be carried out efficiently, and the obtained cured film is also excellent in strength. - Other photopolymerization initiator - Further, in the photosensitive resin composition, in addition to the specific initiator described above, a photopolymerization initiator other than the above may be used as long as the effects of the present invention are not impaired. The photopolymerization initiator usable herein is a compound which is decomposed by light and which initiates and promotes polymerization of a compound having an ethylenically unsaturated group which can be added and polymerized later, preferably at a wavelength of from 00 to 500 nm. The area has an absorber. Examples of the photopolymerization initiator include an organic halogenated compound, an oxadiazole compound, a carbonyl compound, a ketal compound, a benzoin compound, a fluorene compound, an organic peroxidation compound, an azo compound, and a coumarin compound. An azide compound, a metallocene compound, a bisimidazole compound, an organoboric acid compound, a disulfonic acid compound, an oxime ester compound, an iron salt compound, a mercaptophosphine (oxide) compound. In particular, from the viewpoint of high sensitivity, at least one compound selected from the group consisting of a trihalomethyl triple well compound, a bisimidazole compound, and an anthraquinone compound is preferably a bisimidazole compound. The content of the photopolymerization initiator which can be used is preferably 75 mass% or less, more preferably 0 to 50 mass%, in the range of 0 to 50 mass%. Further, the total amount of the specific initiator and the other photopolymerization initiator is preferably from 0.1 to 50% by mass, more preferably from 0.1 to 30% by mass, particularly preferably 0.3, based on the total solid content of the composition. ~20% by mass. Within this range, good sensitivity and pattern formation properties can be obtained. A sensitizer - A sensitizer can be used in such specific initiators. The sensitizer useful in the present invention preferably has a sensitizer by an electron moving mechanism or an energy moving mechanism for a specific initiator. Further, examples of the sensitizer include those exemplified below, and those having an absorption wavelength in a wavelength range of 300 nm (30 30 nm) to 45 0 nm. Specific examples of the sensitizer include polynuclear aromatics (such as phenanthrene, anthracene, anthracene, anthracene, tri-o-phenylene, 9,10-dialkoxyfluorene) and xanthene (such as luciferin). , blush, red erythro, rhodamine B, rose red), thioxanthone (isopropyl thioxanthone, diethyl thioxanthone, chlorothioxanthone), quinoline blue (such as I; Thiocarbonylquinoline blue, oxacarbonylquinoline blue), phthalocyanines (such as phthalocyanine, orthoquinone), phthalocyanine, thiazide (such as sulfur, methylene blue, toluidine blue), hydrazine Pyridines (such as acridine orange, chlorsulfurin, acridine yellow), terpenoids (such as 蒽醌), square key (such as square key), coumarins (such as 7-diethylaminomethyl Beans), keto-coumarins, porphyrins, morphines, phenylethylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes, carbazoles, Porphyrin, spiro compound, quinophthalone, indigo, styryl, pyranyl compound, methylpyrrole compound, pyrazole triazole compound, benzene-15-200837499 thiazole compound, barbituric acid derivative, sulfur Than mud acid derivatives, phenyl ethyl ketone, benzophenone, thioxanthone, Michler's ketone and the like aromatic ketone compounds, N- aryl fathoms thiazolidinedione such heterocyclic compounds. Such a sensitizer can be subjected to various chemical modifications in order to further improve the characteristics of the photosensitive resin composition. For example, the sensitizer may be bonded to an addition polymerizable compound structure (for example, an acrylonitrile group or a methacryl oxime group) by a method such as covalent bonding, ionic bonding, hydrogen bonding, or the like to expose the film. The strength is increased, or a specific sensitizer is precipitated from the film of f ~ after exposure. Further, a sensitizing agent and a partial structure having a radical generating ability in the photopolymerization initiator (for example, a reductive decomposition site such as a halogenated alkyl group, a key, a peroxide, a dimethicone, a sulfonium, a diimidazole, or the like, Or a bond of a oxidative decomposing site of a borate, an amine, a trimethyldecylmethyl group, a carboxymethyl group, a carbonyl group, an imine, etc., in particular, a photosensitive enthalpy in a state where the concentration of the initiator is low is remarkably improved. The sensitizer may be used alone or in combination of two or more. The content of the sensitizer is preferably 〇 1 mass ° / of the total solid content of the photosensitive resin composition. ～2 0% by mass, more preferably 〇. 2% by mass to 2% by mass. In the sensitizer, when a coloring agent is used in the photosensitive resin composition, the concentration of the coloring agent becomes extremely high. When the light transmittance of the colored pattern (photosensitive layer) formed is extremely low, specifically, it is not added. When the photosensitive layer formed by these sensitizers has a light transmittance of 5% or less at 365 nm, a sensitizer can be added, and the effect is remarkably exhibited. In the photosensitive resin composition of the present invention, the resin (A)-based crosslinkable binder has a function as a binder component when forming a laminate of a spacer or a coloring element. For example, a photopolymerizable polymer resin having an allyl group as described in paragraphs [〇〇31] to [0054] of JP-A-2003-131379, which has self-crosslinkability and polymerizability, can be used. A high molecular substance is considered as a preferred example. Further, a polymer having a crosslinkable polar group such as a carboxylic acid group or a carboxylate group in the side chain may be mentioned. The polymer material may be any of a homopolymer of a monomer and a plurality of monomers which are appropriately selected according to the purpose, and may be used alone or in combination of two or more. Examples of the polymer having a polar group such as a carboxylic acid group or a carboxylate group in the side chain include JP-A-59-446-15, JP-A-54-34327, and JP-A-5 The methyl group described in the publications of the Japanese Patent Publication No. Hei. No. 5, No. 5, the disclosure of which is incorporated herein by reference. Acrylic copolymer, acrylic copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, and the like. Further, a cellulose derivative having a carboxylic acid group in a side chain may be mentioned, and it is also preferred to use another polymer having a hydroxyl group as a cyclic acid anhydride. Moreover, as a particularly preferable example, a copolymer of benzyl (meth)acrylate and (meth)acrylic acid, or benzyl (meth)acrylate and (methyl) described in the specification of U.S. Patent No. 4,139,391 can be mentioned. A multi--17-200837499 copolymer of acrylic acid and other monomers. Examples of the monomer having a polymer material having an allyl group include a monomer having an allyl group, a monomer which can be an allyl group, and other monomers, and are not particularly limited, and may be appropriately selected according to the purpose. Other monomers. In the above, for example, alkyl (meth)acrylate, aryl (meth)acrylate, hydroxyalkyl (meth)acrylate, vinyl compound, allyl-containing (meth)acrylate Wait. Further, in the present specification, (meth) acrylate means acrylate or methacrylate. f' I These monomers may be used alone or in combination of two or more. Examples of the alkyl (meth)acrylate and the aryl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate. Butyl acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl acrylate , toluene acrylate, naphthalene acrylate, cyclohexyl acrylate, and the like. ϋ Examples of the hydroxyalkyl (meth)acrylate include hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate. Ester, hydroxyisobutyl (meth)acrylate, hydroxypentyl (meth)acrylate, hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, etc., of which hydroxy(meth)acrylate is particularly preferred. Ethyl ester, hydroxy-n-propyl (meth)acrylate, hydroxy-n-butyl (meth)acrylate, and the like. As the vinyl compound, for example, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, -18-200837499 acrylonitrile, vinyl acetate, N-vinylpyrrole may be suitably used. An anthracene-containing (meth) acrylate such as a ketone, a tetrahydrofurfuryl methacrylate, a polystyrene macromonomer or a polymethyl methacrylate macromonomer, for example, Allyl acrylate, 2-methylallyl acrylate, crotonyl acrylate, chloroallyl acrylate, phenyl allyl acrylate, cyanoallyl acrylate, etc., especially preferably (meth)acrylic acid Allyl ester. Among the above polymer materials, a resin containing at least an allyl group-containing (meth) acrylate as a monomer unit, more preferably an allyl group-containing (meth) acrylate and (preferably) The monomer selected from the group consisting of methyl methacrylate and allylic (meth) acrylate is used as the monomer unit resin. Preferable specific examples of the polymer material include a binary copolymerized resin of (meth)acrylic acid (M1) and allyl (meth)acrylate (M2) [suitable copolymerization ratio [Mo Erbi ] is M\M2 = 2~90:10~98], or (meth)acrylic acid (M3) with ternary (meth) acrylate (M4) and benzyl (meth) acrylate (M5) Copolymerized resin [suitable copolymerization ratio [mole ratio] is M3: M4: M5 = 5 to 40: 20 to 90: 5 to 70^. When the polymer material has an allyl group, the content of the allyl group-containing monomer is preferably 10 mol% or more, particularly preferably 10 to 100 mol%, particularly preferably 15 to 90 mol%. More preferably 2 0~8 5 mol%. The weight average molecular weight of the above polymer substance is preferably 5,000 to 100,000, more preferably 8,000 to 50,000, in terms of polystyrene by gel permeation chromatography (GPC), by making the weight average The molecular weight is in the range of 5,000 〜1 〇〇, 〇〇〇, and the film strength can be improved. -19- 200837499 Further, 'resin (A) consists of a group having a branching and/or alicyclic structure in the side chain: X (X mole%), and a group having an acidic group: Y (y mole %) The group having an ethylenically unsaturated group: Z (z mole %) may further contain (1 mole %) of other groups (L). Further, among a group in the resin (A), X, Y and Z may be plurally combined. A group having a branching and/or alicyclic structure in a side chain: X is the above-mentioned "base having a branching and/or alicyclic structure in a side chain". Γ ' &amp; First, as a branch having a branch in the side chain, a branched alkyl group having 3 to 12 carbon atoms, and examples thereof include an isopropyl group, an isobutyl group, a second butyl group, and the like. Tributyl, isopentyl, neopentyl, 2-methylbutyl, isohexyl, 2-ethylhexyl, 2-methylhexyl, isopentyl, third pentyl, 3-octyl, third Xinji et al. Among these, an isopropyl group, a second butyl group, a tributyl group, an isopentyl group or the like is preferable, and an isopropyl group, a second butyl group, a t-butyl group or the like is particularly preferable. In the alicyclic hydrocarbon group having 5 to 20 carbon atoms, the group having an alicyclic structure in the side chain may, for example, be a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or an original borneol group. , isobornyl, adamantyl tricyclic fluorenyl and the like. Among these, a cyclohexyl group, an borneol group, an isobornyl group, an adamantyltricyclodecyl group or the like is preferable, and a cyclohexyl group, an original borneol group, an isobornyl group or the like is more preferable. Examples of the monomer containing the group having a branching and/or alicyclic structure in the side chain include styrenes, (meth)acrylates, vinyl ethers, vinyl esters, and (meth)acrylic acid. The amines and the like are preferably (meth) acrylates-20-200837499, vinyl esters, (meth) acrylamides, and more preferably (meth) acrylates. Specific examples of the monomer containing the group having a branching structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, and second butyl (meth)acrylate. Tert-butyl (meth)acrylate, isoamyl (meth)acrylate, third amyl (meth)acrylate, second isoamyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, third octyl (meth)acrylate, etc., among which isopropyl (meth)acrylate, isobutyl (meth)acrylate, and third methacrylate are preferred. The ester or the like is more preferably isopropyl methacrylate or butyl methacrylate. In the following, specific examples of the monomer having a group having an alicyclic structure in the side chain include a (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. Specific examples thereof include (meth)acrylic acid (bicyclo-2,2,1-heptyl-2), (meth)acrylic acid-1-adamantyl ester, and (meth)acrylic acid-2-adamantyl ester. , (meth)acrylic acid-3-methyl-1-adamantyl ester, (meth)acrylic acid-3,5-dimethyl-1-adamantyl ester, (meth)acrylic acid-3-ethyl I. Adamantyl ester, 3-methyl-5-ethyl-1-adamantyl (meth)acrylate,-3,5,8-triethyl-1-adamantyl (meth)acrylate, (A) Acetyl-3,5-dimethyl-8-ethyl-1-adamantyl ester, octahydro-4,7-capped-5-yl (meth)acrylate, octahydro(meth)acrylate -4,7-Gate-1-ylmethyl ester, (meth)acrylic acid-1-capped ester, tricyclodecyl (meth)acrylate, 3-hydroxy-2,6,6 (meth)acrylate -trimethyl-bicyclo[3,1,1]heptyl ester, (mercapto)acrylic acid-3,7,7-trimethyl-4-hydroxy-bicyclo[4,1,0]heptyl ester, (methyl Acrylic acid (original) borneol ester, isobornyl (meth)acrylate, decyl (meth)acrylate, (meth)acryl-21-200837499 acid-2,2,5-trimethylcyclohexyl ester, and the like. Among these (meth)propionic acid esters, cyclohexyl methacrylate, (meth)acrylic acid (former) borneol ester, (meth)acrylic acid isobornyl ester, (meth)acrylic acid- 1-adamantyl ester, (meth)acrylic acid-2-adamantane oxime, methacrylate methacrylate, ruthenium-caprate methacrylate, tricyclodecyl (meth) acrylate, etc., particularly preferably methacrylic acid ring Hexyl ester, methacrylic acid (original) borneol ester, isobornyl (meth)acrylate, (methyl)propionic acid-2-adamantyl ester. The group having an acidic group in the side chain: Y - is not particularly limited as the acidic group, and may be appropriately selected from known ones, and examples thereof include a carboxyl group, a sulfonyl group, a sulfonylamino group, a phosphoric acid group, and the like. Phenolic hydroxyl groups and the like. Among these, a carboxyl group or a phenolic hydroxyl group is preferred from the viewpoint of excellent visibility and water resistance of the cured film. The monomer having a group having an acidic group in the side chain is not particularly limited, and examples thereof include styrenes, (meth)acrylates, vinyl ethers, vinyl esters, and (meth)acrylamide. The class or the like is preferably a (meth) acrylate, a vinyl ester or a (meth) acrylamide, more preferably a (meth) acrylate. Specific examples of the monomer having a group having an acidic group in the side chain can be appropriately selected from those skilled in the art, and examples thereof include (meth)acrylic acid, vinylbenzoic acid, maleic acid, and maleic acid monoalkane. Ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid, acrylic acid dimer, addition reaction of a monomer having a hydroxyl group with a cyclic acid anhydride, ω-carboxyl group Polycaprolactone mono(meth)acrylate or the like. These may be used by a suitable manufacturer or a commercially available product. -22-200837499 The monomer having a hydroxyl group used for the addition reaction of the monomer having a hydroxyl group and a cyclic acid anhydride is, for example, 2-hydroxyethyl (meth)acrylate. Examples of the cyclic acid anhydride include maleic anhydride, decanoic anhydride, and cyclohexane dicarboxylic anhydride. As the above-mentioned commercial product, it is exemplified by East Asia Synthetic Chemical Industry Co., Ltd.: Aronix Μ 5 3 00, Aronix Μ 5400, Aronix Μ 5 5 00, Aronix Μ 5600, manufactured by Shin-Nakamura Chemical Co., Ltd.: ΝΚ ester CB -1, Ester CBX-1, Kyoeisha Oil Chemical Industry Co., Ltd. System: HOA-MP, HOA-MS, Osaka Organic Chemical Industry Co., Ltd.: Biscoat #2100, etc. Among these, (meth)acrylic acid or the like is preferred from the viewpoint of excellent developability and low cost. A group having an ethylenically unsaturated group in the side chain: Z - as the above "having an ethylenically unsaturated group in the side chain", and is not particularly limited, and the ethylenically unsaturated group is preferably a (meth)acryl fluorenyl group. . Further, the connection between the ethylenically unsaturated group and the monomer is not particularly limited as long as it is a divalent linking group such as a mercaptoamine group or an amine mercapto group. The method of introducing an ethylene ethylenically unsaturated group in the side chain can be suitably selected from known ones, for example, a method of adding a (meth) acrylate having an epoxy group to an acidic group, and a group having a hydroxyl group. A method of adding a (meth) acrylate having an isocyanate group, a method of adding a (meth) acrylate having a hydroxyl group to a group having an isocyanate group, and the like. Among these, a method of adding a (meth) acrylate having an epoxy group to a repeating unit having an acidic group is preferred from the viewpoint of easiest production and low cost. -23-200837499 The (meth) acrylate having an ethylenically unsaturated bond and an epoxy group is not particularly limited as long as it has such a', for example, it is preferably represented by the following structural formula (1). Compound and compound represented by the following structural formula (2)

Structural formula (1)

However, in the above structural formula (1), R1 represents no hydrogen atom or methyl group. L1 table

However, in the above structural formula (2), R2 represents a hydrogen atom or a methyl group. L2 represents an organic group. W represents an aliphatic hydrocarbon group of 4 to 7 membered rings.

Among the compounds represented by the above structural formula (1) and the compound represented by the structural formula (2), a compound represented by the structural formula (1) is preferred, and in the above structural formulae (1) and (2), L1 and L2 are more preferably an alkylene group having 1 to 4 carbon atoms. The compound represented by the above structural formula (1) or the compound represented by the structural formula (2) is not particularly limited, and examples thereof include the following exemplified compounds (1) to (10). -24- 200837499

The other monomer is not particularly limited as the other monomer, and examples thereof include (meth)acrylic acid vinegar which does not have a branch and/or s ring structure, styrene gas, vinyl ether, A monomer such as a dibasic acid anhydride group, a vinyl ester group or a hydrocarbon alkenyl group. The vinyl ether group is not particularly limited, and examples thereof include a butyl vinyl ether group. The dibasic acid anhydride group is not particularly limited, and examples thereof include a maleic anhydride group and an Ikonic anhydride group. -25- 200837499 The vinyl ester group is not particularly limited, and examples of the gamma include vinyl acetate. The hydrocarbon alkenyl group is not particularly limited, and examples thereof include a butylene group and a prenyl group. In the above resin (A), the content of the other monomer is preferably 0 to 30 mol%, more preferably 〇20 to 20 mol%, based on the molar composition ratio. Specific examples of the resin (A) include compounds represented by the following compound pairs 1 to 28. -26- 200837499

X:y:2»40 :25:35

-27- 200837499

x: y:2 s30 :30:40

P-1I x: y : 2 * 40: 25:35

-28- 200837499

M3

Ρ-Ιβ

C〇〇X^

COOH

?-17 κ: y r z » 46:25; 30

-29- 200837499

P-19 Ρ·20

OH I P-21 x:y:2^45:20 :35

P-2i P-23 30- 200837499

First, the above-mentioned resin (A) is produced by a two-stage step of a (co)polymerization step of a monomer and a step of introducing an ethylenically unsaturated group. First, the (co)polymerization reaction is carried out by (co)polymerization of various monomers, and is not particularly limited, and can be appropriately selected from those skilled in the art. For example, regarding the active species to be polymerized, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization, and the like. Among these, from the viewpoint of easy synthesis and low cost, radical polymerization is preferred. Further, the polymerization method is not particularly limited and can be appropriately selected from those skilled in the art. For example, it is possible to select a whole polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, and the like in the range of -31 to 200837499. Among these, a solution polymerization method is preferred. —Molecular weight— The weight average molecular weight of the above copolymer suitable as the resin (A) is preferably from 7,000 to 100,000, more preferably from 8,000 to 80,000, particularly preferably from 9,000 to 50,000. When the weight average molecular weight is within the above range, it is preferred in terms of the suitability and development of the copolymer. - Glass transition temperature - a suitable glass transition temperature (Tg) of the resin (A), preferably 40 to 180 ° C, more preferably 4 5 to 1 40 ° C, particularly preferably 5 0 to 1 3 0 ° C . When the glass transition temperature (Tg) is within the above preferred range, a light gap having good developability and mechanical strength can be obtained. The preferred range of the suitable acid value of the monovalent acid-resin (A) varies generally with the molecular structure that can be obtained, but is generally preferably 20 mgKOH/g or more, more preferably 50 mgKOH/g or more, and particularly preferably 70. ~130 mg KOH / g. When the acid value is within the above preferred range, an optical spacer having good developability and mechanical strength can be obtained. The glass transition temperature (Tg) of the resin (A) is 40 to 180 ° C, and the weight average molecular weight is 7,000 to 100,000, which is obtained from the viewpoint of obtaining a light gap having good developability and mechanical strength. More suitable. Further, preferred examples of the resin (A) are each a combination of the above molecular weight, glass transition temperature (Tg), and acid value. The copolymerization composition ratio of the above-mentioned respective components of the above-mentioned resin (A) is determined by considering the glass transition temperature and the acid value, and it cannot be ambiguous, but "has a branch and/or a fat in the side chain." The basis of the ring structure is preferably 10 to 70 mol%, more preferably 1 5 to 6 5 mol%, and particularly preferably 2 0 to 60 mol%. When the group having a branching and/or alicyclic structure in the side chain is within the above range, good developability is obtained, and the image forming liquid resistance of the image portion is also good. Further, the "base having an acidic group in the side chain" is preferably from 5 to 70 mol%, more preferably from 10 to 60 mol%, particularly preferably from 20 to 50 mol%. When the group having an acidic group in the side chain is within the above range, good curability and visibility can be obtained. Further, the "base having an ethylenically unsaturated group in the side chain" is preferably from 1 〜 to 70 mol%, more preferably from 20 to 70 mol%, particularly preferably from 30 to 70 mol%. When the group having an ethylenically unsaturated group in the side chain is within the above range, the pigment dispersibility is excellent, and the developability and the curability are also good. The content of the resin (A) is preferably from 5 to 70% by mass, more preferably from 10 to 50% by mass, based on the total solid content of the photosensitive resin composition. The resin (A) may contain other resins described later, but is preferably only the resin (A). ϋ A other resin - The resin which can be used for the above-mentioned resin is preferably a compound which exhibits swelling property with respect to an alkaline aqueous solution, and more preferably a compound which is soluble for an aqueous alkaline solution. The resin which exhibits swellability or solubility in the alkaline aqueous solution is, for example, a compound having an acidic group, and particularly preferably a compound having an ethylenically unsaturated double bond and an acidic group introduced into the epoxy compound. Oxy acrylate compound), an ethylene-33-200837499-based copolymer having a (meth) acrylonitrile group and an acidic group in a side chain, an epoxy acrylate compound, and a (meth) acrylonitrile group and an acid group in a side chain A mixture of a vinyl copolymer, a maleic acid copolymer or the like. The acidic group is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, from the viewpoint of availability of raw materials and the like, Jia can cite the carboxyl group. - the ratio of the resin (A) to the other resin: the total content of the resin (A) and the resin which can be used is preferably from 5 to 70% by mass based on the total solid content of the photosensitive resin composition. Good for 1 〇 ~ 50 0% by mass. When the content of the solid content is less than 5% by mass, the film strength of the photosensitive layer described later tends to be weak, and the adhesiveness of the surface of the photosensitive layer is deteriorated. When the content exceeds 70% by mass, the exposure sensitivity is lowered. Further, the above content means a solid content. In the present invention, as the polymerizable compound (B), the photopolymerization initiator (C), and other components other than the above, a component of a well-known constituent component can be suitably used. For example, the components described in paragraphs [0010] to [0020] of JP-A-2006-23 696, or the paragraph numbers [0027] to [005 3] of JP-A-2006-6492 1 can be cited. The ingredients listed. The mass ratio ((B)/(A) ratio) of the polymerizable compound (B) to the resin (A) is preferably from 0.3 to 1.5, more preferably 〇·4~, in relation to the resin (A). 1.4' is particularly good for 0.5~1·2. If the (Β)/(Α) ratio is within the above preferred range, a light gap having good developability and mechanical strength can be obtained. In the photosensitive resin composition of the present invention, one or two or more kinds of conventional pigments suitable for use in color filters can be selected according to the purpose. (Coloring Pigment) In the photosensitive resin composition of the present invention, one or two or more kinds of conventional pigments suitable for use in color filters can be selected according to the purpose. As the pigment which can be used for the photosensitive resin composition of the present invention, various conventional inorganic pigments or organic pigments can be used. Further, even if it is considered that the photosensitive resin composition to be formed is preferably a high light transmittance, it is preferable to use a pigment having a fine particle diameter as much as possible, and also consider handling property. The average particle diameter of the above pigment is preferably Ο.ΟΙμιη~Ο.ίμιη, more preferably 〇.〇ιμιη~〇·〇5μιη. In addition, examples of the inorganic pigment include a metal compound represented by a metal oxide or a metal salt, and specific examples thereof include iron, cobalt, aluminum, separator, lead, copper, titanium, magnesium, chromium, zinc, and lanthanum. a metal oxide such as a composite oxide of the foregoing metal. Examples of the organic pigment include CI·Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, and 180. , 185, 199; c · I · Pigment Orange 3 6 , 3 8 , 4 3 , 7 1 ; CI Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270; CI Pigment Violet 19, 23, 32, 39; CI Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60 - 35- 200837499 C · I · Pigment Green 7, 3 6, 3 7 ; C. I. Pigment Brown 2 5, 2 8 ; C · I · Pigment Black 1, 7; Carbon Black, etc. In the present invention, it is preferred to use a N atom having a basicity particularly in the structural formula of the pigment. These pigments having a basic N atom exhibit good dispersibility in the composition of the present invention. Although the reason for this is not very clear, it is presumed to affect the affinity of the photosensitive polymer component to the pigment. The pigment which can be preferably used in the present invention includes the following. However, the invention is not limited by these. CI·Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185, c · I · Pigment Orange 3 6 , 7 1 , CI·Pigment Red 122, 150, 171, 175, 177, 2〇9, 224, 242, 254, 255, 264, CI Pigment Violet 19, 23, 32, C·1. Pigment Blue 15 : 1, 15 : 3, 15 : 6, 16, 22 , 6〇, 66 C. I. Pigment Black 1. These organic pigments may be used alone or in order to increase the color purity, and various combinations may be used. The pigments which are red on the following are shown, and specific examples of the combination of the fluorenylpyrrole pigments alone or the like can be used. For example, as a pigment, an anthraquinone pigment, at least one of a diketopyryl, a diazo-yellow yellow-36-200837499 pigment, an isoporphyrin yellow pigment, a quinacone yellow pigment or an anthraquinone red pigment. Mix and so on. For example, as the quinone-based pigment, C. I. Pigment Red 177, as the quinone-based pigment, c · ; [· Pigment Red i 5 5, c · I. Pigment Red 224 ' as two The ketopyrrolopyrrole pigment may, for example, be cI pigment red 2 5 4 '. From the viewpoint of color reproducibility, it is preferably mixed with c · I. Pigment Yellow 1 3 9 . Also, the quality of the red pigment and the yellow pigment is preferably i 〇〇: 5 〜1 00:50. When it is 1 〇〇:4 or less, it is difficult to suppress the light transmittance of 400 nm to 500 nm, and the color purity may not be improved. Further, at 100: 5 i or more, the dominant wavelength is composed of a short wavelength, and the deviation from the N T S C target hue is large. In particular, the above mass ratio is most suitable in the range of 1 〇〇:1 〇1 〇〇:3 。. Further, when the red pigments are combined with each other, they can be adjusted in accordance with the chromaticity. Further, as the green pigment, a halogenated phthalocyanine pigment may be used alone, or a diazo yellow pigment, a quinacone yellow pigment, an azomethine yellow pigment or an isoporphyrin system may be used. A mixture of yellow pigments. For example, as such an example, more preferably C · I · Pigment Green 7, 3 6 , 3 7 and C · I · Pigment Yellow 8 3, C · I · Pigment Yellow 1 3 8 , C · I. Pigment Yellow 1 3 9. C · I · Mixture of Pigment Yellow 150, CI·Pig Yellow 180 or CI Pigment Yellow 185. The quality of the green pigment and the yellow pigment is preferably 100:5 to 1 00:1 50. When the mass ratio is less than 1 〇〇:5, it is difficult to suppress the light transmittance of 400 nm to 450 nm, and the color purity may not be improved. Further, if it exceeds 100:150, the dominant wavelength is composed of a long wavelength, and the deviation from the NTSC target hue is large. The above quality bits are preferably in the range of 100:30 to 100:120. As the blue pigment, a phthalocyanine pigment may be used alone, or -37-200837499 may be used in combination with a diterpene violet pigment. For example, a mixture of ci•pigment blue 15:6 and C丄Pigment Violet 23 is preferred. The quality of the blue pigment and the purple pigment is preferably 100:0 to 1 00:3 0, more preferably 1 〇〇:1 〇 or less. Further, as the pigment for the black matrix, a carbon pigment other than the above-described black pigment, titanium carbon, iron oxide or oxidized oxide may be used singly or in combination, and a combination of the black pigment and titanium carbon is preferred. Further, the mass ratio of the black pigment to the titanium carbon is preferably in the range of 100:0 to 100:60. If it is 1〇0:61 or more, the dispersion stability will be lowered. (The average particle diameter r (unit: nm) of the pigment in the present invention preferably satisfies 20 S rg 300, preferably 125 Si: S250, and particularly preferably satisfies 30 Sr $ 200. By using a pigment having such an average particle diameter r, The red and green pixels of high contrast and high light transmittance. The "average particle diameter" as used herein means the average particle diameter of the secondary particles collected by the primary particles (single microcrystals) of the pigment. The particle size distribution of the secondary particles of the pigment which can be used in the following (hereinafter referred to as "particle size distribution"), and the secondary {: particles in the (average particle size) nm is preferably 70% by mass of the whole The above is preferably 80% by mass or more. <Pigment Dispersant> In the present invention, a known pigment dispersant can be used because a pigment is used as a colorant. As the pigment dispersant, a polymer dispersant can be mentioned. [e.g., polyamine amines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly(methyl)propionic acid esters, (meth)acrylic copolymer, naphthalenesulfonic acid formalin condensate] And polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, polyalcoholamine, pigment-38-200837499 derivative, etc. Polymer dispersant, according to its structure can be more classified into linear polymer, terminal denaturation The polymer, the graft polymer, and the block polymer. The polymer dispersant acts on the surface of the pigment to prevent re-agglomeration. Therefore, a preferred structure is provided for anchoring the surface of the pigment. The terminal modified polymer, the graft polymer, and the block polymer. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the surface of the pigment. Specific examples of the pigment dispersant usable in the invention include "Disperbyk-101 (polyammonium amine phosphate), 1〇7 (carboxylate), and 110 (acid group-containing copolymer) manufactured by BYK Chemie. ), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), manufactured by EFKA Corporation" EFKA4047, 4050, 4010, 4165 (polyurethane system) , EFKA4330, 4 3 4 0 (block copolymer), 4 4 0 0, 4 4 0 2 (modified polyacrylate), 5010 (polyester decylamine), 5 765 (high molecular weight polycarboxylate), 6220 (I fatty acid polyester), 6745 (anthocyanine derivative), 675 0 (azo pigment derivative), "Ajisper PB821, PB822" manufactured by Ajinomoto Precision Technology Co., Ltd., "Floren", Kyoeisha Chemical Co., Ltd. TG-710 (amine acrylate oligomer), "Polyflow Ν〇 50Ε, Νο·3 00 (acrylic copolymer)", Nanben Chemical Co., Ltd. "Dispar Ion KS-860, 873SN, 874, #2150 (aliphatic polyvalent carboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725", "Demoru RN, N (Naphthalenesulfonic acid formalin polycondensate) manufactured by Kao Corporation , MS, C, SN-B (aromatic condensate of aromatic sulfonic acid), "-39- 200837499

Homogenol L-18 (polymeric polydecanoic acid), "Emulgen 920, 930, 93 5, 9 8 5 (polyoxyethylene nonylphenyl ether)", "Acetamine 86 (stearylamine acetate)", "Soluspass 5000 (anthocyanine derivative), 22000 (azo pigment derivative), 1 3240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional portion at the end), 24000, manufactured by LUBRIZOL Co., Ltd. 28000, 32000, 38500 (graft type polymer)", Nikol T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate), etc. . In the photosensitive resin composition, the content of the coloring pigment is preferably 30% by mass or more and 90% by mass or less, more preferably 40% by mass or more and 85% by mass based on the total solid content of the composition. % or less is particularly preferably 50% by mass or more and 80% by mass or less. —Microparticles (D)— In the above photosensitive resin composition, fine particles are preferably added. The fine particles (D) are not particularly limited, and can be appropriately selected according to the purpose. For example, the extender pigments described in JP-A-2003-302639 [0035] to [0〇41] are preferred, wherein From the viewpoint of obtaining a photoclear having good developability and mechanical strength, it is preferable that the average particle diameter of the colloidal vermiculite (D) is from the optical spacer having high mechanical strength. From the viewpoint of preference, it is preferably 5 to 5 nm, more preferably 1 to 40 nm, and particularly preferably 15 to 30 nm. Further, the content of the aforementioned fine particles (D) is higher in the total solid content of the photosensitive resin composition of the present invention -40-200837499 from the viewpoint of obtaining a light spacer having high mechanical strength. Preferably, it is 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 1 to 5 to 30% by mass. [Patterning Step] The patterning step in the present invention is performed by exposing and developing the photosensitive resin layer formed on the support. As a specific example of the patterning step, a formation example described in paragraphs [0071] to [0077] of JP-A-2006-6492 1 or JP-A No. 2-6-23696 can be cited. The steps and the like described in the paragraph numbers [0040] to [005 1] are considered as suitable examples of the present invention. &lt;Substrate for Liquid Crystal Display Device&gt; The substrate for liquid crystal display 7K device of the present invention has the optical spacer obtained by the method for producing the optical spacer of the present invention. The optical spacer is preferably formed on the display light-shielding portion such as a black matrix formed on the support or on a driving element such as a TFT. In addition, a transparent conductive layer (transparent electrode) such as i τ 或 or a liquid crystal alignment film such as polyimide may be present between a light-shielding portion for display such as a black matrix or a driving element such as a TFT and a light gap. . ν For example, when the optical spacer is provided on the display light-shielding portion or the driving element, the support is provided with a display light-shielding portion (black matrix or the like) or a driving element that is disposed in advance, for example, the photosensitive resin is transferred. The photosensitive resin layer of the printing material is laminated on the support surface, and the photosensitive resin layer is peeled off to form a photosensitive resin layer, and then exposure, development, heat treatment, or the like is applied thereto to form a photo spacer, and the liquid crystal display of the present invention can be produced. Substrate for the device. In the substrate for a liquid crystal display device of the present invention, colored pixels such as red (R), blue (Β), and green (G) may be further provided as needed. -41-200837499 &lt;Liquid crystal display element&gt; The substrate for a liquid crystal display device of the present invention can be provided to constitute a liquid crystal display element. In one of the liquid crystal display elements, at least one of the light-transmitting pair of supports (including the substrate for a liquid crystal display device of the present invention) includes at least a liquid crystal layer and a liquid crystal driving means (including a simple matrix driving method and Active matrix drive mode). In this case, the substrate for a liquid crystal display device of the present invention can be configured as a color filter substrate having a plurality of RGB pixel groups and each pixel of the pixel group being separated from each other by a black matrix. . In the color filter substrate, a liquid crystal display element including the color filter substrate is provided in order to provide an optical spacer having a uniform height and excellent deformation recovery property, thereby suppressing the relationship between the color filter substrate and the counter substrate. The occurrence of uneven cell gap (change in cell thickness) effectively prevents the occurrence of display unevenness such as color unevenness. Thereby, the liquid crystal display element produced can display a clear image. Further, as another aspect of the liquid crystal display device, at least one of the light-transmitting pair of supports (including the substrate for a liquid crystal display device of the present invention) 1 may have at least a liquid crystal layer and a liquid crystal driving means. The liquid crystal driving device includes an active device (for example, a TFT), and a predetermined width is controlled by a light spacer having a uniform height and excellent deformation recovery between a pair of substrates. In this case, the liquid crystal display of the present invention is used. The device substrate may be configured as a color filter substrate having a plurality of RGB pixel groups and each pixel of the pixel group being separated from each other by a black matrix. As the liquid crystal which can be used in the present invention, nematic liquid crystal, biliary-42-

C

200837499 Sterol liquid crystal, smectic liquid crystal, ferroelectric liquid crystal. Further, the pixel group of the color filter substrate may be composed of two-color pixels of different colors, or may be composed of three-color pixels and upper pixels. For example, in the case of three colors, it is composed of three hues of red (R) and blue (B). The pixels for RGB three colors are preferably arranged in a mosaic type or a triangular type, and are arranged in a four-color group. In the production of the color filter substrate, after forming a pixel group of two or more colors, black may be formed as described above. Alternatively, a black matrix may be formed to form a pixel group. In the liquid crystal display device of the present invention, the liquid crystal display device of the present invention is constructed by the above-mentioned liquid crystal display device. Further, the liquid crystal display device of the present invention is constituted by a front display element. That is, between the plates disposed opposite to each other, as described above, the predetermined width is controlled by the spacer formed by the optical spacer method of the present invention, and the material is controlled in the controlled gap (the enclosed portion is called It is composed of a liquid crystal layer, and the thickness of the liquid crystal layer is maintained at a desired uniform thickness. The liquid crystal display mode of the liquid crystal display device can be suitably STN type, TN type, GH type, ECB type, ferroelectric liquid crystal, β liquid crystal, VA type, IPS type, OCB type, ASM type, and other names. In the liquid crystal display device, from the viewpoint of the most effective effect of the brightening, it is desirable that the display mode is likely to be uneven due to the cell _ of the liquid crystal cell, and it is preferable that the crystal cell exhibits 5: 4 colors, In the case of the green (G) group, the upper picture can be, for example, a matrix, and the RGB picture is set with a liquid crystal. A pair of base light is used to enter the liquid crystal (the cell is given by a ferroelectric species. I cost L The variation 1 is a VA type display mode, an IPS type display mode, and an OCB type display mode of 2 - 43 - 200837499 to 4 μηι. As a basic configuration of the liquid crystal display device of the present invention, (a) a thin film transistor is exemplified. A driving side substrate in which a driving element such as (TFT) and a pixel electrode (conductive layer) are arranged, and a counter substrate including a counter electrode (conductive layer) are disposed to face each other with a light gap interposed therebetween, and liquid crystal is sealed in a gap portion thereof. Material composition, (b) drive base The liquid crystal display device of the present invention can be suitably used in various liquid crystal display devices, and the counter substrate having the counter electrode (conductive layer) is disposed to face each other with the optical gap interposed therebetween, and the liquid crystal material is sealed in the gap portion. The liquid crystal display device is described in, for example, "Second-generation liquid crystal display technology (Edited by Uchida Natsuo, Side Industry Survey, issued in 1994)." The liquid crystal display device of the present invention includes the liquid crystal display of the present invention. The liquid crystal display device of various types described in the above-mentioned "second-generation liquid crystal display technology" is exemplified, and is particularly effective for a liquid crystal display device constituting a color TFT system. The liquid crystal display device is described in, for example, "Color TFT liquid crystal display (published by the company, published in 1996)". In addition to the liquid crystal display element of the present invention, the liquid crystal display device of the present invention generally uses an electrode. Substrate, polarizing film, retardation film, backlight, spacer It is composed of various types of members such as a wild-field compensation film, an anti-reflection film, a light-diffusing film, and an anti-glare film. These members are described, for example, in the "94 Liquid Crystal Display Peripherals and Chemicals Market (Minami Kentaro, CMC Corporation) , [9,94,4), r 2 〇〇3 Liquid Crystal-44- 200837499 Status and Future Outlook of the Related Markets (Vol. 2) (Former Liangji, Fuji Chimeu Co., Ltd., 2003, etc.) The present invention will be more specifically described by the following examples, but the present invention is not limited by the following examples, and the "%" and "parts" are as long as they are not specified. Based on quality. (Example 1): Preparation of transfer-method for photosensitive transfer film - On a polyethylene collide film temporary support (PET temporary support) having a thickness of 75 μm, the coating was as follows The coating liquid for a thermoplastic resin layer composed of the prescription A was dried to form a thermoplastic resin layer having a dry layer thickness of 6.0 μm. [Prescription of Coating Solution for Thermoplastic Resin Layer] • Methyl methacrylate/acrylate 2-ethylhexyl ester/benzyl methacrylate/methacrylic acid copolymer (= 5 5/ 1 1.7/4.5/2 8.8 [Morby], weight average molecular weight 90,000) • Styrene/acrylic acid copolymer 2 5.0 parts 5 8 · 4 parts (= 63 /3 7 [mole ratio], weight average molecular weight 8,00 0) • 2, 2-bis[4-(methacryloxypolyethoxy)phenyl]propane 3 9.0 parts • Surfactant 1 (Megafac F-7 80-F, manufactured by Dainippon Ink Chemical Industry Co., Ltd.) 1 0,0 parts •Methanol •1 -Methoxy-2-propanol 9 0.0 parts 5 1 . 〇-45- 200837499 • Butanone 700 parts Next, on the formed thermoplastic resin layer, coated by The coating liquid for the intermediate layer composed of the following formulation 使 was dried to laminate an intermediate layer having a dry layer thickness of 1.5 μm. [Prescription of coating solution for intermediate layer] • Polyvinyl alcohol 3.22 parts (PVA-205, saponification rate 80%, manufactured by Kuraray Co., Ltd.) • Polyvinylpyrrolidone 1.49 parts (PVP Κ-30, ISP Manufactured by Japan Co., Ltd.) • Methanol 4 2 · 3 parts • Distilled water 5 2 4 parts, and coated with a photosensitive resin layer consisting of the prescription 1 shown in Table 1 below, on the intermediate layer formed. The cloth liquid was dried to laminate a photosensitive resin layer having a dry layer thickness of 3.9 μm. In the above, the laminated structure of the PET temporary support/thermoplastic resin layer/intermediate layer/photosensitive resin layer (the total layer thickness of the three layers is η.6 μm) is formed (more on the surface of the photosensitive resin layer, heating, Pressing and pasting a film made of polypropylene having a thickness of 1 2 μm as a cover film, and obtaining a photosensitive transfer film (1) for a spacer. -46-200837499 [Table 1] Example 1 Comparative Example 1 Composition of photosensitive resin Prescription 1 Prescription 2 MMPGAC 649 649 Butanone 71.5 71.5 Colloidal vermiculite dispersion (colloidal vermiculite: 30 parts, methyl pentanone: 70 parts, MIBKst, Nissan Chemical Industry) 220 220 Soluspass 20000 (made by ZENECA) 6.6 6.6 DPHA solution (dipentaerythritol hexaacrylate: 76 parts, propylene glycol monomethyl ether acetate: 24 parts) 149 149 CHMA/GMA/MAA (Morby = 30:40:30) resin solution ( Solid content acid value: l〇〇mgKOH/g, Mw: 18,000, MMPGAC 45% solution) 336 336 Initiator A 3.72 0 Initiator B 0 3.72 Hydroquinone monomethyl ether 0.06 0.06 Surfactant 1 0.53 0.53 Victoria Pure Blue 5% of B0HM (made by Hodogaya Chemical Industry Co., Ltd.) Solution 33.7 33.7 (modulation of resin solution shown by CHMA/GMA/MAA (cyclohexyl methacrylate/glycidyl methacrylate/methacrylic acid) = 3 0:40:3 0) Into the reaction vessel, 13.56 parts of methoxymethoxy-2-propanol (MMPGAC, manufactured by DAICEL Chemical Industry Co., Ltd.) was added in advance, and the temperature was raised to 90 ° C. 8.24 parts of cyclohexyl methacrylate from -47 to 200837499, 9 a mixed solution of 84 parts of methacrylic acid, 1 part of an azo polymerization initiator (V-601 manufactured by Wako Pure Chemical Industries, Ltd.), and 13.5 parts of 1-methoxy-2-propanol. Under a nitrogen atmosphere, it was dropped into a reaction vessel at 90 ° C for 2 hours. After the dropwise addition, the reaction was allowed to proceed for 4 hours to obtain an acrylic resin solution. Next, after adding 0.01415 parts of hydroquinone monomethyl ether and 0.06 8 parts of tetraethylammonium bromide to the acrylic resin solution, 9.28 parts of glycidyl methacrylate was added dropwise over 2 hours. After the dropwise addition, the reaction was carried out at 90 ° C for 4 hours while blowing air, and a solvent was added thereto to prepare a solid concentration of 45 %, thereby obtaining the following compound P ( X : y : z = 3 0 : 3 0 : 4 0 (mole ratio)) Resin solution (solid content acid value: l〇〇mgKOH/g, Mw: 18, 〇〇〇, MMPGAC 45% solution). Further, the molecular weight Mw of the resin represented by the above compound P1 means a weight average molecular weight. The measurement method of the above molecular weight is measured by a gel permeation chromatography (GPC).

Compound P

&lt;Initiator A&gt;

&lt;Initiator B&gt; -48 200837499 - Production of color filter substrate (support according to the present invention) - Paragraph No. [0084] to [0095] of JP-A-2005-3 86 1 According to the method described, a color filter having a black matrix, R pixels, G pixels, and B pixels is produced. Next, on the R pixel, G pixel, B pixel, and black matrix of the color filter substrate, a transparent electrode of IT 0 (indium tin oxide) is formed by sputtering. - Fabrication of Optical Gap - The film of the photosensitive transfer film (1) is peeled off from the obtained gap, and the surface of the exposed photosensitive resin layer is superposed on the color of the ITO film formed by sputtering described above. On the IT0 film of the filter substrate, Lamu type II [manufactured by Hitachi Industrial Co., Ltd.] was used, and under the pressure and heating conditions of 10 ON/cm and 130 °C, the conveying speed was 2 m/min. fit. Then, the PET temporary support is peeled off at the interface with the thermoplastic resin layer, and the photosensitive resin layer, the thermoplastic resin layer, and the intermediate layer are transferred (resin layer forming step). Next, a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Co., Ltd.) having an ultrahigh pressure mercury lamp is used, in which the mask and the thermoplastic resin layer face each other, in a photomask (a quartz exposure mask having an image pattern) and When the color filter substrate is disposed in a substantially parallel and vertically erected state, the distance between the surface of the contact surface of the mask layer and the intermediate layer of the photosensitive resin layer is set to be 40 μm 'through the reticle' from the thermoplastic The resin layer side was subjected to proximity exposure at an exposure amount of 100 mJ/cm 2 . -49- 200837499 Next, a triethanolamine-based imaging solution (containing 30% by mass of triethanolamine, trade name: T-PD2, manufactured by Fuji Photo Film Co., Ltd., 12 times by pure water (by 1 part by mass) The ratio of T-PD2 to 11 parts by mass of pure water is mixed) diluted solution, and sprayed at a flat nozzle pressure of 0 · 〇4 Μ P a at 30 ° C for 50 seconds to remove A thermoplastic resin layer and an intermediate layer. Then, after blowing air on the substrate to remove the liquid, pure water was sprayed by a shower for 10 seconds to be washed by pure water spray, and air was blown to reduce the retention of liquid on the substrate. Next, a sodium carbonate-based developing solution (containing 0.38 mol/liter sodium hydrogencarbonate, 0.47 mol/liter sodium carbonate, 5% by mass sodium dibutylnaphthalenesulfonate, an anionic surfactant, defoaming) Agent, stabilizer; trade name · T-CD 1 , manufactured by Fuji Photo Film Co., Ltd.), sprayed for 30 seconds at a cone pressure of 0.1 5 MPa at 29 °C to image the photosensitive resin layer And get a patterned portrait. Then, the detergent (trade name: T-SD3 Fuji Photo Film Co., Ltd.) was diluted 1 times with pure water, and was sprayed by a shower at a pressure of 0.02 MPa at 33 ° C for 20 seconds. Then, the formed image is brushed with a rotating brush having a bristles to remove the residue, and a gap sub-pattern is obtained (patterning step). In addition, the exposure amount at the time of exposure is from 10 to 100 mJ every 10 mJ, and the shape of the patterned optical spacer and the presence or absence of the development step are confirmed, and the minimum exposure necessary for curing the photosensitive resin layer is examined. the amount. If the amount of exposure does not satisfy the necessary amount, the shape or size of the optical spacers may become irregular. The minimum necessary for curing the photosensitive resin layer is -50-200837499, and the exposure amount is 40 mJ/cm2. Then, the surface was exposed from the surface on which the optical spacer was formed (the surface on which the photosensitive resin layer was formed; the surface) by a mercury lamp at 300 mJ/cm 2 . At this time, the exposure amount of the opposite surface of the surface on which the optical spacer was formed (the opposite surface of the surface on which the photosensitive resin layer was formed; the inside) was OmJ/cm2.

Next, the color filter substrate provided with the spacer sub-pattern is subjected to a heat treatment (heat treatment step) at 23 ° C for 44 minutes to produce a photo spacer, and the obtained spacer pattern is 24 μm in diameter. The average height is 3.7 μηη in the shape of a cylinder. Furthermore, a three-dimensional surface structure analysis microscope (manufacturer: ZYGO Corporation, type: New View 5022) was used for each of the obtained optical spacers, and the transparent electrode forming surface of the distance was measured. The highest position, with its average as the average height of the optical gap. &lt;Production of Liquid Crystal Display Device&gt; In the other way, a glass substrate serving as a counter substrate is prepared, and a pattern for PVA mode is applied to the transparent electrode of the color filter substrate obtained above and to the counter substrate. An alignment film made of polyimine is further disposed thereon. Then, the sealant of the ultraviolet curable resin is applied by a dispensing method at a position corresponding to the outer frame of the black matrix provided around the pixel group surrounding the color filter, and the liquid crystal for PVA mode is dropped, and the relative direction After the substrates are bonded together, the bonded substrates are irradiated with UV, and then heat-treated to cure the sealant. On both sides of the liquid crystal cell thus obtained, the polarizing plate HLC2-25 1 8 manufactured by the company is available from -51-200837499. Next, FR1112H (wafer type LED manufactured by STANLEY Electric Co., Ltd.) was used as red (R) LED, DG1112H (wafer type LED manufactured by STANLEY Electric Co., Ltd.) as green (G) LED, DB1112H (STANLEY Electric) A wafer type LED manufactured by the company of the company is a backlight of the side light type as a blue (B) LED, and is disposed on the back side of the liquid crystal cell on which the polarizing plate is provided to form a liquid crystal display device. [Comparative Example 1] The coating liquid for a photosensitive resin layer formed in the prescription 2 of Table 1 was used instead of the coating liquid for the photosensitive resin layer formed in the prescription 1 of Table 1, and Example 1 was used. Similarly, an optical spacer and a liquid crystal display device are obtained. (Example 2): Coating method - Preparation of optical spacer (liquid photoresist method) - On the tantalum film of the color filter substrate on which the tantalum film was formed by sputtering in Example 1, by having a slit The coating liquid for a photosensitive resin composition layer formed by the prescription 1 I shown in Table 1 above was coated with the coating machine MH-1600 (manufactured by FAS Asia Co., Ltd.). Next, a vacuum dryer VCD (manufactured by Tokyo Ohka Co., Ltd.) was used, and a part of the solvent was dried in 30 seconds to lose the fluidity of the coating film, and then prebaked at 120 ° C for 3 minutes to form a film thickness of 3.9 μm. Photosensitive resin composition layer (layer formation step). Next, a light spacer was formed on the color filter substrate by the same patterning step and heat treatment step as in the first embodiment. However, the exposure amount was 300 mJ/cm2, and the development of the lanthanide developing solution was 23 ° C for 60 seconds. The resulting gap sub-pattern was a cylindrical shape of a diameter of 24 μm and an average height of 3·7 μm. After the production of the optical spacer, the PVA of the present invention was produced in the same manner as in Example 1 using this color filter substrate. Mode liquid crystal display device. [Evaluation] The obtained substrate with the spacer was observed from the oblique direction of the substrate by SEM (300 times), and the cross-sectional shape of the spacer was confirmed. A good shape means a smooth cone. [Table 2] Initiator type Cross-sectional shape Example 1 Initiator A Conical taper Example 2 Initiator A Cone ~ Comparative Example 1 Initiator B Inverted cone

As is apparent from the above Table 1, in the examples of the use of the initiator A of the present invention, the obtained cross-sectional shape of the spacer showed a smooth shape and was judged to be good. On the other hand, in the comparative example using the initiator B, the cross-sectional shape was inverted, and it was judged to be inferior. -53-

Claims (1)

200837499 X. Patent application scope: 1 . A photosensitive resin composition comprising a polymerizable compound, a crosslinkable binder, and a photopolymerization initiator represented by the following formula (I), which contains The photopolymerization initiator of 4% by mass or more and 12% by mass or less of the compound, the general formula (I) CHmX3, (in the formula (I), R1 and R2 each independently represent a hydrogen atom, an alkyl group, an aryl group, a group of the following formula (Ι-A) or (IB); and R1 and R2 may be bonded to each other The bonded nitrogen atoms together form a heterocyclic ring formed by a non-metal atom; R3 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group; W represents a halogen atom; and X and Y each independently represent a chlorine atom or a bromine atom. ;m, n each independently represent 〇, 1 or 2), general formula (IB) Formula (I - A) 0 R5 - Ο - 0-CH2 - (In the formula (Ι-A) and (Ι-Β), R5, R6, and R7 each independently represent an alkyl group or an aryl group) ° 2 . The photosensitive resin composition of claim 1, wherein the photosensitive resin composition is formed into a spacer. In the case of the photopolymerization initiator represented by the above formula (1), the counter 3 in the formula (1) is a hydrogen atom, Both m and η are oxime, and both X and Y are chlorine atoms. Both R1 and R2 represent the formula (Ι-Α), and R5 is an alkyl group. 4. A photosensitive resin transfer film which is characterized in that it is a photosensitive resin transfer film having at least a photosensitive resin layer on a temporary support, and the photosensitive resin layer is used in the photosensitive property as in the first aspect of the patent application. A resin composition is formed. A method for producing a light-gap, characterized by the step of forming a photosensitive resin layer on a support by coating using a photosensitive resin composition as in the first aspect of the patent application. 6. A method for producing a light gap, characterized by having a photosensitive resin transfer film using the fourth aspect of the patent application, and transferring the photosensitive film on the support by heat, pressure, or heat and pressure The step of the resin layer. A substrate for a liquid crystal display device, characterized by comprising a photo spacer manufactured by the method of manufacturing a photo spacer according to claim 5 of the patent application. A substrate for a liquid crystal display device characterized by comprising a photo spacer manufactured by the method for producing a photo spacer according to claim 6 of the patent application. A liquid crystal display device comprising the substrate for a liquid crystal display device according to claim 7 of the patent application. A liquid crystal display device comprising the substrate for a liquid crystal display device according to claim 8 of the patent application. -55- 200837499 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 j\ \\ 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: