TWI380132B - Photosensitive resin composition - Google Patents

Description

1380132 25608pifl Revision date June 8, 2011 is No. 96140539 Chinese manual without scribe correction. 6. Description of the invention: 1. Field of the Invention The present invention relates to a process for curing by using a process including light irradiation, which can be carried out. An alkali resin developed and used for forming a photosensitive resin composition for a projection for a liquid crystal display element and a projection for a liquid crystal display element formed using the composition. [Prior Art] The liquid crystal display is displayed such that the display side substrate and the liquid crystal driving side substrate are opposed to each other, and a liquid crystal compound is sealed between the two to form a thin liquid crystal layer, and the liquid crystal driving side substrate is used to electrically control the liquid crystal layer. The liquid crystal is aligned so that the amount of transmitted light or reflected light on the display side substrate is selectively changed to perform display. The driving method of the liquid crystal panel includes: TN (Twisted Nematic) mode, IPS (In-Plane-Switching) mode, VA (Vertical Alignment) mode, simple matrix mode, and active matrix ( Various modes of operation such as Active Matrix). And 'In recent years, from the perspective of improving the contrast and viewing angle of liquid crystal displays, MVA (Multi-domain Vertically Aligned) type LCD (vertical alignment type) has been specially developed in the VA (Vertical Alignment) method. LCD Monitor). The above MVA type LCD utilizes a birefringence mode in which a negative liquid crystal having negative dielectric anisotropy and a vertical alignment film are combined, and a liquid crystal located at a position close to the alignment film even in a state where no voltage is applied. The alignment direction is also substantially vertical, so the contrast, the viewing angle, and the like are excellent. 4 1380132 256〇8pifl is the Chinese manual of 96140539. There is no scribe correction. This correction date is June 8th, 2011. In the above MVA type liquid crystal display, a plurality of alignments can be obtained in one pixel region; the same on the crystal substrate The pixel area poem and method are formed on the light incident side and are right obliquely--in the position of the electrode different from the slit/there is a large slope (semi-convex lens shape, etc.). The sensation of the sensory nucleus forming the above-mentioned surface requires and has a non-(iv) liquid crystal chromaticity and electric dust retention characteristics and phase contrast. In response to the above requirements, some people have studied the use of hydrophilic containing =? A photosensitive resin composition of a polymer (Patent Document 2). However, the above-mentioned photosensitive resin composition has a very poor shadow property. [Patent Document-1] Japanese Laid-Open Patent Publication No. 2004-333964 [Patent Document-2] 曰本特开2〇〇5_221974号 [Abstract] In order to solve the above problems, a photosensitive resin composition for forming a protrusion for liquid enthalpy, particularly a protrusion for a vertical alignment type liquid crystal display element, which has good alkali developability and excellent cured product Liquid crystal alignment and voltage retention characteristics. In order to solve the above problems, the inventors of the present invention conducted intensive studies, and as a result, completed the present invention. That is, the present invention relates to a photosensitive resin composition (Q) for forming a projection for a liquid crystal display element which can be subjected to alkaline development, and the composition includes a hydrophilic resin containing a (fluorenyl) acrylonitrile group and a carboxyl group. (A), polyoxetane (B), and a photoradical polymerization initiator (C); and a protrusion for a liquid crystal display element which is formed by curing the above composition by a process including light irradiation. 5 25608 pi s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s The composition is excellent in developability. The liquid crystal display element has excellent protrusion liquid crystal alignment properties. • The liquid crystal display element bumps have excellent voltage holding characteristics. The above description is only an overview of the technical solutions of the present invention, and the technical means of the present invention can be more clearly understood, and can be implemented in accordance with the description of the present invention. [Embodiment] The photosensitive resin composition of the present invention comprises a hydrophilic resin (A) containing a (meth)acryl fluorenyl group and a carboxyl group (hereinafter referred to as a hydrophilic resin (A) or simply as ( A)]; polyoxyalkylene (B) [hereinafter sometimes only referred to as (B)]; and photoradical polymerization initiator (C) [hereinafter sometimes only referred to as (〇), the composition of the test The liquid crystal display element protrusion which is excellent in liquid crystal alignment property and voltage retention characteristics is provided by the composition. The protrusion for liquid crystal display element of the present invention is a substance for alignment of liquid crystal molecules, and is used. Compared with the gap control material (photospacer) which maintains the thickness of the liquid crystal layer between the color filter substrate and the thin film transistor (TFT) substrate, the purpose and use are completely different. That is, the purpose of the 'gap control material is only: For example, a columnar shape is formed at a position away from the pixel between the substrates so as not to affect the liquid crystal display quality, that is, the alignment property of the liquid crystal molecules as much as possible, while maintaining the interval between the two substrates uniformly and accurately; The purpose of the protrusion is By forming a semi-circular protrusion on the substrate, the liquid crystal 25608pifl sealed between the substrates is corrected on the date of June 8, 101, which is No. 96140539. The description of the surface of the protrusion is not aligned, so that the liquid crystal molecules are in one pixel. The region is capable of obtaining a plurality of alignment directions' to achieve satisfactory optical characteristics. It should be noted that, above and below, a representation of ((fluorenyl) acrylate such as "(fluorenyl) acrylate" means In the following, the essential constituent components (A) to (C) of the photosensitive resin composition of the present invention will be sequentially described. In the present invention, the 'hydrophilic resin (A) The hydrophilicity index is defined by HLb. Generally, the larger the value, the higher the hydrophilicity. The HLB value differs depending on the resin skeleton of (A) (for example, a vinyl resin, an epoxy resin, or a poly-based resin). The preferred range thereof is also different, and is preferably 4 to 19, more preferably 5 to 18, particularly preferably 6 to 17. Difficulty f(10) (4) (4) Development is better at development. Right (A) has an HLB value of 19 or less, and is cured. The resistance of the object is better. It is obvious that the hlb HLB value in the present invention indicates a hydrophilicity/hydrophobic balance value of 1 and a ratio of a predetermined organic value to an inorganic value: an organic compound HLB Pong 1〇χ inorganic Sexual/organic σ. Inorganic axis and money, _ value detailed agent 0 synthesis Μ (4) (synthesis of surfactants and = surface active shop release, Oda, Teramura) 5 〇 1 page or eight applications) (桢 • 界面 界面 界面 界面 》 》 》 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Preferably, it is 7 to 14, 1380132, 25608 pifl, and the date of revision is 61, 8, 曰, and the number of the syllabary correction is more preferably 8 to 13', particularly preferably 11 to 13. When the SP value is 7 or more, the developability can be better exhibited; when the SP value is 14 or less, the water resistance of the solid is better. The SP value in the present invention is a value calculated in accordance with the method described in Fedors et al., which is described in the following documents. POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, VoU4, No. 2, ROBERT F. FEDORS· (pp. 147-154)'' The above SP values indicate that the resins with similar SP values are easily mixed with each other. (Dispersibility 咼), an index in which the resins having large SP values are difficult to mix with each other. One molecule (A) has an average of at least one (fluorenyl) acrylonitrile group. The photocurability can be favorably exhibited by having a (meth) fluorenyl group. The amount of (meth)acryl fluorenyl group contained in (A) is represented by a (meth) acrylonitrile group (mmol/g). The concentration of the preferred (fluorenyl)propenyl group in (A) is from 1 〇 to 5 〇 mmol/g, more preferably from 2.0 to 4.0 mmol/g. The concentration of the '(fluorenyl)propenyl group in the present invention can be measured by a titration method using an addition reaction (Michael addition) of an amine on a double bond. The method is as follows. (1) A sample of about lg was accurately weighed and placed in a conical flask, and then about 10 ml of acetone was added to dissolve it. (ii) Add a morpholine standard solution [a solution of morphine and methanol in a ratio of 1:4 (capacity ratio)], and then add 1.5 ml of 50% acetic acid standard solution [to acetic acid and ion-exchanged water] The solution mixed with ι:ι (R. 25608pifl, dated June 8, 2011, No. 96140539, no-line correction) was shaken well and allowed to stand at room temperature for 15 minutes. (iii) Add 15 ml of acetonitrile and 10 ml of acetic anhydride to the above-mentioned Erlenmeyer flask and thoroughly shake off. (iv) Titration with a solution of 0 5 mol/L hydrochloric acid-sterol titration using a recording type automatic titrator. (v) Simultaneously perform a blank test and calculate using the following formula.

Double bond concentration (mmol/g) = fx(A-B)/2S where 'A : the number of mL of the 0.5 mol/L hydrochloric acid-sterol titration solution required for the titration of the sample. B: The number of mL of the solution for 〇 5 mol/L hydrochloric acid-sterol titration required for the blank test. f: potency of a 0.5 mol/L hydrochloric acid-sterol titration solution. S. Sample size (g). At least one molecule (A) has at least one carboxyl group. The amount of the tick base contained in (A) is represented by an acid value. When the acid value of (A) is greater than or equal to 1〇nigK〇H/g, it is easy to exhibit developability better; when the acid value of (A) is less than or equal to 5〇〇mgK〇H/g, it can be better played. Water resistance of the cured product. The acid value of the present invention can be measured by an indicator titration method using an alkaline titration solution. Methods as below. (1) A sample of about lg was accurately weighed, placed in an Erlenmeyer flask, and then dissolved in a neutral methanol-acetone solution [a solution in which acetone and decyl alcohol were mixed in a ratio of 丨: 容量 (volume ratio)]. (11) Add a few drops of phenolphthalein indicator and titrate with 〇1 m〇1/L potassium hydroxide. 25608pifl Revised date June 8, 101 Stomach and stomach 96140539 Chinese manual without scribe correction. Titration with /liquid. The reddish color of the indicator lasts for 3Q seconds and is the end point of neutralization. (iii) Calculate using the following formula. Acid value (mgKOH/g) = (Axfx5.6l)/s wherein A: 〇·ΐ m〇i/L The number of mL of the potassium hydroxide titration solution. f · 效·1 mol/L Potassium titanate titration solution. S : sample amount (g). t (A): a hydrophilic resin (A1) formed by converting an epoxy resin (hereinafter sometimes referred to simply as (A1)), a hydrophilic vinyl polymer (A2), and a hydrophilic polyester resin (A3), a hydrophilic polyamine resin (10)), a hydrophilic polycarbonate resin (A5), and a hydrophilic polyurethane resin (A6). (a) You can use either __ or two or more. Among them, (A1) is preferable from the viewpoint of photocuring reactivity and liquid crystal alignment property of the photosensitive resin composition. A preferred preparation method of (A1) is to react a monovalent tick acid containing a (meth) acrylonitrile group with an epoxy group in an epoxy resin (A1q) (hereinafter sometimes referred to simply as (A1.)). The epoxy group (IV) is produced, and the ruthenium (iv) acid samarium needle (4) (hereinafter sometimes referred to simply as (8)) and a part of the above-mentioned base group are reacted. (Al〇): an aliphatic epoxy resin [e.g., e卯(6) ri3r=G "2G2, PG-2G7 (all manufactured by Tohto Kasei Co., Ltd.), etc.] or an alicyclic (four) Na [for example, CY_179, CY_m, CY N5 (all are asahi

Epoxy company, etc.] or aromatic epoxy resin [such as benzoquinone, 曱酴 epoxy resin, double _ epoxy resin, biphenyl type epoxy tree 256 〇 8pifl correction date 1 〇 1 June 8 Japanese manual No. 96140539 has no underline correction of the fat and glycidol modified polyvinyl phenol, etc.]. From the viewpoint of curability, (Al) is preferably a monomolecular group containing a (fluorenyl) acrylonitrile group used for the preparation of the aromatic epoxy resin (A1), and examples thereof include acrylic acid and mercaptoacrylic acid. The polybasic decanoic acid and the polybasic acid (6) used in the preparation of (A1) may be γ exemplified by unsaturated polycarboxylic acids (for example, maleic acid, itaconic acid, fumar and methyl maleic acid, etc.) and Their anhydrides (for example, maleic anhydride, etc.) and polybasic (2 to 6-membered) citric acid (for example, oxalic acid, succinic acid, o-dioxadicarboxylic acid: lauric acid, dodecene succinic acid, An aliphatic saturated polycarboxylic acid such as pentadecene succinate and octadecene succinic acid; tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydro phthalic acid, and stupid Aromatic polyhydric acids such as acid, pyromellitic acid, biphenyltetradecanoic acid, and naphthalene tetra-f-acid, and their anhydrides (for example, succinic anhydride, dodecahydrate, hepatic, fifteen-derivatives, and Ten people carbene acryl (four) and other aliphatic residues and multi-needle; phthalic anhydride, tetrahydrophthalic anhydride, hexahydrodicarboxylic acid needle, mercapto tetrahydro phthalic anhydride, stupid three _, Benzene: acid anhydride, biphenyl tetraruthenium and naphthalene tetracarboxylic acid _ aromatics are preferably saturated polyacids in the preparation of (A1) from the viewpoint of reactivity and developability, (methyl) The weight ratio of the olefinic acid/(AM) is preferably such that the concentration of the (meth) acrylonitrile group of _ is greater than the weight ratio of the (meth) acrylic acid of the methicone. From the above, /g Λ ·υ /2 from the upper / 1, more preferably Λ 0.079 ~ discussion. From the above point of view, methyl propyl 2 = selected as _ or _ above / Bu is more preferably 0.10 ~ 0 = excellent 1380132 25608pifl for the 96110539 revised date 101 years The reaction temperature at the time of the reaction of (A1 〇) and (meth)acrylic acid is not particularly limited, and it is preferably 70 to 110 ° C. The reaction time is not particularly limited, but is preferably 5 to 30 hours. A catalyst (for example, Sanbujilin, etc.) and a radical polymerization inhibitor (hydroquinone, p-methoxyphenol, etc.) are used.

The filler equivalent of the polybasic decanoic acid or the polyhectoric anhydride (e) is such that the acid value of (A1) is preferably from 1 〇 to 500 mgKOH/g, based on the weight of the (Al0)(mercapto)acrylic acid adduct. For example, when (4) is a dicarboxylic acid or an anhydride thereof, 'from the above viewpoint, [(e) filler equivalent (milli-equivalent)] / [(Α1〇) (meth)acrylic acid adduct weight (g ) is preferably 〇18 to 8 9 meq/g, more preferably 0.53 to 7.1 meq/g. The reaction temperature at the time of the reaction of the (meth)acrylic acid adduct of (Al〇) and (6) is not particularly limited, but is preferably 7 Å to 11 Å. The reaction time is not particularly limited', and is preferably 3 to 1 hour. From the viewpoint of photocuring reactivity and developability of the photosensitive resin composition, Μη of '(1) is usually 5 〇〇 to 3 〇, 〇〇〇, preferably... (8) to 10,000 ', particularly preferably 1,500 to 5,000 .

The HLB value of (Α1) is preferably 4 to 14, more preferably 5 to 13, and particularly preferably 6 to 12. When the HLB value of (Α1) is 4 or more, the developability can be favorably exhibited. When the HLB value of (Α1) is 14 or less, the compatibility with the following polyoxane can be ensured. The SP value of (Α1) is preferably from 9 to Μ, more preferably from 1 to 13 from the viewpoint of easily setting the difference between the sp value of the following (8) to -4.0 to 4.0 and the developability and the water solubility. It is particularly preferably U-13. In the present invention, as a component in the photosensitive resin composition (Q), 12 1380132 25608pifj is No. 96140539, the Chinese manual has no scribe correction, and the correction date is June 8, 101, oxygen = base. Polyhydrogen alkoxy group having a hydrolyzable alkoxy group, '== Although) __ and 嶋 特性 华 1 = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = w General formula (2)

OR

I - 0 - (2) wherein R represents a filament of the order of 丨~4, ethyl, n-propyl, isopropyl, n-butyl, and secondary and ethyl. _Butyl hydrazine, preferably methyl group The hydrolyzable silk group of the formula (2) can be present only on the repeating unit in the end of the molecule ==. It can be obtained by introducing a green base or the like into the condensation combustion of a low molecular weight Wei compound (B1). (m) in the 'low-molecule Wei (4) condensation (4), which can be exemplified by the formula (1): the compound _ is 2 ^ 25, 25, 608 pifl, the date of correction, June 8, 2011, the number 96140539 This monomer is a condensate in which a part of the alkoxy group [〇R3 in the formula (1) is condensed and polymerized. R1 (1) R2m~S i - (OR3) 3 wherein R1 represents an alkyl group selected from the group consisting of an alkyl group having a carbon number of i~6, and a glycidyloxy group, a glycidyloxy group a group or a plurality of organic groups of a group consisting of a group of amino groups and an amine group; r2 represents an aliphatic saturated hydrocarbon group having a carbon number of 1 to 12 or an aromatic group having 6 to 12 carbon atoms; a hydrocarbon group; R3 represents a burnt group having a carbon number of 4; a melon is a ruthenium or a ruthenium R1 is a reaction which does not occur during the condensation reaction of (cl), and remains in the poly(tetra) post after the condensation reaction, which contributes to The photosensitive resin composition of the present invention contains a functional group which is thermally cured during heat curing.乍ί Rl, from the viewpoint of photocurability, is preferably (meth) gamma ugly soil, metabolite, and from the viewpoint of refining property, preferably glycidyloxy R2, fat, and hydrocarbyl groups are exemplified by: Straight alkyl and alicyclic saturated hydrocarbon groups. Text key

The linear chain can be exemplified by methyl, ethyl, n-propyl, n-butyl A 歹 = and 3, a group and their gas substitutes; the branching appearance group "na, ..., propyl, isobutyl, Saturated hydrocarbon groups such as sec-butyl and ethylhexyl are encapsulated by cyclohexyl, cyclooctyl, cyclohexylmethyl, hexylethyl and methylcyclohexyl, etc. Clothing 1380132 25608pifl Corrected after June 8, 101 Examples of the aromatic hydrocarbon group which is not underlined in the Chinese specification of 96140539 include aryl groups, aralkyl groups and alkylaryl groups. Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group and a hydrazine group thereof. And fluorine substituted or gas substituted; aralkyl group can be exemplified by: tolyl, : benzyl, mesityl and their halides, fluorides or emulsions 2; alkylaryl groups can be enumerated : methylphenyl and ethylphenyl, etc. _ R2 ^, from the viewpoint of curing reactivity, a linear alkyl group, a branched alkyl group = an aryl group; a linear alkyl group and an aryl group are more preferable; Methyl, ethyl, phenyl, and combinations thereof. R can be exemplified by methyl, ethyl, n-propyl, isopropyl, and The base and the sec-butyl group and the like are preferably a methyl group and an ethyl group from the viewpoint of heat curing reactivity. In the formula (1), a calcining compound having a (meth)acryloxyalkylene group as R1 can be enumerated. The following compounds, etc. are obtained. = trimethyl decane compounds having three alkoxy groups are: = dipropylene methoxy propyl trimethoxy decane, 3 - methacryloxyoxy group, 3 _Acrylic oxypropyl tridecyloxy Wei propylene methoxy propyl triethoxy decane, etc. = triethyl decane compounds having two alkoxy groups: oxy = oxymethoxy , 3_mercaptopropyl _ acetophenanthracene, 3-propenyl methoxy propyl fluorenyl bromide, 3-propenyl methoxy propyl fluorenyl diethoxy decane, etc. The alkyl group as the decane compound of R1 is exemplified by the following compounds, etc. The trifunctional decane compound having three alkoxy groups is: 15 25608 pifl is the 9612539 Chinese specification without a sizing correction. June 8曰3-glycidoxypropyltrimethoxy zebra, 3_glycidoxypropyltriethoxy矽 等, etc. m is 1, that is, a trifunctional rock-burning compound having two alkoxy groups: 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropylmethyldi Ethoxy decane, etc. The compound having a sulfhydryl group as R1 may, for example, be exemplified by the following compounds: m is fluorene, that is, a trifunctional decane compound having three alkoxy groups is: 3-mercaptopropyltrimethoxy矽 、, 3 巯 propyl propyl triethoxy decane, etc. m is 1, that is, a trifunctional decane compound having two alkoxy groups: 3-mercaptopropylmethyldimethoxydecane, 3 mercaptopropyl Methyl-dimethoxy decane, etc. The decane compound which has an aminoalkyl group as R1 is the following compound. A trifunctional decane compound having m is 〇, that is, having three alkoxy groups is: N-secondary aminoethyl γ-aminopropyltrimethoxy decane, N-secondary aminoethyl cadaverine propyltriethyl Oxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and the like. A trifunctional decane compound having m of 1, ie having two alkoxy groups is: N-secondary aminoethyl γ-aminopropylmethyldimethoxydecane, fluorenylaminoethyl γ-aminopropyl A fluorenyl diethoxy decane, a 3-aminopropyl decyl dimethoxy oxan, a 3-aminopropyl decyl diethoxy decane, or the like. In (cl), more preferred is a trifunctional decane compound containing (alkyl) propylene oxyalkyl group having three alkoxy groups and a glycidyl containing 1380132 25608 pifl having three alkoxy groups. 8曰 is the Chinese manual of No. 96140539, which does not have a singly modified trioleyl decane compound; particularly preferably 3 propylene methoxy propyl trimethyl decyl decane and 3 glyceroloxy propyl trimethoxy group Simmered. (B1) may be exemplified by a single polycondensate formed only of the calcined compound (8)) and a species obtained by polycondensation of a decane compound (bl) and which may be polycondensed with (cl) and (bl) or one or more other pyroxene compounds ( Polycondensate of b2). The other cerium compound (b2) may be a decane compound represented by the formula (3). R2nSi(〇R3)4,n (3) where 'R2 represents an aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms; and R3 represents a carbon atom number of 丄~斗Burning base; η is an integer of 〇~2. R2 and R3 may be exemplified by the groups exemplified above. And a aryl group, a branched alkyl group and an aryl group are more preferable; a linear alkyl group and an aryl group are more preferable, and a mercapto group, an ethyl group, a phenyl group, and a combination thereof are particularly preferable. R3' is preferably a methyl group and an ethyl group. In the general formula (3), a tetrafunctional stilbene compound in which n is ruthenium, i.e., has four alkoxy groups, may, for example, be tetramethoxy decane or tetraethoxy decane. A trifunctional decane compound having n of 1, that is, having three alkoxy groups may be listed as: streptotrimethoxydecane, phenyltriethoxydecane, methyltrimethoxydecane, and mercaptotriethoxydecane. Wait. Examples of the difunctional decane compound having π of 2, that is, having two alkoxy groups include diphenyldimethoxydecane, diphenyldiethoxydecane, dimethylmethoxymethoxynonane, and dimethyl group. Diethoxy decane, stupid methyl hydrazine 17 1380132 25608pifl Revised date June 8th, 2011 is No. 96140539 Chinese manual No slash correction This oxyshi shochu and phenyl fluorenyl diethoxy shir . From the viewpoint of forming a uniform network of polyoxyalkylene (B1), it is preferable that η is 1, that is, a trifunctional decane compound. Regarding the filler ratio of the other ceramsite compound (b2), the total amount of the other decane compound (b2) is preferably 0.1 to 6.0 mol, more preferably 〇2, from 1 mol (M) from the viewpoint of curing reactivity. ~4 〇 Mo Er.

The condensate (ΒΠ) of the above-mentioned compound (b) can be prepared by, for example, adding a predetermined amount to the compound (M) in a dry environment with stirring for about 1 minute to 6 minutes. The water and the catalyst are added dropwise as needed, and then obtained at a temperature lower than the boiling point of the by-product alcohol (for example, 〇15 〇. under 〇, aging for 1 to 12 hours. When the condensation is added, the amount of water added is χmol When the molar number of the alkoxy group in the Weihua compound is Υ, if the χ/γ is too small, the yield and molecular weight of the condensate are decreased. On the other hand, when the χ/γ is too large, the molecular weight becomes too large. There is a tendency for the stability to tend to decrease. In the above range, Χ^<Χ/Υ<5, preferably in the range of 〇3<χ/γ<3

2 compared. : The added water usually uses ion-exchanged water or distilled water. In order to adjust the molecular weight, a Wei compound having a hydrolyzable hydrolyzable silk group may be added to reduce decane 'methyltrimethoxydecane. The catalyst for an I reaction can be enumerated... Acid, acetic acid dimalonic acid, citric acid, tartaric acid, malic acid, alkaloid, etc. Fuma ^ Benzoic acid, stupid tetracarboxylic acid, p-toluene acid, amorphic acid, diacetic acid and trifluoromethane Equivalent - Yuan, Binary or Sanlinji acid; 2 18 1380132 25608pifl Revised date June 8, 101 is No. 96140539 Chinese manual without scribe correction of constitutive acid, nitric acid, hydrofluoric acid, bromic acid, qi acid and Mineral acid such as chloric acid; gold test•• hydroxide, alkaline earth hydroxide, quaternary ammonium hydroxide or carbonate and primary amine to tertiary amine specific salt Sodium hypogasate; metal alkoxides other than cerium such as tin, zirconium, titanium, and boron, and their chelate complexes. Among them, a chelate compound of an organic acid, an inorganic acid, a metal alkoxide or a metal alkoxide is preferred, and an organic acid is particularly preferred. • The catalyst is added in an amount of 0.0001 to 10 parts by weight, preferably 0.001 to 1 part by weight, per 100 parts by weight of (bl). The method of adding the catalyst is not particularly limited, and it is preferably added as an aqueous solution. A preferred reaction temperature is 20. (:~100. The dish is again in the polyoxane (B1) having two or more hydrolyzable alkoxy groups' as a polyoxyxene obtained by introducing an alkoxy group into a polyoxyalkylene. The decane compound (b3) having one hydrolyzable alkoxy group and other reactive functional groups, and polypyroxyne having two or more functional groups capable of reacting with the above reactive functional groups in one molecule are exemplified ( (b12) The other reactive functional group in (b3) may, for example, be a hydroxyl group, an amine group, a carboxyl group, a thiol group or a glycidyl group, etc. (b3) may be exemplified by a γ-glycidyloxy group. Examples of the functional group in a (b4) include a carboxyl group, an amine group, a hydroxyl group, a thiol group and the like, for example, when other reactions in (b3) are mentioned. When the functional group is a glycidyl group, the functional group in (b4) is preferably a carboxyl group or an amine group; when the other anti-19 1380132 256 〇 8 pifl in (b3) is amended, the date of June 8, 2011 is No. 96140539. When the linear correction functional group is a sulfhydryl group, the functional group in (b4) is excellent. The glycidyl group or the carboxyl group (b4) may, for example, be a polyoxyalkylene having a carboxyl group at both terminals, a polyoxyalkylene having an amine group at both terminals, and a glycidyl polyoxyalkylene at both terminals. & As a preparation method of (B12), for example, γ glycidoxypropyl trimethoxy group and a poly 11 oxygen-burning anti-deer having a hydroxy group at both ends can be mentioned.

In this case, the reaction temperature is not particularly limited, but is preferably 70 to 11 Torr. The reaction time is not particularly limited, and is preferably 5 to 3 hours. A catalyst (e.g., triphenylphosphine, etc.) can also be used depending on the desired. The obtained (Β) can be diluted by adding a predetermined solvent as needed. It is preferable to form a suitable solvent dilution of the (four) photoreceptor composition by the protrusions at this stage, and the following (D4) can be mentioned. The amount of (d) is G~1, GGG parts by weight, preferably 40 to 250 parts by weight, relative to 1 part of the polyoxymethane (8). ,’’,

In terms of compatibility and developability, the difference between (9) and the hydrophilic resin is preferably -4.0 to 4. 〇, more preferably _2. 〇 to 3.8, and especially 〇 〇 5 to 3.6, most preferably 〇 ~3.4. The SP value of (B) is preferably from 7 to 13', more preferably from 8 to 1 from the viewpoint of easy to differ from the above-mentioned (eight) enthalpy value: ''preferably 8 to 11 ' Especially preferred is 8 to 10.5. 2 The sp value of (the sp value is within the above preferred range, for example, can be carried out in a wide range of ways. 20 1380132 25608pifl Correction date June 8th, 2011 is No. 96140539 Chinese manual without scribe correction; φ; (1) Target The chemical composition is decomposed into the atomic groups described in the above-mentioned composition, and the evaporation energy and the molar volume of each atomic group are used to calculate sp. (2) When the SP value is less than the preferred lower limit, the evaporation energy is larger and the molar volume is smaller. A group of atomic groups (for example, a hydroxyl group, a carboxyl group, etc.), and a molecular design in which the value is increased. (3) When the SP value exceeds the upper limit of the preference, an atomic group of a type having a small evaporation energy and a large molar volume is introduced. (For example, a tomb, a pluck, etc.), and a molecular design in which the numerical value is added. & From the viewpoint of voltage holding characteristics at the time of becoming a cured product, (the printed Mn is preferably 500 to 100,000 ', more preferably looo~ 5〇〇〇〇, particularly preferably 2, 〇〇〇~20,000. The photoradical polymerization initiator (C) used as a component in the photosensitive resin composition (Q) may, for example, be a benzyl dioxime Ketal ketone Hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-indolyl-1 phenylpropanyl ketone ketone, benzophenone, benzoyl phthalate, isopropyl thioxanthone, 4, 4 bis (Diammonium) benzophenone, 3,3-dimercapto-4-indolyl benzophenone, anthracene, 2, methyl hydrazine, 2-ethyl hydrazine, tert-butyl fluorene | Kun, benzoin, benzoin, mystery, benzoin, benzoin, acetophenone, 2,2,dimethoxy-2-phenylacetophenone, 2,2- Diethoxyacetophenone, 2-hydroxy-2-mercaptopropiophenone, 4-isopropyl-2-hydrazino-2-mercaptopropiophenone, 2-mercapto-1-(4-(methylthio) Phenyl)_2_morpholinyl-1-propanone, 2-chlorothioxanthene, diethylthioxanthene, isopropylthioxanthone, diisopropylthioxanthone, mipione, benzyl · 2,4,6-(trihalomethyl)triazine, 2-(o-steryl)-4,5-diphenyl-flavored dimer, 9-phenyl. 7_Bis(9_ ° acridinyl)heptane, I,5-bis(9" aridinoyl)pentane, with double (9) bite C 21 1380132 25608pifl Corrected from June 8, 2001 to No. 96140539 Chinese manual without sizing correction of the present alkane, dimercapto ketal ketal, trisyl alum decyl diphenyl a phosphine oxide, tribromoindolyl benzoquinone, and 2-benzyl-2-didecylamino-1-(4-morpholinylphenyl)-butan-1-one, etc. (C) either one can be used. It is also possible to use two or more kinds in combination. A commercially available product of (C) can be easily obtained, for example, as 2-methyl-1-(4-(methylthio)phenyl)-2-morphinyl- 1-Acetone, which can be exemplified by IRGACURE 907; as 2-pyryl-2-diamido-1-(4-morpholinylphenyl)butane ketone,

IRGACURE 369 (manufactured by Ciba_Speciality. Chemicals Co., Ltd.) and the like are listed. The photosensitive resin composition (Q) of the present invention contains the above (A), (B) and (C) and is formed as the content of each component based on the total weight of (Q). The content of (A) is preferably 50 to 98% (hereinafter, unless otherwise specified, "%" means "% by weight (% by weight),), more preferably 6 to 97%, particularly preferably 70 to 70%. 96%. When the content of (A) is 5% or more, the developability can be better exhibited; when the content of (A) is 98% or less, the cured product

The voltage holding characteristics become better. In the present invention, the ''solid content'' means a component other than the solvent. The content of (B) is preferably 丨5 to 45%, more preferably 2 to 5 to 37%, and most preferably 3.5. ~M%. When the content of (B) is 5% or more, the liquid crystal alignment property can be more exhibited, and when the content of (9) is less than or equal to "the developing property is better." /❶呀月 (The content of Q is preferably G.Q1~8%, more preferably (10)$

(When the content of Q is greater than or equal to _, the light curing can be better achieved. 0 J 22 1380132 25608pifl Correction date June 8, 2011 is No. 96140539 Chinese specification without scribe correction; when the content of (C) is less than or equal to 8 In the case of the photosensitive resin composition (Q), the content of (C) is preferably 〇.〇2 from the viewpoint of curability, with respect to the total weight of (A). 〜1〇〇/., more preferably 0.05 to 8%. The photosensitive resin composition (Q) ' may further contain other components (D) as needed.

(D): inorganic fine particles (D1), sensitizer (D2), polymerization inhibitor (D3), solvent (D4), acid generator 〇) 5), polyfunctional (fluorenyl) acrylic acid § ¢)))) and other additives ¢) 7) (for example, inorganic pigments, Shi Xiyuan coupling agent, dyes, fluorescent whitening agents, anti-yellowing agents, antioxidants, defoamers, odorants, Aroma, bactericide, antibacterial and antifungal agent, etc.). As the inorganic fine particles (D1), metal oxides and metal salts can be used.

Examples of the metal oxide include titanium oxide, cerium oxide, and aluminum oxide. The metal salt may, for example, be calcium carbonate or barium sulfate. Among them, from the viewpoints of transparency and chemical resistance, it is preferable that the oxides are more preferably oxygen-cut and titanium oxide, and particularly preferably, oxidized stone. The volume average primary particle diameter of the inorganic fine particles is 1 to 2 Å. From the viewpoint of flexibility, it is preferably 1 to 15 Å, particularly preferably 5 to 20 nm. Nm, from the leg of the leg, more preferably 丨~丨 buckle (10), the weight of the solid component of the coffee day and the product (Q), the content of (D1) is usually 〇~5〇0/, said, ash , U / ° is preferably 1 ~ 45%, especially excellent i 2 ~ 40%. When the (D1) containing 丨 丨 姑 姑 为 为 为 为 为 为 为 为 为 , , , , , , , , , , , 能够 能够 能够 能够 能够 能够 能够 能够 能够 能够 能够 能够 能够 能够 能够 能够 能够 能够 能够 能够 能够 能够 能够 能够Elastic recovery characteristics are particularly excellent 23 1380132 25608pifl Correction date June 8th, 2011 is No. 96140539 Chinese manual without scribe correction The sensitizer (D2) can be used: nitro compounds (for example, 蒽醌, i, 2_ naphthoquinone , 1,4-naphthoquinone, benzofluorenone, P, P,-tetramethyldiaminodibenzophenone, chloroquinone and other carbonyl compounds; nitrobenzene, p-dinitro stupid and 2-nitroguanidine And the like; aromatic hydrocarbons (for example, 'chrysene, etc.); sulfur compounds (for example, diphenyl monosulfide, etc.), and gas compounds (for example, >6 succinyl aniline, 2-gas-4-nitrate Alkyl aniline, 5-stone succinyl-2-aminotoluene, tetracyanoethylene, etc.). The content of the sensitizer (D2) is usually from 0.1 to 100% by weight based on the weight of the photopolymerization initiator (D), preferably from 5 to 80%, particularly preferably from 1 to 7 Å. The polymerization inhibitor (D3) is not particularly limited, and a polymerization inhibitor used in usual reaction can be used. Specific examples thereof include: hydrazil, tri-p-nitrophenylnonane, N-(3-N-hydroxyanilino-i,3·didecylbutylene) oxyaniline, p-benzoquinone , p-tert-butyl catechol, nitrobenzene, picric acid, dithiobenzoquinone disulfide and copper chloride (H). The content of the polymerization inhibitor (D3) is preferably 〇1 to 1% by weight based on the weight of the solid content of the photosensitive resin composition (Q), more preferably 〇〇1 to 0 to 5%, particularly preferably 〇. 〇2~〇.1〇/. . A solvent (D4) may be exemplified by glycol ethers (ethylene glycol single-compartment test and propylene glycol monoalkyl group, etc.); ketones ((tetra), top, methyl isobutyl fluorene, cyclohexanone, etc.); Vinegar (butyl acetate vinegar, ethylene glycol vinegar and propylene glycol singer, etc.). The above dissolution is preferably a ketone or a vinegar. When a solvent is used, the amount of the solvent to be added is not particularly limited, and the amount of the solvent to be added is usually preferably 50 to 1, and more preferably % to 2% based on the weight of the solid content of the photosensitive resin composition (9). . , specifically 80 to 800%. It should be noted that the amount of the solvent added includes the upper 24 1380132 25608pifl, the revised date, June 8, 101, and the 96112539 Chinese specification. The solvent used in the preparation of the descriptions (A) and (B) is not corrected. . : An acid generator (D5) is a compound that generates an acid by light or heat, and an acid generator is added to promote a light or heat curing reaction. (D5) may be exemplified by the following (i) sulfonate (sulfene necnamium), (9) sulfonic acid ester compound, (iii) bismuth imine compound, (iv) A powdered diazo-methyl compound and (v) an iron salt. (i) Continuum # benzamidine methyl phenyl hydrazine, 4-trisyl carbaryl hard-ketone mill, sulfonyl sulfone and their α_diazo compounds. (ii) Continued acid vinegar compound benzoin f benzene sulfonate 'pyrophenol trifluoromethanesulfonate vinegar, pyrogallol sulfonate triester, α-hydroxydecyl benzoin benzene sulfonate And α-hydroxydecyl benzoin 12-burning base acid and so on. (iii) sulfonimide compound 沁(trifluoromethylsulfonyloxy) succinimide, p-toluene oxy) a ring P,2,l]h-5-ene dienyl ruthenium imine , (Perfluorooctyl sulphate _ 醯 oxy) naphthyl imine, N-(phenylsulfonyloxy)bicyclo[2,2,η7_5_women_2 = dicarboxy quinone imine, Ν -(Benzenesulfonyloxy)bicyclo[2,2,1]geptane_5,6-oxy-2'3-dicarboxyarsenine and fluorenyl-(phenylsulfonyloxy)naphthylimine. ' (iv) Disulfonyldiazide compound bis(trifluoromethylsulfonyl)diazonium, bis(stylsulfonyl)diazepine, bis(p-sulfonyl) Diazomethane, bis(2,4-diphenylbenzene benzoate) diazonium decane, bis(1-methylethylsulfonyl)diazononane and bis(1,4-dioxy^ snail [4,5]decane-7-sulfonyl)diazodecane, and the like. ' '' 25 1380132 25608pifl Revised date June 8, 101 Stomach No. 96140539 Chinese manual without scribe correction 0) 镔 salt 铳 salt [bis [4-(diphenyl fluorenyl) phenyl] sulfodied hexafluoro Phosphate, propyl hexafluorophosphate, etc.], iodonium salt (diphenyliodonium hexafluoroantate, etc.), phosphinium salt (ethyl triphenylphosphine ruthenium tetrafluoroborate, etc.), heavy Nitrogen strontium (benzene diazo hexafluorophosphate, etc.), ammonium salt (tetra) 2 - cyanopyridinium hexazone; acid salt, etc.) and ferrocene [(2,4-cyclodecadien-1-yl) [ (丨_methylethyl)benzene] hexafluorophosphate, etc.]. In (D5), a sulfonimide compound and a diterpenoid diazonium compound are preferable, and N-(trifluoromethyl ethoxylated) succinimide or bis(phenylsulfonyl) is more preferable. Diazo decane. The content of (D5) is preferably 1% by weight or less based on the weight of the solid content of the photosensitive resin composition (Q), more preferably 〇1 to 7%, and particularly preferably G.G5 to 5%. When the content of (D5) is greater than or equal to 1%, the month b is sufficient to exhibit the voltage holding property; when the content of (D5) is 10% or less, the developability can be better exhibited. The polyfunctional (meth) acrylate monomer (D6) is not particularly limited as long as it is a known polyfunctional (fluorenyl) acrylate monomer, and it can be exemplified as difunctional (fluorenyl). Acrylic vinegar (D61), trifunctional (fluorenyl) acrylate (D62) and tetra-hexa-functional (fluorenyl) acrylate (D63). A Luneng (meth) acrylate (D61) can be exemplified by ethylene glycol bis(indenyl) acrylate, diethylene glycol bis(indenyl) acrylate, propylene glycol di(meth) acrylate, dipropylene glycol (Meth) acrylate, polyethylene glycol di(meth) acrylate, polypropylene glycol di(meth) acrylate, neopentyl glycol di(decyl) acrylate, glycerol di(decyl) acrylate, 1,4-butanediol di(methyl) 26 25608pifl Corrected from June 8, 2001 to No. 96140539 Chinese manual without sizing correction of the acrylic acid 6曰, 1,6-hexanol II (A Acetate, I, decanediol bis(indenyl) acrylate, 1,10-nonanediol bis(indenyl) acrylate, 3 methyl dec-5 pentanediol bis(indenyl) Acrylate, 2-butyl-2-ethyl-anthracene, 3-propylene glycol di(meth)acrylate, dihydroxyindenyl tricyclodecane bis(indenyl)acrylate, ethylene oxide addition of bisphenol A The bis(indenyl) acrylate of the product, the bis(indenyl) acrylate of the propylene oxide adduct of bisphenol a, the neopentyl glycol di(meth)acrylate of hydroxypivalic acid, and the like. ~ Trifunctional (meth) acrylate (D62) may, for example, be glycerol tris(mercapto) acrylate, trimethylolpropane tris(decyl) acrylate, pentaerythritol tris(decyl) acrylate, trioxindole A tris(indenyl) acrylate of an ethylene oxide adduct of a propane. Examples of the tetra-hexafunctional (fluorenyl) acrylate (D63) include pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(indenyl)acrylate, and dipentaerythritol hexakis(meth)acrylate. Preferred among (D6) are (D62) and (D63), and more preferred are dipentaerythritol pentaacrylate, pentaerythritol triacrylate, and combinations thereof. Examples of (D6) that can be easily obtained from the market are: Aronics M-403 (East Asia Synthetic Co., Ltd.), Light Acrylate PE-3A (Kyoeisha Chemical Co., Ltd.), and Neoma-DA-600 (Sanyo Chemical Co., Ltd.) Industrial (share) system, etc. The content of (D6) is preferably less than or equal to 20%', more preferably from 0.5 to 15%, particularly preferably from 1 to 1%/0, based on the weight of the solid component of (Q). When the content of (D6) is 0.5% or more, the photocuring reactivity of the cured product becomes more desirable; when the content of (D6) is 20% or less, the liquid crystal alignment becomes better. Ϊ380132 Revision date ιοί年6月8曰25608pifl is No. 96140539 Chinese manual without scribe correction. Based on the weight of the photosensitive resin composition (Q), the total amount of (D) content is usually less than or equal to 1, 〇〇〇% It is preferably 80 to 800%. The photosensitive resin composition (Q) of the present invention can be obtained by mixing the above components or the like using a known mixing device such as a planetary mixer. The photosensitive resin composition is usually liquid at room temperature, and has a viscosity at 25 ° C of 0.1 to 100 mPa·s, preferably 1 to 20 mPa·s. The photosensitive resin composition (Q) of the present invention is excellent in developability, and is excellent in liquid crystal alignment property and voltage holding property of the cured product, and thus is suitably used as a protrusion for forming a liquid crystal display element, particularly a vertical alignment type liquid crystal display. The element has a protruding photosensitive resin composition. Hereinafter, the protrusion for a liquid crystal display element of the present invention will be described. The protrusion for a liquid crystal display element of the present invention is a protrusion which is formed by curing the photosensitive resin composition (Q) by a process including light irradiation, and is provided for controlling alignment of the liquid crystal. The preferred formation process of the protrusion of the present invention is a process of forming a pattern after the light is irradiated, and then performing a postbake process. The formation of the protrusions is usually carried out by the following process. (1) A process for applying the photosensitive resin composition of the present invention to a transparent common electrode provided on a substrate colored layer of a liquid crystal display element. The coating method can be exemplified by roll coating, spin coating, spray coating, and slit coating. The coating device includes a spin coating machine, an air knife coating machine, a roll coating machine, a curtain coating machine, and a gravure plate. Coater and comma coater, etc. The film thickness is usually 〇·5~ίο μιη, preferably 1 to 5 μηη. (2) Heat the applied photosensitive resin composition layer as needed to make it 28 25608 pifl. Correction date June 8, 101 is No. 96140539 Chinese manual No scribe line correction Dry (pre-bake) process . The drying temperature is preferably 10 to loot, more preferably 12 to 9 Å, particularly preferably 15 to 6 GC Å, particularly preferably 2 to 耽. The drying time is preferably two 0.5 to 1 minute, more preferably 丨 to 8 minutes, and particularly preferably a minute. The drying may be either a vacuum drying or a normal pressure drying, preferably under reduced pressure. The drying may be carried out either in a jacket gas or in an inert gas, preferably in an inert gas. (3) using a predetermined mask to perform a process of sensing the resin group and exposing the layer using actinic rays. The size of the opening of the photomask to be used is preferably 4 to 15 pm in diameter, more preferably 6 to 12 μm in diameter, and 4 to 15 μm in diameter, and the pattern can be formed with high precision. For example, when the diameter of the opening is 4 to 15 (four), a pattern having a diameter of about 6 to 18 Å can be obtained. Examples of the actinic ray include visible light, ultraviolet light, and laser light. The light source includes solar light, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a semiconductor laser, and the like. The amount of exposure is not particularly limited, but is preferably 2 〇 to 3 〇〇 mJ/cm 2 . In the process of performing the exposure, a component having a (meth)acryl fluorenyl group in the photosensitive resin composition is reacted to carry out a photocuring reaction. (4) Next, a process of removing the unexposed portion by the developer and performing development is carried out. . The developer usually uses an aqueous solution. Examples of the alkaline aqueous solution include aqueous solutions of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; aqueous solutions of carbonates such as sodium carbonate, potassium carbonate and sodium hydrogencarbonate; and hydroxytetramethylammonium 29 1380132 25608pifl corrected date 101 years 6 On the 8th of the month, it is the aqueous solution of the Chinese manual No. 96140539 without organic test. The above-mentioned aqueous test solution may be used singly or in combination of two or more kinds, and a surfactant such as a fresh-faced active agent, a cationic surfactant, an amphoteric surfactant, or a non-green surfactant may be added. The development method has an impregnation method and a mouth shower method, and the temperature is preferably 25 to 15°. The development time is appropriately determined depending on the film thickness and the solubility of the light: fine fat composition. (5) Post-heating (post-baking) process. The post-baking temperature is preferably _~25 (re, more (four)^i5Q~24〇C, particularly preferably 180~23〇ΐ. The post-baking time is $minute~6 hours' preferably 15 minutes~4 hours' special Preferably, it is 3G minutes to 3 hours. The baking may be any type of depressurized baking and atmospheric pressing baking, preferably pressing baking. The baking may be carried out by a hood or may be carried out in a ship gas, preferably in It is carried out in an inert gas. When post-baking is carried out, 'the shape of the columnar shape after exposure with actinic rays is partially cured (4), so that it is easy to form a half-like shape to form a liquid crystal display. A satisfactory shape and size of the protrusion for the element (for example, 'high 1.0 to 2.0 (four), lower bottom diameter 8 〇 〜 2 〇 μπι). Presumably, in the post-heating process, the photosensitive resin remains hot-curable The component of the functional group is thermally reacted and thermally cured. Examples of the thermosetting functional group include a hydrolyzable alkoxy group, a glycidyl group, a thiol group or an amine group in (8); and (in) or (Β) (曱基) 丙 by brewing 30 1380132 25608pifl is the Chinese manual of 96140539 Scribing correction of a trace amount of (meth)acrylonitrile group remaining in the above exposure process on the date of June 8, 101. The protrusion formed by the above process has a height of 0.1 to 3.0 μm, preferably 〇·5. ～2·5 μηη, particularly preferably 1.〇~2.〇μιη. The above process can be stably and productively formed into a shape and size (still with the upper bottom and the lower bottom diameter), which is easy to control and has a pattern shape, heat resistance, and resistance. The liquid crystal display element excellent in liquid crystal alignment property and voltage holding characteristics, etc. can be provided by the fine protrusion which is excellent in the solvent property and transparency, etc. [Examples] Hereinafter, the present invention will be specifically described by way of examples and preparation examples, but the present invention In the following, "parts" means "parts by weight". [Preparation of hydrophilic resin (Α)] <Preparation Example 1> Heating and cooling are provided. Feeding measures, reflux condenser, and dripping The glass flask of the funnel and the nitrogen introduction tube was charged with 2 parts of phenolic novolac type epoxy resin EOCN-102S (manufactured by Nippon Kasei Co., Ltd., epoxy equivalent 2〇0) and 245 parts of propylene glycol monoterpene ether acetate. Heat to 1103⁄4 to dissolve it evenly Next, 76 parts of acrylic acid, 2 parts of triphenylphosphine and 2 parts of p-methoxyphenol were added, and the reaction was carried out for 1 hour at 1 ίο c. Further, 91 parts of tetrahydrogenated stupid was added to the reactant. The acid anhydride was further reacted at 90 ° C for 5 hours, and then diluted with propylene glycol monoterpene ether acetate to have a solid content of 25% to obtain a hydrophilic resin having an acryl-based base and a rebel group (A-1 : Mn : 2,200 ; SP value: 11.26; HLB value: 6.42; acid value: 91 mgK 〇 H / g; propylene sulfhydryl concentration of 2.86 mmol / g) of propylene glycol monoterpene ether acetate solution (solid content of 25%). 31 1380132 25608pifl Revised date June 8th, 2011 is No. 96140539 Chinese manual No underline correction It should be noted that Μη is using GPC analyzer (HLC-8120GPC, TOSHO (manufactured by TOSHO)) and column (2 TSKgel GMHXL + TSKgel Multipore HXL-M, manufactured by TOSHO Co., Ltd., a polystyrene-converted value measured by a GPC method. Further, the SP value, the HLB value, the acid value, and the acrylonitrile group concentration were determined by the above methods. The same measurement method was also used in the following Preparation Examples and Comparative Examples. <Preparation Example 2> Into the same flask as in Preparation Example 1, 19 parts of a phenol novolac type epoxy resin EPPN-201 (manufactured by Sakamoto Chemical Co., Ltd., epoxy equivalent: 19 Å) and 238 parts of propylene glycol monomethyl ether B were charged. The acid ester was heated to 11 (rc to dissolve uniformly. Next, 76 parts of acrylic acid, 2 parts of triphenylphosphine and 2 parts of p-methoxybenzene were added, and the reaction was carried out at 110 C for 1 hour. Further, 91 parts of tetrahydrophthalic anhydride was added to the reaction product, and the reaction was further carried out at 9 ° C for 5 hours, and then diluted with a monomethyl succinic acid to obtain a solid content, thereby obtaining Hydrophilic resin of propylene fluorenyl group and carboxyl group (A_2 : Mn : 2,3 〇〇; SP value 11.11 'HLB value: 6.81; acid value: 94 mgKOH/g; propylene base concentration · 2.94 mmol/g) @ Glycol monof_acetate solution ((iv) φ content was 25%). <Comparative Preparation Example 1> To the same flask as in Preparation Example 1, 2 parts of piranone resin was added. ) company made EP-4〇2〇G) and 238 parts of propylene glycol monomethyl hydrazine B, heated to iron to make it evenly dissolved. Next, add 〇1 knife month iso-ethyl methyl vinegar in C The reaction was carried out for 5 hours. After that, it was diluted with propylene glycol monomethylacetic acid vinegar. 32! 38 〇 132 25608 pifl corrected 曰 101 101 101 101 101 101 101 101 101 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 961 'A propylene glycol having a hydrophilic resin having an acrylonitrile group (A-Γ: Mn: 2,100; SP value: 13.46; HLB value: 6.41; acid value: 〇mgKOH/g, propylene-based concentration: 1.34 mmol/g) Monomethyl Acetate Acetate Solution (solid content: 25%) 〇 <Comparative Preparation Example 2> The same flask as in Preparation Example 1 was charged with 50 parts of isobornylmethyl acrylate (33 mol%). 30 parts of methacrylic acid 2-ethyl ester (33 moles)

%), 20 parts of methacrylic acid (34 mol%) and 15 parts of cyclohexanone, heated to 8 °C. After replacing the gas phase portion of the system with nitrogen, 55 parts of the previously prepared 5 parts of azobisisobutyronitrile (V-60: Wako Pure Chemical Industries, Ltd.) were added dropwise to the 8 〇t: flask in 1Q minutes. Hereinafter, it is called AIBN) a solution dissolved in 5 parts of cyclohexanone, and then reacted at the same temperature for 3 hours to obtain a hydrophilic polymer (A-2,) having a carboxyl group (Mn: 8,800; SP value: 11.86; HLB value: 11.98, g value · 1 〇 2 mgK 〇 H / g) of cyclohexanone solution (solid content of 25%).

[Preparation of polyoxyalkylene (B)] <Preparation Example B-1> Into a glass flask equipped with heating and cooling, lion measures, a flow condenser, a dropping funnel, and 46 parts of 2 molars were added 3 C - Latic earth bis-oxydecane, 160 parts (0.65 moles) diphenyl dimethyl hydrazine and 45 g (2.5 moles) ion-exchanged water, Q 〗 (Please i mole injury) Hey, at 60. Heat the lion for 6 hours under the armpit and remove it for 2 hours by hydrolysis. After that, (4) hexanone is diluted, so that the solid content is moved, get = 33 1380132 25608pifl test 9_9 Chinese __ difficult original correction date _ year June 8 曰 polyoxane (Β-1) (Μη: 2,100 ; viscosity: 20 mPa.s; a cyclohexanone solution with a Sp value of 9. (solid content: 25%). The viscosity is at a constant temperature of 25 Torr) measured by a BL type viscometer (manufactured by Toki Sangyo Co., Ltd.) . The same measurement method was also used in the preparation examples and comparative examples. <Preparation Example Β-2> To the same flask as in Preparation Example Β-1, 17 parts (〇82 parts) of 3-glycidoxypropyltrimethoxywei, 4 parts (〇2〇) were charged. Morephenyl trimethoxy Wei, 30 parts (0. 12 moles) diphenyl dimethyloxan and 4 〇 g (2.2 moles) ion-exchanged water, 〇" parts (〇〇〇1 Moer _ oxalic acid, heated at 6 (TC for 6 hours, and then use an evaporator to remove the by-product methanol produced by hydrolysis for 2 hours under the reduced parts of % jobs. After that, dilute with cyclohexanone to make The solid content was 25%, and a cyclohexanone solution (solid content: 25%) of polyoxyxylene (B-2) (Mn: 7,800; degree: 70 mPa.s; sp value: 8 69) was obtained. Examples 1 to 6 and Comparative Examples 1 to 4 > [Preparation of photosensitive resin composition] According to the number of components of Table 1 [apparent parts by weight of each component, it should be described that 0 is a photosensitive resin The weight percentage of the solid content of each component based on the weight of the solid content of the composition (Q) (the next digit of the decimal point is rounded off)]. Each hydrophilic resin solution and polyoxygen oxide solution are added to the glass container, and then added. under (Cl) and (D-6) were stirred until uniform, and an additional solvent (propylene glycol monomethyl ether acetate) was added to prepare photosensitive resin compositions (Q1) to (Q6) of the examples and comparative examples. Photosensitive resin composition (Y1) ~ (Y4). It should be noted that in the abbreviations in Table 1, except for the above, 34 1380132 25608pifl, the revised period, June 8, 101, is the 96140539 Chinese manual. The slash correction is defined as follows: B 3 · One-side 曱 曱 丙 烤 酿 酿 改性 改性 改性 “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ , SP value: 7.95); ci (photoradical polymerization initiator): "IRGACURE907,, (2 methyl-1-[4_(indolyl)phenyl]_2_morpholinopropane small ketone:

Ciba.Speciality.Chemicals (manufactured by Co., Ltd.); D_6 (polyfunctional (meth) acrylate): [Neoma DA-600] (mixture of dipentaerythritol penta-propionic acid vinegar and dipentaerythritol hexaacrylate; Sanyo Chemical Industrial (share) system) (SP value: 10.55);

35 1380132 25608pifl is the Chinese manual of No. 96140539 without a slash correction. _ Revised date June 8, 101 [Table 1] 1 Product name _ 筻 筻 J 显影 显影 显影 显影 显影 显影 显影 显影 显影 显影 显影 显影 显影 显影 显影Solution (C) (D) (Α) SP value - (B) SP value Α · 1 solution Α-2 solution Β-1 solution Β-2 solution Β-3 Α-Γ solution Α-2, solution C -1 1>^ Solvent Example 1 Q 1 34 0(8 1) 60 (14) 5 (5) A 50 1.9 ◎ LQ 2 340 (81) 60 (14) A 5 (5) - 50 3.22 ◎ 3 AQ 3 30 0(7 1) 100 (24) 5 (5) 50 1.9 〇4 η 340 (81) 15 (14) — — 5 (5) - 50 3.96 〇5 00 0(8 6) 40 (9) 5 (5) ' 50 2.57 ◎ 6 1 Q 6 V 340 (81) 60 (14) _ a 5 (5) 10 50 2.55 ◎ Comparative Example 1 60 (14) 340 (81) Two 5 (5) - 50 4.10 Δ 1 2 V 60 (14) — 340 (81) 5 (5) - 50 2.50 ◎ 4 3 γ 4U 0(9 5) 5 (5) 10 50 — ◎ 4 60 (14) ----— 340 (81 5 (6) - 50 3.17 〇 [Developability evaluation] The photosensitive resin compositions (Q1) to (^6) and (Y1) to (Y4) are spin-coated on each of the glass substrates. The surface film thickness was 5 μηη, dried at 25 ° t for 5 minutes, and then developed with 1% sodium carbonate aqueous solution for 3 sec., and the evaluation was 36 1380132 25608 pifl. The revised period was June 8, 101, and the number was 96140539. The scribe line corrects the umbral. The results are shown in Table 1. The evaluation criteria are as follows. ◎: No residue was observed visually. 〇: There is a little residue in the visual. △: There were many visual residues. [Preparation of protrusions for vertical alignment type liquid crystal display elements] The photosensitive resin compositions (Q1) to (Q6) and (Y1) to (Y4) are spin-coated on a glass substrate on which an ITO (tin-doped indium oxide) film is formed, respectively. The surface film thickness was 2 μηη, and it was dried at 25 ° C for 5 minutes. High-pressure mercury light is illuminated through the reticle with a exposure of loomj/cm2. It should be noted that the exposure is performed under the condition that the interval between the mask and the substrate (exposure gap) is 1 〇〇 μπ!. Development was then carried out using a 1% aqueous solution of sodium carbonate. After washing with water, a protrusion for a vertical alignment type liquid crystal display element was formed on a glass substrate having a ruthenium film after "bake for 60 minutes". - [Measurement of liquid crystal alignment property and voltage retention characteristics] Using a liquid crystal alignment film In a coating machine for printing, a liquid crystal alignment agent AL1H659 (trade name) [manufactured by JSR Co., Ltd.] was applied onto the glass substrate on which the protrusions were formed. Thereafter, it was dried at 160 ° C for 2 hours to form a film thickness of 〇.〇5. The film of μιη was applied onto a glass substrate to which a photosensitive resin composition was not applied, and the liquid crystal alignment agent AL1H659 was applied by the same method as described above, and dried at 160 T: for 2 hours to form a film having a film thickness of 〇.〇5 μιη. Then, 'on the outside of the respective liquid crystal alignment films of the two substrates obtained, the epoxy resin adhesive is applied by screen printing, and the two substrates are superposed and compacted in a manner opposite to the liquid crystal alignment film surface. After curing, 37 1380132 25608pifl is the Chinese manual of No. 96140539. There is no slash correction. The date of this revision is June 1st, 1st, and the liquid crystal injection port is filled between the two substrates by Meluc liquid crystal MLC-6608 ( After the liquid crystal injection port is sealed with an epoxy-based adhesive, a polarizing plate is attached to the outer surface of the two substrates to make the direction of the polarizing plate perpendicular to the vertical alignment type liquid crystal display element. The liquid crystal alignment property is evaluated as follows. : Using a polarizing microscope to observe whether an abnormal region (domain) appears in the liquid crystal cell when the voltage is turned ON or OFF. 'When the abnormal region is not confirmed, it is regarded as "good"; when an abnormal region is confirmed, The evaluation of the voltage holding characteristics was carried out by applying a voltage of 5 V to the liquid crystal display element, turning on the circuit, measuring the holding voltage after 20 msec, and calculating the ratio with respect to the applied voltage (5 V). Table 2]

Excellent protrusion for liquid crystal display elements. Resilience characteristics 38 25608pifi Revision date June 8th, 2011 is No. 96140539 Chinese manual No underline correction In Comparative Example 1, the hydrophilic resin in the photosensitive resin composition (γ1;) used does not contain Since it has a carboxyl group, the developability with respect to an alkaline solution is inadequate. In Comparative Examples 2 and 4, since the hydrophilic resin in the photosensitive resin compositions (Y2, Y4) used does not contain an acrylonitrile group, the liquid crystal alignment property and the voltage retention characteristics are inferior. In the comparative example 3, since the photosensitive resin composition (Y3) used does not contain polyoxyalkylene (B), the liquid crystal alignment property and the voltage retention are poor. When using the photosensitive resin composition Y1~ When the liquid crystal display element of the protrusion formed by γ4 is formed into a liquid crystal panel, the contrast, the viewing angle, and the like are deteriorated. [Industrial Applicability] The photosensitive resin composition of the present invention can be suitably used for forming projections for liquid crystal display members, particularly for vertical alignment type liquid crystal display elements. In addition, the photosensitive resin composition of the present invention is also suitably used as a f-type resist material such as a solder resist, a photosensitive resist film, a photosensitive resin relief, a screen, a photo-adhesive or a hard plating. A photosensitive resin composition for use in agents and the like. Moreover, the photosensitive resin composition of the present invention can also be used as a metal (for example, iron sauqin, matte), plastic (for example, polycarbonate, polyethylene terephthalate, poly(decyl) acrylate) Coatings, coatings, printing inks and #mixtures of various materials such as paper, glass, rubber and materials can also be used as molding materials. Also, the above description is only a preferred embodiment of the present invention, and is not intended to be in any form of the present invention. The invention has been disclosed in the present invention. 1380132 25608pifl The revised period is June 8, 101. The Chinese version of the specification is not limited to the above description, and any skilled person in the art can make use of the structure and technical contents disclosed above without departing from the technical scope of the present invention. The modification or modification is equivalent to the equivalent embodiment of the invention. However, any changes, equivalent changes and modifications made to the above embodiments according to the present invention are not departing from the technical solution of the present invention. Early G [Simple description of the diagram]. Benefit [Main component symbol description]

Claims (1)

Chinese manual no slash correction This correction date is June 8, 101 VII, a # patent range: 1:- Sense resin composition (Q), which can be developed and used to form protrusions for liquid crystal display elements, The composition includes: a hydrophilic resin (4) containing = whey and green; a polymeric material; and a luminescent polymerization initiator (C), wherein the hydrophilic resin (4) is formed by converting an epoxy resin. Hydrophilic resin, and according to the Oda method, the value of (4) (10) is 19 hydrated (b) having two or more hydrolyzable alkoxy groups. 2. The photosensitive resin composition Q) as described in the above-mentioned Japanese Patent Laid-Open Publication No. </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> Monomer condensate: R (1) R xn~S i - (OR3) (wherein R1 represents a (meth) acryloxyalkyl group having a carbon number of from j to 6 selected from an alkyl group, glycidyloxy One or more organic groups of a group consisting of an alkyl group, a mercaptoalkyl group and an aminoalkyl group; R2 represents a carbon, an aliphatic saturated hydrocarbon group having a number of 1 to 12 or a carbon number of 6 to 12 The aromatic hydrocarbon group; R3 represents an alkyl group having a carbon number of i 4; m is ruthenium or 1) 〇3. The photosensitive resin composition (Q) according to the first aspect of the invention, wherein the hydrophilic resin The difference between the solubility parameters of (A) and polyoxyalkylene (B) is -4.0 to 4.0. 4. The photosensitive resin composition (q) according to any one of the items 1 to 3, wherein the solid content of the photosensitive resin composition is 1380132 25608 pifl, which is not defined by the Chinese manual. This correction is based on the total weight of June 8, 101, and contains 5〇~98 wt% of hydrophilic resin (a), 1.5~45 wt% of polyoxyalkylene (B), and 0.01~8 Wt. % photoradical polymerization initiator (C). A projection for a liquid crystal display element which is formed by curing a photosensitive resin composition according to any one of claims 1 to 4 by a process including irradiation with light. 6. The liquid crystal display element protrusion according to the fifth aspect of the invention, wherein the process including light irradiation is characterized in that the pattern is formed after the light irradiation, and the pattern is formed and post-baking is performed. 42