TW200846829A - Photosensitive resin composition - Google Patents

Abstract

A photosensitive resin composition used for the bump formation of a liquid crystal display element is provided. The photosensitive resin composition has an excellent character of alkali development, and a curing of the photosensitive resin composition has excellent liquid crystal alignment capability and an excellent voltage holding ratio. The photosensitive resin composition (Q) includes a hydrophilic resin (A) containing (meth) acryloyl group and carboxyl group; a polysiloxane (B), which has at least two preferably selected hydrolyzable alkoxy groups; and a photo-radical polymerization initiator (C).

Description

200846829 IX. EMBODIMENT OF THE INVENTION The present invention relates to a photosensitive resin composition which is solidified by a process including light irradiation, can be subjected to alkaline development, and is used for forming protrusions for liquid crystal display elements. And a protrusion for a liquid crystal display element formed using the composition. [Prior Art] The liquid crystal display device is configured to display the display side substrate and the liquid crystal, and the crane side substrate is 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. The liquid crystal alignment in the layer selectively changes the amount of transmitted light or reflected light of the display side substrate to perform display. LCD panel driving methods include: TN (Twisted Nematic), IPS (In-Piane, Switching, Coplanar Conversion), VA (VertiCal Alignment), Simple Matrix, Active Various driving methods such as the Matrix (Active Matrix) method. In addition, in recent years, in the VA (Vertical Alignment) mode, MVA (Multi-domain Vertically Aligned) type LCD (vertical alignment) has been specially developed in terms of contrast and viewing angle of liquid crystal displays. Type liquid crystal display). The above MVA type LCD utilizes a birefringence mode in which a negative liquid crystal having a negative dielectric anisotropy and a vertical alignment film are combined, even if _ is in a state where no voltage is applied, is located close to the alignment film. Since the alignment direction of the liquid crystal at the position is also substantially perpendicular, the contrast, the viewing angle, and the like are excellent. 200846829 In the above MVA type liquid crystal display, as a method for enabling liquid crystal to obtain a plurality of alignment directions in the _=pixel region, the same image on the light incident side f-electrode substrate is in the same manner. Different positions of the slits • The protrusions (semi-convex, lens shape, etc.) having a slope are formed. - The photosensitive resin composition for forming the above protrusions is required to have a liquid crystal alignment property and a voltage holding property and a shirting property with respect to the test liquid. In view of the above requirements, a photosensitive resin composition using a hydrophilic polymer containing a sulfhydryl group φ has been studied (Patent Documents _1 and 2). However, the above-mentioned photosensitive resin composition has a problem that the development characteristics with respect to the alkali liquid are extremely poor. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2004-333964 [Patent Document-2] Japanese Laid-Open Patent Publication No. 2005-221974 [Draft of the Invention] This is a disclosure of the present invention. The composition of the glazing resin is a glazing resin composition for a vertical alignment type liquid crystal display device, and the composition has good developability, and the cured product has excellent liquid crystal alignment properties and voltage holding characteristics. After the completion of the problem, the inventors of the present invention performed β卩', and the present invention relates to a projection of a light-emitting tree ageing product (Q) which is subjected to alkali development, and the composition has a A hydrophilic resin of (meth)acrylonyl group and a carboxyl group (protrusion of a liquid crystal display element formed by curing a composition of a ruthenium or a ruthenium on a clothing field.) 200846829, the sensible resin domain of the present invention and The protrusion for a liquid crystal display element exhibits the following effects: 'The photosensitive resin composition is excellent in alkali developability. ・The liquid crystal display element has excellent liquid crystal alignment properties. The above-mentioned description is only a technical means for understanding the present invention, and can be made according to the technical concept of the present invention, and can be composed according to the Japanese patent. The object includes: The pro-f tree is sometimes referred to as a hydrophilic "fat light free beauty to take people 4, to chop the milk to burn (8) [hereinafter sometimes only recorded as (8)]; and ^ Dan = agent (〇[ Only when it is recorded as (c)], the composition of the taxi = 'provided by the composition - a liquid crystal The protrusion for the liquid crystal display element which is excellent in electric conductivity and the four-inch property. The protrusion for the S-crystal display element is used for the liquid crystal molecules, and is used for the color filter and the optical substrate. Thin film transistors (the gap control material (P otospacer) that maintains the thickness of the liquid crystal layer between the two substrates is completely different in purpose and use. The purpose of the L-gap control material is only to avoid pixels between the substrates (10) The domain, for example, has a columnar shape so as not to affect the alignment of the liquid crystal display L-bead crystal molecules as much as possible, and at the same time, the spacing between the two male ridges 1 is accurately and accurately maintained; whereas the purpose of the protrusion of the present invention is It is that by forming a semicircular protrusion on the substrate, the liquid crystal 200846829 enclosed between the substrates is aligned on the surface of the protrusion to enable liquid crystal molecules to obtain a plurality of alignment directions in one pixel region, thereby achieving satisfactory optical characteristics. It should be noted that, in the above and hereinafter, for example, "(mercapto) acrylate," and the like (meth) are referred to as "acrylic acid ester and/or mercapto acrylate" and the like. Next, the photosensitive resin composition of the present invention to be a constituent component (A) ~ (C) will be described sequentially.

In the present invention, the hydrophilicity index of the hydrophilic resin (A) is specified by ugly, and generally, the larger the value, the higher the hydrophilicity. The HLB value of γ ^ is due to the resin skeleton of (4) (for example, an ethylene resin, and its preferred range is also different, and an excellent HLB value of 4 or more is 6 or 2. If the (4) property is better; if the HLB value of (4) is less than or equal to Υ / It is better to develop the image of the 4th. It should be noted that the water resistance of the object of the present day is the value, which means that the organic matter is mixed with the non-touch surface measured by the Oda method. From the organic compound HLB and 1〇χ inorganic/organic 仃. Inorganic value and organic value Detailed 哉 Agent 0 synthesis if Φ application (interface. In the literature "interface activity. Shop distribution, Oda, Temple Village 5) 1 page " or, = and its application) (桢 • 界面 界面 界面 界面 》 》 》 》 》 : : : : : 十 十 十 十 十 十 界面 界面 界面 界面 界面 界面 界面 界面 界面 界面 界面 界面 界面 界面 界面 界面 198 198 198 198 198 198 The solubility parameter of the Chemical Industry Co., Ltd. (4) (hereinafter referred to as the description) is preferably 7 to 14, and 200846829 is 8 to 13', particularly preferably n to 13. When the sp value is greater than or equal to 7, the moon b is better enough. Developability; when the # sp value is less than or equal to Μ, the water resistance of the cured product is better. ^ t ^ SP as Fedors # ^ T^XlIk t The method of calculating the value of the carrier.

POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, VoL14, No. 2, ROBERT F. FEDORS· (pp. 147-154) The above SP values are easy to distinguish between resins with similar SP values. An index of mixing (dispersibility enthalpy) and a resin having a large difference in SP values are not easily mixed with each other. 1 molecule (A) has at least one (meth) acryl fluorenyl group on average. By having a (meth) acrylonitrile group, The photocurability is exhibited satisfactorily. (A) The amount of (meth)acryl fluorenyl group contained is represented by a (meth) acrylonitrile group concentration (mmoi/g). (A) Preferred (meth) acrylonitrile The concentration of the group is from 1 〇 to 5. 〇 mmol / g, more preferably from 2. 0 to 4.0 mmol / g. The concentration of the '(fluorenyl) acrylate group in the present invention can be obtained by utilizing the addition reaction of an amine on a double bond. (Michael Plus) titration was carried out. The method was as follows: (i) Weigh accurately about 1 g of the sample, put it into a conical flask, and then add about 10 ml of acetone to dissolve it. (9) Add 1 〇ml?琳标准液(咖神池血血^-solution) [solution with morpholine and f-alcohol mixed at 1:4 (capacity ratio)] Then add 1.5 ml of 50% acetic acid standard solution [a solution of acetic acid and ion-exchanged water mixed at a ratio of 1 · 1 (volume 200846829)], shake well, and let stand at room temperature for 15 minutes. (111) to the above two Add 15 mi of acetonitrile (aeet〇nitrile) and 10 ml of acetie anhydride to the flask, and shake well. ' (iv) Using a έ-recorded automatic titration device, use ο] dish to touch the ... hydrochloric acid _ - The sterol titration was titrated with a solution. (v) A blank test was simultaneously performed, and calculation was performed by 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-methanol titration solution required for the titration of the sample. B: The number of mL of the solution for titration of 5 mol/L hydrochloric acid-methanol for the blank test. f : The titer of the solution for titration of OJmol/L hydrochloric acid/methanol. 8: The sample size is similar. At least one molecule (A) has at least one carboxyl group. The amount of the slow group contained in (A) is represented by an acid value. When the acid value of (A) is greater than or equal to 1 〇 mgK 〇 H / g, it is easy to produce a better decoloration; when the acid value of (A) is less than or equal to 500 mg KOH / g, the curing can be better Water resistance of the object. The acid value in the present invention can be measured by an indicator titration method using an alkaline titration solution. Methods as below. (Ο Weigh accurately about lg of the sample, put it into a conical flask, and then add it to a neutral methanol-acetone solution [a solution of acetone and methanol mixed in a ratio of 1:1 (capacity ratio)] to dissolve. 11) Add a few drops of phenolphthalein indicator and titrate with 0.1 mol/L potassium hydroxide. 10 200846829 Know JW \J IJ I 滴 Titrate with solution. The reddish color of the indicator lasts for 3 seconds and is the neutralization end point. (iii) Calculate by the following formula: retardation (mgK)^i/g) two (Axfx5e6l)/S .......-......- where A: 0.1mol/L potassium hydroxide titration Use the rainbow number of the solution. f. The titer of the solution for titration of 1 mol/L potassium hydroxide. S : sample amount (g). A hydrophilic tree formed by converting Wei resin: L? (referred to as (Α1)), hydrophilic ethylene-based polymer) can be used as a seed, or two or two kinds of m The photocuring reactivity of the photoreceptor and the liquid crystal alignment property are preferably (Α1). The method of metabolites is to make an epoxy group containing (meth)propenyl group, which is 幡A1〇X or less, sometimes only referred to as (A1〇)). When only the paste and the above thank you should be smuggled 300, ° Yang ^ column, * month for the aliphatic epoxy resin [example * Qiu coffee G7m East pure _ _] or alicyclic ^ reduce paste such as CY_〗 79, CY_177 , CY_ _ =

Epoxy company)) (the spoon is nine chemical fat, a it [for example, benzene secret _ oxygen tree 知 tree know, 酝 type epoxy resin, biphenyl type epoxy tree 200846829, fat and glycidol modified polyethylene Phenol or the like. From the viewpoint of curability, an aromatic epoxy resin is preferred in (Al〇). The (meth)acrylonyl group-containing carboxylic acid used in the preparation of (A1) may, for example, be acrylic acid or the like. Mercaptoacrylic acid. The polycarboxylic acid and the polybasic anhydride (e) used in the preparation of (A1) may, for example, be an unsaturated polycarboxylic acid ( For example, maleic acid, itacon, fumaric acid, and methyl maleic acid, and their anhydrides (for example, maleic anhydride, etc., and saturated polybasic (2 to 6-membered) carboxylic acids (eg, oxalic acid, succinic acid) , an aliphatic saturated polycarboxylic acid such as phthalic acid, adipic acid, lauric acid, dodecyl succinic acid, fifteen carbon diluted short acid and octadecene succinic acid; tetrahydro phthalic acid Aromatic acids such as formic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, trimellitic acid, pyromellitic acid, biphenylic acid, and naphthalenetetracarboxylic acid, and their acids (e.g., an aliphatic anhydride, a 12-carbon rare number # acid liver, a pentylene succinic anhydride, an octadecene succinic anhydride, an aliphatic saturated polycarboxylic anhydride; phthalic anhydride, tetrahydrophthalic anhydride, six Gasification of phthalic anhydride, methyltetrahydrophthalic acid brittle, benzotriene, and aliquot: aromatic polybasic acids such as anhydrides, biphenyl tetracarboxylic anhydride and naphthalene tetracarboxylic anhydride from reactivity and (iv) 彡For the sake of sex, Euler freshly reads the acid field. In the preparation of (A1), the weight ratio of the (meth)acrylic acid/(A1.) filler is preferably (f1) acryloyl group of (A1) The concentration is greater than or equal to the weight ratio of the surface of the olefinic acid. From the above viewpoint, the weight ratio of the acrylic acid / (Al0) is preferably (10) 72 or (10) 72 or more / 0. 079 to 0.72 / 1. The above-mentioned old Lutian Gangong 〆 ~ two "α 4 Na considered, the weight ratio of methyl propyl benzoic acid is preferably 0. G92 or _2 or more / 1, more preferably please ~ 〇. 92 / 1 12 200846829 pair (A1g And (methyl) (iv) enthalpy reaction limitation, preferably 7 〇 ~ boots. The reaction time is not particularly limited ^ 5 to 30 hours. Catalyst can be used as needed

Phosphine, etc.) and free i polymerization inhibitor (Awake, p-methoxy phenyl, etc.). The weight of the dibasic group relative to the (meth)acrylic acid adduct of (Al〇), the filler equivalent of the polybasic or polybasic tarenic anhydride (4) is such that the acid value of (4)) is preferably 5 OOmg KOH/g. The equivalent weight, for example, when (4) is a di-reading acid or a hydrazine thereof, the weight (g) of the [(e) filler equivalent (milli-equivalent)]-based) acrylic acid adduct is preferably 〇18 to 8 9 亳. Preferably, it is from 0.53 to 7.1 milliequivalents/g. The reaction temperature at the reaction of the (meth)acrylic acid adduct of (Al0) and (4) is not particularly limited, and is preferably 7 G to 11 (rc. It is not limited to the reaction, and is preferably 3 to 10 hours. In view of the photocuring reactivity and developability of the resin composition, the Μη of (A1) is usually 500 to 3 Å, _, preferably from 10,000 to 10,000, particularly preferably from 1,500 to 5,000. The value 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 _ is less than or equal to M, The compatibility with the polyoxyalkylene (B) described below can be ensured. The SP value of (A1) is easily set to -4.0 to 4.0 in terms of the difference between the sp value of (B) and the developability. In view of water resistance, it is preferably 9 to 14, more preferably 1 to 13, and particularly preferably η to η. In the present invention, 5 is a component in the photosensitive resin composition (Q) and 13 200846829 is ff: There are two or two decomposing oxy groups in one molecule, and 1 has a water oxygen _). 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。.狎4 寸 4 inch 1 knives with two or more hydrolyzed marryes | μh = can be enumerated: 1 in the molecule with two ==: no hydrolyzable alkoxy polyoxyl alkyl. , (2)

OR

I (2) a group of 4 to 4, such as methyl, wherein 'R represents a carbon number of 1, preferably methyl ethyl, n-propyl, isopropyl, n-butyl and sec-butyl, etc. And ethyl. The hydrolyzed silkoxy group represented by the formula (2) may be present in the material element =, and may be present only at the molecular end or in the presence of a 'sub-oxygen-4==:r compound. The complex (b1) represented by the formula (1) obtained by the condensation of the substance is a must-have precursor, and the known oxygen group [part of the 0R spoon in the general formula (1) A polymerized condensate. I生细合反反14 (1) (1)200846829 si -(OR3) where 'R1 is selected from the stone mountain of each Han...: propylene methoxyalkyl, shrinking water ^^^, the number of children is 1 a di- or di-decylalkyl group, a mercaptoalkyl group and an aminoalkyl aromatic hydrocarbon of the group consisting of hexamethylene groups of 6 to 6 or an & an atom having a number of 6 to 12 is a celebrity , 妓 is an alkyl group of 1 to 4; m is 0 or 1. After the reaction, the reaction did not occur in the course of the reaction. The condensation of the lipid composition was carried out by heat curing. The photosensitive tree in the present invention was used as a functional group of R] TM . The oxy-warm group is a (meth)propionate group. For the sake of consideration, it is preferred that the glycidyloxyalkyl silk base is a fine base or a branched chain, and examples thereof include methyl group, ethyl group, n-propyl group, n-butyl group, column = and their cation substitution. a compound; a carboxy group, a butyl group, a sec-butyl group, a 2-butyl group, and the like; and a cyclohexyl group, a cyclooctyl group, a cyclohexylmethyl group, a cyclohexyl group. Ethyl and methylcyclohexyl and the like. The aromatic hydrocarbon group may, for example, be an aryl group, an aralkyl group or an alkylaryl group. Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group and an aryl substitution thereof, a fluorine substitution product or a chlorine substitution product; and an aralkyl group: a tolyl group, 15 200846829 zjuuopif ^ fluorenyl group, and a uniformity Mesityl and their tellurides, fluorides or chlorides 2; alkyl aryl groups include methylphenyl and ethylphenyl groups. Alkyl 2 aryl; more preferred is a linear alkyl aryl; particularly preferred are methyl, ethyl, phenyl and combinations thereof. The methyl group, the ethyl group, the n-propyl group, the isopropyl group, the n-butyl group and the sec-butyl group are preferably fluorenyl groups and ethyl groups from the viewpoint of thermal curing reactivity. In the general formula (1), the following compound or the like can be given as the alkylene compound having a (meth) propylene oxime group as R]. A trifunctional decane compound having m of 0, that is, having three alkoxy groups is: 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyloxypropane, 3 _ propyl methoxypropyl trimethoxy decane, 3 propylene methoxy propyl triethoxy decane and the like. A trifunctional decane compound having m of 1, ie having two alkoxy groups is: ^methacryloxypropylmethyldimethoxydecane, 3-methylpropoxypropylmethyldiethyl Oxydecane, 3-propenyloxypropylmethyldimethoxycarbazide, 3-propenyloxypropylmethyldiethoxydecane, and the like. The decane compound having a glycidoxyalkyl group as R1 may, for example, be the following compounds. —m is 〇, that is, a trifunctional decane compound having three alkoxy groups is: 3: condensed in glyceroloxypropyltrimethoxy decane, > glycidoxypropyldiethoxy sec-second, etc. . A trifunctional decane compound having m of 1, ie having two alkoxy groups, is: 16 200846829 3 · glycidoxypropyl hydrazine Ψ 石 夕 、, 3-glycidoxy propyl methyl diethoxy decane Wait. The decane compound of Ri as a base of Ri can be exemplified by a trifunctional sulphur compound having two alkoxy groups: 3 μpropyl propyl dimethoxy decane, 3 fluorenyl group Propyltriethoxydecane, and the like. A trifunctional decane compound having m of 1, ie having two alkoxy groups, is:

3, propyl methyl dimethoxy decane, 3 - mercaptopropyl methyl diethoxy decane, and the like. The decane compound having a decyl fluorenyl group as R1 may, for example, be a compound or the like. The trifunctional decane compound having m is 〇, that is, having three alkoxy groups is: N-second aminoethyl γ-aminopropyltrimethoxy oxime, N-secondary aminoethyl hydrazine Ethoxy decane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and the like. A trifunctional decane compound having m of 1, that is, having two alkoxy groups is: N-secondary aminoethyl γ-aminopropylmethyldimethoxydecane, N-secondary aminoethyl γ-amino group Propylmercaptodiethoxydecane, 3-aminopropylmethyldimethoxydecane, 3-aminopropylmethyldiethoxydecane, and the like. More preferably, in (cl), a trifunctional decane compound having a (alkyl) acryloxyalkyl group having three alkoxy groups and a trifunctional decane having a glycidoxyalkyl group having three alkoxy groups a compound; particularly preferred is a 3-propenyloxypropyltrimethoxy-combustible and a 3-glycidoxypropyltrimethoxy-oxygenated calcination 0 17 200846829 ^.juuopn (B1) can be exemplified by: only Wei compound (M) formed a single polycondensate = and the compound (10) and a polycondensate which can be polycondensed with (cl) and (Μ) or other decane compound (t > 2) . Other Shixia compound _ can be exemplified by a stilbene compound represented by the formula (3). R2nSi(OR3)4.n (3) wherein R represents an aliphatic saturated hydrocarbon group having a carbon number of 丨~;

An aromatic hydrocarbon group having 6 to 12 carbon atoms; R3 represents a burnt group having 1 to 4 carbon atoms; and η is an integer of 〇 2 to 2. R2 and R3 may be exemplified by the groups exemplified above. Among R, a linear alkyl group, a branched alkyl group and an aryl group are preferred; a linear alkyl group and an aryl group are more preferred; and a mercapto group, an ethyl group, a phenyl group and a combination thereof are particularly preferable. As R3, a methyl group and an ethyl group are preferable. In the general formula (3), a tetrafunctional decane compound having η of 0, i.e., having four alkoxy groups, may be exemplified by tetradecyloxydecane, tetraethoxydecane, and the like. The trifunctional decane compound having η of 1, that is, having three alkoxy groups may, for example, be phenyltrimethoxydecane, phenyltriethoxydecane, decyltrimethoxy decane, and methyltriethoxydecane. Wait. The difunctional decane compound having 2 or 2 alkoxy groups may, for example, be diphenyl dimethoxy decane, diphenyl diethoxy decane, di: methoxy decane, dimethyl Diethoxydecane, phenylmethyldimethoxydecane, phenylmethyldiethoxydecane, and the like. In the case of the formation of a uniform network (neteork) of the team Shixi Oxygen (Β1), the η is 1、1, that is, the trifunctional stone smelting compound. 18 200846829 -^.^UUOpu (Μ) filler (10), from the curing reactivity considerations relative to! Moer (10), other. For example, the retraction of the compound (10) of the Shi Xiyuan compound can be as follows - under the scale. For example, in a dry environment, - while stirring - use about 1 〇 二蒂八二!; 石夕Add a predetermined amount of water to the composition (4) and, as needed; drop port = scrape, then obtain a stagnation temperature lower than the by-product alcohol (for example, 〇~15 ❿ is obtained by aging for 1 to 12 hours. *... If the right χ/γ is too small, the yield of the condensate and the knife are lowered. On the other hand, when χ/γ is too large, the molecular weight is too large, and the storage stability tends to be. #上上情况=/Υ< In the range of 5, the range of ship 〇 3 < χ / γ < 3 is ideal for J. The added water is usually adjusted by using ion-exchanged water or base = Bu, or it can be added with one hydrolysis. Gas • ^ (4): Mb compound. Wei Huahe, which has a ruthenium, is listed as phenyl trioxetane, methyl trimethoxy, etc. The catalyst for the condensation reaction can be exemplified by citric acid. , acetic acid, oxalic acid, malonic acid, citric acid, tartaric acid, malic acid, oleic acid, acid, phthalic acid, stupid tetracarboxylic acid, Toluenesulfonic acid, formazanic acid field: mono-, di- or ternary organic acids such as gas acetic acid and trifluoroanthracene: acid salt - Wei, acid, guaic acid, bromic acid, chloric acid and A mineral acid such as chloric acid, which is a basic salt such as a hydroxide, an alkaline earth hydroxide, a quaternary ammonium hydroxide, or a primary or tertiary amine; a quaternary alkyl ammonium halogenated 'dioxin, _ popular Acid 19 200846829 Sodium; metal alkoxides other than cerium such as tin, hammer, titanium, aluminum and boron, and their chelate complex, etc. Among them, organic acids, inorganic alcoholic acids, metal alkoxides, metals are preferred. Alkoxide chelate (delate c〇mp〇un sentence, etc. acid, preferably organic acid.................................. The amount of the catalyst added is 〇〇〇〇1 to 10 parts by weight, preferably 0.001 part by weight, based on 100 parts by weight of (M).

/ There is another 4 inch specification, preferably added in an aqueous solution. The preferred reaction temperature is 2 CTC 〜 l 〇〇 °c. In a polyoxane having two or more hydrolyzable alkoxy groups (in B1, 'as a polyoxo-oxygenated gas obtained by introducing a decyloxy group into a polyoxanthene, month = 举: 丨 molecule The towel is sprayed with the oxy- and other reactive sulphide compounds (4) and the anti-pain (to) of the poly-wei (four) functional group having two or more fresh functional groups in the i molecule. Examples of the other reactive functional group include a county, a benzyl group, a fluorenyl group, a glycidyl group, etc. The soil is, for example, m glyceryloxy (tetra)trimethoxy sulphate k, 2-mercaptoethyltrimethoxy decane, etc., for example, when (d) The other reactive functional group in the like is preferably a functional group in the 'b4). When the under-glycerol-based functional group is a fluorenyl group, the other anti- or a few groups in the oxime. M) may be exemplified by a oxy-oxygen having a filament at both ends, a polyoxo-oxygen having an amine group at both ends of 20 200846829 ^JUUOpn, and a polyoxane, etc. 隹 City+鳊 has a glycidyl group [^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ Difficult (four) New Zealand

The needle and the reaction temperature are not particularly limited, and preferably 70 to bribe. The reaction time is not particularly limited. It is also possible to use a catalyst (for example, triphenylphosphine or the like = small - if necessary, (8) can be added as needed to be diluted by adding a predetermined solvent. ^ At this stage · protrusion shape sensitivity In the case of Griffin 1%, W Wei (B), (D4) is used in an amount of 40 to 250 parts by weight. Ricci, Yuting is the difference between the SP values from the compatibility and developability. Preferably, the amount of the _4.0 to 40, and the water-based resin (4) is preferably from 2.0 to 3.8, particularly preferably from -0.5 to 3.6, and most preferably from 〇 to 3.4. 4 = 2" is set in the range of the difference between the above and the above-mentioned _SP values: Preferably, it is preferably 7 to 13, more preferably 8 to 12, particularly preferably δ to η, and particularly preferably 8 to 10.5. In order to make the SP value of (9) within the above preferred range, for example, it can be carried out according to the following method: Each of the atomic groups described in the above literature is calculated from the emission energy of each atomic group and the molar volume of SP. (7) When SP When the value is less than the preferred lower limit, the atomic _ of the type having a larger evaporation energy, 200846829, and the smaller volume of the corpse if the molar volume is introduced, and the molecular design whose value is increased is increased. 1 'base, rebel, etc.' (3) Although the SP value is higher than the preferred value of the old Moer, the old-fashioned bribes are less energetic, and the addition of Wei-valued ages such as 1 base, Wei Ke, etc.), the voltage retention characteristic Mn 1 is:) 00~100,000, more 2, _~20, _. ~~ 50,000' is particularly preferably used as one of the photosensitive resin compositions (9) = fluorenyl winter methyl + phenyl propyl phase, diphenyl Ketone, benzoic acid, isopropyl hydrazine _, 4,4 bis (dimethylamino) dibenzomethyl methoxy benzophenone,酉昆, 2-methyl 蒽, B, 酉, 叔, 叔, benzoin, benzoin, benzoin, benzoin, acetophenone, 2 , 2 dimethoxy phenyl acetophenone, 2,2-diethoxyacetophenone, 2_trans-base 2_methyl phenylacetone, heart propyl 2 _ light base-2-methyl _ , 2_f base " county deep base) _2_ linalyl-1-propanone, 2-chlorothioxanthone, diethyl xanthone, isopropyl thiazepine, diisopropyl thioxanthone, rice Ketone, benzyl-2,4,6-(tri-methyl)triazine, 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer, 9-phenyl acridine, hydrazine Bis, a certain base), heptane, 1,5-bis(9-acridinyl)pentane, bismuth(9) acridinepropane, dimethylbenzyl ketal, trimethylbenzylidene diphenyl Phosphonium oxide, dimethylene sulfone and 2-pyryl-2-dimethylamino-indole-(4-morpholinylphenyl)-butan-1-one, etc. (C) can be used either Two or more kinds of 22 200846829 may be used in combination. Commercially available products of (c) can be easily obtained, for example, as a odor-1-(4-(methylthio)carbyl)-2-yllinyl-1 - Bing Meng, you can cite ^ IRGACURE9〇7; For example, IRGACURE 369 (manufactured by Ciba. Specialty Chemicals Co., Ltd.) and the like are exemplified as '2-benzyl group, 2-dimethylamino group> <4_?? phenyl)-butylene-1-ketone. The resin composition (Q) is formed by containing the above (A), (shirt) and (C), and the content of each component is as follows based on the total weight of (Q): 0 (A) is preferably 50~ 98% (Below, unless otherwise specified, beryllium %'' means "% by weight (wt 〇 / 0),), more preferably 6 〇 to 97%, particularly preferably 70 to 96%. When the content of (A) is 5% by weight or more, the developability can be exhibited more satisfactorily. When the content of (A) is 98% or less, the voltage holding property of the cured product becomes better. It should be noted that the "solid component" in the present invention means a component other than the solvent.

The content of (B) is preferably 1.5 to 45%, more preferably 2.5 to 37%, particularly 3.5^29% 〇, ^ is better to give Weijing alignment; when t(B) is less than 45%, Better developability. (The content of Q is preferably O.OH%, more preferably 〇〇5 to 7%. When the sale is 0.01% or more, the photocuring reactivity can be better exhibited' (when the content of cerium is 8% or less) It is possible to better exert the resolution. In the sensible resin composition (Q), the content of (C) is preferably 0.02 to 10% in terms of the weight of the material. , 23 200846829. ^ V ww is more preferably 0.05 to 8%. Sub-(9) photosensitive resin composition (Q), if necessary, may further contain other 1 (D) can be listed _: no noodle collar, sensitizer (D2), blocking butterfly (four), mwen = acid = Π (for example, inorganic pigments, coupling rights, anti-caries and anti-fungal agents, etc.) S fine particles (D1) can use metal oxides and metal salts. For example, titanium oxide, cerium oxide, aluminum oxide, etc., such as: cerium carbonate and cerium sulfate, etc., are considered to be excellent in oxygen and two in terms of properties of Niya and Wei. More preferably, cerium oxide and titanium oxide are used, and particularly preferably: cerium oxide. The average primary particle diameter is from 1 to fine, and particularly preferably from 1. = 1 to 150 nm', more preferably from 1 to 12 °. The weight of the solid component of the New Zealand silk (Q) is usually 0 to 5 %, preferably 1 to 41 H ° °: when the content of (D1) is 50% or less, the difference can be better. ^, although the content of (m) is 2 to 40%, the elastic recovery characteristic is particularly excellent sensitizer _ can be 石: stone Schottky compound (for example, έ酉, α: dinaphthoquinone, benzofluorenone, ρ, ρ,, mercaptodiaminodibenzophenone, quinone-reduced carbon-based compound; nitrobenzene, p-dinitrobenzene, and 2_苟, etc.; 24 200846829f onion and chrysene, etc.; sulfur compound (for example) , diphenyl claws, etc.; and nitrogen compounds (such as soil ': soil ^ nitroaminotoluene and tetracyanoethylene, etc.), etc., based on the weight of the photopolymerization initiator (9), sensitization _ lion, hanging (U ~ just %, preferably 0.5 ~ 8 〇%, particularly preferably for the job. The drag agent (D3) is not particularly limited 'can be used in the usual reaction. Specific examples can be listed Phenylhydrazine (hyd fine), three pairs

Stone f 本本甲垸, NH phenylaminodimethylbutylene oxide aniline 1 p-benzophenone, p-tert-butyl catechol, nitrobenzene, picric acid, dithiobenzamide II Sulfide and copper (II) chloride, etc. The content of the polymerization inhibitor (D3) is preferably 〇~][·〇%, more preferably 〇.〇1 to 0.5%, based on the weight of the solid content of the photosensitive resin composition (Q), and particularly preferably It is 0.02~0.1%. Examples of the solvent (D4) include glycol ethers (such as ethylene glycol monoalkyl ether and propylene glycol monoalkyl ether); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.); And esters (butyl acetate, ethylene glycol alkyl ether acetate, propylene glycol alkyl ether acetate, etc.). Among the above solvents, ketones and esters are preferred. When the solvent is used, the amount of the solvent to be added is not particularly limited, and the amount of the solvent added is usually preferably from 50 to 1,000%, more preferably 70%, based on the weight of the solid component of the photosensitive resin composition (Q). 900%, particularly preferably 80 to 800%. It should be noted that the solvent used in the preparation of the above (A) and (B) is also included in the amount of the solvent to be added. The acid generator (D5) is a compound which generates an acid by light or heat, and an acid generator is added to promote a light or heat curing reaction. 25 200846829 (D5) can be exemplified by the following (i) sulfone compound, (ii) sulfonic acid ester compound, (iii) scutellaria imine compound, (iv) Base heavy nitrogen sulphur compound and (V) rust salt. : (1) Sulfonate...................................................... ........ • Benzhydryl phenyl sulfone, 4-trityl hydrazine methyl sulfone-ketone oxime, sulfonylsulfone and their α-diazo compounds. (ii) sulfonate compound benzoin terpene ester, pyrotriene tritrifluoromethane oleic acid vinegar, eschar • age-based sulphuric acid diterpene, (X-methyl methacrylate) (1) Sulfonimide compound (trimethane fluorescein oxy) succinate imine ί ( ) 甲苯 甲苯 黄 酉 酉 酉 。 。 。对 笨 黄 ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) , N-(Benzene oxy)bicyclo[2,2,i]7_5_women_2 3 Dicarboxy quinone imine, N_(phenylsulfonyloxy)bicyclo[2,251]heptane _5 , 6_oxy-2'3_dicarboxyarsenine and N-(phenylsulfonyloxy)naphthylimine, and the like. 10 (iv) Disulfonyldiazomethane compounds. Bis(difluorodecylsulfonyl)diazomethane, bis(stupyl sulphate)diazomethane, bis(p-phenylenesulfonyl)diazomethane, Bis(2,4-dimethylbenzenesulfonyl) diazonium tert- sulphide, bis(1-mercaptoethyl sulphate) diazonium tricarbide and bis(Meoxaspiro[4,5]decane-7- Sulfhydryl) diazonium and the like. ...一平#, (v) wrong salt • strontium salt [bis[4_(diphenylstil)phenyl]sulfide bishexafluorophosphate, allyl sulfonium hexafluorophosphate, etc.], iodonium salt (diphenyl) Iodine iodine hexafluoroantimonate 26 200846829, etc.), phosphine salt (ethyl triphenylphosphonium tetrafluoroborate and other nitrogen hexafluorophosphate, etc.), pound house hex 9 drive its name ~, (four) one ♦ Salt 卞 卞 _2 · 减 · · 六 六 六 六 六 六 六 · · 六 六 六 六 六 六 六 1 六 六 六 六 六 六 六 六 六 六 六 六 六 六 六 六 六 六 六 六 六 六 六 六In the case of J ^ ; , it is preferably a sulfonimide compound and a disulfonyldiazomethane N•(trifluoromethylheptyloxy)succinimide, a double The weight of the solid component of the composition (Q) is based on the weight of the solid component of the composition (Q), and the content of (D5) is preferably less than 5% «for (10) 1 to 7%. ,special

At .. ^ § (D:>) When the I contains 0.001% or more, the month b is better enough to exert the voltage of the captive ln〇/prfc soil protection and ^ inch, when the content of (D5) is less than or equal! 〇 ▲%,, = is enough to develop developability. The yttrium (meth)propionate monomer (IV) is a well-known eve g month. (A) propylene sulfonate monomer can be used without particular limitation, and dimethicone (meth) acrylate vinegar ((10)), trifunctional (methyl decenoate _) And tetra-hexa-functional (methyl) propyl vinegar (D63). Difunctional (meth)acrylic acid (D61) can be exemplified by ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and propylene glycol di(f)propene. Acid ester, dipropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, glycerin II Methyl) acrylate, 〗 〖, 4-butanediol di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, ,, 壬 diol di(meth) acrylate, 1,1〇-癸diol di(meth)acrylate, 3-methyl-1,5-pentanol-(methyl) di-stearate, 2-butyl-2_ethyl_ι,3 - propylene glycol bis (a 27 200846829f propylene-sintering addition-addition - (f-alkenene _, bis(meth)acrylic acid (fluorenyl) acrylate of the A complex of the substance A, etc.... -乂.:. Kexin 酉 酉 戍 戍 一 一 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 甘油 甘油 甘油 甘油 甘油 甘油 甘油 甘油 甘油 甘油 甘油 甘油 甘油 甘油 甘油 甘油 甘油: base) ring of acrylic vinegar, trimethylolpropane Ethylene oxide adduct

(Meth) acrylate, etc. / Lu Yuexi (methyl) propionate (D63) can be exemplified by: pentaerythritol tetrakis (methyl) propylene, dipentaerythritol penta (methyl) acrylate, dipentaerythritol hexa (methyl) ) Acrylate and the like. Preferred among (D6) are (D62) and (D63), more preferably dipentaerythritol pentapropenyl ester, 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.), Ne〇ma-DA, 6 〇〇 (Sanyo Chemical Industry Co., Ltd.) and so on. The content of (D6) is preferably as small as 20% by weight based on the weight of the solid component of (Q), more preferably 5 to 15%, particularly preferably 1 to 1% by weight. 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. The total content of (D) is usually 1,000 or less, preferably 80 to 800%, based on the weight of the photosensitive resin composition (Q). The photosensitive resin composition (Q) of the present invention can be obtained by mixing the above components, for example, by a mixing device of the type known as Planet 28 200846829. The photosensitive tree composition is usually liquid at room temperature, and has a dryness of 0·1 to 100 mPa·s in the built-up basin, preferably a Bujia can be used. 'The first-generation resin group salt (Q) of the present invention is excellent in liquid crystal alignment property and voltage retention property of the Qinxian County. Mo_, _ and i/, and the cured product is suitable for exhibiting protrusions and components. It is a photosensitive tree composition for crystal display reading protrusions. Hereinafter, the protrusion for a liquid crystal display element of the present invention will be described. The ruthenium is a protrusion formed by solidification of a TiO2 resin composition (Q) including light irradiation, and is provided for controlling the daily alignment of the liquid. The preferred formation process of the growth = 1 = protrusion is as follows: after the light is irradiated, the process of forming the pattern is performed, and then the process of baking (4) bake is performed. The formation of the protrusions is usually carried out by the following processes (1) to (3). A process for producing a photosensitive resin composition of the present invention by using a transparent pass on a substrate colored layer of a liquid crystal display element. Roller f, spin coating, spray and slit coater, inexpensive coater, gravure coater and comma coater. The skin thickness is usually from 0.5 to 10 μm, preferably from 5 to 5. Drying is a process in which the coating layer of the coating (four) New Resin is heated to make it a pre-bake.

The drying temperature is preferably from 10 to just. C is preferably 15 to 6 (ΤΓ, less gan, 4 inch U/, 毹 2 〇 5 〇. 〇. drying time is preferably 29 200846829 ^. ^uuopii more preferably 1 to 8 minutes, particularly preferred It is 2~5: two d: It is any type in vacuum drying and normal pressure drying, and it is preferable to carry out either in air or in an inert gas, and it is carried out in an inert gas. ...................................................... .............................

The photoreceptor of the Precursor &amp;amplifier is used to perform the photosensitive resin group Μ 1% light system &amp; The size of the mask used is such that the diameter of the reticle is preferably 15 or more, more preferably 6 to 12 angstroms, and when straight Μ ～1:&gt; μιη, the pattern can be formed with high precision. For example, when the number of straight passes is 4 to 15 frames, a pattern having a diameter of about 6 to 18 μm can be obtained. Examples of the xenon rays include visible light, ultraviolet light, and laser light.戸&quot;Factory lists: sunlight, high-pressure mercury lamps, low-pressure mercury lamps, metal-made lamps, semiconductor lasers, etc. The amount of light in the team is not particularly limited, but is preferably 2G to 3GG m!/Cm2. In the process of performing exposure, m is reacted by a component having a acrylonitrile group in the photosensitive resin composition to carry out a photocuring reaction. () Next, an unexposed portion was removed by an image forming liquid, and development was carried out. • The liquid usually uses an alkaline aqueous solution. The alkaline aqueous solution may, for example, be an aqueous solution of an alkali metal hydroxide such as sodium hydride or potassium hydroxide; an aqueous solution of a carbonate such as carbon ruthenium, potassium hydride or sodium hydrogencarbonate; hydroxytetramethyl γ &amp; B. A special aqueous solution for organic testing. The above alkaline aqueous solution may be used singly or in combination of two or more kinds, and a sub-interface/tongue agent, a cationic surfactant, an amphoteric surfactant 30 200846829 agent, a nonionic surfactant, etc. may be added. Surfactant. Dan / u 仏 / X / shell mode and spray method, preferably spray method. It is determined that the solubility of the resin composition is 25^40〇c °. ............................... (5) Post-heating (post-baking) The post-baking temperature is preferably (10)~ 25 (rc, more preferably i5Q 24 24 = ' is preferably (10) to 23 (rc. The post-baking time is 5 minutes to 6 hours, day:, the length is 15 minutes to 4 hours, particularly preferably 3 minutes) 〜3小8, 〇 baking can be any of decompression baking and atmospheric baking, preferably under reduced pressure baking. Baking can be carried out in money, and it is also feasible 'preferably in an inert gas. ^ In the post-baking, the semi-circular shape is easily formed by using actinic rays, and the shape and size of the liquid crystal display element are easily formed (for example, high μηη, 8&gt; 2 ^ changed to the Bb group. The heat-curable functional group is exemplified by a hydrolyzable oil group in (B), a thiol group or an amine group; and (4) or (B) a group of The protrusions formed are high in GJ~, preferably 〜5~2·5 μιη, particularly preferably U~厶〇μιη. Slope 1- is 31 200846829 ^^OU6pu The above process can be box; fixed day & too (high and Upper bottom. Lower bottom and) Rong ^ Production ¥ Good The shape and the size of the overalls are not 7G pieces. [Embodiment] The following invention is not limited thereto and the present invention is specifically described by the embodiment and the preparation example, but the present invention will be specifically described below. "Parts," means "parts by weight." [Preparation of hydrophilic wax (A)] <Preparation Example 1> Air conduction. Release measures, reflux condenser, dropping funnel, and two-frequency + loading f _ _ resin EOCN-102S (Japanese chemical system, Lu Wu Mudan μ soil 匕 匕 曰 曰 _ _ _ _ _ _ ^ ^) and 245 parts of propylene glycol single boots, so that they are all dissolved. Next, add η. Knife '酉 、, 2 parts of diphenyl phosphine and 0.2 parts of p-oxyphenyl hydrazine, reacted under + for 10 hours. Add 91 parts of tetracarboxylic acid monocarboxylic anhydride to the reactants, Dan After reacting at 9 (rc for 5 hours, and then diluting with propylene glycol = methyl acetate vinegar) to a solid content of 25%, a hydrophilic resin having a propylene group and a silk was obtained (H ·· Shi: 2,·; ··· Π·26 ' HLB value · 6·42 ; acid value: 9111 ^ 〇 11 / name; propylene sulfhydryl concentration · 2.86 mmol / g) of propylene glycol monoterpene ether acetate solution (solid content 25%) 〇 It should be noted that Μη is a Gpc meter (HLC-8120GPC, manufactured by TOSHO) and a column (2 TSKgd GMHXL + TSKgel 32 200846829 M_&gt;0re HXL_M, T〇SH〇 (Production), the value of polyphenylene = olefin measured by the Gj &gt; c method, and the method of the sp value, the brain value, the acid value, and the acrylic acid concentration. In the preparation examples and comparative examples of the town, the same measurement was also used. ..........................................................<Preparation example 2 &gt; ^Into the same flask as in Preparation Example 1, 190 parts of phenol novolac type • Milk tree, ΕΡΡΝ·201 (manufactured by Nippon Kasei Co., Ltd., epoxy equivalent) and 238 parts of C = alcohol monomethyl ether acetate Heat to 11 Torr. 〇, to dissolve it uniformly. Next, 76 parts of acrylic acid, 2 parts of triphenylphosphine and 2 parts of p-methoxy phenanthine were added and reacted at 110 C for 1 hr. Further, 91 was added to the reaction product: hydrogenated phthalic anhydride, and further reacted at 9 Torr for 5 hours, and then diluted with propylene alcohol early methyl ether acetate to obtain a solid content of 25%. Hydrophilic tree deer with a propylene sulfhydryl group and a carboxyl group (A_2 : Mn : 2,3 〇〇; = value j 11.91 ; HLB value: 6.81; acid value: 94 mg KOH/g; acryl thiol group / Chen 2 · 2 · 94 mmol/g) propylene glycol monomethyl ether acetate solution (solid content: 25%) 〇 <Comparative Preparation Example 1> To the same flask as in Preparation Example 1, 2 parts of cresol novolac resin was charged. (Stock) company EP-4020G) and 238 parts of propylene glycol monomethyl ether B = ester, heated to not:, so that it is evenly dissolvedNext, butyl ruthenium laurate and 20 parts of ethyl decyl acrylate were added and reacted at 〇 C for 5 hours. Thereafter, using propylene glycol monoterpene ether acetate to dilute 33 200846829 z.^^uopn release 'to make a solid content of 25%, to obtain a hydrophilic resin having an acryl fluorenyl group (A-Γ: Mn: 2,1 〇〇; SP value: 13.46; HLB value: 6.41; acid value ^ 〇 mgKOH / g; propylene sulfhydryl concentration: 1.34 mmol / g) propylene glycol monoterpene ether acetate solution (solid content of 2 you). ... 2 <Comparative Preparation Example 2>

To the same flask as in Preparation Example 1, 50 parts of isobornyl methacrylate (33 mol%), 30 parts of 2-hydroxyethyl methacrylate (33 mol%), and % by weight of methacrylic acid were placed. 34 mol%) and 150 parts of cyclohexanone, heated to 80 C. After replacing the gas phase in the system with nitrogen, it was directed to (6) in 1 minute. Into a flask, 55 parts of a solution prepared by dissolving 5 parts of azodi-butylidene (V-60: Wako Pure Chemical Industries, hereinafter referred to as AIBN) in 5 parts of cyclohexane = 1 was prepared by adding dropwise The reaction was carried out for 3 hours at the same temperature to obtain a ring of a hydrophilic polymer (A-2,) having a carboxyl group (Mn: 8,800; SPi:u.86; HLB^: 11·98; acid value·102 mgK0H/g). Essential solution (solid content is

[Preparation of polyoxyalkylene (B)] &lt;Preparation Example B-1&gt; 46 parts of a glass flask equipped with a heating cold stirring, stirring means, a reflux condenser, and a nitrogen = inlet tube (Μ莫尔亚丙Lactopropyltrimethoxywei, (10) parts (α65 parts) of diketone Xixuan and 45 g (2.5 moles) of ion-exchanged water, G ^ part of soldering acid, heated and stirred at 60t: for 6 hours, and then used The evaporator is at: 34 200846829

=% of the slanting of the product with 2 small shafts to produce methanol. After 'diluted with cyclohexanone to make the solid content 25%, get the hard stone simmering milk (Β·1) (10): 2, _; dryness: 2G mpa.s; sp value: 9 36) f ^ The content of the ketone paste (4) was measured by a M BL^ meter (manufactured by Toki Sangyo Co., Ltd.) at a constant temperature of 23⁄4. In the following I example and comparison, the _ same method is also used. &lt;Preparation Example Β-2&gt; Into the same flask as in Preparation Example Β-1, 17 parts (〇·82 mol =) 3, glyceryloxypropyl dimethoxy group, and * part ( 〇·2. Moer> Samples of trimethoxy Wei, 3G parts ((U2 molar) diphenyl dimethoxy shi k k and 40 g (2.2 moles) ion-exchanged water, 〇 1 part... Stem ear) Early acid: Heated at 6 (TC) for 6 hours, and then used the evaporator under the reduced pressure of % melon culvert for 2 hours to remove the by-product methanol produced by hydrolysis. Dilute to a solid content of 25% to obtain a cyclohexanone solution (solid content of 25%) of ash 2 2 2 (Μη: 7,800; viscosity · 7 〇 mpa.s; 卯: 8.69). Examples 1 to 6 and Comparative Examples 1 to 4 &gt; [Preparation of photosensitive resin composition] According to the number of components of Table 1 [apparent parts by weight of each component, it should be noted that 0 represents a composition of a photosensitive resin The weight percentage of the solid content of each component of the substance (Q) (under the decimal point == five in)]. Adding the hydrophilic resin solution to the surface preparation n, the poly-stone oxygen 35 200846829 -i. JUUOpif burning solution 'Additional to the following (C- l), (D-6) 'Stirring to uniformity, adding an additional solvent (propylene glycol monoterpene ether acetate), and damaging the photosensitive resin compositions (Q1) to (Q6) of the examples and the comparative examples Resin composition (γι) ~ (Y4). Describes the slight planting in Table 1; the definition of Y in addition to the above is defined as follows. B-3: Unilateral terminal mercapto acrylonitrile-based modified poly Shixi Oxygen ("X-22_174DX,": Shin-Etsu Chemical Co., Ltd.) [dryness: 6〇mpa.s, SP value 7.95); cl (photoradical polymerization initiator): "IRGACURE907,, (2-f race (methylthio)phenyl]-2-morpholinopropanone _:

Ciba'SpecialityChemicals (manufactured by the company); D-6 (polyfunctional (meth) acrylate): [Ne〇ma DA_6〇〇] (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate; Yucheng Industrial Co., Ltd.) (SP value: 10.55);

36 200846829 [Table 1]

Product name ratio (parts by weight) (A) SP value ~ - (B) SP value, shadow b solution (B). Solution _ .. Comparison of dissolved - (€) (D)- .. ..... Α-1 solution A-2 solution B-1 solution B-2 solution B-3 Α-Γ solution A-2, solution C-1 Ί&gt;6 Solvent Example 1 Q 1 34 0 (8 1 60 (14) 5 (5) 50 1.9 ◎ 2 Q 2 340 (81) 60 (14) - a 5 (5) - 50 3.22 ◎ 3 Q 3 30 0 (7 1) 100 (24) 5 (5) 50 1.9 〇4 Q 4 340 (S1) 15 04) A 5 (5) a 50 3.96 〇5 Q 38 0(8 6) 40 (9) 5 (5) 50 2.57 ◎ 6 Q 6 340 (81) 60 04 ) 5 (5) 10 50 2.55 ◎ Comparative Example I Υ 1 60 (14) 340 (81) — 5 (5) — 50 4.10 Δ 2 Υ 2 60 (14) 340 (81) 5 (5) — 50 2.50 ◎ 3 Υ 3 40 0 (9 5) 5 (5) 10 50 ◎ 4 Υ 4 60 (14) 340 (81) 5 (6) — 50 3.17 〇[Developability evaluation] Rotate and apply sensitization on each glass substrate Resin composition (Q1) ~ (^Q6) and (Y1) ~ (Y4), the surface film thickness is 5 μπι, drying at 25 ° C for 5 knives, and then developing with Ρ / ϋ sodium carbonate aqueous solution 3 〇 Second, evaluate the odds 37 2 00846823⁄4 影性. The results are shown in Table 1. The evaluation criteria are as follows. ◎: No residue was observed visually. (3) There is a little residue △: There are many residues in the first sight. ...........

[Vertical matching bribe crystal riding (4)] There is ITO (tin indium oxide) film in Yuancheng^

The amount of light: shot 1f &quot; 5 minutes. Pass the reticle with 100-two mercury lights. It is noted that the exposure is performed under the conditions of the reticle and the substrate i% s/^4 optical aperture. Then, the liquid crystal ageing plate is aligned vertically [Measurement of liquid crystal alignment property and voltage retention characteristics] Using a liquid crystal alignment film coating printer, a liquid crystal alignment agent AL m659 (trade name) is applied onto the above-mentioned protrusion-defining substrate. After the film was dried at 160 ° C for 2 hours, a film having a film thickness of Ε 5 μΕη was formed. On the glass substrate on which the photosensitive resin composition was not applied, the same method as described above was used. The liquid crystal alignment agent AL1H659 was applied and dried at 16 ° C for 2 hours to form a film having a film thickness of 0·05 μm. ' Then, on the outside of the respective liquid crystal alignment films of the obtained two substrates, screen printing was performed. The epoxy resin adhesive is applied, and the two substrates are superposed and compacted in such a manner that the liquid crystal alignment film faces face to cure the adhesive. Thereafter, 38 200846829f is prepared from liquid crystal injection - σ A soil and interplate between Meluc Corporation. For 曰MLC-capsule (trade name), seal the liquid crystal with epoxy-based dry agent. Note 2: In the two-layer substrate, the ray plate is used to make the polarized wire 6 straight, and the vertical alignment type liquid crystal display element is produced..... ....... force direction liquid crystal matching The evaluation of the directionality is as follows: whether the 液晶 ΐ ΐ 到 、 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶

When it comes to the hanging area, it is considered "not good." Tian Zheng (10) out of the relative voltage after 2Q milliseconds, and the ratio of the voltage (5V).

From the surface composition, it can be seen that the excellent liquid s/developability is excellent, and the liquid crystal alignment property and the voltage holding property are excellent for the liquid crystal alignment property and the voltage retention property. 39

200846829 A "W V t J is not sufficient. There is silk" (four) in the development of the test solution (four) two = #_r contains propylene, the "liquid crystal alignment ... inch 4 inch twins. In Comparative Example 3, the composition of the composition of (^3) does not contain agglomerated, and the characteristics of the electric charge are poor, and when the liquid is right, the alignment of the liquid is adjusted to Υ4 f for use. The resin composition is Υ1 degree, and the field of view crystal display element is used. [Industrial Applicability] The photosensitive resin composition of the present invention can be suitably used for forming a liquid display element ==, and Γ is a vertical alignment type liquid crystal display element; The photosensitive resin composition of the present invention is also suitably used as a material, for example, a solder resist, a photosensitive film, a screen, a photo-paste, or a paste. Etc.), such as polycarbonate (polycarbonate, polystyrene), paper, glass, rubber, and wood-making materials such as molding materials, printing inks and drilling agents, can also be used as The invention is not limited to the preferred embodiment of the present invention, and is not limited to the above description of any of the above-mentioned 40 200846829, however, #非田,,,,,,,,,,,,,,,, The invention is not limited to the invention, and any technology that is familiar with the present invention can be used without departing from the scope of the technical solutions of the present invention. Any simple modifications, equivalent changes and modifications made to the above embodiments are still within the scope of the technical solution of the present invention. [Simplified description of the drawings] Benefits [Main component symbol description] Benefit 41

Claims (1)

200846829 一w VW r _»&gt;▲ X. Patent application scope: L. A photosensitive resin composition (Q) 'which can be subjected to in-situ development and used to form protrusions for liquid crystal display elements, the composition including: Methyl). Hydrophilic wax of propylene sulfhydryl group and carboxyl group (A), polyoxymethane (B); and ^. Free radical polymerization initiator (〇. 2) The photosensitive resin composition as described in claim 1 (Q), wherein the polyoxyalkylene (Β) has two or more hydrolyzable alkoxy groups. 3. The photosensitive resin composition (Q) as described in claim 1 ', Wherein the polyoxyalkylene (8) is a condensate in which the decane compound (cl) represented by the following formula (1) is an essential constituent monomer: R1 - 2 i K m - si - (OR.) 31 (1) j in the formula "Rl A group consisting of a group consisting of a (meth) _ $wineoxy group, a glycidoxyalkyl group, a mercaptoalkyl group, and an aminoalkyl group p having 1 to 6 carbon atoms selected from an alkyl group Or one or more organic groups; R2 represents a carbon f group, an aliphatic saturated hydrocarbon group of 1 to 12 or a non-base group having a carbon number of 6 to 12, and R3 represents a alkyl group having 1 to 4 carbon atoms; The photosensitive resin composition as described in the above-mentioned Japanese Patent Application No. 1 wherein the hydrophilic resin (Α) is a hydrophilic resin formed by converting an epoxy resin. 5. The photosensitive resin composition as described in claim 1 of the patent scope 42 200846829 (differential difference between the solubility parameters of the water resin (eight) and the polywei paste #^如申料_1 to the fifth shot-reward Based on the subtracted - ten weight 1 reference, containing 50 to 98 wt% of hydrophilic resin (A), L5 to 45 wt% of polyoxyalkylene (B), and o. oi to 8 wt% of photoradicals a polymerization initiator (C). A projection for a liquid crystal display element, which is a photosensitive resin according to any one of claims 1 to 6 by a process including light irradiation. The liquid crystal display element protrusion described in the seventh aspect of the invention is characterized in that the light irradiation process is characterized in that after light irradiation, alkali development is performed to form a pattern, and then Post-baking. 43 200846829 VII. Designation of representative drawings: (1) The representative representative of the case is: No (2) The symbol of the symbol of the representative figure is simple: .......... None.... ............--.........-........................... ...-· VIII. If there is a chemical formula in this case, please reveal the best display. Chemical formula of the characteristic: