TW200949445A - Photosensitive resin composition, photospacer and method of manufacturing the same, protective film, colored pattern, substrate for display device, and display apparatus - Google Patents

Abstract

To increase the polymerized hardness during photo exposure, and to form pattern structure and protective film at low heating temperature or under no heating process. Solution: Photosensitive resin composition containing resin, polymerized chemical compound having the following structure part (I) [in the structure part (I), X represents hydrogen atoms or methyl group, and * represents combining bond], and photosensitive resin composition of photo-polymerization inducer. Said polymerized chemical compound preferably has two or more than three structure parts (I) in the molecule.

Description

[Technical Field] The present invention relates to a photosensitive resin composition, a photo spacer, a method for forming the same, a protective film, a colored pattern, a substrate for a display device, and a display device. [Prior Art] A liquid crystal display device is widely used in a display device for displaying a high-quality image. The liquid crystal display device is generally disposed between a pair of substrates (hereinafter also referred to as "display device substrate"), and a liquid crystal layer capable of forming an image is arranged in accordance with a predetermined alignment, and the substrate interval, that is, the liquid crystal layer is uniformly maintained. The thickness is one of the elements determining the image quality, and a spacer for fixing the thickness of the liquid crystal layer is disposed for this purpose. The thickness between the substrates is generally referred to as "cell thickness", and the cell thickness is generally the thickness of the liquid crystal layer, in other words, the distance between the two electrodes for applying an electric field to the liquid crystal in the display region. The display device substrate (for example, a color filter substrate, an active matrix substrate, or the like) is formed by forming a structure such as a colored pattern or a protective film on the substrate. Among these structures, the method of forming the colored pattern and the protective film is a method in which a photosensitive resin composition is used and formed by lithography. Further, the spacer is conventionally formed by scattering of beads. However, in recent years, a photosensitive resin composition has been used, and by lithography, a spacer having high positional accuracy can be formed. A spacer formed using such a photosensitive resin composition is referred to as a photo spacer. For the photosensitive resin composition, various kinds of tests have been made in the past. For example, it has been disclosed that a copolymer of an ethylenically unsaturated compound such as an ethylenically unsaturated carboxylic acid and a specific photopolymerization initiator are used. Further, a constituent unit of an aliphatic cyclic hydrocarbon group having a specific structure, a constituent unit having an acidic functional group, and a radical polymerizable group have been disclosed (see, for example, JP-A-2007-86565). The aliphatic cyclic hydrocarbon group of the molecular structure of the constituent unit contains a curable resin composed of a copolymer (for example, see JP-A-2002-293837). [Invention] Φ According to the aspect of the present invention, it is possible to provide an exposure improvement. Photopolymerization hardenability, pattern structure under low temperature heating or no heat treatment, photosensitive resin composition which is possible to form a protective film, photo spacer using the same, a method for forming the same, a protective film, a coloring pattern, and A substrate for a display device and a display device including the substrate for the display device. The photosensitive resin composition A polymerizable compound containing a resin and having the following structural part (I) [in the structural part (I), X represents a hydrogen atom or a methyl group, * represents a bonding bond], and a photosensitive resin composition with a photopolymerization initiator The polyadhesive compound preferably has two or more structural moieties (I) in the molecule.

X OH * (I) In the conventional photosensitive resin composition, general photopolymerization 200949445 single system uses ethylene such as dipentaerythritol hexaacrylate or dipentaerythritol pentaacrylate. Monomer of unsaturated bonds. However, in the case where a conventional photosensitive resin composition is used to form a pattern structure (for example, a photo spacer, a colored pattern, or the like, the same applies hereinafter) and a protective film is formed on the substrate, the polymerization hardening is not necessarily sufficient only by exposure. Moreover, it is necessary to apply a high-temperature heat treatment after exposure and development. Further, when a pattern structure such as a fine photo spacer is required to be formed, it is generally considered that the polymerization Φ reaction at the time of exposure is fast as desired in order to prevent the shape from shifting. The present invention has been made in view of the above, and has an object to achieve the following object. That is, the present invention provides excellent polymer curability at the time of exposure, and can obtain a pattern structure and protection under low-temperature heat treatment or no heating. The photosensitive resin composition of the film is intended for the purpose. Further, the present invention has an object of providing a photo spacer having a high cross-sectional shape with high uniformity and excellent uniformity in height and a method for producing the same. Further, the present invention is intended to provide a protective film having excellent film thickness uniformity or a colored pattern having a uniform cross-sectional shape and excellent film thickness uniformity. Further, the present invention has an object of providing a display device substrate capable of suppressing display unevenness and a display device having suppressed display unevenness when used in a display device. Means for Solving the Problems According to the present invention, a polymerizable compound having a specific structural moiety in a molecule is rapidly polymerized by providing light, so that the formability is excellent, and the shape is excellent, and it is different from the high temperature heating which has been called so-called post-baking. For example, it can be improved by heating at a low temperature of less than 200 ° C or improving the hardenability even without heat treatment, and is completed based on the knowledge. The specific means for achieving the above problems are as follows. <1> A photosensitive resin composition containing a resin, a polymerizable compound having the following structural portion (I), and a photosensitive resin composition with a photopolymerization initiator. In the following structural part (I), X represents a hydrogen atom or a methyl group, and "*" represents a bond.

The photosensitive resin composition of the above-mentioned <1>, wherein the polymerizable compound has at least two of the aforementioned structural moieties in the molecule (Ib &lt; 3 &gt; The photosensitive resin composition described in the above-mentioned <1>, wherein the polymerizable compound has a symmetrical structure in which two groups of the above-mentioned structural portion (1) are bonded to each other. &lt;4 &gt; The photosensitive resin composition according to the above-mentioned <1>, wherein the polymerizable compound having the structural moiety (I) is a polymerizable compound represented by the following structural formula (η).

In the formula, R represents a linking group containing at least one ether bond between carbon and carbon of a divalent hydrocarbon group. X is a hydrogen atom or a methyl group. <5> The photosensitive resin composition according to the above <4>, wherein R is -CH2-〇-Ra-〇-CH2-, and Ra is selected from the group consisting of The linking group of the group formed by the base portion, the aryl group, and the portion in which these are combined. The photosensitive resin composition according to any one of the above-mentioned items, wherein the resin has a branching and/or alicyclic structure and an acid in a side chain.

A base, and an ethylenically unsaturated bond. The photosensitive resin composition of the above-mentioned <6>, wherein the acid value of the resin is 20 mgKOH/g or more. The photosensitive resin composition according to the above-mentioned <6>, wherein the group having a branched and/or alicyclic structure is a group represented by the following formula (3).

In the formula (3), X represents a divalent organic linking group, and may be unsubstituted or may have a substituent. 7 indicates that 1 or 2'11 represents an integer of 〇~15. &lt;9&gt; A photo spacer formed by using the photosensitive resin composition according to any one of the above items <1> to <8>. &lt;10&gt; - A method for producing a photo spacer, which comprises at least the following steps (A) to (C): (a) the photosensitivity of any of the above &lt;1&gt; to the aforementioned &lt;8&gt; a step of forming a film of the resin composition on the substrate; 200949445 (b) exposing at least a portion of the film to an exposure step; (c) a step of developing the film after the imagewise exposure. &lt;11&gt; The method for producing a photo spacer according to the above <1>, wherein the heating step of the film after heating is further performed, and the maximum temperature during heating is 40 ° C or higher, 14 Below 5 °c. &lt;12&gt; A protective film formed by using the photosensitive resin composition according to any one of the above items <1> to <8>. &lt;13&gt; The coloring pattern is formed by using the photosensitive resin composition according to any one of the above &lt;1&gt; to &lt;8&gt; The substrate for a display device, wherein the photo spacer, the protective film, and the photosensitive spacer are formed by using the photosensitive resin composition according to any one of the above items <1> to <8>. At least one of the aforementioned coloring patterns. &lt;15&gt; A display device comprising the substrate for a display device according to the above &lt;14&gt;. [Embodiment] The embodiment of the invention is described in detail below. The photosensitive resin composition of the present invention will be described in detail, and the photo spacer using the photosensitive resin composition, a method for forming the same, a protective film, a colored pattern, and a display device will be described in detail. a substrate, and a display device. <<Photosensitive Resin Composition>> The photosensitive resin composition of the present invention is at least a resin, a polymerizable compound having the structural portion (I) shown below, and a photopolymerization initiator. Further, other components may be further used as needed. In the case where a photosensitive resin composition is generally used to form a pattern structure (for example, a photo spacer, a coloring pattern, or the like, the same applies hereinafter) and a protective film in the case of 200949445, it is easy to cause polymerization hardening to be caused by exposure alone. Sufficient, in order to further accelerate the polymerization hardening, it is generally applied to heat treatment at a high temperature after exposure to development. However, when a heat treatment is applied at a high temperature, the formed pattern structure or the protective film is deteriorated, or the pattern structure and the protective film which have been formed on the substrate are deteriorated by repeated application of heat. For example, in the case of forming a photo spacer on a color filter substrate having a colored pattern, the photo spacer itself thus formed may be deteriorated, and the colored pattern already formed on the substrate may be imparted by The heat is getting worse. On the other hand, in the present invention, since the composition of the photosensitive resin composition accelerates the polymerization during the exposure, the moldability is excellent, and the polymer hardenability at the time of exposure is improved, and the film is heated at a low temperature (for example, 1 45 ° C or less). A uniform pattern structure or a protective film may be formed without heat treatment. Thereby, it is possible to suppress not only the pattern structure and the shape shift of the protective film, but also to effectively suppress the deterioration of the pattern structure and the protective film formed as described above, and the established pattern structure and protective film on the substrate. Deterioration due to repeated heat. 〇 Hereinafter, a resin, a polymerizable compound having a structural portion (I), a photopolymerization initiator, and other components will be described. &lt;Polymerizable compound having a structural part (I)&gt; The photosensitive resin composition of the present invention contains a polymerizable compound having the following structural part (I) (hereinafter referred to as "specifically polymerizable compound J") At least one type of polymerizable compound is subjected to a radical reaction from a photopolymerization initiator to be described later, and causes a polymerization reaction to form a cured film. The effect by the specific polymerizable compound is not clear, but it is presumed that The structure shown in the following structural part (I) is such that the reaction of the unsaturated double-10-200949445 bond portion at the time of exposure is accelerated, so that it is excellent in polymerization hardenability.

X OH (I) ’ In the above structural part (I), the 'X system represents a hydrogen atom or a methyl group, and the "*" in the formula represents a bond. Φ The specific polymerizable compound of the present invention is not particularly limited as long as it is a compound having a structural portion (I), and any one or two or more of the photosensitive resin compositions of the present invention can be selected. The compound having a structural moiety (I) may, for example, be a compound having one structural moiety (1), or two or more structural components (I) via a divalent or trivalent or higher valence between each bonding bond (*). The compound to which the linking group is bonded and the two structural parts (I) are compounds which are directly bonded by each bonding bond (*). The compound having one structural moiety (I) may, for example, be a bond (*) in the structural moiety (I), for example, a carbon-carbon in a monovalent hydrocarbon group, and the bond contains at least one ether bond (-〇) -) a compound of a linking group. Specific examples of the compound having one structural portion (I) include the following compounds. Further, each of the specific examples described below indicates that "-X" is a compound of "-Η" or "_CH3". -11- 200949445 χ ΟΗ

'CH-O- -CH2j-〇-CH3 ’η

Χο X ΟΗ η is an integer from 1 to 8 ο. , CH-0-{-CH2j-0-CH2CH3 /η

OH n is an integer from 1 to 8 ΟΗ , ο. Φ ο ❿

Oh2o-ch2—ch-ch2-o-ch3 ch3 ch2-〇-ch2—CH-CH2-O-CH3

η CH2j-CH3 n, m is an integer from 1 to 8 H3C ch3\/ CH2-〇-CH2—C-CH2-O-CH3 CH2-〇-CH2-( )-CH2-O-CH3

X OH

200949445

X OH

e 〇 〇 OCCH3 H3CC〇v 1 OCH2 〇 〇 H3CCO. 〇 11 H3CCO*

HO. HO-HKT Ό

OCH2 〇 OCCH3 OH OCH: ΌΗ, 〇H OH X 〇 〇

OH X 〇 〇

X Among them, from the viewpoints of solubility, viscosity, etc., it is preferable to bond a compound such as an ether group, an oxirane group or an alcohol group to a bond (*) of the structure (i). It is preferably an ether, an oxirane group or the like. The above-mentioned divalent or trivalent or higher linking group may be arbitrarily selected from the polyvalent group, and examples thereof include a divalent or trivalent or higher hydrocarbon group and a carbon-carbon intermetallic group having a divalent or trivalent or higher hydrocarbon group. A group containing one or two or more ether bonds (-0-), -〇-, -S_, an ester bond, a guanamine group, an amine group, and the like, and a divalent group or the like in which at least two of them are combined. Specific examples of the linking group of divalent or trivalent or higher are as follows. However, φ is not limited to this invention in the present invention. Further, "*" in the specific example indicates a binding key. ^ 瘳 -14- 200949445

OH * —CH2-O-CH2-CH-CH2-O-CH2- *

* One H2CO

* One CH2-0~CH2-CH-0-CH2— *

HO, OCH2—* HO OCH2-* * _CH2-0_CH2-CH2_CH2-CH2-0-CH2_ * HO^J^O *-h2co^

CH3CH3 * —CH2-0-CH2-C-CH2-0-CH2-* OCH2一* * - H2CO Human OCH2 - * CH2~0-CH2~ ** -CH2-0-CH2 HO- -H2C〇&quot; och2 . 'OCH,-

*-H2CO I OCH2 - * *_h2co,"

*-h2co och2-* * -HjCO^ ^OCHj - * *-h2co och2-* Fast and good hardening from polymerization at the time of exposure, even after low-temperature heating and no heat treatment, to form uniformity The viewpoint of the pattern structure and the protective film is preferably a specific polymerizable compound having two or more of the structural portions (I) in the molecule. Further, based on the same point of view, it is preferred to have two structures in the molecule: -15-200949445 (I), and the bond contains the same two bases of the structure (1).

It is preferred to form a compound having a symmetrical structure in which the entire molecular structure of the linking group linking the two structural portions (I) is contained. Preferred compounds of the symmetrical structure include, for example, the compounds represented by the following structural formula (11).

The carbon-carbon of the divalent hydrocarbon group contains at least one ether bond (-〇-) linking group, and preferably a linking group containing at least one ether bond (-0-) between the carbon-carbon of the divalent hydrocarbon group. The "divalent hydrocarbon group-containing group" represented by R is, for example, a divalent group composed only of a hydrocarbon group represented by CnH2n (ng 1), and a hydrocarbon group represented by CnH2n (n 21), and a combination thereof. A divalent group derived from at least one of an ether bond, an ester bond, a guanamine group, and an amine group. The range of η is suitable from 1 to 8. In addition, the "linking group containing at least one ® ether bond between carbon-carbon of a divalent hydrocarbon group" includes one or two or more oxygen atoms and carbon atoms and hydrogen disposed between carbon and carbon. The atomic divalent group is not particularly limited, and may include, for example, - (AL and/or AR)_0 - (AL and / or aR) _, - (AL and / or AR) - 0 - (AL and / or AR)-0-, -(AL and / or AR)-0-(AL and / or AR)_〇_(AL and / or 2 valence is suitable. In addition, AL stands for extension, AR The above-mentioned stretching group (AL) may be any of a straight chain or a branched chain, and the alkylene group and the extended aryl group (AR) may be unsubstituted or substituted. The substituents in the case of substitution may, for example, be the same groups as those exemplified below in Μ -16- 200949445. In the case of R, polymerization from exposure is rapid and can be carried out. The point of good hardening is preferably a case where two or more oxygen atoms are contained, and more preferably -CH2-〇-Ra-〇-CH2-. Here, the Ra system is represented by a stretching base portion and an extended aryl portion. And the group selected by the combination of these parts The linking group is selected. One or two or more ether bonds may be further disposed between the carbon-carbon bonds of the alkyl group represented by Ra. The alkyl group represented by the above Ra is not particularly limited, and may be omitted. The substituent may be substituted or substituted with a substituent. The substituent in the case of substitution may, for example, be an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, butyl group, hexyl group or octyl group). A monovalent substituent such as a hydroxyl group or a halogen group. Specific examples of the alkylene moiety include a methylene group, an ethyl group, a propyl group, a butyl group, a 2-hydroxypropyl group, and a 2-methyl group. Ethyl, 2-dimethylexylethyl, cyclohexyl, etc. wherein the alkylene moiety is from a solvent solubility and precipitation inhibition point, and a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms is Preferably, the alicyclic or unsubstituted alkylene group having 1 to 6 carbon atoms is preferred. The exoaryl moiety represented by the above Ra is not particularly limited and may be unsubstituted or substituted with a substituent. The substituent in the case of substitution may, for example, be the same substituent as in the case of the above alkylene moiety. Specific examples of the aryl moiety For example, a phenyl group, a naphthyl group, etc., a carbon number is taken, and a point 8 is a number of carbons, and a solution is obtained, and the dissolution of the aromatic swellable agent is taken from the no-position or the partial base. The extension of the ο, ί zhong 6 number of examples can be tied to the group of the base part of the base of the ο 圭 伸 MB compared to the base aryl aralkyl extension, take no or -17- 200949445 such as: -C6H4 -C(CH3}2-C6H4-, -(CH2)2-〇-C6H4-C(CH3)2-C6H4-〇-(CH2)2-, -(CH2)3-〇-C6H4-C(CH3) 2-C6H4-〇-(CH2)3- and the like. Specific examples of "-CH2-〇-Ra-〇-CH2-" represented by the above R are as follows. However, the invention is not limited thereto. This # ' stomach stomach

The "*" in the example indicates a binding key. (1) OH , CH2_〇~CH2_ * —CH2-〇-CH2~CH-CH2-〇-CH2** (6) * —CH2-〇-CH2 (7)

(3) CH3 * -ch2-o-ch2-ch-o-ch2-* (4) * -CH2-O-CH2-CH2-CH2-CH2-O-CH2· ❹ (5) C^CH3 •—CH2 -〇-CH2-C-CH2-〇-CH2— * (8) -H2CO' HO&quot; (9) Xi H, och2-,

HO 〇CH2_* H0 ten. Further, the OH *-H2co UH is preferably a symmetrical structure in which the linking group represented by the above-mentioned Ra is excellent in polymerization reactivity at the time of exposure. Specific examples of the linking group of the symmetrical structure include, for example, the specific examples (1), (2), (4) to (9) described above, and are exemplified as specific examples. The molecular weight of the specific polymerizable compound in the present invention is preferably from 100 to 3,000 by weight average of from -18 to 200949445, and more preferably from 100 to 2,000 is more preferably -100 to 1500. The molecular weight of the specific polymerizable compound is 1 Å or more, which is desirable from the viewpoint of suppressing sublimation, and 3,000 or less is desirable from the viewpoint of solubility. Further, the weight average molecular weight is measured by gel permeation chromatography (GPC). The GPC system is shown in detail in the item of the following example. Hereinafter, specific examples (exemplary compounds (1) to (20) and (M-1) to (M-15)) of the specific polymerizable compound having the structural portion (I) will be described. However, 0 is not limited to this invention in the present invention.

-19- 200949445

(1) 〇H 〇

OH

OH

(5) OH CH2-O-CH2-CH-CH2-O-CH2

CH3 I CH2-0-CH2-CH-0-CH2

OH

OH

OH

OH 〇, OH2-O-CH-CH2-CH2-O-CH2

CH 3

-20- 200949445 (6)

OH nr O, , /CH3 o CH2-0-CH2-C-CH2-0-CH2 , σ

OH o (7) OH 0, CHfO-CH:

.CH2-O-CH2 11 γ^〇Λ^&gt;

OH Ο (8) OH recognize CHrO 〇 o

O-CH2 |[

OH

(9) O

O 〇

HO-

OH (10)

OH 10 ~~H2C〇y 〇 /〇H OH OCH2—1 -° -21 - 200949445 (11) OH Ο ch3 〇 (1&gt;3 Λγ° 〇

OH CH 3 Reference (13)

〒Η3 CH2-O-CH2-CH-O-CH2 Ο 〇

OH CH3 OH 〇O, 〇

〇

〇 OH CH3 OH CH2 -〇-CH-CH2-CH2-〇-CH2 ch3 〇 ❹ OH ihu -22- 200949445 (16) CH3Λτ°' ο

OH C々3/CH3 Hn-C-CH^ 〇 CH2~0~0H2~0&quot;0H2~0~0H2 (17) OH CH3 ,ch2-o-ch2 CH3

OH Ό人 f OH CH3 , CHr〇-CH2

(18)

-twenty three-

200949445 (Μ-D (Μ-2) ^Ύ'

ΟΗ I ~CHr0-CH2-CH-CH2-0-CH3

PCI (Μ-3)

1, m = 1 ~ 8 of the whole religion (Μ-4) OCH〇

(M-5) OH —〇Η2·〇,

❹ (M-7)

(M-6) &quot;Y-r0 Ho O o-ch3 \A OCHy OH OCH2

OH I och2 ^OCHo nrc .0 OH HO. /OCH2 I N f OH οοηΓι^ 0 i^〇ch2-L/°'Y^ —och2 )CH2 oh (M-8)

° OH ° OH och2 och2 un^°r 丫&quot;r och2, N)CH2 ?h , 0, 200949445 (M-9) ch3

OH

OH Q\^—CH2-〇-CH2—CH-CH2-O-CH3

(M-10)

(M-12)

-25- 200949445 (Μ-13)

(Μ-14) OH ΗΟ, och2

Ο OH~~οαί ο Ό

(Μ-15) ch3 oh h OH ' och2

OH -〇CH2

-26 200949445 The content of the polymerizable compound (specifically polymerizable compound) having a structure (I) in the photosensitive resin composition is preferably from 1 to 60% by mass based on the total solid content of the composition, 10~ 55 mass% is preferred. When the content of the specific polymerizable compound is 1% by mass or more, the polymer curable property at the time of exposure is good, and a pattern structure or a protective film which suppresses the shape shift can be formed, and heat treatment at a low temperature or There is no deterioration of the pattern structure formed by the heat treatment, the deterioration of the protective film, or the established pattern structure or the protective film. When the amount is 60% by mass or less, the viscosity of the liquid, the hardness of the cured product, and the like, and the adjustment of the exposure sensitivity are effective. In addition to the specific polymerizable compound described above, the photosensitive resin composition of the present invention may further contain another polymerizable compound having an ethylenically unsaturated bond. Other polymerizable compounds may be selected from the group of the polymerizable compounds constituting the well-known composition, and the composition of the paragraph number [0010] [0020], and the special opening 2006 of JP-A-2006-23696, for example. -6492 Paragraph No. 1 No. 1 [0027] [0053] The components described in [0053]. ® may contain other polymerizable compounds within the range not impairing the effects of the present invention. In the present invention, the mass ratio of the total amount of the polymerizable compound containing the specific polymerizable compound to the total amount of the resin to be described later (the total amount of the polymerizable compound/the total amount of the resin) is from the developing property and the mechanical property. The viewpoint is preferably 0.5 to 2.0, 0.6 to 1.8 is preferred, and 0.7 to 1_5 is particularly good. When the mass ratio is within the above range, good developability can be obtained, for example, when a photo spacer or the like is formed, a photo spacer having mechanical strength can be obtained. &lt;Resin&gt; -27- 200949445 The photosensitive resin composition of the present invention contains at least one kind of resin. The resin is not particularly limited, and is preferably a compound which exhibits swellability to an aqueous alkaline solution, and preferably a compound which exhibits solubility in an aqueous alkaline solution. The resin which exhibits swellability or solubility in an aqueous alkaline solution is, for example, a compound having an acidic group, and specifically a compound (epoxy acrylate compound) in which an ethylenically unsaturated double bond and an acidic group are introduced into an epoxy compound. a mixture of a vinyl copolymer φ having a (meth) acryl fluorenyl group and an acidic group, an epoxy acrylate compound, and a vinyl copolymer having a (meth) acryl fluorenyl group and an acidic group in a side chain A maleic acid-based copolymer or the like is preferred. The acidic group is not particularly limited, and may be appropriately selected depending on the intended purpose, and examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among them, a carboxyl group is preferred from the viewpoint of the starting property of the raw material and the like. The content of the resin in the photosensitive resin composition of the present invention is preferably from 5 to 70% by mass based on the total solid content of the photosensitive resin composition, and is preferably from 1 to 50% by mass. When the content is 5% by mass or more, the film strength of the photosensitive resin layer can be maintained, and the surface adhesiveness of the photosensitive resin layer can be favorably maintained. When the content is 70% by mass or less, the exposure sensitivity is good. The resin in the present invention is excellent in deformation recovery property when deformed by applying an external force after polymerization hardening, and preferably contains a branching and/or alicyclic structure, an acidic group, and an ethyl group in a side chain. At least one of a resin having an unsaturated bond (hereinafter also referred to as "resin A"). Resin A has an acidic group and has developability, and has an ethylenically unsaturated bond, and has high polymerization reactivity, and has excellent liquid preservability of -28-200949445 and storage over time of dry film. Since the pattern structure can be controlled to have a desired shape and controllability of the film thickness (height, etc.). Further, it has a branching and/or alicyclic structure, and can improve the compressive modulus of elasticity of the formed pattern structure when subjected to an external force, and the deformation recovery property by compression deformation. Therefore, it is useful for forming a pattern structure such as a photo spacer for a display device. Here, the branching and/or alicyclic structure, the acidic group, and the ethylenically unsaturated bond may be contained in different side chains, or may be combined in one part and 0 in the same side chain, They may all be contained in the same side chain. Further, in the present specification, the (meth)acrylonitrile group means an acryl fluorenyl group or a methacryl fluorenyl group, and the (meth) acrylate type means an acrylate or methacrylate type '(meth)acrylic acid means acrylic acid Or methacrylic acid, (meth) acrylamide refers to acrylamide or methacrylamide, and (meth) acryl anilide means acrylamide or methacrylamide. (Branch and/or alicyclic structure) Resin A is composed of at least one kind of branching and/or alicyclic structure bonded to the side chain of the resin main chain. The branched and/or alicyclic structure may be plurally contained in the side chain of the resin A. Further, the branching and/or alicyclic structure may be contained in the side chain of the resin A together with the acidic group and/or the ethylenically unsaturated bond. Further, the 'branched and/or alicyclic structure can be directly bonded to the main chain of the resin A' and the side chain of the resin A can be formed only by the branching and/or alicyclic structure, and the organic chain can also be transmitted through the divalent organic The linking group is bonded to the main chain of the resin a to form a side chain of the resin A having a branching and/or alicyclic structure. The above divalent organic linking group is preferably selected from one of an alkylene group, an extended aryl group, a vinegar group, an amine group, and an ether group, or a combination thereof. The alkylene group -29-200949445 is preferably an alkylene group having a total carbon number of from 1 to 20, particularly preferably from 1 to 10. Specifically, for example, a methylene group, an ethylidene group, a propyl group, a butyl group, a pentyl group, a hexyl group, a decyl group, a dodecenyl group, an octadecyl group, etc. may be mentioned. Branch/ring structure, functional group, especially preferably methylene, ethyl, and octyl. The above-mentioned aryl group is preferably a aryl group having a total carbon number of 6 to 20, particularly preferably 6 to 12. Specifically, for example, a phenyl group, a phenylene group, a naphthyl group or a fluorenyl group may be mentioned, and these may have a branch or a functional group, and more preferably a phenyl group or a phenyl group. The branching and/or alicyclic structure is preferably in a form capable of permeating at least the ester group (-COO-) to the main chain of the resin A from the viewpoints of developmental properties, elastic recovery ratio, and the like. The branching and/or alicyclic structure of the form is not limited to a form in which the main chain of the resin A is bonded only by the ester group (-COO-), and the branch and/or the alicyclic structure may be configured to transmit the ester group. The divalent linking group of (-COO-) is bonded to the main chain of the resin A. That is, other atoms and other linking groups may be contained between the branching and/or alicyclic structure and the ester chain, and/or between the ester chain and the main chain of the resin A. ® The aforementioned branched structure may, for example, be a branched alkyl group having 3 to 12 carbon atoms, for example, an isopropyl group, an isobutyl group, a second butyl group, a third butyl group, an isobutyl group, a neopentane group. A group, 2-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, isopentyl group, a third pentyl group, a 3-octyl group, a third octyl group or the like is preferred. Among these, an isopropyl group, a second butyl group, a tert-butyl group, an isopentyl group or the like is more preferable, and an isopropyl group, a second butyl group, a third butyl group or the like is particularly preferable. The alicyclic structure may, for example, be an alicyclic hydrocarbon group having 5 to 20 carbon atoms, for example, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a decyl group, an isodecyl group, an adamantyl group, Tricyclodecyl, dicyclopentenyl, dicyclopentyl, -30- 200949445 tricyclopentenyl, and tricyclopentyl, and the like, especially dicyclopentenyl, Cyclohexyl, norbornyl, isodecyl, tricyclodecyl, tricyclopentenyl, tricyclopentyl, etc. are more cyclopentenyl, cyclohexyl, norbornyl, isodecyl, tricyclopentene Preferably, dicyclopentenyl and tricyclopentenyl are particularly preferred. Further, the base having a branched and/or alicyclic structure is preferably a form having a group represented by (3).

In the formula (3), X represents a divalent organic linking group and may have a substituent. 7 is a 1 or 2, and 11 is a 0 to 15. The divalent organic linking group is preferably one selected from the group consisting of an alkyl group, an ester group, a decyl group, and an ether group, or a combination thereof. Substituent. ® The above alkylene group is an alkylene group having a total alkyl group of 1 to 20 carbon atoms and preferably 1 to 10 alkyl groups. Specifically, for example, a group such as a methylene group, an ethylidene group, a butyl group, a pentyl group, a hexyl group, a decyl group, a dodecenyl group, or the like may be mentioned, and these may have a branched/annular structure. The function is methylene, ethyl, and octyl. The above-mentioned aryl group is an extended aryl group having a total carbon number of 6 to 20 and preferably an extended aryl group of 6 to 12. Specifically, for example, a phenyl group, a stretched group, a fluorenyl group or the like may be mentioned, and these may have a branch or a functional group, and particularly preferably; good. Such a group, a ruthenium, or a dibasic group is an integer of the following formula (3) unsubstituted, &gt;. The aryl group, the aryl group, etc. may also be a base, a propyl group, an octadecyl group, preferably a phenyl group, a naphthoquinone phenyl group, a substituent substituted in the case of -31-200949445, For example, it has an alkyl group, a hydroxyl group, an amine group, a halogen group, an aromatic ring group, an alicyclic structure, and the like. In the synthesis of the resin A, a single system for introducing a branching and/or alicyclic structure into a side chain may, for example, be a styrene, a (meth) acrylate, a vinyl ether or a vinyl ester. The (meth) acrylates, vinyl acetates, and (meth) acrylamides are preferred, and (meth) acrylates are preferred. In the synthesis of the resin A, a specific system for introducing the branched structure into the side chain may, for example, be isopropyl (meth)acrylate, isobutyl (meth)acrylate or (meth)acrylic acid. Dibutyl ester, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, third amyl (meth)acrylate, second isoamyl (meth)acrylate, (meth)acrylic acid 2 -octyl ester, 3-octyl (meth)acrylate, third octyl (meth)acrylate, etc., among which isopropyl (meth)acrylate, isobutyl (meth)acrylate, methacrylic acid The third butyl ester or the like is preferred, and isopropyl methacrylate, butyl methacrylate or the like is preferred. In the synthesis of the resin A, the monofluorene system for introducing the alicyclic structure to the side chain may, for example, be a (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. Specific examples include (meth)acrylic acid (bicyclo[2.2.1]heptyl-2) ester, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, (a) 3-methyl-1-adamantyl acrylate, 3,5-dimethyl-1-adamantyl (meth) acrylate, 3-ethyladamantyl (meth) acrylate, (methyl) 3-methyl-5-ethyl-1-adamantyl acrylate, 3,5,8-triethyl-1-adamantyl (meth)acrylate, 3,5-dimethyl (meth)acrylate - 8-Ethyl-1-adamantyl ester, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, (meth)acrylic acid 3 -Hydroxy-Ι α- 200949445 Adamantyl ester, octahydro-4,7-captoalkyl-5-ester (meth) acrylate, (methyl) acrylic acid octahydro _4,7-glycine base -1-methyl ketone, (meth) acrylic acid | __ capping ester, tricyclodecyl (meth) acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo(methyl) acrylate [3.1.1]heptyl ester, 3,7,7-trimethyl-4-hydroxy-bicyclo[4_1.0]heptyl (meth)acrylate, (meth)acrylic acid (nor) decyl ester, Isodecyl (meth)acrylate, fenyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid Dicyclopentenyl ester, tricyclopentenyl (meth) acrylate, etc. Among these (meth) acrylates, the functional group having a larger volume is more compressive and the recovery property is better. Cyclohexyl (meth) acrylate, decyl methacrylate, isodecyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate , fenyl (meth)acrylate, 1-caprate (meth)acrylate, tricyclodecyl (meth)acrylate, dicyclopentenyl (meth)acrylate, tricyclopentene (meth)acrylate Preferred as esters, such as cyclohexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, 2-adamantyl (meth)acrylate, (methyl) Acrylic acid dicyclopentenyl ester, tricyclopentenyl (meth)acrylate is particularly preferred. Also, in the synthesis of resin A The single system for introducing the alicyclic structure into the side chain may, for example, be a compound represented by the following formula (4) or (5). Here, in the general formulae (4) and (5), X represents 2 The organic linking group of a valence, R represents a hydrogen atom or a methyl group, y represents 1 or 2, and η represents 〇~15. Among the general formulae (4) and (5), y=l or 2, η Preferably, 0 to 8 is preferable, and y = 1 or 2, and n = 0 to 4 (more preferably n = 0 to 2). Preferred specific examples of the compound represented by the formula (4) or (5) For example, the following compounds D-1 to D-11 and T-1-T-12 are preferable. Among them, from the point of the deformation recovery rate, it is preferably a compound of the following formula (4): -33-200949445.

General formula (4)

Ch2 General formula (5) In the above formulae (4) to (5), the divalent organic linking group represented by X may be unsubstituted or may have a substituent, and X in the above formula (3) The two-valent organic linking groups shown are synonymous, and the preferred aspects are also the same.

-34· 200949445 Η Η2〇=〇—O-CH2CH2-Ο-H2C=CH-C-〇—D- ι D-3 H2C=C—C-〇-CH2CH2-〇^J]^ H2C=CH-C -0-0^) D- 2 ❹ D-49^3 Η2〇=〇Η-〇-0-φ3 D- 5 CH3 H2C=iC-〇CH2CH2CH2—〇II 〇

D—6 〇h3 H2C=i-C-〇CH2CH2CH2CH2—〇 〇

D-7

H3 H2C=C-C-OCH2CH2OCH2CH2—0 士 into L> o ch3 I J H2〇=C_C —OCH 2CH 2〇C H2CH2—〇 o ch3 H2C=i-C-OCH2CH2OCH2CH2OCH2CH2—〇 十 O

D-9 D-8

D-10

Ch3 H2C=C-C-OCH2CHII ] 0 CH -O-h-

D-11 -35- 3 200949445 ^°-Θ3〇 ο 0+

-1 Τ-5

Τ-6 Τ-2

Τ- Τ-3

Τ-4 々〇

〇η3 h2c=c-c-och2ch2och2ch2—ο- ο Τ-8

Τ-9 ❹ CH3 H2C=i-C-OCH2CH2OCH2CH2—〇- ο

Τ-10

-36- 200949445 In the synthesis of the resin A, the monomer for introducing the alicyclic structure into the side chain can be suitably used, or a commercially available product can be used. The commercially available product may be, for example, a Hitachi Chemical Industry Co., Ltd.; FA-511A, FA-512A (S}, FA-512M, FA-513A, FA-513M, TCPD-A, TCPD-M, H-TCPD -A, H-TCPD-M, TOE-A, TOE-M, H-TOE-A, H-TOE-M, etc. Among these, from the viewpoint of excellent developability and excellent deformation recovery rate, Preferably, FA-512A (S) or 512 M. φ (Acid) The resin A has at least one acidic group bonded to the side chain of the main chain, and the acidic group may be contained in the side chain in plural. Further, the acidic group may be contained in the side chain of the resin A together with the branching and/or alicyclic structure and the ethylenically unsaturated bond disposed between the main chain and the ester group. The base system may be directly bonded to the main chain of the resin A to form a side chain of the resin A only by an acidic group, or may be bonded to the main chain of the resin A through a divalent organic linking group to be acidic. The base of the tree is a side chain of the lipid A. Here, the divalent organic linking group may be, for example, a divalent organic linking group exemplified in the description of the branching and/or alicyclic structure. Good range is also the same The acidic group is not particularly limited, and may be appropriately selected from among those skilled in the art, and examples thereof include a carboxyl group, a sulfonic acid group, a sulfonylamino group, a phosphoric acid group, a phenolic hydroxyl group, and the like. The image and the water resistance of the cured film are excellent, and a carboxyl group or a phenolic hydroxyl group is preferred. In the synthesis of the resin A, a specific example of the monomer for introducing the acidic group can be appropriately selected from the well-known ones. For example, (meth)-37-200949445 acrylic acid, vinyl benzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid , α-cyano cinnamic acid, acrylic acid dimer, addition reaction of a monomer having a hydroxyl group and a cyclic acid anhydride, ω-carboxy-polycaprolactone mono(meth)acrylate, etc. A commercially available product may be used as a suitable manufacturer. The monomer having a hydroxyl group used in the addition reaction of the monomer having a hydroxyl group and a cyclic acid anhydride may, for example, be 2-hydroxyethyl (methyl). Acrylate, etc. The cyclic acid anhydride may, for example, be maleic acid Anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride, etc. Commercially available monomers include, for example, East Asian Synthetic Chemical Industry Co., Ltd.; ARONIX®-5300, ARONIX®-5400, ARONIX M-5500 , ARONIX Μ-5600, Xinzhongcun Chemical Industry Co., Ltd.; ΝΚ ESTER CB-1, NK ESTER CBX-1, Kyoeisha Oil Chemical Industry Co., Ltd.; HOA-MP, HOA-MS, Osaka Organic Chemical Industry (Stock) system; VISCOAT #2 100, etc. Among these, (meth)acrylic acid, etc. are preferable from the point of excellent imaging performance and low cost. © (Ethylene Unsaturated Bond) Resin A contains at least one ethylenically unsaturated bond in the side chain. In the resin A, the ethylenically unsaturated bond is preferably disposed between the main chain through the ester group. The ethylenically unsaturated bond may be plurally contained in the side chain. Further, the ethylenically unsaturated bond may be contained in the side chain of the resin A together with the above-mentioned branching and/or alicyclic structure and/or the above acidic group. Further, the ethylenically unsaturated bond may be bonded to the main chain of the resin A through at least one ester group (-COO-), or may be formed only by an ethylenically unsaturated bond and an ester group. chain. Further, between the main chain of the resin A and the ester group of -38 to 200949445, and/or between the ester group and the ethylenically unsaturated bond, the divalent organic linking group may be further provided, and the ethylenically unsaturated bond is also A side chain of the resin A which has a "base having an ethylenically unsaturated bond disposed through the ester group between the main chain" can be formed. Here, the divalent organic linking group may, for example, be a divalent organic linking group exemplified in the description of the branching and/or alicyclic structure, and the preferred range is also the same. Further, the ethylenically unsaturated bond is preferably disposed by introducing a (meth) acrylonitrile group.

In the synthesis of the resin A, a method of introducing a (meth) acrylonitrile group into a side chain can be appropriately selected from known methods, and for example, a (meth) acrylate having an epoxy group is added. a method of adding a repeating unit having an acidic group, a method of attaching an (-) acrylate having an isocyanate group to a repeating unit having a hydroxyl group, and attaching a (meth) acrylate having a hydroxyl group to a repeating unit having an isocyanate group. Method, etc. Among them, a method of adding a (meth) acrylate having an epoxy group to a repeating unit having an acidic group is particularly easy to manufacture, and it is preferable from the viewpoint of low cost. The (meth) acrylate having an epoxy group is not particularly limited, and for example, a compound represented by the following structural formula (A) and a compound represented by the following structural formula (B) are preferred.

Structural Formula (A> -39- 200949445 In the above structural formula (A), R1 represents a hydrogen atom or a methyl group, and Li represents an organic group.

In the above structural formula (B), R2 represents a hydrogen atom or a methyl group. L2 _ _ shows an organic group. The W system represents an aliphatic hydrocarbon group of 4 to 7 membered rings. Among the compounds represented by the above structural formula (A) and the structures represented by the structural formula (B), the compound represented by the structural formula (A) is more preferable than the structural formula (B). In the above structural formulae (A) and (B), it is preferred that Li and L2 are each independently an alkyl group having a carbon number of 1-4. The compound represented by the above structural formula (A) or the compound represented by the structural formula (B) is not particularly limited, and examples thereof include the following exemplified compounds (1)-(10) 0 Ο -40 · 200949445

-41 - 200949445 ~~ Other monomers ~~ In the resin A of the present invention, other monomers may be introduced into other groups. The other single system is not particularly limited, and examples thereof include (meth) acrylate, styrene, and a monomer having a vinyl ether group, a dibasic acid anhydride group, a vinyl ester group, or a hydrocarbon alkenyl group. The vinyl ether group is not particularly limited, and examples thereof include a butyl vinyl ether group and the like. The above-mentioned dibasic acid anhydride group is not particularly limited, and examples thereof include a maleic anhydride group and an itaconic anhydride group. The vinyl ester group is not particularly limited, and examples thereof include a vinyl acetate group and the like. The hydrocarbon alkenyl group is not particularly limited, and examples thereof include a butadienyl group and an isoprene group. The content ratio of the other monomers in the above-mentioned resin A is from 1 to 40 mass. /〇 is better, 2~30 quality. /. For better. Specific examples of the resin A include, for example, compounds represented by the following structures (exemplary compounds p-1 to P-56). Further, X, y, and z in the exemplified compounds indicate the composition of each repeating unit. The ratio (mass ratio) is preferably in the form of a preferred range to be described later. Further, the weight average molecular weight of each of the exemplified compounds is also preferably in the form of a preferred range described later. -42 - 200949445

y COOH

P-1 x:y:2=41:24:35 〇 coo, ^ person COOH COO eight gamma octopus &lt; x:y:z=48:22:30 P-2 φ

Fy COOH P~3 OH I X:y:2=45:20:35 〇

〇 P-4 x:y:z=40:25:35

-43- 200949445

〇 coo

COOH ch2ch2-o P-8 OH 1 x:y:z=42:23:35

O

P-10 x:y:z=50:24:26

x:y:z=40:25:35

COO

COOH

x:y:z=30:30:40 -44- 200949445

HOco〇

x:y:z=45:15:40

COO,

COOH

P-17 x:y:z=45:25:30 -45 200949445

^ 人 coo gossip, 〇人丫^ M8 OH ' x:y:z=40:25:35 o

❿

x COO

cooyN 〇 P-20 x:y:z=40:30:30 〇

/y COOH

COO^Y^O^f^ p_2i OH I x:y:z=45:20:35

X coo

y COOH

X coo

COOH co〇y^\ 〇 P-23 HO Everyone x:y:z=40:20:40 -46 - 200949445

y C〇〇H

COO

P-25 x:l:y:z=46:2:20:32

O

COO^^^COOMe COOH

z COO 〇

P-26 OH ' x:I:y:z=45· 5:2:19:33.5 coo

❹ Ό

Fy C〇〇H

P-27 x:y:z=48:22:30

七^七 JL COOH 〇 P-28 OH · x:y:z=51.5:18.5:30 -47- 200949445

Coo^Y^o^y^ OH I P-29

COOijo

COOH

x:y:z=40:25:35 O People OH丨 P-30 Ο x:y:z=41:24:35 coo CH2CH2~〇

^ II COO^^Y^O^S^ OH 丨

O P-31

'y COOH

x:y:z=39:26:35

七七, coo COOH C p-32 ❹

OH x:y:z=35:30:35

x P-33

OH x:y:z=42:28:30 -48- 200949445

COOH

ο OH 丨 P-35 x:y:z=39:26:35 o -49- 200949445

Coo.

v COOH

Coo, ❹

y COOH

COO.

y COOH

G P-36 x:y:z=45:20:35 P-37 x:y:z=40:25:35 〇

y COOH

\ / 卜 too, 〆 COOH (

/y P-38 x:y:z=40:20:40 COO 丫,^ 〇 P-39 x:y:z=40:30:30 P-40

COO HO

x:y:z=45:20:35 P-41 COOH 〇 x:y:z=40:20:40 -50 200949445

y COOH

'X

Rz coa COOH 〇 P-43

H〇人乂〇人〆 x:y:z=35:30:35

COOH

Fz 〇 P—44 x:y:z=30:25:45 hct

Coo

COOH

-51 - 200949445

rX COO

IQ

f/y ^ X COOH Au I

P-46 x:y:z:St=30:24:38:8

COO

y COOH

P-47 x:y:z:St=34:24:36:6

COO

y COOH

fZ

COO^^Y^X) OH 〇

P-48, VII s BU COCL A COOH c x:y:z:St=40:23:35:2 〇 P-49 OH 丨 x:y:z=32:25:43

Rx

COO COOH

〇 COO-^Y^O^1^ OH I

P-50 x:y:z:St=25:25:40:10 52 200949445

φ coo COOH COO^Y^O&quot;Y^ 0h2CH2-〇 ou 1Qr&gt; ο ( P-53 OH ' x:y:z=46. 2:24.3:29.5

P-54 x: y: z: St=25:25:40 ·· 10 ❿

(xHcoo “ °°〇1々 iH2CH2OCH2CH2-0-|^[3 O COO C〇〇H COO^oV· OH 1 CH2CH—〇-^Q>Ah3 P-55 x:y:z=46:24:30

P-56 x:y:z=46:24:30 -53 200949445 ~Synthesis method ~ Resin A can be a two-stage step of the (co)polymerization step of the monomer and the step of introducing the ethylenically unsaturated group. Perform the synthesis. First, the '{co)polymerization reaction can be produced by various monomer (co)polymerization reactions, and is not particularly limited, and can be appropriately selected from among those skilled in the art. For example, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization, and the like can be appropriately selected as the active species to be polymerized. Among these, radical polymerization is preferred from the point of synthesis being easy to low cost. Further, the method of the polymerization is not particularly limited, and can be appropriately selected from among those skilled in the art. For example, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, or the like can be appropriately selected. Among these, the solution polymerization method is particularly desirable. ~ Carbon number ~ The total carbon number of the main chain of the resin A is preferably from 10 or more from the point of elasticity coefficient (hardness). Among them, the total carbon number is preferably 10 to 30, and particularly preferably 1 to 15 . ® ~Molecular Weight ~ The molecular weight of Resin A is 1〇 by weight average molecular weight, 〇〇〇~ι〇 is better, 12,000~60,000 is better, and 15,000~45,000 is especially good. When the weight average molecular weight is within the above range, it is desirable from the viewpoint of the production suitability and developability of the resin (preferably a copolymer). Further, the shape formed by the decrease in the melt viscosity is preferably from the point where the collapse is not likely to occur, and the point where the residue is not easily broken, and the residue having no spacer shape in the development is preferable. The weight average molecular weight is determined by gel permeation chromatography (G PC) from -54 to 200949445. The GPC system is shown in detail in the item of the following example. ~ Glass transition temperature ~ The glass transition temperature (Tg) of Resin A is preferably 40 to 180 ° C, 45 to 140 ° C is preferred, and 50 to 130 ° C is particularly preferred. Glass transition temperature (Tg) Within the above preferred range, a spacer having good developability and mechanical strength can be obtained. ~ Acid value ~ The acid value of the resin A is preferably changed by the molecular structure obtained. However, it is preferably 20 mgKOH/g or more, 40 mgKOH/g or more, and 50-130 mgKOH/g. . When the acid value is within the above preferred range, a spacer having good developability and mechanical strength can be obtained. ~Tg~ The resin A is preferably a glass transition temperature (Tg) of 40 to 180 ° C and a weight average molecular weight of 10,000 to 100,000 from the viewpoint of obtaining a spacer having good developability and mechanical strength. The Tg is 45 to 14 CTC (more preferably 50 to 130 ° C), and the weight average molecular weight is preferably 12,000 to 60,000 (more preferably 15,000 to 45,000). Further, the preferred embodiment of the above resin A is more preferably a combination of the above-mentioned preferred molecular weight, glass transition temperature (Tg), and acid value. In the present invention, a preferred embodiment of the resin A has a branching and/or alicyclic structure, an acidic group, and an ethylenically unsaturated bond (preferably disposed between the main chain and the ester group). Copolymerization of the above copolymer in the other three repeating units (copolymerization units), deformation recovery rate, development residue, and network structure when forming a pattern structure (for example, a spacer for a color filter) It is better from a point of view. -55- 200949445 Specifically, the resin A contains at least: a repeating unit having a branching and/or alicyclic structure: X (x mole %), a repeating unit having an acidic group: Y (y mole %), It is preferred to copolymerize the above with a ternary unit having a repeating unit of an ethylenically unsaturated bond (preferably disposed between the main chain and having an ester group): Z (z mole). Furthermore, other repeating units may be included as needed: L (1 mol. / 〇). Such a copolymer is obtained, for example, by copolymerizing a monomer having a branched and/or alicyclic structure, a monomer having an acidic group, a monomer having an ethylenically unsaturated bond, and other monomers required as φ as needed. . In particular, the monomer represented by the above formula (4) is copolymerized to have at least the aforementioned branch and/or from the viewpoint that the compressive modulus and the recovery property of the functional group having a large volume can be improved. It is preferred that the monomer of the alicyclic structure is introduced into a copolymer having a branching and/or alicyclic structure. In this case, the resin A has a constituent unit derived from the monomer represented by the above formula (4) in the main chain. The copolymerization composition ratio in the case where the aforementioned resin A is a copolymer can be determined by considering the glass transition temperature and the acid value. Although it can't be seen at a glance, it can be found in the following range. The composition ratio (X) of the repeating unit having a branching and/or alicyclic structure in the resin A is preferably from 10 to 70 mol%, more preferably from 15 to 65 mol%, and most preferably from 20 to 60 mol%. good. When the composition ratio (x) is within the above range, good development performance can be obtained. At the same time, the image forming liquid resistance of the image portion is also good. The composition ratio of the repeating unit having an acidic group in the resin A is preferably from 5 to 70 mol%, and is preferably ’ 〇 6 〇 耳. It is better, 2〇~5〇莫耳. When the composition ratio (y) is within the above range, good hardenability and developability can be obtained. -56- 200949445 The composition ratio (z) of the repeating unit having an ethylenically unsaturated bond in the resin A is 10 to 70 m. /. For better, 20 to 70 m. /. For better, 3〇~7〇% is especially good. When the composition ratio (z) is in the above range, the pigment dispersibility is excellent, and the simultaneous sensitivity and the polymerization hardenability are good, and the liquid storage property after liquid adjustment and the dry film state after application are maintained for a long period of time. When the stability is good, the composition ratio (X) of the resin A is 10 to 70 mol% (more preferably 15 to 65 mol%, particularly preferably 20 to 50 mol%), and the composition ratio ( y) is 5~70 莫 Mo Er. /. (more preferably 10-60% by mole, especially preferably 30~70% by mole), and the composition ratio (z) is 10~70 moles. The case of /〇 (more preferably 20 to 70% by mole, and particularly preferably 30 to 70% by mole) is preferred. In the above, a preferred embodiment of the resin A is described. In a preferred embodiment of the photosensitive resin composition of the present invention, the resin is preferably a resin A, and the polymerizable compound is specific to the structural formula (I). Exemplary compounds (3), exemplified compounds (10), exemplified compounds (M-5), exemplified compounds (M-6), exemplified compounds (M-7), and exemplified compounds (M) of the specific compound in the polymerizable compound -8), an exemplary compound (M-14) or the like is preferably combined. When the photosensitive resin composition of the present invention is configured as described above, the effects of the present invention can be more effectively exhibited. In the case where the photosensitive resin composition of the present invention contains the resin A, the content ratio of the resin A in the photosensitive resin composition is preferably 5 to 50% by mass based on the total resin amount (mass) in the composition. 10-40% by mass is preferred. The resin A may be used in combination with other resins, and it is preferable to use the resin A alone. -57-200949445 &lt;Photopolymerization Initiator&gt; The photosensitive resin composition of the present invention contains one type of photopolymerization initiator. The photopolymerization initiator in the present invention is not particularly limited, and a well-known photopolymerization initiator can be used. A known photopolymerization initiator is, for example, the one described in paragraph number [0010] [0020] of JP-A-2006-23696, and paragraph number [0027] to [0053] of JP-A-2006-6492 Agent. In the case of the photopolymerization initiator, a known example is an aminoacetophenone-based compound, a mercaptophosphine oxide-based compound or an oxime ester-based compound other than the above. Specific examples of the aminoacetophenone-based compound include, for example, 11^8 01; 1^(11^)9〇7 (Ciba Specialty Chemicals Co., Ltd.), etc. Specific examples of the fluorenylphosphine oxide-based compound For example, DAROCUR TPO, Irgacurenrg MW (above, Ciba Specialty Chemicals Co., Ltd.), etc., and specific examples of the vinegar-based compound are exemplified by IRGACURE (Irg) 〇 XE 〇 1, (above, Ciba Special chemical (stock) system. The following shows the structure of these initiators. -58- 200949445 <Aminoacetophenone-based compounds>

Irg907

<醯-based phosphine oxide compound>

DAROCUR TPO

Irg 819

<肟 ester compound> IrgOXEOI

The total amount of the photopolymerization initiator in the photosensitive resin composition is preferably from 5% to 25% by mass based on the total solid content of the photosensitive resin composition, and is preferably 20% by mass. &lt;Particles&gt; The photosensitive resin composition of the present invention preferably contains at least one kind of fine particles of -59 to 200949445 from the viewpoints of a resin, a polymerizable compound, a photopolymerization initiator, and a mechanical strength. The fine particles are not particularly limited, and can be appropriately selected according to the purpose. For example, the extender pigments described in JP-A-2003-302639 [0035] to [0041] are preferred, and good development properties can be obtained. In terms of the optical spacer of the mechanical strength, colloidal vermiculite is preferred. The average particle diameter of the fine particles is a point at which a high mechanical strength can be obtained in a structure in which an external force which easily absorbs a photo spacer or the like is formed, preferably 5 to 50 nm, preferably 10 to 40 nm, and 15 to 30 nm. It is especially good.前述 The content of the fine particles in the photosensitive resin composition (the photo spacer (or the photosensitive resin layer constituting the photo spacer) is increased from the viewpoint of improving the mechanical strength (for example, high mechanical strength can be obtained). The total solid content (mass) in the photosensitive resin composition is preferably 5 to 50% by mass, preferably 10 to 40% by mass, and 15 to 30% by mass. Very good. &lt;Others&gt; The photosensitive resin composition of the present invention may contain a photopolymerization starter or the like as needed in addition to a resin, a specific polymerization compound, a photopolymerization initiator, and, if necessary, fine particles. Other ingredients. The photosensitive resin composition can be used as a further additive component by using a photopolymerization initiation aid. The photopolymerization initiation aid can be used in combination with a photopolymerization initiator because it promotes polymerization of a polymerizable compound which initiates polymerization by a photopolymerization initiator. The photopolymerization initiation aid is preferably at least one of an amine compound. Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, and 4-dimethyl-60-200949445 ethyl benzoic acid ethyl ester. , 4-dimethylamino benzoic acid isovalerone, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylhexyl benzoate N,N-dimethyl pair Toluidine, 4,4'-bis(dimethylamino)diphenyl ketone (commonly known as Michlerone), 4,4,-bis(diethylamino)diphenyl ketone, 4,4' - bis(ethylmethylamino)diphenyl ketone or the like, among which 4,4'-bis(diethylamino)diphenyl ketone is particularly preferred. Further, it may be used in combination with a plurality of amine-based or other photopolymerization initiators. Other photopolymerization initiation aids other than the above may, for example, be an alkoxy group, an anthraquinone compound, an oxonium compound, or a coumarin compound. The alkoxy ruthenium compound may, for example, be 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene or 2-B. Base - 9,10-diethoxyanthracene and the like. The oxysulfonium III phonic compound may, for example, be 2-isopropylthioguanidine, 4-isopropylthioguanidine, 2,4-diethylthioguanidine, 2,4-di Sodium oxychloride sulphate, 1-chloro-4-propoxy sulphide, and so on. Further, a commercially available person can also be used as a photopolymerization starting aid. The commercially available photopolymerization starter is, for example, a trade name "EAB-F" (manufactured by Hodogaya Chemical ® X Co., Ltd.). The content of the photopolymerization initiator in the photosensitive resin composition is preferably 0.6 parts by mass or more and 20 parts by mass or less, and 1 part by mass or more and 15 parts by mass or less based on 1 part by mass of the photopolymerization initiator. More preferably, it is preferably 1.5 parts by mass or more and 15 parts by mass or less. Further, the other components may be selected and used as a component constituting a well-known composition, and may be, for example, the paragraph number of [0010] [0020] and JP-A-2006-64921. The component described in 0027 [0053]. -61- 200949445 The photosensitive resin composition of the present invention can be suitably used for pattern partition walls (for example, black matrix, etc.) and alignment, in addition to being suitable for use in forming a photo spacer, a colored pattern, and a protective film to be described later. Formation of other pattern structures and films such as protrusions for control. <<Photo spacer and method for forming the same>> The photo spacer of the present invention is formed by using the photosensitive resin composition of the present invention described above. The details and preferred aspects of the photosensitive resin composition are as described above.光 Since the photo-spacer of the present invention is formed by using the photosensitive resin composition of the present invention, it has a cross-sectional shape with high uniformity and can suppress a height shift. Further, in the case where the photosensitive resin composition of the present invention contains the resin A, a photo spacer having a high compression modulus and deformation recovery property which is necessary as a photo spacer can be obtained. Here, in the present invention, the pattern structure such as the photo spacer is described as having a "uniform cross-sectional shape". In the state in which the pattern structure has a "uniform cross-sectional shape", it is preferable that the cross-sectional shape of the pattern structure is close to the shape of the rectangle in a plurality of places (preferably three or more) in the substrate. The above-mentioned "a shape close to a rectangle" is parallel to the normal direction of the substrate, and is cut in a plane perpendicular to the normal direction of the substrate of the pattern structure and the tight edge (the wiring of the edge of the cylindrical structure). In the cross section when the pattern structure is broken, the angle formed by the line corresponding to the side surface of the pattern structure and the line corresponding to the lower surface of the pattern structure (hereinafter also referred to as "taper angle") is 80. Above, 100. The following shapes are preferred. Here, the pattern structure is hereinafter referred to as the contact surface of the substrate on which the pattern structure is formed, in the surface of the pattern structure -62-200949445. Further, the side surface of the pattern structure is formed on the surface of the pattern structure, and is not the lower surface of the pattern structure, and is not the upper surface of the pattern structure (the (for example, parallel) surface facing the lower surface of the pattern structure, and The face that is not in contact with the aforementioned lower ground). The photo spacer of the present invention can be formed by any method by using the photosensitive resin composition of the present invention by using a method comprising the steps (A) to (c) shown below (the photointerval of the present invention). The method of preparation can be optimally formed. The method for producing a photo spacer of the present invention comprises the steps of: (a) forming a film of the photosensitive resin composition of the present invention described above on a substrate (hereinafter, also referred to as "film formation step" And (b) an exposure step (hereinafter also referred to as "exposure step") of exposing at least a portion of the film, and a development step of the film after exposure to (c) exposure (hereinafter also referred to as In the "development step", a heating step (hereinafter also referred to as "film heating step") of the film after heating and development, and other steps may be provided as needed. (A) Film formation step The film formation step is a film on which a photosensitive resin composition of the present invention described above is formed on a substrate. The photosensitive resin layer in which the photosensitive resin layer is formed as a film can be formed into a photo-spacer capable of uniformly maintaining a cell thickness by a further step such as an exposure step or a developing step to be described later. By using the photo spacer of the present invention, particularly in an image of a display device (particularly a liquid crystal display device) which is liable to cause display unevenness due to variations in cell thickness, display unevenness can be effectively eliminated. -63-200949445 A method of forming a photosensitive resin layer on a substrate, for example, (a) coating method of applying a photosensitive resin composition containing at least a resin, a polymerizable compound, and a photopolymerization initiator described above And (b) a transfer method in which a photosensitive transfer material having the photosensitive resin layer is used, and a photosensitive resin layer is laminated and transferred by heating and/or pressurization. (a) Coating method The coating method of the photosensitive resin composition can be applied by a well-known coating method, for example, spin coating method, curtain coating method, slit coating method, dip coating method, squeegee coating method, roll coating method, metal The bar coating method, the gravure coating method, or the extrusion molding method using a popper described in the specification of U.S. Patent No. 2,681,294. In particular, JP-A-2004-89851, JP-A-2004-17043, JP-A-2003-170098, JP-A-2003-164787, JP-A-2003-10767, JP-A-2002- A method of a slit nozzle or a slit coater described in JP-A-2001-310147, etc. is a suitable "®" (b) transfer method using a photosensitive transfer material, for example, heating and/or Or a pressure roller or a flat plate, after the photosensitive resin layer formed on the temporary support is bonded to the desired substrate surface by calendering or heat rolling, the temporary support is peeled off to transfer the photosensitive resin layer. Printed onto the substrate. Specifically, a laminator and a lamination method described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In view of the above, it is preferable to use the method described in Japanese Laid-Open Patent Publication No. H7-110575. -64-200949445 In the case of forming a photosensitive resin layer, an oxygen blocking layer (hereinafter also referred to as "oxygen interrupting film" or "intermediate layer") may be further provided between the photosensitive resin layer and the temporary support. Thereby, the exposure sensitivity can be improved. Further, in order to improve the transfer property, a cushioning thermoplastic resin layer may be provided. A temporary support constituting a photosensitive transfer material, an oxygen barrier layer, a thermoplastic resin layer, another layer, and a method for producing the photosensitive transfer material are disclosed in JP-A No. 2 006-2 3 696 The composition and production method described in paragraph number [0024] [0030].情 In the case where the photosensitive resin layer is formed together by the (a) coating method and the (b) transfer method, the layer thickness is preferably 〇.5~10.0#111, and 1~6#111 is preferable. When the layer thickness is in the above range, the occurrence of pinholes can be prevented at the time of coating formation at the time of production, and the development of the unexposed portion without development does not require a long time. Examples of the substrate on which the photosensitive resin layer is formed include a transparent substrate (for example, a glass substrate or a plastic substrate), a substrate with a transparent conductive film (for example, an ITO film), and a substrate with a color filter (also referred to as a color filter). A light sheet substrate), a drive substrate to which a driving element (for example, a thin film transistor [TFT]) is attached, or the like. The thickness of the substrate © is generally preferably 700 to 1200 μm. (B) Exposure step, (c) development step In the exposure step, at least a portion of the film formed in the film formation step is exposed to form a latent image. In the subsequent development step, the film exposed in the above-described exposure step is developed to form a spacer pattern of a desired shape. Specific examples of such steps include a formation example described in paragraph numbers [〇〇71] to [〇077] of JP-A-2006-6492, and a paragraph number [0040] of JP-A-2006-23696. The procedure of -65-200949445 described in [0051] is taken as a suitable example in the present invention. The photo spacer of the present invention may be provided with a (but) film heating step as described below, and the film heating step may not be provided by increasing the exposure amount during the exposure (hereinafter, also referred to as "no heating step"). It is also possible to form a photo spacer having a uniform cross-sectional shape and excellent height uniformity. By the "no heating step", it is possible to more effectively suppress deterioration of the formed photo spacer, deterioration of the already formed pattern structure (coloring pattern, etc.), and protective film 〇. The exposure amount for the "no heating step" is preferably from 1 to 500 mJ/cm2, preferably from 10 to 300 mJ/cm2. (D) Film Heating Step The photo spacer of the present invention can also be provided with a film heating step of heating the film after the development of the developing step. By heating, the hardening of the film can be further promoted, and a photo spacer having high strength can be obtained. Further, in the case where the photosensitive resin composition contains the resin A, a photo spacer having a higher compression elastic ratio and deformation recovery property can be obtained. Here, the maximum temperature at the heating varies depending on the heating time, preferably 40 ° C to 145 ° C, and more preferably 40 ° C to 140 ° C. When the maximum temperature is in the range of 40 ° C to 1 4 5 t, the deterioration of the formed photo spacer, the formation of the patterned structure (coloring pattern, etc.), and the deterioration of the protective film can be more effectively suppressed. Among them, the maximum temperature during heating is from 80 ° C to 140 ° C, and the heating time is preferably from 1 hour to 3 hours (more preferably from 0 to 2 hours to 1 hour). -66- 200949445 As described above, a substrate for a display device including a photo spacer can be fabricated on a substrate. The photo spacer is preferably formed on a black light-shielding portion such as a black matrix formed on a substrate, or a driving element such as a TFT. In addition, a transparent conductive layer (transparent electrode) such as ITO or an alignment film such as polyimide may be present between a black light-shielding portion such as a black matrix or a driving element such as a TFT and a photo spacer. For example, in the case where the photo spacer is provided on the black light-shielding portion or the driving element, a black light-shielding portion (black matrix or the like) of the substrate and a driving element may be coated in advance, for example, a photosensitive transfer material may be used. The photosensitive resin layer is laminated on the support surface, and after being subjected to release transfer to form a photosensitive resin layer, exposure, development, heat treatment, or the like is applied thereto to form a photo spacer, whereby a substrate for a display device can be produced. In the substrate for a display device of the present invention, colored pixels of three colors of red (R), blue (B), and green (G) can be provided as needed. The photo spacer of the present invention can be formed after forming a color filter including a black mask portion such as a black matrix or a colored portion such as a color pixel. The black shielding portion, the coloring portion, and the photo spacer can be arbitrarily combined: a coating method of applying a photosensitive resin composition, and a transfer of a transfer material using a photosensitive resin layer composed of a photosensitive resin composition. Formed by law. The black shielding portion, the colored portion, and the photo spacer may be formed of a photosensitive resin composition, and specifically, the photosensitive resin composition of the liquid is directly applied onto the substrate to form a photosensitive resin. After the layer, exposure and development are performed, and the black shielding portion and the colored portion are formed into a pattern, and then the photosensitive resin composition provided with another liquid is used on another substrate different from the substrate (temporary - 67-200949445 support material) is formed by forming a transfer material made of a photosensitive resin layer and after transferring the transfer material to the front side of the black masking portion and the coloring portion 2 to transfer the photosensitive resin layer The photo spacer can be formed into a pattern by performing exposure and development. Thus, a color filter in which a photo spacer is provided can be produced. "Protective film" The protective film of the present invention is formed by using the photosensitive resin composition of the present invention described above.保护 Since the protective film of the present invention is formed by using the photosensitive resin composition of the present invention, even when it is formed at a low heating temperature or without heat treatment, the film thickness uniformity is excellent. The protective film of the present invention can be formed by any method using the method of the photosensitive resin composition of the present invention, and can be formed by the same method as the above-described method of producing the optical spacer of the present invention. Here, in the case where the protective film is not patterned, that is, in the case where the protective film is formed into a so-called beta film, the above-mentioned (b) exposure step is performed by the method of fully exposing the film. suitable. <<Coloring Pattern>> The coloring pattern of the present invention is formed by using the photosensitive resin composition of the present invention described above. Here, the photosensitive resin composition is preferably in a form containing at least one of a coloring agent in addition to the components described above. The coloring agent is not particularly limited and may be appropriately selected from among known coloring agents. Specific examples of the known coloring agent include, for example, JP-A-2005-17716 [0038] [0054], which is described in JP-68-200949445, and dyes, and JP-A-2004-361447 [0 0 6 8 The pigment described in [0 0 7 2 ], and the coloring agent described in JP-A-2005-17521 [0080] [0088]. Since the colored pattern of the present invention is formed by using the photosensitive resin composition of the present invention, even in the case of forming at a low heating temperature or without heat treatment, a cross-sectional shape having high uniformity and a film thickness are obtained. Uniformity is also excellent. Further, the coloring pattern of the present invention is a case where a color filter having a plurality of colors is used as a single element, and at least one coloring pattern can be formed using the photosensitive resin composition of the present invention. The colored pattern of the present invention can be formed by any method using the photosensitive resin composition of the present invention, and can be formed, for example, by the same method as the above-described method for producing a photo spacer of the present invention. <<Substrate for Display Device>> The substrate for a display device of the present invention comprises the above-described photo spacer of the present invention, the protective film of the present invention, and one or more selected from the colored pattern of the present invention. of. The substrate for a display device of the present invention has a cross-sectional shape and uniformity of film thickness (height) formed by using the photosensitive resin composition of the present invention (the photo spacer of the present invention, the protective film of the present invention) Further, at least one of the color patterns of the present invention is used in the display device to suppress display unevenness when the image is displayed. Here, the substrate for a display device refers to at least one of the pair of support members constituting the display device. The specific example of the display device substrate differs depending on the configuration of the display device and the display device, and may be, for example, a color filter substrate having a coloring pattern of -69 to 200949445 (hereinafter also referred to as "colored pixel"). a substrate having a driving means (for example, a passive matrix substrate or an active matrix substrate), and a substrate having a partition wall attached to the partition wall (for example, a substrate having a black matrix and a black matrix) A color filter array (on array) substrate having both a colored pattern and a driving means, a glass substrate having no pattern structure or a film, and the like. The coloring pattern group (colored pixel group) of the color filter substrate may be composed of pixels of two colors that do not appear to be different colors, or may be composed of pixels of Φ three colors or pixels of four or more colors. For example, in the case of three colors, the three colors of red (R), green (G), and cyan (B) are formed. In the case of arranging pixel groups of three colors of RGB, it is preferable to arrange them in a mosaic type or a triangular type, and it is possible to arrange any of the four or more pixel groups. The color filter substrate can be formed, for example, by forming a pixel group of two or more colors in a manner as described above, or conversely, forming a pixel group after forming a black matrix. For the formation of RGB pixels, JP-A-2004-347831 and the like can be referred to. ❹ <<Display Element>> The display element can be formed using the substrate for a display device of the present invention described above. In one of the display elements, for example, at least one of the light-transmitting pair of supports (including a substrate for a display device) includes at least a liquid crystal layer and a liquid crystal driving means (including a passive matrix driving method and The liquid crystal display element of the source matrix driving method). In the case of the liquid crystal display device, the substrate for the display device can be used as a color filter substrate having a plurality of RGB pixel groups, and each pixel system constituting the pixel group is 70-200949445, which is separated from each other by a black matrix. To use. Since the color filter substrate is provided with a pattern structure having a uniform cross-sectional shape and uniformity of film thickness (height), the liquid crystal display element including the color filter substrate can be effectively suppressed: resulting from a color filter The variation in the cell pitch (cell thickness) between the substrate and the counter substrate occurs due to unevenness in color unevenness due to partial deviation of the liquid crystal material or low-temperature foaming. Thereby, the liquid crystal display element produced can display a clear image. Further, in a more detailed aspect of the liquid crystal display device, for example, at least one of the light transmissive pair of supports (including a substrate for a liquid crystal display device) includes at least a liquid crystal layer and a liquid crystal driving means. The liquid crystal driving means has an active element (for example, a TFT), and a pair of substrates is formed by defining a predetermined width of the photo spacer. In the display device of the present invention, the display device of the present invention includes a display device of the present invention having a cross-sectional shape and a uniform film thickness (height) uniformity. With the ® substrate, $ can suppress uneven display. The display device may be, for example, a display device such as a liquid crystal display device, a plasma display display device, an EL display device, or a CRT display device. The definition of the display device and the description of each display device are described in, for example, "Electronic display device (sasaki Sasaki, Industrial (stock) survey society issued in 1990)", "display device (Ibuki Shunzhang, industrial book (share) ) issued in the first year of Heisei). Among the display devices, a liquid crystal display device is preferred. For example, the liquid crystal display device defines a predetermined width between a pair of substrates facing each other with a photo spacer, and is sealed in a predetermined gap (the sealed portion is referred to as a liquid crystal layer) liquid crystal material. Further, the thickness (cell thickness) of the liquid crystal layer is maintained to a desired uniform thickness. The liquid crystal display mode in the liquid crystal display device may be, for example, STN type, TN type, GH type, ECB type, ferroelectric liquid crystal, antiferroelectric liquid crystal, VA type, IPS type, OCB type, ASM type, or the like. It is suitable. In the liquid crystal display device of the present invention, from the viewpoint of the most effective effect of the present invention, the display mode in which display unevenness is unlikely to occur due to the Φ variation of the cell thickness of the liquid crystal cell is It is desirable that the VA type display mode, the IPS type display mode, and the OCB type display mode in which the cell thickness is 2 to 4/zm is preferable. Further, the liquid crystal used in the present invention may, for example, be a nematic liquid crystal, a cholesteric liquid crystal, a smectic liquid crystal or a ferroelectric liquid crystal. In the basic configuration of the liquid crystal display device, for example, (a) a light-transmitting spacer is used, and a driving side substrate including a driving element such as a thin film transistor (TFT) and a pixel electrode (conductive layer) is arranged and aligned. The electrode (conductive layer) is disposed opposite to the substrate, and is formed by sealing a liquid crystal material in a gap portion thereof; (b) transmitting the light spacer to provide a pair of the driving substrate and the counter electrode (conductive layer) The liquid crystal display device of the present invention can be suitably used for various liquid crystal display devices, in which the substrate is disposed to face each other and a liquid crystal material is sealed in the gap portion. The liquid crystal display device is described in, for example, "Second Generation Liquid Crystal Display Technology (Edited by Uchida Natsuo, Side Industry Survey, issued in 1994)". The liquid crystal display device of the present invention is not particularly limited, except for the liquid crystal display device of the present invention. For example, the liquid crystal display device can be configured in various manners as described in the "Second Generation Liquid Crystal-72-200949445 Display Technology". Among them, it is effective particularly in a liquid crystal display device constituting a color TFT system. The liquid crystal display device of the color TFT system is described, for example, in "Color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., issued in 1996)". In addition to the above-described photo spacer, colored pattern, protective film, substrate for liquid crystal display device, and liquid crystal display device, an electrode substrate, a polarizing film, a retardation film, a backlight, a photo spacer, and the like can be generally used. A wide variety of members such as a viewing angle compensation film, an antireflection film, a light diffusion film, and an antiglare film are used. These components are, for example, "'94 Liquid Crystal Display Peripherals, Chemicals Markets (Island Kentaro, CMC (shares), issued in 1994), "2003 Liquid Crystal Related Market Status and Future Outlook (Volume 2)" There are records in Table Liangji, Fuji Chimera (shares), 2003, etc.). The present patent application claims the benefit of priority to the patent application No. 2 0 08-09 2583, filed on March 31, 2008, and the Japanese Patent Application No. 2008-092584, the entire disclosure of which is incorporated herein by reference. This article is cited in this article. ® EXAMPLES Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to the following examples as long as it does not exceed the gist thereof. In addition, "parts" are quality standards unless otherwise specified. Further, the weight average molecular weight was measured by gel permeation chromatography (G PC). For the GPC system, HLC-8020GPC (manufactured by Tosoh Corporation) was used, and three TSKgels, Supermultipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID x 15 cm) were used for the column, and THF (tetrahydrofuran) was used as the eluent. Further, the conditions were such that the sample concentration was 〇.〇45 mg/mL, the flow rate was 0.35 mL/min, and -73-200949445, the sample injection amount was l〇#L, and the measurement temperature was 40 ° C, and the IR detector was used. In addition, the calibration line is made by Tosoh (standard) TSK standard, polystyrene; "F-40", "F-20", "F-4", "Fl", "A-5000" Eight kinds of samples of "A-2500", "A-1000", and "n-propylbenzene" were produced. &lt;Synthesis of Resin A&gt; First, the synthesis of the exemplified compounds P-52, P-5 1 'P-53, P-46, and P-47 exemplified as the specific examples of the resin A described above was carried out. It is used as a resin used in a photosensitive resin composition. Further, the other resin A used in the present embodiment can also be synthesized by a similar method of changing the corresponding monomer. (Synthesis of exemplified compound P-52) In a reaction vessel, 7.48 parts of 1-methoxy-2-propanol (MFG, manufactured by EMULSION, Japan) was added in advance, and the temperature was raised to 90 ° C, which was obtained from styrene ( St) 3_1 parts, tricyclopentenyl methacrylate (TCPD-M manufactured by Hitachi Chemical Co., Ltd.; x} 4.28 parts, methyl acrylate (MAA; y) 11.7 parts, azo® polymerization a mixed solution of 2.08 parts of a reagent (manufactured by Wako Pure Chemical Industries Co., Ltd., V-60 1) and 55.2 parts of 1-methoxy-2-propanol, and dropped to 90 ° for 2 hours under a nitrogen atmosphere. In the reaction vessel of C. After the dropwise addition, the mixture was reacted for 4 hours to obtain an acrylic resin solution. Next, 0.15 parts of hydroquinone monomethyl ether and 0.34 parts of tetraethylammonium bromide were added to the acrylic resin solution. 26.4 parts (GLM-MAA; z) of glycidyl methacrylate (GLM, manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped for 2 hours. After dropping, the reaction was carried out at 90 ° C for 4 hours while blowing air. Thereafter, a solvent of 1-methoxy-2-propyl acetate (MMPGAc) was added in the form of a formula of -74-200949445 having a solid concentration of 45%. Modification by Daisy Chemical Industry Co., Ltd. to obtain an exemplary compound P-52 (Resin A) in which a structural unit derived from styrene was added to the previously described exemplified compound P-51 having an unsaturated group. Resin solution (solid content acid value; 76.0 mg KOH / g, Mw; 25,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution) (x; y; z; St = 30 mol%; 2 7 m ο 1 % ; 3 7 m ο 1 % ; 6 m ο 1 %). Here ' GLM-MAA shows glycidyl methacrylate and methacrylic acid bonded Further, the molecular weight Mw of the exemplified compound P-5 2 represents a weight average molecular weight, and the measurement of the weight average molecular weight is carried out by gel permeation chromatography (GPC method) (the same applies hereinafter). (Example compound P Synthesis of -51) In the synthesis of the above-exemplified compound P-5 2, except that styrene was not used, x; y; z in the exemplified compound P-51 was 34 mol%; 27 mol%; 39 mol%, and TCPD-M was changed. The addition of (x), methacrylic acid (y), and GLM-MAA(z) ® is the same as the synthesis of the above-exemplified compound P-52. The synthesis was carried out to obtain a resin solution of the exemplified compound P-51 (resin A) having an unsaturated group (solid content acid value; 72.5 mgKOH/g, Mw; 22,000, 1-methoxy-2-propanol/1- Methoxy-2-propyl acetate 45% solution}. (Synthesis of the exemplified compound P-53) In the synthesis of the above-exemplified compound P-5 2, except that styrene and dicyclopentenyloxyethyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.) were not used. FANCRYL FA-512M) Substituting tricyclopentene methacrylate-75-200949445 ester, making x in the exemplified compound P-53; y; z is 46.2 mol%; 24.3 mol%; 29.5 mol%, and changing FA-512M In addition to the addition amount of (x), methacrylic acid (y), and GLM-MAA (z), the synthesis is carried out by the same method as the above-exemplified compound P-52 to obtain an exemplified compound having an unsaturated group. Resin solution of P-53 (Resin A) (solid content acid value; 71.2 mg KOH/g, Mw; 25,500, 1-methoxy-2-propanol/1-methoxy-2-propyl acetate 45 % solution). (Synthesis of the exemplified compound P-46) Ο In the synthesis of the above-exemplified compound P-52, in place of the triphenylpentenyl methacrylate substituted by ADMA (manufactured by Idemitsu Kosan Co., Ltd.), the compound P-1 is exemplified. Adding the composition X from the structural unit of styrene; y; z; st is 30 mol%; 24 mol%; 38 mol%; 8 mol%, changing ADMA (x}, methacrylic acid (y), GLM-MAA (z), In addition to the addition amount of styrene, the synthesis was carried out in the same manner as in the synthesis of the above-exemplified compound P-52 to obtain an example in which a structural unit derived from styrene was added to the exemplified compound P-1 having an unsaturated group. Resin solution of Compound P-46 (Resin A) (solid content acid value; 74·1 mgKOH/g, Mw; 29,000, 1-methoxy-2-propanol/1-methoxy-2-propyl Acetate 45% solution) (Synthesis of exemplified compound P-47) In the synthesis of the above-exemplified compound P-52, in place of isopropyl methacrylate (IBXMA, manufactured by Wako Pure Chemical Industries, Ltd.) Tricyclopentenyl acrylate, the composition X of the structural unit derived from styrene is added to the exemplified compound P-2; y; z; St is 34 mol% 24 mol%; 36 mol%; 6 mol%, modified IBXMA (x), methacrylic acid (y), GLM-MAA (z), and styrene added, by synthesis with the exemplified compound P-52 - 76- 200949445 The same method was used for the synthesis to obtain a resin solution (solid component acid value) of the exemplified compound P-4 7 (resin A) from the structural unit of styrene added to the exemplified compound P-2 having an unsaturated group. 72.9 mg K〇H/g, Mw; 29,000, 1-methoxy-2-propanol/1-methoxy-2-propyl acetate 45% solution) [Example 1]: Coating method &lt;Production of Color Filter Substrate&gt; A black matrix, an R (red) pixel, and a G (green) pixel are produced according to the method described in paragraph number [0084] [0095] of JP-A-2005-3861. A color filter of B (blue) pixels (hereinafter, referred to as a color filter substrate). Here, the substrate size of the color filter substrate is 550 mm x 650 mm, and then, on the R pixel, the G pixel, and the B pixel and the black matrix of the obtained color filter substrate, ITO (Indium Tin Oxide) is further sputtered. , formed by a transparent electrode of indium tin oxide. &lt;Formation of Photo Spacer&gt; ® On the ITO transparent electrode of the color filter substrate formed by the above-described ITO transparent electrode sputtering, the formulation shown in Table 1 below was applied by a rotator and a slit ( In the first embodiment, the coating liquid for a photosensitive resin layer composed of the formulation 1) was used. Then, using a vacuum dryer VCD (manufactured by Tokyo Ohka Co., Ltd.), a part of the solvent was dried for 30 seconds until the coating film had no fluidity, and then prebaked on a hot plate at 90 ° C for 3 minutes to form a film. A photosensitive resin layer having a thickness of 5.2/m (film formation step). Continue, using a proximity type exposure machine with ultra-high pressure mercury lamp (Hitachi Hi-Tech Electronic Engineering Co., Ltd.)' in the mask (circular figure with diameter 15#111 -77-200949445 square to vertical to vertical phase The straight layer of the fat-lined tree is slightly flat and the mask is used as the shutter. The base and the piece are covered by the mask. The mask is opaque and the glare is exposed. The distance between the surfaces of the resin layer was set to 100 #m, and the ultraviolet ray filter (UV-35, Toshiba Glass Co., Ltd.) was irradiated with ultraviolet light at a strength of 365 nm of 250 W/m2 through the mask. (Exposure amount 200 mJ/cm2; exposure step). Next, a Na carbonate-based developing solution (containing 0.38 mol/liter sodium hydrogencarbonate, 0.47 mol/liter sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, an anionic surfactant, and an antifoaming agent) was used. And stabilizers; trade name: T-CD 1 (made by Fujifilm (manufactured by Fujifilm)) diluted with pure water to a 10-fold dilution), at 30 ° C for 30 seconds, with a cone nozzle pressure of 0.15 M Pa Shower the image to form a pattern image (development step). Then, using a detergent (containing phosphate, citrate, nonionic surfactant, antifoaming agent, stabilizer; trade name: T-SD3 (made by Fujifilm)), diluted 10 times with pure water. The diluted solution was showered at 33 ° C for 20 seconds at a conical nozzle pressure of 0.02 M Pa, and the residue around the formed pattern image was removed to form a circle® columnar spacer pattern at 300/. The zmx300/zm is separated by one spacer. Next, the color filter substrate provided with the spacer pattern was subjected to heat treatment (heating step) at 140 ° C for 60 minutes to form a photo spacer on the color filter substrate. Here, one of the obtained photo spacers was measured using a three-dimensional surface structure analysis microscope (manufacturer; ZYGO Corporation, type: New View 5022), and the upper surface of the ITO transparent electrode (two faces parallel to the substrate) was measured. Among them, the distance from the side of the substrate to the highest position of the photo spacer (hereinafter, the distance is also referred to as -78-200949445 "the height of the photo spacer"), and the average 値 is used as the photo spacer. average height. Further, the measurement of the bottom area of the obtained photo spacer was carried out using SEM photographing. The result was a cylindrical shape having a diameter of 15.1/zm and an average height of 4.7 ym. Table 1 Coating liquid formulation 1 for photosensitive resin layer (Examples 17, Comparative Example 1) Formulation 2 (Example 18 &gt; Formulation 3 (Example 20) Formulation 4 (Example 19 &gt; Formulation 5 (Comparative Example 2) 1 -Methoxy-2-propyl acetate 26 26 26 26 35 Methyl ethyl ketone 28 28 28 28 30 Colloidal vermiculite dispersion (knee vermiculite: 30 parts, methyl isobutyl ketone: 70 parts) , Nissan Chemical Industry Co., Ltd.: MIBKst&gt; 0 0 14.1 0 0 Solospose 20000 0.42 0.42 0.42 0.42 0.42 The polymerizable compound described in Table 2 13.8 13.8 13.8 6.9 0 DPHA liquid (dipentaerythritol hexaacrylate vinegar: 76 parts, 1- Methoxy-2-propyl acetate: 24 parts} 0 0 0 9.08 18.2 A solution of Resin A (however, the resin is as described in Table 2 below) 20.5 0 20.5 20.5 20.5 Methyl propylene acid/methyl Acrylic acid propylene vinegar copolymer (Morby &gt; = 20/80 (reset average molecular weight = 36,000) 0 9.17 0 0 0 CGI242 (Ciba specialty chemicals (stock), photopolymerization initiator} 0.227 0.227 0.227 0.227 0.23 Hydroquinone monomethyl ether 0.0036 0.0036 0.0036 0.0036 0.0036 Interface Remuneration 1 (MEGAFAC F780-F, Dainippon Ink Chemical Industry Co., Ltd. &Gt; 0.032 0.032 0.032 0.032 0.032 Victoria Pure Blue -NAPS (Hodogaya Chemical Industry Co., Ltd.) was 5% methanol solution of 2.05 0 0 0 0

Unit: -79-200949445 &lt;Production of Liquid Crystal Display Device&gt; In addition, a glass substrate is prepared as a counter substrate, and a PVA mode is applied to each of the transparent electrode and the counter substrate of the color filter substrate obtained above. The patterning is further provided with an alignment film formed of polyimine. Then, the sealing agent for the ultraviolet curable resin is applied by a dispenser method so as to surround the pixel group surrounding the color filter, and the liquid crystal for PVA mode is dropped and the counter substrate After the bonding, the UV-irradiated substrate is subjected to heat treatment to harden the sealing teeth. On both sides of the thus obtained liquid crystal cell, a polarizing plate HLC2-2518 made of SANRITZ (share) was attached. Next, FR1112H (a substrate type LED made by STONELEY Electric Co., Ltd.) was used as a red (R) LED, and DG 1 1 1 2 H (substrate type LED made by STO NE LEY Electric Co., Ltd.) was used as green (G). LED, DB 1 1 1 2H (base-type LED made by STONELEY Electric Co., Ltd.) is a blue (B) LED to form a backlight of the sidelight type, and the polarizing plate is disposed in the liquid crystal cell set in the ® The back side is formed to form a liquid crystal display device. &lt;Evaluation&gt; The following evaluation was performed on the obtained photo spacer and liquid crystal display device. The results of the measurement evaluation are shown in Table 2 below. (The cross-sectional shape of the photo-spacer) The heat-treated photo spacer obtained in the above-mentioned <Formation of photo spacer> is cut by a plane parallel to the normal direction of the substrate, and observed by a scanning electron microscope. Cut the shape of the section. The observation system was performed on a total of five locations on the peripheral portion of the substrate and the central portion of the substrate, and the cross-sectional shape of the spacer between -80 and 200949445 was evaluated in accordance with the following criteria. ~ Evaluation criteria ~ A; In all five places, a photo spacer having a cross-sectional shape having a taper angle of 45 or more and 90 or less is formed. B; in all of the five places, although a light spacer having a cross-sectional shape having a taper angle of 45° or more and 95° or less is formed, the angle from the taper angle is slightly larger than the above A. It is getting worse. C; a photo spacer having a cross-sectional shape having a taper angle of 40° or more and 100° ❹ or less is formed in all five places, but the point from the taper angle is larger than the above A and B. It is getting worse. D; at 1 to 4 places of 5, a photo spacer having a taper angle not in the range of 40° or more and 100° or less is formed. E; a photo spacer having a taper angle not in the range of 40° or more and 100° or less is formed in all five places. (the height uniformity of the photo spacer) The difference between the maximum 値 and the minimum 算出 is calculated from the result of the height of the photo spacer 1000 Å measured by the formation of the above-mentioned &lt;photo spacers&gt; To evaluate. The high uniformity indicates that the smaller the difference in enthalpy, the more excellent the uniformity. ~ Evaluation Criteria ~ A: The difference between the maximum 値 and the minimum 高度 of the height of the photo spacer is less than 0.2 // m. B: The difference between the maximum 値 and the minimum 高度 of the height of the photo spacer is 0.2#m or more and less than 0.3/zm. C: The difference between the maximum 値 and the minimum 高度 of the height of the photo spacer is -81 - 200949445 〇.3&quot;m or more, lower than 〇.4/zm. D: The difference between the maximum 値 and the minimum 高度 of the height of the photo spacer is 〇.4//m or more and less than 〇.5/zm. E: The difference between the maximum 値 and the minimum 高度 of the height of the photo spacer is 0.5 / zm or more. (Evaluation of heat treatment conditions &gt; Evaluation of heat treatment conditions by the following procedure.) First, in addition to changing the exposure amount to In the same manner as in the above-mentioned &lt;formation of photo spacers&gt;, the operation after the residue treatment and the heat treatment was performed to prepare a sample for evaluation having a spacer pattern. The obtained evaluation sample 'evaluates the cross-sectional shape of the photo spacer and the height uniformity of the photo spacer when the heating treatment is performed without changing the heating temperature and the heating treatment is performed (the heating treatment time is fixed to 60 minutes). The method for evaluating the cross-sectional shape of the photo spacer and the height uniformity of the photo spacer is as described above. ® Based on the evaluation results of the cross-sectional shape of the photo spacer and the height uniformity of the photo spacer, the following criteria are used. Evaluation of the heat treatment conditions. In the following evaluation criteria, the state of "cross-sectional shape excellent in uniformity" is in the above-mentioned light interval. In the evaluation criteria of the cross-sectional shape, the state of A, B, or C is used. In the following reference, the state of "excellent height uniformity" is used in the evaluation criteria of the height uniformity of the photo spacer. Refers to the state of A, B, or C. ~ Evaluation criteria ~ A; without heat treatment, the uniformity and height of the cross-sectional shape are obtained -82- 200949445 Excellent spacer pattern B. Heating temperature is lower than A spacer pattern having excellent uniformity and height uniformity in cross-sectional shape at 80 ° C. C; heating temperature of 80 ° C or more and less than 150 t, and obtaining an interval excellent in uniformity of cross-sectional shape and high uniformity D. The heating temperature is 150 ° C or higher and lower than 20 CTC, and a spacer pattern having excellent cross-sectional shape uniformity and high uniformity is obtained. E; heating temperature is 200 ° C or higher, and a cross-sectional shape is obtained. A spacer pattern having excellent homogeneity and high uniformity. (Deformation recovery rate) The obtained photo spacer was measured by a micro hardness tester (DUH-W20 1 and Shimadzu Corporation) as follows. , The measurement method is carried out by using a round hammer pressure of 5O/zm0, with a maximum load of 50 mN and a holding time of 5 seconds, according to the load-load-removal test method. From this measurement, the deformation recovery rate is obtained according to the following formula [ %], and evaluated according to the following evaluation criteria. The measurement was carried out in an environment of 22 ± 1 ° C and 50% RH. 〇 Deformation recovery rate (%) = (recovery amount after load opening 丨〆 m) / Deformation amount at load [μ m]) X 1 00 ~ Evaluation criterion ~ A: Deformation recovery rate is 90% or more" B: Deformation recovery rate is 87% or more and less than 90% C: Deformation recovery rate is 85% Above, less than 87%. D: The deformation recovery rate is 80% or more and less than 85%. E: The deformation recovery rate is 75% or more and less than 80%. -83- 200949445 F: The deformation recovery rate is less than 75%. (Display unevenness of the liquid crystal display device) The liquid crystal display device produced as described above was visually observed for the gray scale display when the test signal of the gray scale was input, and the presence or absence of the display unevenness was evaluated in accordance with the following evaluation criteria. The evaluation results are shown in Table 2 below. ~ Evaluation Criteria ~ A: No unevenness was displayed, and a very good display image was obtained. B: Although the edge portion of the glass substrate was slightly uneven, it did not affect the display portion and the display image was good. c: A slight unevenness was observed in the display section, but it was within the practical tolerance range. D: Unevenness was observed on the display unit. [Examples 2 to 13]: Coating method In the first embodiment, a photo spacer and a liquid crystal display were produced in the same manner as in Example 1 except that the type of the polymerizable compound was changed to that shown in Table 2 below. Device. The same evaluation as in Example 1 was carried out on the obtained photo spacer and liquid crystal display device. The evaluation results are shown in Table 2 below. [Examples 14 to 18]: The coating method was carried out in the same manner as in Example 1 except that the type of the polymerizable compound and the resin was changed as shown in the following Table 2, and a photo spacer was produced. Liquid crystal display device. Further, the formulation of the photosensitive resin composition was the first formulation of Examples 14 to 17 and the formulation 2 of the above Example 18 was used. Further, the same evaluation as in Example 1 was carried out on the obtained optical spacer and liquid crystal display device. Evaluation -84- 200949445 The results are shown in Table 2 below. [Example 19]: Coating method In the first embodiment, a photo spacer and a liquid crystal display were produced in the same manner as in Example 1 except that the formulation of the photosensitive resin composition was changed to the formulation 4 in Table 1. Device. The same evaluation as in Example 1 was carried out on the obtained photo spacer and liquid crystal display device. The evaluation results are shown in Table 2 below. [Example 20]: Transfer method © In Example 1, the formulation of the coating liquid for a photosensitive resin layer was replaced with the formulation of the coating liquid for the photosensitive resin layer, and the coating liquid for the photosensitive resin layer was replaced with the coating solution. A photo spacer and a liquid crystal display device were produced in the same manner as in Example 1 except that the photosensitive transfer film was transferred by the transfer of the photosensitive transfer film described below. The resulting photo spacer is cylindrical in shape. The same evaluation as in Example 1 was carried out on the obtained photo spacer and liquid crystal display device. The evaluation results are shown in Table 2 below. &lt;Production of Photosensitive Transfer Film for Spacer&gt; ® A coating liquid for a thermoplastic resin layer composed of the following Formula A was applied to a polyethylene terephthalate film temporary support having a thickness of 75 #m ( The PET was temporarily supported on the body and allowed to dry to form a thermoplastic resin layer having a dry layer thickness of 15.0 # m. ~Preparation of coating solution for thermoplastic resin layer A~•Methyl methacrylate/2-ethylhexyl acrylate/benzyl methacrylate/methacrylic acid copolymer 25.0 parts (= 55/11.7/4.5/28.8[ Mo Erbi], weight average molecular weight 90,000) -85- 200949445 58.4 parts • styrene/acrylic acid copolymer (=63/37 [mole ratio], average halo of molecular weight 8,000) • 2,2 - double [4 - (methyl propyl decyloxy polyethoxy) phenyl propyl propylate 39.0 parts. The following surfactant 1 10.0 parts. methanol 9 0 · 0 parts. 1-methoxy-2-propanol 51.0 parts . Methyl ethyl ketone 700 parts ❹

* Surfactant 1. The following structure 1 3 % %. Methyl ethyl ketone 70% Structure 1

-(CH2-CH)y — 0=C 0(E0)7H

—(CH2-CH)x — o=c A(PO)7H -(CH2_CH)4〇 — o=c OCH2CH2CnF2n+i (n=6, x=55, y=5,

Mw = 33940, Mw / Mn = 2.55 PO: propylene oxide, EO: ethylene oxide. Next, a coating liquid for an intermediate layer composed of the following Formula B is applied onto the formed thermoplastic resin layer, and Dry to a laminate dry layer thickness of 1.5; zm of the intermediate layer. ~ Formulation of coating solution for intermediate layer B~. 3.22 parts of polyvinyl alcohol (PVA-205 (saponification rate 80%), Kuraray (made by the company))) Polyvinylpyrrolidone 1.49 parts -86- 200949445 (PVP K -30, ISB. Japan Co., Ltd.) • 42.3 parts of methanol • 5 2 4 parts of distilled water, and then coating the photosensitive resin layer composed of the formulation 3 shown in Table 1 above on the formed intermediate layer The liquid was dried to form a photosensitive resin layer having a thickness of 5.0 m. The laminated structure of the PET temporary support/thermoplastic resin layer/intermediate layer/photosensitive resin layer was formed as described above (3 layers) After the total thickness of the layer is ❹ 21.5 μm, the surface of the photosensitive resin layer is heated and pressure-applied as a polypropylene film having a thickness of 12/zm covering the film to obtain a photosensitive transfer film for spacers. &lt;Production of photo spacer&gt; The spacer obtained by peeling off the spacer film of the photosensitive transfer film, and superimposing the surface of the exposed photosensitive resin layer on the ITO transparent electrode produced in the same manner as in Example 1 ITO transparent electricity of the color filter substrate In the above, a laminating machine of the type of Lamic II (manufactured by Hitachi Industrial Co., Ltd.) was used, and it was bonded at a conveying speed of 2 m/min under pressure and heating conditions of a pressure of 100 N/cm and 130 °C. The PET temporary support is peeled off at the interface with the thermoplastic resin layer, and the photosensitive resin layer is transferred together with the thermoplastic resin layer and the intermediate layer (film formation step). Continue, using a proximity type having an ultrahigh pressure mercury lamp The exposure machine (Hitachi Hi-Tech Electronic Engineering Co., Ltd.) has a color filter substrate disposed in a mask (a quartz exposure mask having an image pattern) disposed opposite to the mask and the thermoplastic resin layer. In a state of being vertically erected, the distance between the surface of the mask and the surface of the photosensitive resin layer close to the intermediate layer is l〇〇Am, and -87-200949445 is transmitted through the mask from the side of the thermoplastic resin layer with an exposure amount of 90 Next exposure (exposure step) is carried out at mJ/cm2. Next, a triethanolamine-based developing solution (containing 30% of triethanolamine, trade name: T-PD2 (made by Fujifilm)) is diluted 12 times with pure water. (to T-PD2 A dilution of 1 part of the mixture with a ratio of 11 parts of pure water) was carried out at 30 ° C for 50 seconds, and a shower nozzle was applied at a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer. After the air is blown on the upper surface of the glass substrate to be liquid-cut, the pure water is showered for 10 seconds, and the pure water shower is washed, and the air is blown to reduce the liquid on the substrate. Imaging solution (0.38 mol/L sodium bicarbonate, 0.47 mol/L sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, and stabilizer); : T-CD1 (Fuji film (manufactured by Fujifilm)) diluted with pure water to a 10-fold dilution), at 29 ° C for 30 seconds, with a conical nozzle pressure 〇 15 MPa for shower imaging to form a pattern Image (development step}. Next, the detergent is diluted with pure water (containing phosphate, citrate, non-ion ion surfactant, defoamer, stabilizer); trade name: T-SD3 (made by Fujifilm) 〇倍的稀释液, at 33 °C for 20 seconds, with a conical nozzle pressure 〇. 〇 2MPa shower and blowing, the surrounding residue of the formed pattern image is removed, so that the cylindrical spacer pattern is 300// Mx300ym is formed by a spacer interval of one. Then, the color filter substrate having the spacer pattern was patterned and heat-treated at 130 ° C for 60 minutes (film heating step) to form a photo spacer on the color filter substrate. The obtained photo spacer has a cylindrical shape with a diameter of 15.1 μm and an average height of 4.7 μm. * 88- 200949445. Similarly, in the same manner as in the first embodiment, a color filter substrate 'made of a photo spacer is used. A PVA mode liquid crystal display device was fabricated. [Comparative Example 1] An optical spacer and a liquid crystal display device were produced in the same manner as in Example 1 except that the polymerizable compound was changed to the following comparative compound W-1. The same evaluation as in Example 1 was carried out for the photo spacer and the liquid crystal display device. The evaluation results are shown in Table 2 below. ❹—CH2-CH2-O-CH3

Comparative Example W—·I [Comparative Example 2] In Example 1, except that the composition of the photosensitive resin composition was changed to Formulation 5 and the polymerizable compound was changed to DPH A (dipentaerythritol hexaacrylate), A photo spacer and a liquid crystal display device were produced in the same manner as in the first embodiment. The same evaluation as in Example 1 was carried out for the photo spacer and the liquid crystal display device. The evaluation results are shown in Table 2 below.

-89- 200949445 Table 2

Polyfluorene (*1) Resin (*2) Particle formation method evaluation result Average particle diameter [nm] Profile height uniform heat treatment condition Deformation recovery rate shows unevenness Example 1 Illustrative compound (1) P-53 Provocation /«,, Coating BBBBA Example 2 Exemplary Compound (2) P-53 Jfrrt m 涂布 Coated AAAAA Example 3 Exemplary Compound (3} P-53 inL m Uncoated AAAAA Example 4 Exemplary Compound (M-1) P-53 Non-woven cloth AABBA Example 5 Exemplary compound (M-3} P-53 /m* Λ Λττΐ Tear-coated AABAA Example 6 Illustrative compound (M-5) P-53 No coating AAAAA Example 7 Illustrative compound (M- 6) P-53 /fm* m Arr m Coating AAAAA Example 8 Illustrative Modification M-7) P-53 M Artr m Coating AAAAA Example 例 Exemplary Compound (M-8) P-53 No Arre No Coating AAAAA Implementation Example 10 Illustrative Compound (M-13) P-53 No-coating AAAAA Example 11 Exemplary Compound (M-14) P-53 IHr v»\\ An* m Coated AAAAA Example 12 Exemplary Compound (M-15) P -53 No Jfrrt uncoated AAAAA Example 13 Exemplary compound (12) P-53 /nrr m ΑττΤ M Coating AABAA Example 14 Illustrative compound (M-7) P-49 No JRrf uncoated AAABA Example 15 Illustrative compound (M-8&gt; P-31 cup/1\, none Coating AAAAA Example 16 Illustrated Cosmetics (M-13) P-46 Μ /»&gt;&gt; An* Tear-coated AAAAA Example 17 Exemplary Compound (M-14) P-47 Ατι* Pick-free AAAAA Example 18 Illustrative Modification M-7) Methacrylic Acid / Methacrylic Acid Acetate Copolymer Μ Arrf m Coating BBBCA Example 19 Exemplary Compound (M-6) / DPHA = 1 / 1 P-53 Jnf m M Coating ABC c A Example 20 exemplified compound (M-7) P-53 MIBK st 20 Transfer ABAAA Comparative Example 1 W-1 P-53 ΑττΤ No coating CCEEA Comparative Example 2 DPHA P-53 No inL. Coating CCEEA * 1 ^Polymerizing compound The exemplified compound in the column is a polymerizable compound having a structural portion (1). * 2 : The symbol of P-53 or the like in the column of "resin" indicates the exemplified compound number described previously. -90-

A 200949445 As shown in the above Table 2, the photo spacer of the embodiment has high uniformity in cross-sectional shape and can suppress height shift. Further, the liquid crystal display device including the obtained photo spacer can suppress display unevenness. [Embodiment 2 1] &lt;Formation of Protective Film&gt; 'In the production of the color filter substrate of Example 8, after forming a black matrix, R pixels, G pixels, and B pixels, and then on a black matrix A photosensitive resin composition composed of the above-described Formula 1 is applied to each of the pixels, and exposure (overall exposure) and heat treatment are performed without passing through a concealing cover to form a protective film. Here, the conditions of coating, exposure, and heat treatment were the same as those for coating, exposure, and heat treatment in the formation of the photo spacer of Example 8 except that the film was not exposed through the mask. Next, a transparent electrode of ITO (Indiuin Tin Oxide) was sputter-coated on the obtained protective layer. &lt;Formation of photo-spacer&gt; The ITO transparent electrode formed as described above was used in the same manner as in Example 1 except that the photosensitive resin composition used in Comparative Example® 2 was used as the photosensitive resin composition. Method to form a photo spacer. &lt;Production and Evaluation of Liquid Crystal Display Device&gt; Next, a liquid crystal display device was produced by the same method as in Example 1 using a color filter substrate on which the photo spacers were formed. The obtained protective film and liquid crystal display device were evaluated in the same manner as in Example 1. Further, the evaluation of the film thickness uniformity was carried out in the same manner as in "the height uniformity of the photo spacer" of Example 1. The evaluation results are shown in Table 3. -91-200949445 ^ [Comparative Example 3] In the same manner as in Example 21, except that the polymerizable compound was changed to the comparative compound W-1, a protective film, a photo spacer, and The liquid crystal display device was subjected to the same evaluation. The evaluation results are shown in Table 3 below. [Example 2 2] &lt;Formation of coloring pattern&gt; In the production of the color filter substrate of Example 8, the same procedure as in Example 8 was carried out except that the R pixel was formed by the following method. Color filter substrate. In other words, Pigment Red 254 (19.4 parts) and Pigment Red 177 (4.83 parts) were added to the above-mentioned Formulation 1 to prepare a photosensitive resin composition for R pixels. R pixels were formed by the same method as the formation of the photo spacers of Example 1, except that the photosensitive resin composition for R pixels to be prepared and the photomask for R pixels were used as the photomask. After the R pixel, the G pixel, and the stomach B pixel of the color filter substrate to be formed are formed, a transparent electrode of ITO (Indium Tin Oxide) is formed by sputtering on each pixel. &lt;Formation of photo-spacer&gt; The same procedure as in Example 1 was carried out except that the photosensitive resin composition used in Comparative Example 2 was used as the photosensitive resin composition on the ITO transparent electrode formed as described above. To form a photo spacer. &lt;Production and Evaluation of Liquid Crystal Display Device&gt; Next, a liquid crystal display device was produced by the same method as in Example 1 using a color filter substrate on which the photo spacer was formed. / -92- 200949445 The obtained protective film and liquid crystal display device were evaluated in the same manner as in Example 1. Further, the evaluation of the film thickness uniformity was carried out by the same method as the "height uniformity of the photo spacer" of Example 1. The evaluation results are shown in Table 3. [Comparative Example 4] A coloring pattern, a photo spacer, and a liquid crystal display device were produced in the same manner as in Example 22 except that the polymerizable compound was changed to the above-mentioned comparative compound W-1. The same evaluation. The β evaluation results are shown in Table 3 below. table 3

Polymeric compound structure F-price result Cross-sectional shape Film thickness uniformity Heat treatment conditions showed unevenness Example 21 Exemplary compound (Μ-7) Protective film-AAA Comparative Example 3 (for Example 21) W-1 Protective film - BEA Example 22 Exemplary Compound (Μ-7) Colored Pattern 1 - AA Comparative Example 4 (Comparative Example 22) W-1 Colored Pattern - EA As shown in Table 3 above, the photosensitive resin composition of the present invention was used to form In the case of the protective film and the colored pattern, the same results as in the case of forming the photo spacer can be obtained. According to the present invention, it is possible to provide excellent polymer hardenability at the time of exposure, and to form a pattern structure under low-temperature heat treatment or without heating. Further, according to the present invention, it is possible to provide a photo spacer having a high cross-sectional shape with high uniformity and excellent uniformity of height, and a method for producing the same. 4 - 93 - 200949445 Further, according to the present invention A protective film having excellent film thickness uniformity or a colored pattern having a uniform cross-sectional shape and excellent film thickness uniformity can be provided. It is possible to provide a display device substrate capable of suppressing display unevenness when used in a display device, and a display device capable of suppressing display unevenness. The above description of the present invention is provided for the purpose of description and description. The present invention is not intended to be limited to the scope of the invention disclosed, or to be construed as limited to the scope of the invention. The application is selected, and therefore, should be applicable to the specific use of the person attempted by the other person, and can be various forms and various modifications, and the present invention can be understood by others of the industry. All journals and patent applications and technical standards in this specification, especially in the case where their individual journals and patent applications, and technical standards are cited and individually specified, will be the same as the cited documents. The limited scope is incorporated in the present specification. The details of the preferred embodiment of the present invention described above may of course be based on the state of the applicant's application. The scope of the present invention is determined by the following patent application scope and its equivalents. [Simplified description of the drawings] None. [Main component symbol description] None. -94-

Claims (1)

200949445 VII. Patent application scope: I—a photosensitive resin composition containing a resin, a polymerizable compound having the following structural part (I), and a photopolymerization initiator, [In the structural part (1), the term "x is a hydrogen atom or a methyl group" is a photosensitive resin composition according to the first aspect of the invention, wherein the polymerizable compound has a molecule in the molecule. At least two of the aforementioned structural portions (I). 3. The photosensitive resin composition of the first aspect of the invention, wherein the polymerizable compound has a symmetrical structure in which two groups including the structural portion (1) are bonded. 4. The photosensitive resin composition of the first aspect of the invention, wherein the polymerizable compound having the structural portion (1) is a polymerizable compound represented by the following structural formula (π). (Λ, 〇 [wherein R represents a linking group containing at least one ether bond between carbon and carbon of a divalent hydrocarbon group, and X represents a hydrogen atom or a methyl group]. 5. In the fourth aspect of the patent application The photosensitive resin composition' is in the structural formula (Π) of the former -95-200949445, the R system represents -CH2-0-Ra-0-CH2-, and the Ra system is selected from the alkyl group and the aromatic A photosensitive resin composition according to the first aspect of the invention, wherein the resin has a branching and/or alicyclic structure in a side chain, 7. The photosensitive resin composition of the sixth aspect of the invention, wherein the acid value of the resin is 20 mgKOH/g or more. The photosensitive resin composition of claim 6, wherein the base having a branched and/or alicyclic structure is a group represented by the following formula (3), 〇•O+X—O————(3) In the formula (3), X represents a divalent organic linking group, which may be unsubstituted or substituted, and 5^ represents 1 or 2 The 11 series represents an integer from 0 to 15. A photo spacer formed by using the photosensitive resin composition according to any one of claims 1 to 8. 10, a method for producing a photo spacer, comprising at least the following steps (A) to (c): (a) forming a photosensitive resin composition on a substrate as in any one of the claims a step of forming a film; (b) exposing at least a portion of the film to an exposure step; (c) a step of developing the film after the imagewise exposure. 11. The method for preparing a photo spacer according to claim 10, wherein the method further comprises -96-200949445 heating step of the film after heating and developing, and the maximum temperature during heating is 40 ° C or more, 1 4 5 ° C or lower. 12. A protective film formed by using a photosensitive resin composition as set forth in any one of claims 1 to 8. A coloring pattern formed by using the photosensitive resin composition according to any one of claims 1 to 8. 14. A substrate for a display device comprising at least one of a light spacer®, a protective film, and a colored pattern formed using the photosensitive resin composition according to any one of claims 1 to 8. . 15. A display device comprising a substrate for a display device as claimed in the scope of claim 1 * 97 -97- 200949445 IV. Designation of representative drawings: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 jw\ 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention. X OH