JP5191244B2 - Photosensitive resin composition, photospacer and method for forming the same, protective film, coloring pattern, substrate for display device, and display device - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a photospacer and a method for forming the same, a protective film, a coloring pattern, a display device substrate, and a display device.

Liquid crystal display devices are widely used in display devices that display high-quality images.
In a liquid crystal display device, a liquid crystal layer capable of displaying an image with a predetermined orientation is generally disposed between a pair of substrates (hereinafter also referred to as a “display device substrate”). Maintaining uniformity is one of the factors that determine image quality, and for this purpose, a spacer is provided to keep the thickness of the liquid crystal layer constant. The thickness between the substrates is generally referred to as “cell thickness”, and the cell thickness usually indicates the thickness of the liquid crystal layer, in other words, the distance between two electrodes applying an electric field to the liquid crystal in the display region. Is.

  A display device substrate (for example, a color filter substrate, an active matrix substrate, or the like) has a structure in which structures such as a colored pattern and a protective film are formed on the substrate. Among these structures, a method of forming a colored pattern or a protective film by photolithography using a photosensitive resin composition has become the mainstream.

  In addition, spacers have conventionally been formed by bead dispersion, but in recent years, spacers with high positional accuracy have been formed by photolithography using a photosensitive resin composition. A spacer formed using such a photosensitive resin composition is called a photospacer.

Regarding the photosensitive resin composition, various studies have been made conventionally. For example, a photosensitive resin using a copolymer of an ethylenically unsaturated carboxylic acid or the like and an ethylenically unsaturated compound and a specific photopolymerization initiator. A resin composition is disclosed (for example, see Patent Document 1). Further, from an aliphatic cyclic hydrocarbon group-containing copolymer having a molecular structure in which a structural unit having an aliphatic cyclic hydrocarbon group having a specific structure, a structural unit having an acidic functional group, and a structural unit having a radical polymerizable group are linked. A curable resin is disclosed (for example, see Patent Document 2).
JP 2007-86565 A Japanese Patent Laid-Open No. 2002-293737

  In the conventional photosensitive resin composition, a monomer having an ethylenically unsaturated bond such as dipentaerythritol hexaacrylate or dipentaerythritol pentaacrylate is generally used as a photopolymerizable monomer.

  However, when a pattern structure (for example, photo spacer, colored pattern, etc.) and a protective film are formed on a substrate using a conventional photosensitive resin composition, polymerization and curing are insufficient only by exposure. In some cases, it may be necessary to perform high-temperature heat treatment after exposure and development.

This invention is made | formed in view of the above, and makes it a subject to achieve the following objectives.
That is, an object of the present invention is to provide a photosensitive resin composition that is excellent in polymerization curability at the time of exposure and can form a pattern structure or a protective film without a low heating temperature or heat treatment.
Another object of the present invention is to provide a photospacer excellent in uniformity in cross-sectional shape and height uniformity even when formed at a low heating temperature or without heat treatment, and a method for producing the same.
In addition, the present invention provides a protective film having excellent film thickness uniformity even when formed at a low heating temperature or no heat treatment, or a cross-section even when formed at a low heating temperature or no heat treatment. It aims at providing the coloring pattern which is excellent in the uniformity of a shape and film thickness uniformity.
It is another object of the present invention to provide a display device substrate capable of suppressing display unevenness when used in a display device, and a display device in which display unevenness is suppressed.

As a result of intensive studies, the present inventor obtained knowledge that the above-mentioned problems can be solved by using a specific polymerizable compound, and completed the present invention based on the knowledge.
That is, specific means for achieving the above-described problem are as follows.
<1> Copolymer having at least a repeating unit having an alicyclic structure, a repeating unit having an acidic group, and a repeating unit having an ethylenically unsaturated bond arranged via an ester bond between the main chain A dipole having a resin that is a coalescence, a 5-membered or 6-membered cyclic structure having a linking site containing C═O and / or a linking site containing P═O, and an ethylenically unsaturated double bond A photosensitive resin composition comprising a polymerizable compound having a moment of 4.12 Debye or more and a photopolymerization initiator.

<2> A photospacer formed using the photosensitive resin composition according to <1> .

<3> A method for forming a photospacer comprising at least the following steps (a) to (c).
(B) A step of forming a film of the photosensitive resin composition according to <1> on a substrate (b) A step of exposing at least a part of the film (c) A step of developing the film after exposure <4 > The method for forming a photospacer according to <3> , further comprising a step of heating the coated film after development, wherein a maximum temperature in the heating is 40 ° C. or higher and 145 ° C. or lower.

<5> A protective film formed using the photosensitive resin composition according to <1> .
<6> A colored pattern formed using the photosensitive resin composition according to <1> .
<7> A substrate for a display device comprising at least one of the photo spacer according to <2> , the protective film according to <5> , and the coloring pattern according to <6> .
<8> A display device comprising the display device substrate according to <7> .

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which is excellent in the polymerization curability at the time of exposure, and can form a pattern structure and a protective film without a low heating temperature or heat processing can be provided.
In addition, according to the present invention, it is possible to provide a photospacer excellent in uniformity in cross-sectional shape and uniformity in height even when formed at a low heating temperature or without heat treatment, and a method for producing the same.
In addition, according to the present invention, it is possible to provide a protective film having excellent film thickness uniformity even when formed at a low heating temperature or without heat treatment, and when formed at a low heating temperature or without heat treatment. In addition, a colored pattern having excellent cross-sectional shape uniformity and film thickness uniformity can be provided.
In addition, according to the present invention, it is possible to provide a display device substrate capable of suppressing display unevenness when used in a display device, and a display device in which display unevenness is suppressed.

  Hereinafter, the photosensitive resin composition of the present invention will be described in detail, and a photo spacer using the photosensitive resin composition and a method for forming the same, a protective film, a coloring pattern, a display device substrate, and a display device will also be described. To do.

≪Photosensitive resin composition≫
The photosensitive resin composition of the present invention is a repeating unit having an ethylenically unsaturated bond arranged via an ester bond between a repeating unit having an alicyclic structure, a repeating unit having an acidic group, and a main chain. A resin that is a copolymer having at least, a linking site containing C═O and / or a 5-membered or 6-membered cyclic structure having a linking site containing P═O, and an ethylenically unsaturated double bond And having a dipole moment of 4.12 Debye or more and a photopolymerization initiator.
In general, when a pattern structure (for example, a photo spacer, a colored pattern, etc.) and a protective film are formed on a substrate using a photosensitive resin composition, polymerization and curing are insufficient only by exposure. In order to advance polymerization and curing, it is necessary to perform a high-temperature heat treatment after exposure and development.
However, this high-temperature heat treatment may deteriorate the pattern structure or protective film to be formed, or may deteriorate the pattern structure or protective film already formed on the substrate. For example, when a photo spacer is formed on a color filter substrate having a colored pattern, the photo spacer to be formed may deteriorate, or the colored pattern already formed on the substrate may deteriorate.
Therefore, by setting the photosensitive resin composition to the configuration of the present invention, the polymerization curability at the time of exposure is improved, and a pattern structure or a protective film can be formed without a low heating temperature or heat treatment. For this reason, it is possible to effectively suppress the deterioration of the pattern structure and the protective film to be formed and the deterioration of the pattern structure and the protective film already formed on the substrate.

Hereinafter, the heavy polymerizable compounds, resins, photopolymerization initiator and the other components will be described.

<Polymerizable compound>
The photosensitive resin composition of the present invention contains at least one polymerizable compound having a dipole moment of 4.12 Debye or more (hereinafter also referred to as “specific polymerizable compound”).
The polymerizable compound undergoes a polymerization reaction under the action of radicals from the photopolymerization initiator described later to form a cured film. In particular, this specific polymerizable compound has a high polymerization reactivity, and is polymerized and cured during exposure. Excellent in properties.
Here, the dipole moment of the specific polymerizable compound indicates a value calculated by Scigress Explorer Professional Version 7.6.0.52 (manufactured by Fujitsu Limited).

The dipole moment of the specific polymerizable compound is 4 from the viewpoint of polymerization curability during exposure. More 40Debye is good Masui.

The specific polymerizable compound includes a 5-membered or 6-membered cyclic structure having a linking site containing C═O and / or a linking site containing P═O, and an ethylenically unsaturated divalent dimer from the viewpoint of polymerization curability at the time of exposure. double bond and, that have a.

Examples of the linking moiety containing C═O include a moiety represented by the following formula.
In the present specification, the bond is indicated by *.

  Examples of the linking moiety containing P = O include a moiety represented by the following formula.

  Further, specific examples of the 5-membered or 6-membered cyclic structure having a linking site containing C═O and / or a linking site containing P═O are not particularly limited. For example, a structure represented by the following formula Can be mentioned.

  Among 5-membered or 6-membered cyclic structures having a linking site containing C═O and / or a linking site containing P═O, from the viewpoint of polymerization curability, a 5-membered or linking site containing C═O A 6-membered ring structure is more preferred.

The specific polymerizable compound that have a ethylenically unsaturated double bond.
At this time, from the viewpoint of polymerization curability, the ethylenically unsaturated double bond is preferably contained as a part of the (meth) acryloyl group in the specific polymerizable compound.

  In the present specification, (meth) acryloyl group represents acryloyl group or methacryloyl group, (meth) acrylate represents acrylate or methacrylate, (meth) acryl represents acryl or methacryl, and (meth) acrylamide represents acrylamide. Alternatively, it represents methacrylamide, and (meth) acrylanilide represents acrylanilide or methacrylanilide.

  The “polymerizable compound having a 5-membered or 6-membered cyclic structure having a linking site containing C═O and / or a linking site containing P═O and an ethylenically unsaturated double bond” is, for example, macromolecules, Vol36, No. 11, 2003, can be synthesized by the method described in p3871.

Specific examples of the polymerizable compound of the present invention (Exemplary compounds M- 2 to M-7, M-9 to M-11, M-13 to M-15, M-17 to M-22, M-24 to M-26, M-28 to M-30), but the present invention is not limited thereto.

Exemplified compounds M- 2 to M-7, M-9 to M-11, M-13 to M-15, M-17 to M-22, M-24 to M-26, M-28 to M-30 dipole moment obtained by the method, respectively, is M -2 4.12Debye, M-3 is 4.54Debye, M-4 is 4.62Debye, M-5 is 5.30Debye, the M-6 5.92 Debye, M-7 is 6.50 Debye , M- 9 is 5.50 Debye, M-10 is 5.10 Debye, M-11 is 4.70 Debye , M- 13 is 5.30 Debye, and M-14 is 4.4. 30Debye, M-15 is 4.90Debye, M -17 is 4.12Debye, M-18 is 4.54Debye, M-19 is 4.62Debye, M-20 is 5.30Debye, M-21 is .92Debye, M-22 is 6.50Debye, M -24 is 5.50Debye, M-25 is 5.10Debye, M-26 is 4.70Debye, M -28 is 5.30Debye, M-29 is 4.30Debye , M-30 is 4.90 Debye.

The photosensitive resin composition of this invention may contain the polymeric compound which has an ethylenically unsaturated bond other than the said specific polymeric compound.
The polymerizable compound can be selected from polymerizable compounds constituting a known composition and used, for example, the components described in paragraph numbers [0010] to [0020] of JP-A-2006-23696. And the components described in paragraph numbers [0027] to [0053] of JP-A-2006-64921.

  In the present invention, the mass ratio [total amount of resin / total amount of polymerizable compound] of the total amount of the polymerizable compound including the specific polymerizable compound and the total amount of the resin described later is 0.5 to 2.0. It is preferable that it is 0.6 to 1.8, more preferably 0.7 to 1.5. When the mass ratio is within the above range, a photospacer having good developability and mechanical strength can be obtained.

<Resin>
The photosensitive resin composition of the present invention is a repeating unit having an ethylenically unsaturated bond arranged via an ester bond between a repeating unit having an alicyclic structure, a repeating unit having an acidic group, and a main chain. And at least one resin which is a copolymer having at least
Although there is no limitation in particular as said resin, The compound which shows swelling property with respect to alkaline aqueous solution is preferable, and the compound which shows solubility with respect to alkaline aqueous solution is more preferable.
As the resin exhibiting swellability or solubility with respect to an alkaline aqueous solution, for example, those having an acidic group are preferably mentioned. Specifically, an ethylenically unsaturated double bond and an acidic group are introduced into an epoxy compound. Compound (epoxy acrylate compound), vinyl copolymer having (meth) acryloyl group and acidic group in side chain, epoxy acrylate compound and vinyl copolymer having (meth) acryloyl group and acidic group in side chain And the like, and a maleamic acid copolymer are preferable.
The acidic group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, the availability of raw materials, etc. From the viewpoint, a carboxyl group is preferable.

  As content of resin in the photosensitive resin composition of this invention, 5-70 mass% is preferable with respect to the total solid of the photosensitive resin composition, and 10-50 mass% is more preferable. When the content is 5% by mass or more, the film strength of the photosensitive resin layer can be maintained, and the tackiness of the surface of the photosensitive resin layer can be maintained well. When the content is 70% by mass or less, the exposure sensitivity is good. become.

<Resin A>
Resin in the present invention, the side chain, alicyclic structure, an acidic group, and a resin having an ethylenically unsaturated bond A (hereinafter, simply referred to as "resin A") at least one of including the.

The resin A has an acidic group and developability, and has an ethylenically unsaturated bond, so that it has high polymerization reactivity and has excellent liquid storage stability and storage stability with time in a dry film. Therefore, it is possible to impart controllability that allows the pattern structure to be controlled to have a desired shape and film thickness (such as height). Also it has an alicyclic structure, compressive modulus when subjected to an external force of the formed pattern structure, it is possible to improve the elastic recovery from compressive deformation. Thus, for example, it is useful for constructing a pattern structure such as a photo spacer for a display device.

Here, alicyclic structure, an acidic group, and an ethylenically unsaturated bond, each may be contained in the different side chains may be included in the same side chain part are combined All may be contained in the same side chain.

(Alicyclic structure)
Resin A comprises a side chain bonded to the main chain of the resin, at least one alicyclic structure. Alicyclic structure may include a plurality in the side chain of the resin A. Further, alicyclic structure in the side chain of the resin A, an acidic group, and / or may be included with the ethylenically unsaturated bond.
Further, alicyclic structure may constitute the side chains of only the resin A alicyclic structure directly bonded to the main chain of the resin A, via a bivalent organic linking group to the main chain of the resin A binding Te and may constitute the side chain of the resin a as the group having an alicyclic structure.

  The divalent organic linking group is preferably one or a combination selected from an alkylene group, an arylene group, an ester group, an amide group, and an ether group. As said alkylene group, a C1-C20 alkylene group is preferable, More preferably, 1-10 are preferable. Specific examples include methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene, dodecylene, octadecylene, and the like, which may have a branched / cyclic structure or a functional group, and more preferably a methylene group. , Ethylene group and octylene group are preferable. As the arylene group, an arylene group having a total carbon number of 6 to 20 is preferable, and 6 to 12 is more preferable. Specific examples include a phenylene group, a biphenylene group, a naphthalene group, and an anthracene group, which may have a branched or functional group, and more preferably a phenylene group or a biphenylene group.

Alicyclic structure, developability, from the viewpoint of elastic recovery, the form as it is bonded to the main chain of the resin A through at least an ester group (-COO-) is preferred. This embodiment is not limited to the embodiments alicyclic structure is bonded to the main chain of the resin A only through the ester group (-COO-), alicyclic structures divalent containing ester groups (-COO-) The form couple | bonded with the principal chain of resin A through the coupling group may be sufficient. That is, between the alicyclic structure and an ester chain, and / or, between the main chain of the ester chains and the resin A, may contain other atoms or other linking groups.

When the resin A includes a branched structure in the side chain, examples of the branched structure include branched alkyl groups having 3 to 12 carbon atoms, such as i-propyl group and i-butyl group. , S-butyl group, t-butyl group, isopentyl group, neopentyl group, 2-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, i-amyl group, t-amyl group, 3-octyl, t-Octyl and the like are preferable. Among these, i-propyl group, s-butyl group, t-butyl group, isopentyl group and the like are more preferable, and i-propyl group, s-butyl group, t-butyl group and the like are particularly preferable.

  Examples of the alicyclic structure include alicyclic hydrocarbon groups having 5 to 20 carbon atoms, such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group, adamantyl group, A tricyclodecyl group, a dicyclopentenyl group, a dicyclopentanyl group, a tricyclopentenyl group, a tricyclopentanyl group, and the like, and groups having these are preferable. Among these, dicyclopentenyl group, cyclohexyl group, norbornyl group, isobornyl group, adamantyl group, tricyclodecyl group, tricyclopentenyl group, tricyclopentanyl group and the like are more preferable, dicyclopentenyl group, cyclohexyl group, norbornyl Group, isobornyl group, tricyclopentenyl group and the like are more preferable, and dicyclopentenyl group and tricyclopentenyl group are particularly preferable.

Furthermore, as the group having an alicyclic structure, form, which is configured with a group represented by the formula the following general formula (3).

  In the general formula (3), X represents a divalent organic linking group, which may be unsubstituted or may have a substituent. y represents 1 or 2, and n represents an integer of 0 to 15.

The divalent organic linking group is preferably one or a combination selected from an alkylene group, an arylene group, an ester group, an amide group, and an ether group, and these may have a substituent.
As said alkylene group, a C1-C20 alkylene group is preferable, More preferably, it is a 1-10 alkylene group. Specific examples include groups such as methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene, dodecylene, and octadecylene, which may have a branched / cyclic structure or a functional group, and more preferably, A methylene group, an ethylene group and an octylene group;
The arylene group is preferably an arylene group having a total carbon number of 6 to 20, more preferably 6 to 12. Specific examples include a phenylene group, a biphenylene group, a naphthalene group, and an anthracene group, which may have a branched or functional group, and more preferably a phenylene group or a biphenylene group.
Examples of the substituent when substituted include an alkyl group, a hydroxy group, an amino group, a halogen group, an aromatic ring group, and a group having an alicyclic structure.

Examples of the monomer for introducing an alicyclic structure in the side chain of the resin A, styrenes, (meth) acrylates, vinyl ethers, vinyl esters, include (meth) acrylamides, (meth) acrylate , Vinyl esters and (meth) acrylamides are preferred, and (meth) acrylates are more preferred.

When the resin A contains a branched structure in the side chain, monomers for introducing the branched structure into the side chain of the resin A include styrenes, (meth) acrylates, vinyl ethers, vinyl esters. (Meth) acrylamides, (meth) acrylates, vinyl esters, and (meth) acrylamides are preferable, and (meth) acrylates are more preferable. Specific monomers include i-propyl (meth) acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, and (meth) acrylic acid. i-amyl, (meth) acrylic acid t-amyl, (meth) acrylic acid sec-iso-amyl, (meth) acrylic acid 2-octyl, (meth) acrylic acid 3-octyl, (meth) acrylic acid t-octyl Among them, i-propyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl methacrylate and the like are preferable, and i-propyl methacrylate, t-butyl methacrylate and the like are more preferable.

Examples of the monomer for introducing the alicyclic structure into the side chain of the resin A include (meth) acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. Specific examples include (meth) acrylic acid (bicyclo [2.2.1] heptyl-2), (meth) acrylic acid 1-adamantyl, (meth) acrylic acid 2-adamantyl, (meth) acrylic acid 3 -Methyl-1-adamantyl, 3,5-dimethyl-1-adamantyl (meth) acrylate, 3-ethyladamantyl (meth) acrylate, 3-methyl-5-ethyl-1-adamantyl (meth) acrylate, ( 3,5,8-triethyl-1-adamantyl (meth) acrylate, 3,5-dimethyl-8-ethyl-1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, (meth ) 2-ethyl-2-adamantyl acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, octahydro-4,7 (meth) acrylate Mentanoinden-5-yl, octahydro-4,7-mentanoinden-1-ylmethyl (meth) acrylate, 1-menthyl (meth) acrylate, tricyclodecyl (meth) acrylate, (meth) acrylic acid 3-hydroxy-2,6,6-trimethyl-bicyclo [3.1.1] heptyl, 3,7,7-trimethyl-4-hydroxy-bicyclo [4.1.0] heptyl (meth) acrylate, ( (Meth) acrylic acid (nor) bornyl, (meth) acrylic acid isobornyl, (meth) acrylic acid fuentyl, (meth) acrylic acid 2,2,5-trimethylcyclohexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid di Examples include cyclopentenyl and tricyclopentenyl (meth) acrylate.
Among these (meth) acrylic acid esters, bulky functional groups have better compressive modulus and elastic recoverability, and (meth) acrylic acid cyclohexyl, (meth) acrylic acid (nor) bornyl, and (meth) acrylic. Isobornyl acid, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, fuentyl (meth) acrylate, 1-menthyl (meth) acrylate, tricyclodecyl (meth) acrylate, (meth) acrylic Dicyclopentenyl acid, tricyclopentenyl (meth) acrylate and the like are preferable, cyclohexyl (meth) acrylate, (nor) bornyl (meth) acrylate, isobornyl (meth) acrylate, 2-adamantyl (meth) acrylate, (Meth) acrylic acid dicyclopentenyl, (meth) acrylic acid tricyclo Nteniru is particularly preferred.

Moreover, as a monomer for introduce | transducing an alicyclic structure into the side chain of resin A, the compound represented by following General formula (4) or (5) is mentioned. Here, in the general formulas (4) and (5), X represents a divalent organic linking group, and R represents a hydrogen atom or a methyl group. y represents 1 or 2, and n represents 0-15. Among the general formulas (4) and (5), y = 1 or 2, n = 0 to 8 is preferable, more preferably y = 1 or 2, n = 0 to 4 (more preferably n = 0 to 2). ). Preferred specific examples of the compound represented by the general formula (4) or (5) include the following compounds D-1 to D-11 and T-1 to T-12.
Especially, the compound represented by following General formula (4) is preferable at the point of an elastic recovery factor.

  In the general formulas (4) to (5), the divalent organic linking group represented by X may be unsubstituted or may have a substituent, and X in the general formula (3) It is synonymous with the bivalent organic coupling group represented, and its preferable aspect is also the same.

As a monomer for introducing the alicyclic structure into the side chain of the resin A, an appropriately produced monomer may be used, or a commercially available product may be used.
As said commercial item, Hitachi Chemical Co., Ltd. product: 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 and the like can be mentioned. Among these, FA-512A (S) and 512M are preferable because they are excellent in developability and excellent in the deformation recovery rate.

(Acidic group)
Resin A contains at least one acid group in the side chain connected to the main chain. A plurality of acidic groups may be contained in the side chain. Further, the acidic group is in the side chain of the resin A, prior Kiabura ring structure, and may be included with the ethylenically unsaturated bond.
The acidic group may be directly bonded to the main chain of the resin A to form a side chain of the resin A with only the acidic group, or may be bonded to the main chain of the resin A via a divalent organic linking group. The side chain of the resin A may be constituted as a group having an acidic group. Here, the divalent organic linking group include a divalent organic linking groups exemplified in the description before Kiabura ring structure, preferred ranges are also the same.

  There is no restriction | limiting in particular as said acidic group, It can select suitably from well-known things, For example, a carboxyl group, a sulfonic acid group, a sulfonamide group, a phosphoric acid group, a phenolic hydroxyl group etc. are mentioned. Among these, a carboxy group and a phenolic hydroxyl group are preferable from the viewpoint of excellent developability and water resistance of the cured film.

  Specific examples of the monomer for introducing the acidic group into the resin A can be appropriately selected from known ones such as (meth) acrylic acid, vinyl benzoic acid, maleic acid, and maleic acid monoester. Alkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid, acrylic acid dimer, addition reaction product of monomer having hydroxyl group and cyclic acid anhydride, ω-carboxy-poly Examples thereof include caprolactone mono (meth) acrylate. As these, those produced as appropriate may be used, or commercially available products may be used.

  Examples of the monomer having a hydroxyl group used in the addition reaction product of the monomer having a hydroxyl group and a cyclic acid anhydride include 2-hydroxyethyl (meth) acrylate. Examples of the cyclic acid anhydride include maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride.

  Commercially available monomers include Toa Gosei Chemical Industry Co., Ltd .: Aronix M-5300, Aronix M-5400, Aronix M-5500, Aronix M-5600, Shin-Nakamura Chemical Co., Ltd .: NK Ester CB -1, NK ester CBX-1, manufactured by Kyoeisha Oil and Chemical Co., Ltd .: HOA-MP, HOA-MS, manufactured by Osaka Organic Chemical Industry Co., Ltd .: Biscote # 2100, and the like. Among these, (meth) acrylic acid and the like are preferable in terms of excellent developability and low cost.

(Ethylenically 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 arranged between the main chain via an ester group.
A plurality of ethylenically unsaturated bonds may be contained in the side chain. Also, ethylenically unsaturated bond, in the side chain of the resin A, prior Kiabura ring structure, and / or may be included together with the acidic group.

The ethylenically unsaturated bond is bonded to the main chain of the resin A via at least one ester group (—COO—), and the side chain of the resin A is bonded only by the ethylenically unsaturated bond and the ester group. You may comprise. In addition, the resin A may have a divalent organic linking group between the main chain of the resin A and the ester group and / or between the ester group and the ethylenically unsaturated bond. May constitute the side chain of the resin A as a “group having an ethylenically unsaturated bond arranged via an ester group between the main chain” and the resin A. Here, the divalent organic linking group, include a divalent organic linking groups exemplified in the description of the alicyclic structure, preferred ranges are also the same.

The ethylenically unsaturated bond is preferably arranged by introducing a (meth) acryloyl group.
The method for introducing the (meth) acryloyl group into the side chain of the resin A can be appropriately selected from known methods. For example, a (meth) acrylate having an epoxy group is added to a repeating unit having an acidic group. Examples thereof include a method, a method of adding (meth) acrylate having an isocyanate group to a repeating unit having a hydroxyl group, and a method of adding (meth) acrylate having a hydroxy group to a repeating unit having an isocyanate group.
Among these, the method of adding (meth) acrylate having an epoxy group to a repeating unit having an acidic group is most preferable because it is the easiest to produce and is low in cost.

  Although there is no restriction | limiting in particular as (meth) acrylate which has the said epoxy group, For example, the compound represented by following Structural formula (1) and the compound represented by following Structural formula (2) are preferable.

However, in the structural formula (1), R ¹ represents a hydrogen atom or a methyl group. L ¹ represents an organic group.

However, in the above structural formula (2), R ² represents a hydrogen atom or a methyl group. L ² represents an organic group. W represents a 4- to 7-membered aliphatic hydrocarbon group.

Of the compound represented by the structural formula (1) and the compound represented by the structural formula (2), the compound represented by the structural formula (1) is more preferable than the structural formula (2). In the structural formulas (1) and (2), it is more preferable that L ¹ and L ² are each independently an alkylene group having 1 to 4 carbon atoms.

  Although there is no restriction | limiting in particular as a compound represented by the said Structural formula (1) or a structural formula (2), For example, the following exemplary compounds (1)-(10) are mentioned.

~~ other monomers ~~
In the resin A in the present invention, other groups may be introduced using other monomers.
The other monomer is not particularly limited, and examples thereof include (meth) acrylic acid ester, styrene, vinyl ether, dibasic acid anhydride group, vinyl ester group, hydrocarbon alkenyl group and the like. Can be mentioned.

There is no restriction | limiting in particular as said vinyl ether group, For example, a butyl vinyl ether group etc. are mentioned.
The dibasic acid anhydride group is not particularly limited, and examples thereof include a maleic anhydride group and an itaconic anhydride group.
There is no restriction | limiting in particular as said vinyl ester group, For example, a vinyl acetate group etc. are mentioned.
There is no restriction | limiting in particular as said hydrocarbon alkenyl group, For example, a butadiene group, an isoprene group, etc. are mentioned.

  As content rate of the other monomer in the said resin A, it is preferable that a composition ratio is 1-40 mass%, and it is more preferable that it is 2-30 mass%.

Specific examples of the resin A include compounds represented by the following structures (Exemplary compounds P-1 to P-35, P-45 to P-56).
In addition, x, y, and z in the exemplified compound represent a composition ratio (mass ratio) of each repeating unit, and a form configured in a preferable range described later is preferable. Moreover, the form comprised also in the preferable range mentioned later of the weight average molecular weight of each exemplary compound is suitable.

~ Synthetic method ~
Resin A can be synthesized from a two-stage process including a monomer (co) polymerization reaction process and an ethylenically unsaturated group introduction process.
First, the (co) polymerization reaction is made by a (co) polymerization reaction of various monomers, and is not particularly limited and can be appropriately selected from known ones. For example, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization and the like can be appropriately selected for the active species of polymerization. Among these, radical polymerization is preferable from the viewpoint of easy synthesis and low cost. Moreover, there is no restriction | limiting in particular also about the polymerization method, It can select suitably from well-known things. For example, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method and the like can be appropriately selected. Among these, the solution polymerization method is more desirable.

~ Carbon number ~
The total number of carbon atoms in the branched and / or alicyclic structure of the resin A is preferably 10 or more in terms of elastic modulus (hardness). Especially, as for total carbon number, 10-30 are more preferable, Most preferably, it is 10-15.

~ Molecular weight ~
The molecular weight of the resin A is preferably 10,000 to 100,000 in terms of weight average molecular weight, more preferably 12,000 to 60,000, and particularly preferably 15,000 to 45,000. When the weight average molecular weight is within the above range, it is desirable from the viewpoint of production suitability and developability of the resin (preferably copolymer). Further, it is preferable in that the shape formed by the decrease in melt viscosity is difficult to be crushed, in that it is difficult to cause crosslinking failure, and there is no residue in the spacer shape during development.
The weight average molecular weight is measured by gel permeation chromatography (GPC). GPC will be described in detail in the section of the examples described later.

~Glass-transition temperature~
The glass transition temperature (Tg) of the resin A is preferably 40 to 180 ° C, more preferably 45 to 140 ° C, and particularly preferably 50 to 130 ° C. When the glass transition temperature (Tg) is within the preferred range, a spacer having good developability and mechanical strength can be obtained.

~ Acid value ~
The preferred range of the acid value of the resin A varies depending on the molecular structure that can be taken, but generally it is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, and 50 to 130 mgKOH / g. Is particularly preferred. When the acid value is within the preferred range, a spacer having good developability and mechanical strength can be obtained.

~ Tg ~
The resin A has a glass transition temperature (Tg) of 40 to 180 ° C. and a weight average molecular weight of 10,000 to 100,000 in that a spacer having good developability and mechanical strength can be obtained. It is preferable that Tg is 45 to 140 ° C. (more preferably 50 to 130 ° C.) and the weight average molecular weight is 12,000 to 60,000 (more preferably 15,000 to 45,000).
Furthermore, a preferable example of the resin A is more preferably a combination of the preferable molecular weight, glass transition temperature (Tg), and acid value.

Resin A in the present invention has a cycloaliphatic structure, an acidic group, the ethylenically unsaturated bond disposed via an ester group between a main chain, a separate repeating unit (copolymerization units) A terpolymer or higher copolymer is preferable from the viewpoint of deformation recovery rate, development residue, and reticulation when a pattern structure (for example, a spacer for a color filter) is formed.
Specifically, the resin A, the repeating unit having an alicyclic structure: and X (x mol%), recurring units having an acidic group: and Y (y mol%), the ester group between the main chain And a repeating unit having an ethylenically unsaturated bond arranged via: Z (z mol%), and a copolymer of at least terpolymer. Furthermore, you may have other repeating units: L (1 mol%) as needed.
Such copolymers have, for example, a monomer having an alicyclic structure, a monomer having an acidic group, an ethylenically unsaturated bond disposed via an ester group between the main chain It can be obtained by copolymerizing a monomer and, if necessary, another monomer. Among these, bulky functional group compressive modulus, in that the elastic recovery becomes better, as the monomer having at least before Kiabura ring structure, co-monomers represented by the general formula (4) by polymerization, when a group having an alicyclic structure is a copolymer which is introduced is preferred. In this case, the resin A has a structural unit derived from the monomer represented by the general formula (4) in the main chain.

The copolymer composition ratio when the resin A is a copolymer is determined in consideration of the glass transition temperature and the acid value. Although it cannot be generally stated, the following ranges can be adopted.
The composition ratio (x) of the repeating unit having a branched and / or alicyclic structure in the resin A is preferably 10 to 70 mol%, more preferably 15 to 65 mol%, and particularly preferably 20 to 60 mol%. When the composition ratio (x) is within the above range, good developability is obtained and the developer resistance of the image area is also good.
The composition ratio (y) of the repeating unit having an acidic group in the resin A is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and particularly preferably 20 to 50 mol%. When the composition ratio (y) is within the above range, good curability and developability can be obtained.
The composition ratio (z) of the repeating unit having an “ethylenically unsaturated bond arranged through an ester group with the main chain” in the resin A is preferably 10 to 70 mol%, and preferably 20 to 70 mol%. More preferably, 30 to 70 mol% is particularly preferable. When the composition ratio (z) is within the above range, the pigment dispersibility is excellent, the sensitivity and the polymerization curability are good, the liquid storage stability after preparation, and the dry film state after application are maintained for a long time. The stability over time is improved.
Further, as the resin A, the composition ratio (x) is 10 to 70 mol% (more preferably 15 to 65 mol%, particularly 20 to 50 mol%), and the composition ratio (y) is 5 to 70 mol%. % (Further 10 to 60 mol%, especially 30 to 70 mol%) and the composition ratio (z) is 10 to 70 mol% (further 20 to 70 mol%, especially 30 to 70 mol%). Is preferred.

  As mentioned above, although the preferable form of resin A was demonstrated, as a preferable form of the photosensitive resin composition of this invention, the preferable form of the said resin A is used as resin, The said exemplary compound M-1 to M as a specific polymerizable compound The form using -7 is preferable. When the photosensitive resin composition of this invention is comprised in this way, the effect by this invention will be show | played more effectively.

  When the photosensitive resin composition of this invention contains the said resin A, as content in the photosensitive resin composition, 5-70 mass% is preferable with respect to the total solid of a composition, 10-50 mass % Is more preferable.

<Photopolymerization initiator>
The photosensitive resin composition of the present invention contains at least one photopolymerization initiator.
There is no limitation in particular as a photoinitiator in this invention, A well-known photoinitiator can be used. Known photopolymerization initiators include, for example, the start described in paragraphs [0010] to [0020] of JP-A-2006-23696 and paragraphs [0027] to [0053] of JP-A-2006-64921. An agent can be mentioned. As examples of known photopolymerization initiators, aminoacetophenone compounds, acylphosphine oxide compounds, and oxime ester compounds other than those described above are preferable in terms of sensitivity.
Specific examples of the aminoacetophenone compound include IRGACURE (Irg) 907 (manufactured by Ciba Specialty Chemicals Co., Ltd.). Specific examples of the acylphosphine oxide compound include DAROCUR TPO, Irgacure (Irg) 819 (manufactured by Ciba Specialty Chemicals Co., Ltd.), and the like. Specific examples of the oxime ester compound include IRGACURE (Irg) OXE01, CGI242 and the like (manufactured by Ciba Specialty Chemicals Co., Ltd.). The structures of these initiators are shown below.

  0.5-25 mass% is preferable with respect to the total solid of the photosensitive resin composition, and, as for the total amount in the photosensitive resin composition of a photoinitiator, 1-20 mass% is more preferable.

<Fine particles>
The photosensitive resin composition in the present invention preferably contains at least one fine particle in terms of mechanical strength together with the resin, the polymerizable compound, and the photopolymerization initiator.
The fine particles are not particularly limited and may be appropriately selected depending on the intended purpose. For example, extender pigments described in JP-A-2003-302039 [0035] to [0041] are preferable, and among them, good development is preferable. Colloidal silica is preferable from the viewpoint of obtaining a photospacer having good properties and mechanical strength.

  The average particle diameter of the fine particles is preferably 5 to 50 nm, and more preferably 10 to 40 nm in that a high mechanical strength can be obtained when forming a structure that is susceptible to external force such as a photospacer. It is particularly preferably 15 to 30 nm.

  The content of the fine particle photosensitive resin composition (when forming the photospacer, the photospacer (or the photosensitive resin layer constituting the photospacer) is a photosensitive resin from the viewpoint of obtaining a photospacer having high mechanical strength. The total solid content (mass) in the composition is preferably 5 to 50 mass%, more preferably 10 to 40 mass%, and particularly preferably 15 to 30 mass%.

<Others>
In addition to the resin, the specific polymerizable compound, the photopolymerization initiator, and the fine particles contained as necessary, the photosensitive resin composition in the present invention further contains other components such as a photopolymerization initiation aid as necessary. May be included.

  The photosensitive resin composition may use a photopolymerization initiation assistant in combination as another additive component. The photopolymerization initiation assistant can be used in combination with a photopolymerization initiator in order to promote polymerization of a polymerizable compound that has been polymerized by the photopolymerization initiator. As the photopolymerization initiation assistant, it is preferable to use at least one amine compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4 Examples include '-bis (ethylmethylamino) benzophenone, and 4,4'-bis (diethylamino) benzophenone is particularly preferable. Further, a plurality of amine-based and other photopolymerization initiation assistants may be used in combination.
Examples of other photopolymerization initiation assistants other than the above include alkoxyanthracene compounds, thioxanthone compounds, and coumarin compounds. Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. It is done. Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.
Moreover, a commercially available thing can also be used as a photoinitiation adjuvant. Examples of commercially available photopolymerization initiation assistants include trade name “EAB-F” (manufactured by Hodogaya Chemical Co., Ltd.).

  As content in the photosensitive resin composition of a photoinitiator adjuvant, 0.6 mass part or more and 20 mass parts or less are preferable with respect to 1 mass part of said photoinitiator, 1 mass part or more and 15 mass parts. Part or less is more preferable, and 1.5 parts by weight or more and 15 parts by weight or less is particularly preferable.

  Further, as other components, they can be selected from components constituting a known composition and used, for example, paragraph numbers [0010] to [0020] of JP-A-2006-23696 and JP-A-2006-64921. Ingredients listed in paragraphs [0027] to [0053] of the gazette.

  The photosensitive resin composition of the present invention can be suitably used for forming a photo spacer, a colored pattern, a protective film, which will be described later, a separation wall (for example, a black matrix), an alignment control protrusion, and the like. It can be suitably used for the formation of pattern structures and coatings.

≪Photospacer and its formation method≫
The photospacer of the present invention is formed using the above-described photosensitive resin composition of the present invention. Details and preferred embodiments of the photosensitive resin composition are as described above.
Since the photospacer of the present invention is constituted by using the photosensitive resin composition of the present invention, the cross-sectional shape uniformity and the height uniformity are excellent (that is, the cross-sectional shape variation and the height variation).
Further, when the photosensitive resin composition of the present invention contains the resin A, a photospacer having a high compression modulus and deformation recovery required as a photospacer can be obtained.

In the present invention, the pattern structure such as a photo spacer is “excellent in the uniformity of the cross-sectional shape”. The shape of the cross-sectional shape of the pattern structure is almost rectangular at a plurality of positions (preferably three or more) in the substrate. The state which becomes is preferable.
As the shape close to the rectangle, in the cross section of the pattern structure, an angle formed by a line corresponding to the side surface of the pattern structure and a line corresponding to the bottom surface of the pattern structure (hereinafter also referred to as “taper angle”) is 40 ° or more. A shape that is 100 ° or less is more preferable.
Here, the lower surface of the pattern structure means a contact surface of the surface of the pattern structure with the base on which the pattern structure is formed. Further, the side surface of the pattern structure is a pattern structure upper surface (a surface parallel to the lower surface of the pattern structure and not in contact with the base) among the surfaces of the pattern structure. Also refers to a surface that does not fall under.

The photospacer of the present invention may be formed by any method as long as it is a method using the photosensitive resin composition of the present invention, but it is a method comprising the following steps (i) to (c) (this It can be most suitably formed by using the photospacer forming method of the invention.
The method for forming a photospacer of the present invention comprises (a) a step of forming a film of the above-described photosensitive resin composition of the present invention on a substrate (hereinafter also referred to as “film formation step”), and (b). A step of exposing at least a part of the coating (hereinafter also referred to as “exposure step”) and (c) a step of developing the coating after exposure (hereinafter also referred to as “development step”) are provided. If necessary, (d) a step of heating the coating after development (hereinafter also referred to as “coating heating step”) and other steps may be provided.

(A) Film formation process A film formation process forms the film of the photosensitive resin composition of this invention as stated above on a board | substrate. A photosensitive resin layer can be formed as a film, and this photosensitive resin layer constitutes a photospacer that can maintain a uniform cell thickness by passing through other steps such as an exposure step and a development step described later. By using the photospacer of the present invention, display unevenness in an image in a display device (particularly a liquid crystal display device) that tends to cause display unevenness due to a change in cell thickness is effectively eliminated.

  As a method for forming a photosensitive resin layer on a substrate, (a) a coating method in which a photosensitive resin composition containing at least the above-described resin, polymerizable compound, and photopolymerization initiator is applied, and (b) the above-mentioned A transfer method in which a photosensitive transfer material having a photosensitive resin layer is used, and the photosensitive resin layer is laminated and transferred by heating and / or pressurization is preferable.

(A) Application method The photosensitive resin composition is applied by a known application method such as spin coating, curtain coating, slit coating, dip coating, air knife coating, roller coating, or wire bar coating. , A gravure coating method, or an extrusion coating method using a popper described in US Pat. No. 2,681,294. Among them, JP 2004-89851 A, JP 2004-17043 A, JP 2003-170098 A, JP 2003-164787 A, JP 2003-10767 A, JP 2002-79163 A, A method using a slit nozzle or a slit coater described in JP 2001-310147 A is suitable.

(B) Transfer method Transfer is performed using a photosensitive transfer material, for example, a roller or flat plate in which a photosensitive resin layer formed in a film shape on a temporary support is heated and / or pressed on a desired substrate surface. Then, the photosensitive resin layer is transferred onto the substrate by peeling off the temporary support. Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From the viewpoint, it is preferable to use the method described in JP-A-7-110575.

In the case of forming the photosensitive resin layer, an oxygen blocking layer (hereinafter also referred to as “oxygen blocking film” or “intermediate layer”) can be further provided between the photosensitive resin layer and the temporary support. Thereby, exposure sensitivity can be improved. In order to improve transferability, a thermoplastic resin layer having cushioning properties may be provided.
Paragraph numbers [0024] to [0024] of Japanese Patent Application Laid-Open No. 2006-23696 describe the temporary support, the oxygen-blocking layer, the thermoplastic resin layer, and other layers constituting the photosensitive transfer material and the method for producing the photosensitive transfer material. The structure and manufacturing method described in [0030] can be applied.

  When the photosensitive resin layer is formed by both the coating method (a) and the transfer method (b), the layer thickness is preferably 0.5 to 10.0 μm, and more preferably 1 to 6 μm. When the layer thickness is in the above range, the generation of pinholes during the formation of coating during production is prevented, and development and removal of unexposed portions can be performed without requiring 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 plastics substrate), a substrate with a transparent conductive film (for example, an ITO film), a substrate with a color filter (also referred to as a color filter substrate), and the like. Examples thereof include a drive substrate with a drive element (for example, a thin film transistor [TFT]). 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 part of the coating formed in the coating formation step is exposed to form a latent image. In the subsequent development step, the coating film exposed in the exposure step can be developed to form a spacer pattern having a desired shape.

  Specific examples of these processes include the formation examples described in paragraphs [0071] to [0077] of JP-A-2006-64921, and paragraph numbers [0040] to [0051] of JP-A-2006-23696. The process described in 1 can be given as a suitable example in the present invention.

The method for forming a photospacer of the present invention may be provided with a film heating step described later (d), but without providing a film heating step by increasing the exposure amount in the exposure (hereinafter referred to as “heating step”). It is also possible to form a photo spacer having excellent cross-sectional shape uniformity and excellent height uniformity.
By setting “no heating process”, it is possible to more effectively suppress the deterioration of the photo spacer to be formed and the deterioration of the already formed pattern structure (colored pattern, etc.) and protective film.
As an exposure amount in the case of “no heating step”, 1 to 500 mJ / cm ² is preferable, and 10 to 300 mJ / cm ² is preferable.

(D) Film heating step The photospacer forming method of the present invention may include a film heating step of heating the film after development in the development step. By heating, curing of the film is further promoted, and a photospacer having high strength is obtained. Moreover, when the photosensitive resin composition contains the resin A, a photospacer having a good compressive modulus and elastic recoverability can be obtained.

Here, the maximum temperature in heating varies depending on the heating time, but is preferably 40 ° C to 145 ° C, more preferably 40 ° C to 140 ° C, and particularly preferably 80 ° C to 140 ° C. . When the maximum temperature is within a range of 40 ° C. to 145 ° C., the deterioration of the photo spacer to be formed, and the deterioration of the already formed pattern structure (colored pattern, etc.) and protective film are more effectively suppressed. it can.
Especially, it is more preferable that the maximum temperature in heating is 80 ° C. to 140 ° C., and the heating time is 0.1 hour to 3.0 hours (more preferably 0.2 hour to 1 hour).

  As described above, a display device substrate including a photospacer on a substrate can be manufactured. The photo spacer is preferably formed on a black light shielding portion such as a black matrix formed on the substrate or on a driving element such as a TFT. Further, 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, a driving element such as a TFT, and a photo spacer.

For example, when the photo spacer is provided on the black light shielding portion or the driving element, the black light shielding portion (black matrix or the like) or the driving element previously disposed on the substrate is covered with, for example, a photosensitive transfer material. A photosensitive resin layer is laminated on the support surface, peeled and transferred to form a photosensitive resin layer, which is then subjected to exposure, development, heat treatment, etc. to form a photo spacer, thereby producing a display device substrate. can do.
The display device substrate may further be provided with colored pixels of three colors such as red (R), blue (B), and green (G) as necessary.

The photospacer of the present invention can be formed after forming a color filter including a black shielding portion such as a black matrix and a colored portion such as a colored pixel.
The black shielding part and the colored part and the photo spacer are a combination of an application method for applying a photosensitive resin composition and a transfer method using a transfer material having a photosensitive resin layer made of a photosensitive resin composition. It is possible to form.
The black shielding part, the colored part, and the photospacer can each be formed from a photosensitive resin composition. Specifically, for example, the photosensitive resin layer is formed by directly applying the liquid photosensitive resin composition to a substrate. After the formation, exposure / development is performed to form the black shielding part and the colored part in a pattern, and then the photosensitive resin composition of another liquid is different from the substrate (temporary support). Using a transfer material prepared by forming a photosensitive resin layer on the surface, this transfer material was brought into close contact with the substrate on which the black shielding portion and the colored portion were formed to transfer the photosensitive resin layer. Later, by performing exposure and development, the photospacer can be formed in a pattern.
In this manner, a color filter provided with a photospacer can be manufactured.

≪Protective film≫
The protective film of the present invention is formed using the above-described photosensitive resin composition of the present invention.
Since the protective film of the present invention is constituted by using the photosensitive resin composition of the present invention, it is excellent in film thickness uniformity even when formed at a low heating temperature or without heat treatment.

  The protective film of the present invention may be formed by any method as long as it is a method using the photosensitive resin composition of the present invention, but is formed by a method similar to the method for forming the photospacer of the present invention described above. it can. Here, when the protective film is not patterned, that is, when the protective film is formed as a so-called solid film, a method of exposing the entire surface of the film in the (b) exposure step is preferable.

≪Coloring pattern≫
The colored pattern of the present invention is formed using the above-described photosensitive resin composition of the present invention. Here, it is preferable that the photosensitive resin composition further contains at least one colorant in addition to the components described above.
The colorant is not particularly limited and can be appropriately selected from known colorants. Specific examples of the known colorant include pigments and dyes described in JP-A-2005-17716 [0038] to [0054] and JP-A-2004-361447 [0068] to [0072]. And pigments described in JP-A-2005-17521 [0080] to [0088].

Since the colored pattern of the present invention is formed using the photosensitive resin composition of the present invention, the cross-sectional shape uniformity and film thickness uniformity are excellent even when formed at a low heating temperature or without heat treatment.
In addition, when the coloring pattern of the present invention is used as one element of a color filter having a plurality of colored patterns, it is sufficient that at least one colored pattern is formed using the photosensitive resin composition of the present invention. .

  The colored pattern of the present invention may be formed by any method as long as it is a method using the photosensitive resin composition of the present invention. For example, the same method as the method for forming a photospacer of the present invention described above is used. Can be formed.

≪Display device substrate≫
The display device substrate of the present invention includes at least one of the photospacer of the present invention, the protective film of the present invention, and the colored pattern of the present invention.
The substrate for a display device of the present invention is a structure formed using the photosensitive resin composition of the present invention and having a good cross-sectional shape and uniform film thickness (height) (the photo spacer of the present invention, the present invention Since at least one of the protective film and the coloring pattern of the present invention (hereinafter the same) is provided, display unevenness can be suppressed when used in a display device.

Here, the display device substrate refers to at least one of a pair of supports for constituting the display device.
Specific examples of the display device substrate vary depending on the configuration of the display element and the display device. For example, a color filter substrate having a colored pattern (hereinafter, also referred to as “colored pixel”), and a driving unit having a driving unit. Substrates (for example, simple matrix substrates, active matrix substrates, etc.), substrates with separation walls (for example, substrates with black matrix having a black matrix, etc.), both coloring patterns and driving means Examples thereof include a color filter-on-array substrate, a glass substrate on which a pattern structure or a film is not provided.

  The colored pattern group (colored pixel group) of the color filter substrate may be composed of two-color pixels exhibiting different colors, or may be composed of three-color pixels, four-color pixels or more. For example, in the case of three colors, it is composed of three hues of red (R), green (G), and blue (B). When arranging pixel groups of three colors of RGB, arrangement of mosaic type, triangle type, etc. is preferable, and when arranging pixel groups of four colors or more, any arrangement may be used. For producing the color filter substrate, for example, a black matrix may be formed as described above after forming a pixel group of two or more colors, or conversely, a pixel group may be formed after forming a black matrix. Good. Regarding the formation of RGB pixels, JP 2004-347831 A can be referred to.

≪Display element≫
A display element can be formed using the substrate for a display device of the present invention.
As one of the display elements, a liquid crystal layer and a liquid crystal driving means (including a simple matrix driving method and an active matrix driving method) are provided between a pair of supports (including a display device substrate) at least one of which is transparent. The liquid crystal display element provided at least is mentioned.

  In the case of this liquid crystal display element, the substrate for a display device can be used as a color filter substrate having a plurality of RGB pixel groups and each pixel constituting the pixel group being separated from each other by a black matrix. Since this color filter substrate is provided with a structure having a good cross-sectional shape and uniform film thickness (height), a liquid crystal display element including the color filter substrate is provided between the color filter substrate and the counter substrate. It is possible to effectively prevent the occurrence of display unevenness such as color unevenness due to uneven distribution of liquid crystal material due to fluctuations in cell gap (cell thickness) and low temperature foaming. Thereby, the produced liquid crystal display element can display a vivid image.

  Further, as a more detailed aspect of the liquid crystal display element, at least one of them includes a liquid crystal layer and a liquid crystal driving means between a pair of transparent substrates (including a substrate for a liquid crystal display device), Include an active element (for example, TFT), and a pair of substrates is regulated to a predetermined width by a photo spacer.

≪Display device≫
The display device of the present invention includes the display device substrate described above.
Since the display device of the present invention includes the display device substrate of the present invention provided with a structure having good cross-sectional shape uniformity and film thickness (height) uniformity, display unevenness is suppressed.

  Examples of the display device include display devices such as a liquid crystal display device, a plasma display display device, an EL display device, and a CRT display device. For the definition of display devices and explanation of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, published by Kogyo Kenkyukai 1990)”, “Display Device (written by Junaki Ibuki, Industrial Books Co., Ltd.) Issued in the first year).

Among the display devices, a liquid crystal display device is preferable.
In a liquid crystal display device, for example, a pair of substrates arranged to face each other is regulated to a predetermined width by a photo spacer, and a liquid crystal material is enclosed in the regulated gap (an enclosed portion is referred to as a liquid crystal layer). Thus, the thickness of the liquid crystal layer (cell thickness) is maintained at a desired uniform thickness.

  The liquid crystal display mode in the liquid crystal display device includes STN type, TN type, GH type, ECB type, ferroelectric liquid crystal, antiferroelectric liquid crystal, VA type, IPS type, OCB type, ASM type, and various other types. Preferably mentioned. Among them, in the liquid crystal display device of the present invention, from the viewpoint of exhibiting the effect of the present invention most effectively, a display mode that easily causes display unevenness due to fluctuations in the cell thickness of the liquid crystal cell is desirable, and the cell thickness is 2 to 4 μm. The VA display mode, the IPS display mode, and the OCB display mode are preferably configured.

  Examples of the liquid crystal that can be used in the present invention include nematic liquid crystal, cholesteric liquid crystal, smectic liquid crystal, and ferroelectric liquid crystal.

  The basic configuration of the liquid crystal display device includes: (a) a driving side substrate in which driving elements such as thin film transistors (TFTs) and pixel electrodes (conductive layers) are arranged; and a counter electrode (conductive layer). The counter substrate is arranged to be opposed to each other with a photo spacer interposed therebetween, and a liquid crystal material is sealed in the gap, and (b) the driving substrate and the counter substrate having the counter electrode (conductive layer) are arranged as a photo spacer. The liquid crystal display device of the present invention can be suitably applied to various types of liquid crystal display devices.

  The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, side industry research committee, published in 1994)”. The liquid crystal display device of the present invention is not particularly limited except that it includes the liquid crystal display element of the present invention. For example, the liquid crystal display device can be configured as various types of liquid crystal display devices described in the “next-generation liquid crystal display technology”. . In particular, it is effective in constructing a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., issued in 1996)”.

The liquid crystal display device includes an electrode substrate, a polarizing film, a retardation film, a backlight, a photo spacer, and the like except that it includes the photo spacer, the coloring pattern, the protective film, the substrate for the liquid crystal display device, and the liquid crystal display element. It can generally be configured using various members such as a viewing angle compensation film, an antireflection film, a light diffusion film, and an antiglare film. Regarding these members, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima, CMC Co., Ltd., published in 1994)”, “Current Status and Future Prospects of the 2003 Liquid Crystal Related Market (Part 2)” (Fuji Chimera Research Institute, Inc., 2003, etc.) ”.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.

  The weight average molecular weight was measured by gel permeation chromatography (GPC). GPC uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel, Super Multipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) as columns, and THF (tetrahydrofuran) as an eluent. ) Was used. The conditions were as follows: the sample concentration was 0.35 / min, the flow rate was 0.35 ml / min, the sample injection amount was 10 μl, the measurement temperature was 40 ° C., and an IR detector was used. In addition, the calibration curve is “standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, It produced from eight samples of "A-2500", "A-1000", and "n-propylbenzene".

<Synthesis of Resin A>
First, resin A (Exemplary compounds P-52, P-53, P-54, P-46, P-48, P-3) was synthesized as a resin in the photosensitive resin composition.

(Synthesis of Exemplified Compound P-52)
In the reaction vessel, 7.48 parts of 1-methoxy-2-propanol (MFG, manufactured by Nippon Emulsifier Co., Ltd.) was added in advance, the temperature was raised to 90 ° C., 3.1 parts of styrene (St), tricyclopentenyl meta Acrylate (TCPD-M; manufactured by Hitachi Chemical Co., Ltd.) 4.28 parts, methacrylic acid (MAA; y) 11.7 parts, azo polymerization initiator (Wako Pure Chemical Industries, Ltd., V-601) ) A mixed solution consisting of 2.08 parts and 55.2 parts of 1-methoxy-2-propanol was dropped into a 90 ° C. reaction vessel over 2 hours under a nitrogen gas atmosphere. After dripping, it was made to react for 4 hours and the acrylic resin solution was obtained.
Next, 0.15 part of hydroquinone monomethyl ether and 0.34 part of tetraethylammonium bromide were added to the acrylic resin solution, and then 26.4 parts of glycidyl methacrylate (GLM, manufactured by Tokyo Chemical Industry Co., Ltd.) was added for 2 hours. (GLM-MAA; z). After dripping, after reacting at 90 ° C. for 4 hours while blowing air, a solvent 1-methoxy-2-propyl acetate (MMPGAc, manufactured by Daicel Chemical Industries, Ltd.) is added so that the solid concentration is 45%. A resin solution of an exemplary compound P-52 (resin A) obtained by adding a structural unit derived from styrene to an exemplary compound P-51 described later having an unsaturated group (solid content acid value; 76.0 mgKOH / g, Mw; 25,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution) (x: y: z: St = 30 mol%: 27 mol%: 37 mol%: 6 mol%) .
Here, GLM-MAA indicates a compound in which glycidyl methacrylate is bonded to methacrylic acid (the same applies hereinafter).
In addition, molecular weight Mw of exemplary compound P-52 showed the weight average molecular weight, and the measurement of the weight average molecular weight was performed using the gel permeation chromatograph method (GPC method) (hereinafter the same).

(Synthesis of Exemplified Compound P-53)
In the synthesis of Exemplified Compound P-52, without using styrene, tricyclopentenyl methacrylate was replaced with dicyclopentenyloxyethyl acrylate (Fanacryl FA-512A manufactured by Hitachi Chemical Co., Ltd.), and Exemplified Compound P-53 The amount of FA-512A (x), methacrylic acid (y), GLM-MAA (z) added so that x: y: z is 46.2 mol%: 24.3 mol%: 29.5 mol% The compound solution was synthesized by the same method as the synthesis of Exemplified Compound P-52, and the resin solution of Exemplified Compound P-53 (Resin A) having an unsaturated group (solid content acid value: 71.2 mgKOH / g) Mw; 25,500, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution).

(Synthesis of Exemplified Compound P-54)
In the synthesis of Exemplified Compound P-52, tricyclopentenyl methacrylate was replaced with dicyclopentenyl acrylate (Fanacryl FA-511A manufactured by Hitachi Chemical Co., Ltd.), and x: y: z in Exemplified Compound P-54: Except for changing the addition amount of FA-511A (x), methacrylic acid (y), GLM-MAA (z), and styrene (St) so that St becomes 25 mol%: 25 mol%: 40 mol%: 10 mol%. The resin solution of the exemplified compound P-54 (resin A) having an unsaturated group (solid content acid value: 78.7 mgKOH / g, Mw; 28, 000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution).

(Synthesis of Exemplified Compound P-46)
In the synthesis of the exemplified compound P-52, the composition x: y: z: St is obtained by replacing tricyclopentenyl methacrylate with ADMA (manufactured by Idemitsu Kosan Co., Ltd.) and adding a structural unit derived from styrene to the compound P-1. Exemplified Compound P-, except that the addition amounts of ADMA (x), methacrylic acid (y), GLM-MAA (z), and styrene were changed so as to be 30 mol%: 24 mol%: 38 mol%: 8 mol%. 52. Resin solution (solid content acid value; 1 mg KOH / g, Mw; 29,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution).

(Synthesis of Exemplified Compound P-48)
In the synthesis of the exemplified compound P-52, the composition x: y: z: St is 40 mol%: 23 mol% in which tricyclopentenyl methacrylate is replaced with norbornyl methacrylate and a structural unit derived from styrene is added to the compound P-2: 35 mol%: Same as the synthesis of Exemplified Compound P-52, except that the addition amounts of norbornyl methacrylate (x), methacrylic acid (y), GLM-MAA (z), and styrene were changed so as to be 2 mol%. A resin solution of the exemplified compound P-48 (resin A) obtained by adding a structural unit derived from styrene to the compound P-2 having an unsaturated group (solid content acid value; 67.7 mgKOH / g, Mw; 12,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution).

(Synthesis of Exemplified Compound P-3)
In the synthesis of the exemplary compound P-52, styrene is not used and tricyclopentenyl methacrylate is replaced with cyclohexyl methacrylate so that x: y: z in the exemplary compound P-3 is 45 mol%: 20 mol%: 35 mol%. In addition, except that the addition amount of cyclohexyl methacrylate (x), methacrylic acid (y), and GLM-MAA (z) was changed, the unsaturated group was synthesized by the same method as the synthesis of Exemplified Compound P-52. Resin solution of the exemplified compound P-3 (resin A) having a solid content acid value: 74.0 mg KOH / g, Mw; 30,700, 45% 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate solution )

[ Reference Example 1 ]: Coating method <Preparation of color filter substrate>
A color filter having a black matrix, an R (red) pixel, a G (green) pixel, and a B (blue) pixel was produced by the method described in paragraph numbers [0084] to [0095] of JP-A-2005-3861. (Hereinafter, this is referred to as a color filter substrate). Here, the substrate size of the color filter substrate was set to 550 mm × 650 mm.
Next, a transparent electrode of ITO (Indium Tin Oxide) was further formed on the R pixel, G pixel, B pixel and black matrix of the obtained color filter substrate by sputtering.

<Formation of photo spacer>
On the ITO transparent electrode of the color filter substrate on which the ITO transparent electrode produced above was formed by sputtering, a coating solution for the photosensitive resin layer having the formulation shown in Table 1 below (formulation 1 in Reference Example 1) was applied using a spinner. A slit was applied. Subsequently, after part of the solvent was dried for 30 seconds using a vacuum dryer VCD (manufactured by Tokyo Ohka Kogyo Co., Ltd.) to eliminate the fluidity of the coating film, it was pre-baked on a 90 ° C. hot plate for 3 minutes to obtain a film thickness of 5 A photosensitive resin layer having a thickness of 2 μm was formed (film formation step).

Subsequently, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, a mask (quartz exposure mask having a circular pattern with a diameter of 15 μm), the mask and the photosensitive resin layer In a state where the color filter substrate placed so as to face each other is set up substantially in parallel and vertically, the distance between the mask surface and the surface of the photosensitive resin layer is set to 100 μm, and an intensity of 250 W at 365 nm is passed through the mask. / M ² was exposed to ultraviolet light transmitted through an ultraviolet transmission filter (UV-35, manufactured by Toshiba Glass Co., Ltd.) (exposure process, exposure amount 200 mJ / cm ² ).

  Next, a sodium carbonate-based developer (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, an anionic surfactant, an antifoaming agent, and a stabilizer Containing agent: Trade name: T-CD1 (manufactured by Fuji Film Co., Ltd.) diluted 10-fold with pure water, and shower-developed at 29 ° C. for 30 seconds at a cone type nozzle pressure of 0.15 MPa. An image was formed (development process). Subsequently, a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer; trade name: T-SD3 (Fuji Film Co., Ltd.)) diluted 10 times with pure water ) For 20 seconds at 33 ° C. with a cone-type nozzle pressure of 0.02 MPa, and the residue around the formed pattern image is removed to form a cylindrical spacer pattern with one spacer of 300 μm × 300 μm. It formed so that it might become a space | interval.

Next, the color filter substrate provided with the spacer pattern was subjected to a heat treatment at 130 ° C. for 60 minutes (heating step) to produce a photo spacer on the color filter substrate.
Here, about 1000 photo spacers obtained, using a three-dimensional surface structure analysis microscope (manufacturer: ZYGO Corporation, model: New View 5022), the top surface of the ITO transparent electrode (of the two surfaces parallel to the substrate, from the substrate) The distance from the far side) to the highest position of the photo spacer (hereinafter, this distance is also referred to as “the height of the photo spacer”) is measured, and the average value of 1000 photo spacers is determined as the average height of the photo spacer. did.
Moreover, the measurement of the bottom area of the obtained photospacer was performed using the SEM photograph. As a result, it was a cylindrical shape having a diameter of 15.1 μm and an average height of 4.7 μm.

<Production of liquid crystal display device>
Separately, a glass substrate was prepared as a counter substrate, and the PVA mode was patterned on the transparent electrode and the counter substrate of the color filter substrate obtained above, and an alignment film made of polyimide was further provided thereon.

  After that, a UV curable resin sealant is applied by a dispenser method at a position corresponding to the outer periphery of the black matrix provided so as to surround the pixel group of the color filter, and a liquid crystal for PVA mode is dropped and attached to the counter substrate. After bonding, the bonded substrate was irradiated with UV, and then heat-treated to cure the sealant. Polarizing plates HLC2-2518 manufactured by Sanlitz Co., Ltd. were attached to both surfaces of the liquid crystal cell thus obtained.

  Next, FR1112H (chip type LED manufactured by Stanley Electric Co., Ltd.) as a red (R) LED, DG1112H (chip type LED manufactured by Stanley Electric Co., Ltd.) as a green (G) LED, and DB1112H (as a blue (B) LED. A side-light type backlight was constructed using a chip-type LED manufactured by Stanley Electric Co., Ltd. and placed on the back side of the liquid crystal cell provided with the polarizing plate to obtain a liquid crystal display device.

<Evaluation>
The following evaluation was performed on the obtained photospacer and liquid crystal display device. The results of measurement evaluation are shown in Table 2 below.

(Photo spacer cross-sectional shape)
The cross-sectional shape of the photospacer after the heat treatment obtained in <Formation of photospacer> was observed using a scanning electron microscope. The observation was performed at a total of five locations including four locations (four corners) at the periphery of the substrate and one location at the center of the substrate.
Furthermore, the cross-sectional shape of the photo spacer was evaluated according to the following criteria.

~Evaluation criteria~
A: Photospacers having a cross-sectional shape with a taper angle of 45 ° or more and 90 ° or less were formed at all five locations.
B: Photo spacers having a cross-sectional shape with a taper angle of 45 ° or more and 95 ° or less were formed at all five locations, but did not fall under A above.
C: Photospacers having a cross-sectional shape with a taper angle of 40 ° or more and 100 ° or less were formed at all five locations, but none of the above A and B was applicable.
D: Photo spacers outside the range of the taper angle of 40 ° or more and 100 ° or less were formed at 1 to 4 out of 5 locations.
E: Photo spacers outside the range of the taper angle of 40 ° or more and 100 ° or less were formed at all five locations.

(Photo spacer height uniformity)
The difference between the maximum value and the minimum value was calculated from the result of the height of 1000 photospacers measured in <Formation of Photospacer> and evaluated according to the following criteria.
The smaller the difference, the better the uniformity.

~Evaluation criteria~
A: The difference between the maximum value and the minimum value of the height of the photospacer was less than 0.2 μm.
B: The difference between the maximum value and the minimum value of the height of the photospacer was 0.2 μm or more and less than 0.3 μm.
C: The difference between the maximum value and the minimum value of the height of the photospacer was 0.3 μm or more and less than 0.4 μm.
D: The difference between the maximum value and the minimum value of the height of the photo spacer was 0.4 μm or more and less than 0.5 μm.
E: The difference between the maximum value and the minimum value of the height of the photo spacer was 0.5 μm or more.

(Evaluation of heat treatment conditions)
The heat treatment conditions were evaluated according to the following procedure.
First, for the evaluation having a spacer pattern, after the residue treatment and before the heat treatment, in the same manner as in the above <photo spacer formation> except that the exposure was changed to 250 mJ / cm ² and the exposure was performed. A sample was made.
About the obtained sample for evaluation, when the heat treatment is not performed, and when the heat treatment is performed by changing the heating temperature in various ways (the heat treatment time is fixed at 60 minutes), the cross-sectional shape of the photo spacer and the photo spacer The height uniformity was evaluated. The method for evaluating the cross-sectional shape of the photospacer and the height uniformity of the photospacer 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 heat treatment conditions were evaluated according to the following criteria.
In the following criteria, the “excellent uniformity in cross-sectional shape” state refers to a state of A, B, or C in the evaluation criteria for the cross-sectional shape of the photospacer.
Further, in the following criteria, the “excellent height uniformity” state refers to a state of A, B, or C in the evaluation standard for the height uniformity of the photospacer.

~Evaluation criteria~
A: A spacer pattern excellent in uniformity in cross-sectional shape and uniformity in height was obtained without heat treatment.
B: A spacer pattern excellent in uniformity in cross-sectional shape and uniformity in height was obtained at a heating temperature of less than 80 ° C.
C: A spacer pattern excellent in uniformity in cross-sectional shape and uniformity in height was obtained at a heating temperature of 80 ° C. or higher and lower than 150 ° C.
D: A spacer pattern excellent in uniformity in cross-sectional shape and uniformity in height at a heating temperature of 150 ° C. or higher and lower than 200 ° C. was obtained.
E: A spacer pattern excellent in uniformity in cross-sectional shape and uniformity in height was obtained at a heating temperature of 200 ° C. or higher.

(Deformation recovery rate)
The obtained photo spacer was measured and evaluated by a micro hardness tester (DUH-W201, manufactured by Shimadzu Corporation) as follows. The measurement was performed by a load-unloading test method using a frustum-type indenter with a diameter of 50 μm, a maximum load of 50 mN, and a holding time of 5 seconds. From this measured value, the deformation recovery rate [%] was obtained by the following formula and evaluated according to the following evaluation criteria. The measurement was performed in an environment of 22 ± 1 ° C. and 50% RH.
Deformation recovery rate (%)
= (Recovery amount after release of load [μm] / Deformation amount under load [μm]) × 100

~Evaluation criteria~
A: The deformation recovery rate was 90% or more.
B: The deformation recovery rate was 87% or more and less than 90%.
C: The deformation recovery rate was 85% or more and less than 87%.
D: Deformation recovery rate was 80% or more and less than 85%.
E: Deformation recovery rate was 75% or more and less than 80%.
F: Deformation recovery rate was less than 75%.

(Display unevenness of liquid crystal display device)
About the liquid crystal display device produced above, the gray display when a gray test signal was input was visually observed, and the presence or absence of display unevenness was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 2 below.

~Evaluation criteria~
A: There was no display unevenness and a very good display image was obtained.
B: Although the edge portion of the glass substrate was slightly uneven, the display image was good without affecting the display portion.
C: Slight unevenness was observed in the display portion, but it was within a practically acceptable range.
D: Unevenness was observed in the display section.

[Examples 2-7, 9-12 , 19 , Reference Example 2 ]: Coating method Photo spacer and liquid crystal display device in the same manner as Reference Example 1 except that the type of polymerizable compound was changed as shown in Table 2 below. Was made.
In addition, the prescription of the photosensitive resin composition is the said prescription 1 about Example 2-7 , 9-12 , the reference example 2 , and the said prescription 4 about Example 19. FIG.
The obtained photospacer and liquid crystal display device were evaluated in the same manner as in Reference Example 1 . The evaluation results are shown in Table 2.

[Examples 13 to 16, Reference Example 3 ]: Coating Method Photospacers and liquid crystal display devices were produced in the same manner as Reference Example 1 except that the type of resin was changed as shown in Table 2 below.
In addition, the prescription of the photosensitive resin composition is the said prescription 1 about Examples 13-16, and is the said prescription 2 about the reference example 3. FIG.
The obtained photospacer and liquid crystal display device were evaluated in the same manner as in Reference Example 1 . The evaluation results are shown in Table 2.

[Example 18]: Transfer method The photosensitive resin composition was changed to the formulation 3 in Table 1, and transfer using the photosensitive transfer film for spacers shown below was performed to form a photosensitive resin layer. Except for this, a photospacer and a liquid crystal display device were produced in the same manner as in Reference Example 1 . The obtained photospacer was cylindrical. The obtained photospacer and liquid crystal display device were evaluated in the same manner as in Reference Example 1 . The evaluation results are shown in Table 2.

<Preparation of photosensitive transfer film for spacer>
On a polyethylene terephthalate film temporary support (PET temporary support) having a thickness of 75 μm, a thermoplastic resin layer coating solution having the following formulation A is applied and dried to form a thermoplastic resin layer having a dry layer thickness of 15.0 μm. did.

~ Prescription A of coating solution for thermoplastic resin layer ~
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer 25.0 parts (= 55 / 11.7 / 4.5 / 28.8 [molar ratio], weight average molecular weight 90,000)
-Styrene / acrylic acid copolymer: 58.4 parts (= 63/37 [molar ratio], weight average molecular weight 8,000)
2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane
39.0 parts, surfactant 1 below 10.0 parts methanol 90.0 parts 1-methoxy-2-propanol 51.0 parts methyl ethyl ketone 700 parts

* Surfactant 1
・ The following structure 1… 30%
・ Methyl ethyl ketone 70%

  Next, on the formed thermoplastic resin layer, an intermediate layer coating solution having the following formulation B was applied and dried to laminate an intermediate layer having a dry layer thickness of 1.5 μm.

~ Prescription B of coating solution for intermediate layer ~
Polyvinyl alcohol: 3.22 parts (PVA-205 (saponification rate 80%), manufactured by Kuraray Co., Ltd.)
・ Polyvinylpyrrolidone: 1.49 parts (PVP K-30, manufactured by ISP Japan Co., Ltd.)
・ Methanol: 42.3 parts ・ Distilled water: 524 parts

  Next, a photosensitive resin layer coating solution having the formulation 3 shown in Table 1 was further applied and dried on the formed intermediate layer to laminate a photosensitive resin layer having a dry layer thickness of 5.0 μm.

  As described above, after forming a laminated structure of PET temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer (total thickness of three layers: 21.5 μm), the surface of the photosensitive resin layer is formed. Further, a polypropylene film having a thickness of 12 μm was applied as a cover film by heating and pressing to obtain a photosensitive transfer film for spacers.

<Production of photo spacer>
The cover film of the obtained photosensitive transfer film for spacer was peeled off, and the ITO transparent electrode of the color filter substrate on which the ITO transparent electrode produced in the same manner as in Example 1 was formed by sputtering on the exposed surface of the photosensitive resin layer. The film was laminated on top and laminated using a laminator Lamic II type (manufactured by Hitachi Industries, Ltd.) under a linear pressure of 100 N / cm and a pressurization / heating condition of 130 ° C. at a conveyance speed of 2 m / min. Thereafter, the PET temporary support was peeled and removed at the interface with the thermoplastic resin layer, and the photosensitive resin layer was transferred together with the thermoplastic resin layer and the intermediate layer (film formation step).

Subsequently, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, the mask (quartz exposure mask having an image pattern) and the mask and the thermoplastic resin layer face each other. The distance between the mask surface and the surface of the photosensitive resin layer on the side in contact with the intermediate layer is set to 100 μm with the color filter substrate placed on the substrate in a state where the color filter substrate stands substantially parallel and vertically, and the thermoplastic resin layer is interposed through the mask. Proximity exposure was performed from the side at an exposure amount of 150 mJ / cm ² (exposure process).

Next, a triethanolamine developer (containing 30% triethanolamine, trade name: T-PD2 (manufactured by Fujifilm Corporation) 12 times with pure water (1 part of T-PD2 and 11 parts of pure water) The mixture was diluted with a ratio at a flat nozzle pressure of 0.04 MPa for 30 seconds at 30 ° C. to remove the thermoplastic resin layer and the intermediate layer. Subsequently, after air was blown off on the upper surface of the glass substrate, pure water was sprayed for 10 seconds by a shower, pure water shower cleaning was performed, and air was blown to reduce a liquid pool on the substrate. Subsequently, a sodium carbonate developer (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, an anionic surfactant, an antifoaming agent, and a stabilizer. Containing agent: Trade name: T-CD1 (manufactured by Fuji Film Co., Ltd.) diluted 10-fold with pure water, and shower-developed at 29 ° C. for 30 seconds at a cone type nozzle pressure of 0.15 MPa. An image was formed (development process).
Subsequently, a solution obtained by diluting a cleaning agent (phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer; trade name: T-SD3 (Fuji Film Co., Ltd.)) 10 times with pure water Using a spray with a cone type nozzle pressure of 0.02 MPa for 20 seconds at 33 ° C., the residue around the formed pattern image is removed, and a cylindrical spacer pattern is formed with one spacer interval of 300 μm × 300 μm. It formed so that it might become.
Next, the color filter substrate provided with the spacer pattern was subjected to a heat treatment at 130 ° C. for 60 minutes (coating heating step) to produce a photo spacer on the color filter substrate. The obtained photospacer had a cylindrical shape with a diameter of 15.1 μm and an average height of 4.7 μm.
And the PVA mode liquid crystal display device was produced like Example 1 using the color filter substrate with which the photo spacer was produced.

[Comparative Example 1]
A photospacer and a liquid crystal display device were produced in the same manner as in Reference Example 1 except that the polymerizable compound was changed to the following comparative compound Z-1. The photo spacer and the liquid crystal display device were evaluated in the same manner as in Reference Example 1 . The evaluation results are shown in Table 2.

A photospacer and a liquid crystal display device were produced in the same manner as in Reference Example 1 except that the polymerizable compound was changed to DPHA (dipentaerythritol hexaacrylate) by changing the composition of the photosensitive resin composition to Formulation 5. The photo spacer and the liquid crystal display device were evaluated in the same manner as in Reference Example 1 . The evaluation results are shown in Table 2.

In Table 2, symbols such as M-1, P-52, and Z-1 in the polymerizable compound column and the resin column represent the exemplified compound number or the comparative compound number.
The dipole moment in the polymerizable compound column is a value obtained by Scigress Explorer Professional Version 7.6.0.52 (manufactured by Fujitsu Limited).

  As shown in Table 2, the photo spacers of the examples had a uniform cross-sectional shape and suppressed height variation. Further, the display unevenness is suppressed in the liquid crystal display device provided with the photo spacer.

Example 20
<Formation of protective film>
In Example 10, in the production of the color filter substrate, after forming the black matrix, the R pixel, the G pixel, and the B pixel, a photosensitive resin composition of Formula 1 was further applied onto the black matrix and each pixel. Then, exposure was performed without using a mask (entire exposure), and heat treatment was performed to form a protective film. Here, the conditions of application | coating, exposure, and heat processing are the same as the conditions of application | coating, exposure, and heat processing in formation of the photospacer of Example 10 except exposing not through a mask.
Next, a transparent electrode of ITO (Indium Tin Oxide) was further formed on the obtained protective layer by sputtering.

<Formation of photo spacer>
On the ITO transparent electrode formed as described above, a photospacer was formed in the same manner as in Example 10 except that the photosensitive resin composition used in Example 10 was used as the photosensitive resin composition.

<Production and Evaluation of Liquid Crystal Display Device>
Next, a liquid crystal display device was produced by the same method as in Example 10 using the color filter substrate on which the photospacer was formed.
The obtained protective film and liquid crystal display device were evaluated by the same method as in Reference Example 1 . The evaluation results are shown in Table 3.

Example 21
<Formation of colored pattern>
In Example 11, a color filter substrate was produced in the same manner as in Example 11 except that the R pixel was formed by the following method in producing the color filter substrate.
That is, Pigment Red 254 (19.4 parts) and Pigment Red 177 (4.83 parts) were further added to Formula 1 to prepare a photosensitive resin composition for R pixels.
R pixels were formed in the same manner as in the formation of the photospacer of Example 11, except that the prepared photosensitive resin composition for R pixels was used and the photomask for R pixels was used as a photomask.

  After forming the R pixel, G pixel, and B pixel of the produced color filter substrate, a transparent electrode of ITO (Indium Tin Oxide) was further formed on each pixel by sputtering.

<Formation of photo spacer>
On the ITO transparent electrode formed as described above, a photospacer was formed in the same manner as in Example 11 except that the photosensitive resin composition used in Example 11 was used as the photosensitive resin composition.

<Production and Evaluation of Liquid Crystal Display Device>
Next, a liquid crystal display device was produced by the same method as in Example 11 using the color filter substrate on which the photospacer was formed.
The obtained protective film and liquid crystal display device were evaluated by the same method as in Reference Example 1 . The evaluation results are shown in Table 3.

[Comparative Examples 3 and 4]
In Comparative Example 3, except that the polymerizable compound Z-1 was used in place of the polymerizable compound M-10 in Example 10, and in Comparative Example 4, DPHA was used in place of the polymerizable compound M-13 in Example 11. A protective film and a coloring material were prepared in the same manner as in Examples 10 and 11 except that they were used, and evaluated in the same manner.

  As shown in Table 3, when a protective film and a colored pattern were formed using the photosensitive resin composition of the present invention, good results were obtained as in the case where a photospacer was formed.

Claims (8)

It is a copolymer having at least a repeating unit having an alicyclic structure, a repeating unit having an acidic group, and a repeating unit having an ethylenically unsaturated bond arranged via an ester bond between the main chain. A resin, a 5-membered or 6-membered cyclic structure having a linking site containing C═O and / or a linking site containing P═O, an ethylenically unsaturated double bond, and a dipole moment of 4 .12 A photosensitive resin composition comprising a polymerizable compound of Debye or more and a photopolymerization initiator. A photospacer formed using the photosensitive resin composition according to claim 1 . A method for forming a photospacer comprising at least the following steps (A) to (C).
(B) A step of forming a film of the photosensitive resin composition according to claim 1 on a substrate (b) A step of exposing at least a part of the film (c) A step of developing the film after exposure The method for forming a photospacer according to claim 3 , further comprising a step of heating the film after development, wherein a maximum temperature in the heating is 40 ° C. or higher and 145 ° C. or lower. A protective film formed using the photosensitive resin composition according to claim 1 . The coloring pattern formed using the photosensitive resin composition of Claim 1 . A display device substrate comprising at least one of the photospacer according to claim 2 , the protective film according to claim 5 , and the colored pattern according to claim 6 . A display device comprising the display device substrate according to claim 7 .