TWI447521B - Manufacturing method of photospacer - Google Patents

Description

Method of making light spacers

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

A liquid crystal display device is widely used in a display device that displays a high-quality image.

The liquid crystal display device is generally disposed between a pair of substrates (hereinafter also referred to as "display device substrate"), and a liquid crystal layer capable of forming an image display is arranged in accordance with a predetermined alignment, and the substrate interval, that is, the liquid crystal layer is uniformly maintained. The thickness is one of the elements determining the image quality, and a spacer for fixing the thickness of the liquid crystal layer is disposed for this purpose. The thickness between the substrates is generally referred to as "cell thickness", and the cell thickness is generally the thickness of the liquid crystal layer, in other words, the distance between two electrodes for applying an electric field to the liquid crystal in the display region.

The display device substrate (for example, a color filter substrate or an active matrix substrate) is formed by forming a structure such as a colored pattern or a protective film on the substrate. Among these structures, a method of forming a colored pattern or a protective film is a method in which a photosensitive resin composition is used and formed by lithography.

Further, the spacer is formed by scattering of beads in the related art. However, in recent years, a photosensitive resin composition is used and a spacer having a high positional accuracy can be formed by lithography. The spacer formed using such a photosensitive resin composition is called a photo spacer.

The photosensitive resin composition has been examined variously, and for example, a photosensitive resin composition using a copolymer of an ethylenically unsaturated carboxylic acid such as an ethylenically unsaturated carboxylic acid and a specific photopolymerization initiator has been disclosed. (For example, refer to Japanese Laid-Open Patent Publication No. 2007-86565). Further, an aliphatic cyclic hydrocarbon group-containing copolymer having a molecular structure in which a constituent unit of an aliphatic cyclic hydrocarbon group having a specific structure, a constituent unit having an acidic functional group, and a constituent unit having a radical polymerizable group are bonded is disclosed. A curable resin is formed (for example, see JP-A-2002-293837).

According to the aspect of the present invention, it is possible to provide a photosensitive resin composition which is improved in polymerization hardenability at the time of exposure, a pattern structure under low-temperature heating or no heat treatment, a formation of a protective film, a photo spacer using the same, and The formation method, the protective film, the colored pattern, the substrate for a display device including the same, and the display device including the substrate for the display device. The photosensitive resin composition contains a resin and a polymerizable compound having the following structural part (I). In the structural part (I), X represents a hydrogen atom or a methyl group, * represents a bond, and photopolymerization is initiated. In the photosensitive resin composition of the agent, the polymerizable compound preferably has two or more structural portions (I) in the molecule.

Problem to be solved by the invention

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

However, in the case where a conventional photosensitive resin composition is used to form a pattern structure (for example, a photo spacer, a colored pattern, or the like, the same applies hereinafter) and a protective film is formed on the substrate, polymerization hardening is not necessarily sufficient only when exposed. Moreover, it is necessary to apply a high-temperature heat treatment after exposure and development. Further, when a pattern structure such as a fine photo spacer is required to be formed, it is generally considered that the polymerization reaction at the time of exposure is as fast as possible in order to prevent the shape from shifting.

The present invention has been made in view of the above, and it is an object to achieve the following objects.

In other words, the present invention has an object of providing a photosensitive resin composition which is excellent in polymerization hardenability at the time of exposure and which can obtain a pattern structure or a protective film under low-temperature heat treatment or without heating.

Further, the present invention has an object of providing a photo spacer having a high cross-sectional shape with high uniformity and excellent uniformity of height and a method for producing the same.

Further, the present invention has an object of providing a protective film having excellent film thickness uniformity or a colored pattern having a uniform cross-sectional shape and excellent film thickness uniformity.

Moreover, the present invention has an object of providing a display device substrate capable of suppressing display unevenness and a display device having suppressed display unevenness when used in a display device.

Means of solving problems

In the present invention, a polymerizable compound containing a specific structural moiety in a molecule is rapidly polymerized by providing light, and therefore it is excellent in moldability, and is different from high-temperature heating which is conventionally referred to as post-baking, for example, less than 200 ° C. It is known that the heating is performed at a low temperature or the curing property can be improved without performing heat treatment, and is completed based on the knowledge.

The specific means for achieving the above problems are as follows.

<1> A photosensitive resin composition containing a resin, a polymerizable compound having the following structural part (I), and a photosensitive resin composition with a photopolymerization initiator. In the following structural part (I), X represents a hydrogen atom or a methyl group, and "*" represents a bond.

The photosensitive resin composition of the above-mentioned <1>, wherein the polymerizable compound has at least two structural portions (I) in a molecule.

The photosensitive resin composition of the above-mentioned <2>, wherein the polymerizable compound has a symmetrical structure in which two groups including the structural portion (I) are bonded.

The photosensitive resin composition of the structure (I) is a polymerizable compound represented by the following structural formula (II).

[In the formula, R represents a linking group containing at least one ether bond between carbon and carbon of a divalent hydrocarbon group. X is a hydrogen atom or a methyl group.

<5> The photosensitive resin composition according to <4> above, wherein in the above structural formula (II), R represents -CH ₂ -OR ^a -O-CH ₂ -, and R ^a is selected from the group consisting of alkylene The linking group of the group formed by the base portion, the aryl group, and the portion in which these are combined.

The photosensitive resin composition according to any one of the above-mentioned items, wherein the resin has a branching and/or alicyclic structure, an acidic group, and an ethylenic unsaturated group in a side chain. key.

The photosensitive resin composition as described in the above <6>, wherein the acid value of the resin is 20 mgKOH/g or more.

The photosensitive resin composition of the above-mentioned <6>, wherein the base having a branched and/or alicyclic structure is a group represented by the following formula (3).

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

<9> A photo-resin formed by using the photosensitive resin composition according to any one of the above items <1> to <8>.

<10> A method for producing a photo spacer, which comprises at least the following steps (A) to (C):

(a) a step of forming a film of the photosensitive resin composition according to any one of the items <1> to <8> on the substrate;

(b) exposing at least a portion of the film to an exposure step;

(c) a developing step of the above-mentioned film after development exposure.

<11> The method for producing a photo-spacer according to the above <10>, which further comprises the step of heating the film after heating and developing, and the maximum temperature during heating is 40° C. or higher and 145° C. or lower.

<12> A protective film formed by using the photosensitive resin composition according to any one of the above items <1> to <8>.

<13> A coloring pattern formed by using the photosensitive resin composition according to any one of the above <1> to <8>.

The substrate for a display device, comprising the photo-spacer, the protective film, and the coloring pattern formed by using the photosensitive resin composition according to any one of the above items <1> to <8> At least one of them.

<15> A display device comprising the substrate for a display device according to the above <14>.

Form of implementing the invention

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

"Photosensitive Resin Composition"

The photosensitive resin composition of the present invention is composed of at least a resin, a polymerizable compound having the structural portion (I) shown below, and a photopolymerization initiator. Further, other components may be further used as needed.

In general, when a photosensitive resin composition is used to form a pattern structure (for example, a photo spacer, a colored pattern, or the like, the same applies hereinafter) or a protective film on a substrate, polymerization hardening is likely to be insufficient because it is only exposed. Therefore, in order to further accelerate the polymerization hardening, it is generally applied to heat treatment at a high temperature after exposure and development. However, when a heat treatment is applied at a high temperature, the formed pattern structure, the deterioration of the protective film, or the already established pattern structure on the substrate, and the protective film are deteriorated by repeated application of heat. For example, in the case of forming a photo spacer on a color filter substrate having a colored pattern, the photo spacer itself thus formed may be deteriorated, and the colored pattern already formed on the substrate may be imparted by The heat is getting worse. On the other hand, in the present invention, since the composition of the photosensitive resin composition accelerates the polymerization during the exposure, the moldability is excellent, and the polymerization hardenability at the time of exposure is improved, and the mixture is heated at a low temperature (for example, 145 ° C or lower). A uniform pattern structure or a protective film can also be formed without heat treatment. Thereby, it is possible to suppress not only the pattern structure and the shape shift of the protective film, but also to effectively suppress the deterioration of the pattern structure and the protective film formed as described above, and the established pattern structure and protective film on the substrate. Deterioration due to repeated heat.

Hereinafter, a resin, a polymerizable compound having a structural portion (I), a photopolymerization initiator, and other components will be described.

<Polymerizable compound having a structural part (I)>

The photosensitive resin composition of the present invention contains at least one of a polymerizable compound having the following structural portion (I) (hereinafter also referred to as "specific polymerizable compound"). The polymerizable compound is a person who receives a radical from a photopolymerization initiator to be described later and causes a polymerization reaction to form a cured film. The effect by the specific polymerizable compound is not clear, but it is presumed that by having the structure shown in the following structural part (I), the reaction of the unsaturated double bond portion at the time of exposure is accelerated, so that it is polymer hardened. Excellent sex.

In the above structural portion (I), X represents a hydrogen atom or a methyl group, and "*" in the formula represents a bond.

The specific polymerizable compound in the present invention is not particularly limited as long as it is a compound having the structural portion (I), and any one or two or more kinds of the photosensitive resin compositions of the present invention can be selected.

The compound having a structural moiety (I) may, for example, be a compound having one structural moiety (I), or two or more structural components (I) via a divalent or trivalent bond between each bonding bond (*). The compound which is bonded by the above-mentioned linking group, and the two structural parts (I) are compounds which are directly bonded by each bonding bond (*).

The compound having one structural moiety (I) may, for example, be a bond (*) in the structural moiety (I), for example, a carbon-carbon in a monovalent hydrocarbon group, and the bond contains at least one ether bond (-O) -) a compound of a linking group. Specific examples of the compound having one structural portion (I) include the following compounds. Further, specific examples of each of the following lines represent "-X" to "-H" or both compounds "-CH _3" of.

Among them, from the viewpoints of solubility, viscosity, and the like, a compound having an ether group, an oxirane group, an alcohol group or the like bonded to the bond (*) of the structural moiety (I) is preferred, particularly an ether or a ring. An oxyethane group or the like is preferred.

The above-mentioned divalent or trivalent or higher linking group may be arbitrarily selected from the polyvalent group, and examples thereof include a divalent or trivalent or higher hydrocarbon group and a carbon-carbon intermetallic group having a divalent or trivalent or higher hydrocarbon group. A group containing one or two or more ether bonds (-O-), -O-, -S-, an ester bond, a guanamine group, an amine group, and the like, and a divalent group or the like in which at least two of them are combined.

Specific examples of the linking group of divalent or trivalent or higher are as follows. However, the invention is not limited thereto. Further, "*" in the specific example means a bond.

It is preferable to carry out 2 or 3 molecules in the molecule from the viewpoint of rapid polymerization at the time of exposure and good hardening, and even if it is subjected to low-temperature heating and no heat treatment, and a uniform pattern structure or a protective film can be formed. The specific polymerizable compound of the above structural part (I).

Further, based on the same viewpoint, it is preferable to have two structural parts (I) in the molecule, and the same two basic structures of the structure containing the structural part (I), that is, the two structural parts (I) The molecular structure of the linking group is preferably a compound having a symmetrical structure. Preferred compounds of the symmetrical structure include, for example, the compounds represented by the following structural formula (II).

In the above structural formula (II), R represents a group containing a divalent hydrocarbon group or a linking group containing at least one ether bond (-O-) between carbon-carbons of a divalent hydrocarbon group, preferably at a valence of 2 The carbon-carbon of the hydrocarbon group contains a linking group of at least one ether bond (-O-).

"Divalent hydrocarbon group having the" system R for example can be represented as: only divalent group _{C n H 2n (n ≧ 1} ) of the hydrocarbon group shown constituted, and to _{C n H 2n (n ≧ 1} ) The hydrocarbon group shown is a combination of a divalent group selected from at least one of an ether bond, an ester bond, a guanamine group, and an amine group. The range of n is suitable from 1 to 8.

In addition, the "linking group containing at least one ether bond between the carbon-carbon of the divalent hydrocarbon group" represented by R includes one or two or more oxygen atoms and carbon atoms and hydrogen atoms disposed between the carbon and carbon. The two-valent group is not particularly limited, and examples thereof include -(AL and/or AR)-O-(AL and/or AR)-, -(AL and/or AR)-O-(AL and / or AR) -O-, - (AL and / or AR) - O - (AL and / or AR) - O - (AL and / or AR) - the divalent group is suitable. Further, AL represents an alkylene group and AR represents an extended aryl group.

The alkylene group (AL) may be any of a straight chain or a branched chain, and the alkylene group and the extended aryl group (AR) may be unsubstituted or substituted with a substituent. The substituent in the case of substitution may, for example, be the same group as the substituents listed below in R ^a .

Among R, it is preferred that the polymerization at the time of exposure is rapid and can be well cured, and it is preferable to contain two or more oxygen atoms, and more preferably -CH ₂ -OR ^a -O-CH ₂ -. Here, R ^a represents ^a linking group selected from the group consisting of an alkyl group, an aryl group, and a combination thereof. Further, one or two or more ether bonds may be disposed between the carbon-carbon bonds of the alkyl group represented by R ^a .

The alkylene moiety represented by the above R ^a is not particularly limited and may be unsubstituted or substituted with a substituent. The substituent in the case of substitution may, for example, be a monovalent substituent such as an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, butyl group, hexyl group or octyl group), a hydroxyl group or a halogen group.

Specific examples of the alkylene moiety include, for example, methylene, ethyl, propyl, butyl, 2-hydroxypropyl, 2-methylexylethyl, 2-dimethylexylethyl , stretching the ring and so on.

Wherein, the alkylene group is preferably a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms and a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms from the viewpoint of solvent solubility and precipitation inhibition. Preferably.

The exoaryl moiety represented by the above R ^a is not particularly limited and may be unsubstituted or substituted with a substituent. The substituent in the case of substitution may, for example, be the same substituent as in the case of the alkylene moiety described above.

Specific examples of the aryl group moiety include a phenyl group and a naphthyl group. Among them, the aryl group is preferably a solvent having a carbon number of 6 to 10 or an unsubstituted aryl group, and a substituted or unsubstituted aryl group having a carbon number of 6 to 8 is a solvent-soluble or precipitation-inhibiting point. Preferably.

Further, the combination of the alkyl group and the aryl group may be, for example, -C ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -, -(CH ₂ ) ₂ -OC ₆ H ₄ - C(CH ₃ ) ₂ -C ₆ H ₄ -O-(CH ₂ ) ₂ -, -(CH ₂ ) ₃ -OC ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O-(CH ₂ ) ₃ - wait.

Specific examples of "-CH ₂ -OR ^a -O-CH ₂ -" represented by the above R are as follows. However, the invention is not limited thereto. Further, "*" in the specific example means a bond.

Further, the linking group represented by the above R ^a is preferably a symmetrical structure because the polymerization reactivity at the time of exposure is good. Specific examples of the linking group of the symmetrical structure include, for example, the specific examples (1), (2), (4), and (9) described above as specific examples.

The molecular weight of the specific polymerizable compound in the present invention is preferably from 100 to 3,000 in terms of weight average molecular weight, more preferably from 100 to 2,000, and particularly preferably from 100 to 1,500. The molecular weight of the specific polymerizable compound is preferably 100 or more, and is desirably from the viewpoint of suppressing sublimation, and is preferably 3,000 or less from the viewpoint of solubility.

Further, the weight average molecular weight is measured by gel permeation chromatography (GPC). The GPC system is shown in detail in the item of the following example.

Hereinafter, specific examples of the specific polymerizable compound having the structural portion (I) [exemplary compounds (1) to (20) and (M-1) to (M-15)] are shown. However, the invention is not limited thereto.

The content of the polymerizable compound (specifically polymerizable compound) having the structural portion (I) in the photosensitive resin composition is preferably 1 to 60% by mass, and 10 to 55% by mass based on the total solid content of the composition. It is better. When the content of the specific polymerizable compound is 1% by mass or more, the polymer curable property at the time of exposure is good, and a pattern structure or a protective film which suppresses the shape shift can be formed, and heat treatment at a low temperature or There is no deterioration of the pattern structure formed by the heat treatment, the deterioration of the protective film, or the established pattern structure or the protective film. In addition, when it is 60% by mass or less, adjustment of the viscosity of the liquid, the hardness of the cured product, and the like, adjustment of the exposure sensitivity, and the like are effective.

In addition to the specific polymerizable compound described above, the photosensitive resin composition of the present invention may further contain another polymerizable compound having an ethylenically unsaturated bond. Other polymerizable compounds may be selected from the group of the polymerizable compounds constituting the well-known composition, and the components described in paragraph numbers [0010] to [0020] of JP-A-2006-23696, and The components described in paragraphs [0027] to [0053] of the publication No. 2006-64921.

Other polymerizable compounds may be contained within the range not impairing the effects of the present invention.

In the present invention, the mass ratio of the total amount of the polymerizable compound containing the specific polymerizable compound to the total amount of the resin to be described later [the total amount of the polymerizable compound/the total amount of the resin) is based on the development property and the mechanical property. The viewpoint is preferably 0.5 to 2.0, 0.6 to 1.8 is preferred, and 0.7 to 1.5 is particularly preferred. When the mass ratio is within the above range, good developability can be obtained. For example, when a photo spacer or the like is formed, a photo spacer having mechanical strength can be obtained.

<Resin>

The photosensitive resin composition of the present invention contains at least one kind of resin. The resin is not particularly limited, and a compound which exhibits swelling properties with respect to an aqueous alkaline solution is preferred, and a compound which exhibits solubility in an aqueous alkaline solution is preferred.

The resin which exhibits swellability or solubility in an alkaline aqueous solution is, for example, a compound having an acidic group, and specifically a compound (epoxy acrylate compound) in which an ethylenically unsaturated double bond and an acidic group are introduced into an epoxy compound. a vinyl copolymer having a (meth)acrylonyl group and an acidic group in a side chain, an epoxy acrylate compound, and a vinyl copolymer having a (meth)acrylonyl group and an acidic group in a side chain, A maleic acid-based copolymer or the like is preferred.

The acidic group is not particularly limited, and may be appropriately selected depending on the purpose, and examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, a carboxyl group is preferred from the viewpoint of the starting property of the raw material and the like.

The content of the resin in the photosensitive resin composition of the present invention is preferably from 5 to 70% by mass, preferably from 10 to 50% by mass, based on the total solid content of the photosensitive resin composition. When the content is 5% by mass or more, the film strength of the photosensitive resin layer can be maintained, and the surface adhesiveness of the photosensitive resin layer can be favorably maintained. When the content is 70% by mass or less, the exposure sensitivity is good.

The resin in the present invention is excellent in deformation recovery property when deformed by applying an external force after polymerization hardening, and preferably contains a branching and/or alicyclic structure, an acidic group, and an ethyl group in a side chain. At least one of a resin having an unsaturated bond (hereinafter also referred to as "resin A").

Resin A has an acidic group and has developability, and has an ethylenically unsaturated bond, and has high polymer reactivity, excellent liquid storage stability, and long-term storage stability of a dry film. The pattern structure can be controlled to have a desired shape and controllability of film thickness (height, etc.). Further, it has a branching and/or alicyclic structure, and can improve the compressive modulus of elasticity of the formed pattern structure when subjected to an external force, and the deformation recovery property by compression deformation. Therefore, it is useful for forming a pattern structure such as a photo spacer for a display device.

Here, the branching and/or alicyclic structure, the acidic group, and the ethylenically unsaturated bond may be contained in different side chains, or may be combined in one part and contained in the same side chain, or may be all Contained in the same side chain.

Further, in the present specification, the (meth)acrylonitrile group means an acryloyl group or a methacryloyl group, the (meth)acrylate means an acrylate or a methacrylate, and the (meth)acrylic means an acrylic acid. Or methacrylic acid, (meth) acrylamide refers to acrylamide or methacrylamide, and (meth) acryl anilide means acrylamide or methacrylamide.

(branched and / or alicyclic structure)

Resin A is bonded to the side chain of the resin main chain and contains at least one type of branching and/or alicyclic structure. The branched and/or alicyclic structure may be plurally contained in the side chain of the resin A. Further, the branching and/or alicyclic structure may be contained in the side chain of the resin A together with the acidic group and/or the ethylenically unsaturated bond.

Further, the branching and/or alicyclic structure may be directly bonded to the main chain of the resin A, and may constitute a side chain of the resin A only by a branching and/or alicyclic structure, or may be a divalent organic substance. The linking group is bonded to the main chain of the resin A to form a side chain of the resin A having a branching and/or alicyclic structure.

The divalent organic linking group is preferably selected from one of an alkylene group, an extended aryl group, an ester group, a decylamino group, and an ether group, or a combination thereof. The alkylene group is preferably an alkylene group having a total carbon number of from 1 to 20, particularly preferably from 1 to 10. Specifically, for example, a methylene group, an ethylidene group, a propyl group, a butyl group, a pentyl group, a hexyl group, a decyl group, a dodecenyl group, an octadecyl group, etc., may be mentioned. Branch/ring structure, functional group, especially preferably methylene, ethyl, and octyl. The above-mentioned aryl group is preferably a aryl group having a total carbon number of 6 to 20, particularly preferably 6 to 12. Specifically, for example, a phenyl group, a phenylene group, a naphthyl group, a fluorenyl group or the like may be mentioned, and these may have a branch or a functional group, and more preferably a phenyl group or a phenyl group.

The branching and/or alicyclic structure is preferably a form capable of permeating at least an ester group (-COO-) to the main chain of the resin A from the viewpoints of developmental properties, elastic recovery ratio, and the like. The branching and/or alicyclic structure of the form is not limited to a form in which the main chain of the resin A is bonded only by the ester group (-COO-), and the branch and/or the alicyclic structure may be configured to transmit the ester group. The divalent linking group of (-COO-) is bonded to the main chain of the resin A. That is, between the branch and/or alicyclic structure and the ester chain, and/or between the ester chain and the main chain of the resin A, other atoms and other linking groups may be contained.

The above branched structure may, for example, be a branched alkyl group having 3 to 12 carbon atoms, for example, an isopropyl group, an isobutyl group, a second butyl group, a tert-butyl group, an isopentyl group or a neopentyl group. Further, 2-methylbutyl, isohexyl, 2-ethylhexyl, 2-methylhexyl, isopentyl, third amyl, 3-octyl, trioctyl or the like is preferred. Among these, an isopropyl group, a second butyl group, a tert-butyl group, an isopentyl group or the like is more preferable, and an isopropyl group, a second butyl group, a third butyl group or the like is particularly preferable.

The alicyclic structure may, for example, be an alicyclic hydrocarbon group having 5 to 20 carbon atoms, for example, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a lower group. Basis The base, adamantyl group, tricyclodecyl group, dicyclopentenyl group, dicyclopentyl group, tricyclopentenyl group, and tricyclopentyl group, and the like are preferred. Among these, especially dicyclopentenyl, cyclohexyl, and descending Basis More preferably, adamantyl, tricyclodecyl, tricyclopentenyl, tricyclopentyl or the like is dicyclopentenyl, cyclohexyl, or Basis More preferably, a tricyclopentenyl group or the like is preferable, and a dicyclopentenyl group or a tricyclopentenyl group is particularly preferred.

Further, it is preferred that the base having a branched and/or alicyclic structure is constituted by a group having a group represented by the following formula (3).

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

The divalent organic linking group is preferably one selected from the group consisting of an alkylene group, an extended aryl group, an ester group, a decylamino group, and an ether group, or a combination thereof, and these may have a substituent.

The alkylene group is preferably an alkylene group having a total carbon number of 1 to 20, particularly preferably an alkylene group having 1 to 10 carbon atoms. Specifically, for example, a group such as a methylene group, an exoethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a decyl group, a dodecenyl group, an octadecyl group or the like may be mentioned. It has a branched/annular structure and a functional group, and is particularly preferably a methylene group, an ethyl group, and an extended octyl group.

The above-mentioned aryl group is preferably an extended aryl group having a total carbon number of 6 to 20, and particularly preferably an extended aryl group of 6 to 12. Specifically, for example, a phenyl group, a phenylene group, a naphthyl group, a fluorenyl group or the like may be mentioned, and these may have a branch or a functional group, and more preferably a phenyl group or a phenyl group.

The substituent in the case of substitution may, for example, be an alkyl group, a hydroxyl group, an amine group, a halogen group, an aromatic ring group or a alicyclic structure.

In the synthesis of the resin A, a single system for introducing a branching and/or alicyclic structure into a side chain may, for example, be a styrene, a (meth) acrylate, a vinyl ether or a vinyl ester. The (meth) acrylates, vinyl esters, and (meth) acrylamides are preferred, and (meth) acrylates are preferred.

In the synthesis of the resin A, a specific single system for introducing the branched structure into the side chain may, for example, be isopropyl (meth)acrylate, isobutyl (meth)acrylate, or (meth)acrylic acid second. Butyl ester, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, third amyl (meth)acrylate, second isoamyl (meth)acrylate, 2-(meth)acrylate Octyl ester, 3-octyl (meth)acrylate, and third octyl (meth)acrylate, among which isopropyl (meth)acrylate, isobutyl (meth)acrylate, methacrylic acid Tributyl ester or the like is preferred, and isopropyl methacrylate, butyl methacrylate or the like is preferred.

In the synthesis of the resin A, a single system for introducing an alicyclic structure to a side chain may, for example, be a (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. Specific examples include (meth)acrylic acid (bicyclo[2.2.1]heptyl-2) ester, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, (A) 3-methyl-1-adamantyl acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyladamantyl (meth)acrylate, (methyl) 3-methyl-5-ethyl-1-adamantyl acrylate, 3,5,8-triethyl-1-adamantyl (meth)acrylate, 3,5-dimethyl (meth)acrylate -8-ethyl-1-adamantyl ester, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, (meth)acrylic acid 3 -hydroxy-1-adamantyl ester, octahydro-4,7-(meth)acrylate Alkyl oxime-5-ester, octahydro-4,7-(meth)acrylate Alkyl inden-1-yl methyl ester, (meth)acrylic acid 1- Ester, tricyclodecyl (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl (meth)acrylate, 3,7,7 (meth)acrylic acid -trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl ester, (meth)acrylic acid (decreasing) Ester, (meth)acrylic acid Ester, fenyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, ( Tricyclopentenyl ester of methyl) acrylate.

Among these (meth) acrylates, the higher the volume of the functional group, the better the compression modulus and the recovery property of the deformation, and the cyclohexyl (meth)acrylate and the (meth)acrylic acid (lower) Ester, (meth)acrylic acid Ester, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fenyl (meth)acrylate, 1-(meth)acrylate Ester, tricyclodecyl (meth)acrylate, dicyclopentenyl (meth)acrylate, tricyclopentenyl (meth)acrylate, etc., preferably cyclohexyl (meth)acrylate, (methyl) Acrylic (lower) Ester, (meth)acrylic acid The ester, 2-adamantyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and tricyclopentenyl (meth)acrylate are particularly preferred.

In the synthesis of the resin A, the single system for introducing the alicyclic structure into the side chain may, for example, be a compound represented by the following formula (4) or (5). Here, in the general formulae (4) and (5), X represents a divalent organic linking group, R represents a hydrogen atom or a methyl group, y represents 1 or 2, and n represents 0-15. Among the general formulae (4) and (5), y=1 or 2 and n=0 to 8 are preferable, and y=1 or 2 and n=0 to 4 (more preferably n=0). 2). Preferable specific examples of the compound represented by the formula (4) or (5) include the following compounds D-1 to D-11 and T-1 to T-12.

Among them, from the point of the deformation recovery rate, a compound represented by the following formula (4) is preferred.

In the above formulae (4) to (5), the divalent organic linking group represented by X may be unsubstituted or may have a substituent, and may be a divalent group represented by X in the above formula (3). The organic linking group is synonymous, and the preferred aspect is also the same.

In the synthesis of the resin A, a single system for introducing the alicyclic structure into the side chain can be used as a suitable manufacturer, and a commercially available product can also be used.

The commercially available product may, for example, be manufactured by Hitachi Chemical Co., Ltd.; FA-511A, FA-512A(S), FA-512M, FA-513A, FA-513M, TCPD-A, TCPD-M, H-TCPD -A, H-TCPD-M, TOE-A, TOE-M, H-TOE-A, H-TOE-M, and the like. Among these, FA-512A (S) and 512 M are preferable from the viewpoint of excellent developability and excellent deformation recovery.

(acid base)

Resin A has at least one acidic group bonded to the side chain bonded to the main chain. The acidic group may be plurally contained in the side chain. Further, the acidic group may be contained in the side chain of the resin A together with the branching and/or alicyclic structure and the ethylenically unsaturated bond disposed between the main chain and the ester group.

Further, the acidic group may be directly bonded to the main chain of the resin A to form a side chain of the resin A only by an acidic group, or may be bonded to the main chain of the resin A through a divalent organic linking group. A side chain of the resin A which is constituted by a group having an acidic group. Here, the divalent organic linking group may be, for example, a divalent organic linking group exemplified in the description of the branching and/or alicyclic structure, and the preferred range is also the same.

The acidic group is not particularly limited, and may be appropriately selected from among those skilled in the art, and examples thereof include a carboxyl group, a sulfonic acid group, a sulfonylamino group, a phosphoric acid group, and a phenolic hydroxyl group. Among these, a carboxyl group and a phenolic hydroxyl group are preferred from the viewpoints of excellent development properties and water resistance of the cured film.

In the synthesis of the resin A, a specific example of the monomer for introducing the acidic group described above can be appropriately selected from known ones, and examples thereof include (meth)acrylic acid, vinylbenzoic acid, maleic acid, and Malay. Addition reaction of acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyano cinnamic acid, acrylic acid dimer, monomer having hydroxyl group and cyclic acid anhydride , ω-carboxy-polycaprolactone mono(meth)acrylate, and the like. These may be used by a suitable manufacturer or a commercially available product.

The monomer having a hydroxyl group used in the addition reaction of the monomer having a hydroxyl group and the cyclic acid anhydride may, for example, be 2-hydroxyethyl (meth)acrylate. Examples of the cyclic acid anhydride include maleic anhydride, phthalic anhydride, and cyclohexane dicarboxylic anhydride.

Commercially available monomers include, for example, East Asian Synthetic Chemical Industry Co., Ltd.; ARONIX M-5300, ARONIX M-5400, ARONIX M-5500, ARONIX M-5600, and New Nakamura Chemical Industry Co., Ltd.; NK ESTER CB-1, NK ESTER CBX-1, Kyoeisha Oil Chemical Industry Co., Ltd.; HOA-MP, HOA-MS, Osaka Organic Chemical Industry Co., Ltd.; VISCOAT #2100. Among these, (meth)acrylic acid or the like is preferred from the viewpoint of excellent developability and low cost.

(ethylenically unsaturated bond)

Resin A contains at least one kind of ethylenically unsaturated bond in a side chain. In the resin A, the ethylenically unsaturated bond is preferably disposed between the main chain through the ester group. The ethylenically unsaturated bond may be plurally contained in the side chain. Further, the ethylenically unsaturated bond may be contained in the side chain of the resin A together with the above-mentioned branching and/or alicyclic structure and/or the aforementioned acidic group.

Further, the ethylenically unsaturated bond may be bonded to the main chain of the resin A through at least one ester group (-COO-), or may form the side of the resin A only by an ethylenically unsaturated bond and an ester group. chain. Further, a divalent organic linking group may be further provided between the main chain of the resin A and the ester group, and/or between the ester group and the ethylenically unsaturated bond, and the ethylenically unsaturated bond may also constitute A side chain of the resin A having a group having an ethylenically unsaturated bond disposed through the ester group with the main chain. Here, the divalent organic linking group may, for example, be a divalent organic linking group exemplified in the description of the branching and/or alicyclic structure, and the preferred range is also the same.

Further, the ethylenically unsaturated bond is preferably disposed by introducing a (meth)acrylonitrile group.

In the synthesis of the resin A, a method of introducing a (meth) acrylonitrile group into a side chain can be appropriately selected from known methods, and for example, a (meth) acrylate having an epoxy group may be added. a method of adding a repeating unit having an acidic group, a method of attaching a (meth) acrylate having an isocyanate group to a repeating unit having a hydroxyl group, and attaching a (meth) acrylate having a hydroxyl group to a repeating unit having an isocyanate group. Method, etc.

Among them, a method of adding a (meth) acrylate having an epoxy group to a repeating unit having an acidic group is particularly easy to manufacture, and it is preferable from the viewpoint of low cost.

The (meth) acrylate having an epoxy group is not particularly limited, and for example, a compound represented by the following structural formula (A) and a compound represented by the following structural formula (B) are preferred.

In the above structural formula (A), R ¹ represents a hydrogen atom or a methyl group. L ¹ represents an organic group.

In the above structural formula (B), R ² represents a hydrogen atom or a methyl group. L ² represents an organic group. The W system represents an aliphatic hydrocarbon group of a 4 to 7 membered ring.

Among the compounds represented by the above structural formula (A) and the compounds represented by the structural formula (B), the compound represented by the structural formula (A) is more preferable than the structural formula (B). In the above structural formulae (A) and (B), it is preferred that each of L ¹ and L ² is independently an alkyl group having 1 to 4 carbon atoms.

The compound represented by the above structural formula (A) or the compound represented by the structural formula (B) is not particularly limited, and examples thereof include the following exemplified compounds (1) to (10).

~~Other monomers~~

In the resin A of the present invention, other monomers may be introduced into other groups.

The other single system described above is not particularly limited, and examples thereof include (meth) acrylate, styrene, and a monomer having a vinyl ether group, a dibasic acid anhydride group, a vinyl ester group, or a hydrocarbon alkenyl group.

The vinyl ether group is not particularly limited, and examples thereof include a butyl vinyl ether group and the like.

The dibasic acid anhydride group is not particularly limited, and examples thereof include a maleic anhydride group and an itaconic anhydride group.

The vinyl ester group is not particularly limited, and examples thereof include a vinyl acetate group and the like.

The hydrocarbon alkenyl group is not particularly limited, and examples thereof include a butadienyl group and a prenyl group.

The content ratio of the other monomer in the resin A is preferably from 1 to 40% by mass, more preferably from 2 to 30% by mass.

Specific examples of the resin A include, for example, compounds represented by the following structures (exemplary compounds P-1 to P-56).

Further, x, y, and z in the exemplified compound indicate the composition ratio (mass ratio) of each repeating unit, and the form constituting the preferred range described later is suitable. Further, the weight average molecular weight of each of the exemplified compounds is also preferably in the form of a preferred range described later.

~Synthesis method~

The resin A can be synthesized by a step of (co)polymerization of a monomer and a two-stage step of a step of introducing an ethylenically unsaturated group.

First, the (co)polymerization reaction can be produced by various monomer (co)polymerization reactions, and is not particularly limited, and can be appropriately selected from among those skilled in the art. For example, as the active species to be polymerized, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization, or the like can be appropriately selected. Among these, from the viewpoint of easy synthesis and low cost, radical polymerization is preferred. Further, the polymerization method is not particularly limited, and can be appropriately selected from among those skilled in the art. For example, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, or the like can be appropriately selected. Among these, the solution polymerization method is particularly desirable.

~Core number~

The total carbon number of the main chain of the resin A is preferably 10 or more from the viewpoint of the modulus of elasticity (hardness). Among them, the total carbon number is preferably 10 to 30, and particularly preferably 10 to 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 the production suitability and developability of the resin (preferably a copolymer). Further, the shape formed by the decrease in the melt viscosity is preferably from the point where the collapse is not likely to occur, and the point at which the residue of the spacer is not visible in the development is preferable.

The weight average molecular weight is determined by gel permeation chromatography (GPC). The GPC system is shown in detail in the item of the following example.

~ glass transfer temperature ~

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

~acid price~

The acid value of the resin A is preferably in a range which is preferably changed by the molecular structure obtained, but is preferably 20 mgKOH/g or more, more preferably 40 mgKOH/g or more, and particularly preferably 50 to 130 mgKOH/g. When the acid value is within the above preferred range, a spacer having good developability and mechanical strength can be obtained.

~Tg~

The resin A is preferably a glass transition temperature (Tg) of 40 to 180 ° C and a weight average molecular weight of 10,000 to 100,000, and a Tg of 45 to a point at which a spacer having good developability and mechanical strength can be obtained. It is preferably 140 ° C (more preferably 50 to 130 ° C) and has a weight average molecular weight of 12,000 to 60,000 (more preferably 15,000 to 45,000).

Further, a preferred example of the above resin A is more preferably a combination of the above preferred molecular weight, glass transition temperature (Tg), and acid value.

In the present invention, a preferred embodiment of the resin A has a branching and/or alicyclic structure, an acidic group, and an ethylenically unsaturated bond (preferably disposed between the main chain and the ester group). Copolymerization of the above copolymer in the other three repeating units (copolymerization units), deformation recovery rate, development residue, and network structure when forming a pattern structure (for example, a spacer for a color filter) It is better from a point of view.

Specifically, the resin A contains at least: a repeating unit having a branching and/or alicyclic structure: X (x mole %), a repeating unit having an acidic group: Y (y mole %), and having Preferably, the repeating unit of the ethylenically unsaturated bond which is disposed between the main chain and the ester group is a copolymer of 3 or more of Z (z mole %). Furthermore, other repeating units: L (1 mol%) may be contained as needed.

Such a copolymer is obtained, for example, by copolymerizing a monomer having a branched and/or alicyclic structure, a monomer having an acidic group, a monomer having an ethylenically unsaturated bond, and other monomers as needed. In particular, the monomer represented by the above formula (4) is copolymerized to have at least the aforementioned branch and/or from the viewpoint that the compressive modulus and the recovery property of the functional group having a large volume can be improved. It is preferred that the monomer of the alicyclic structure is introduced into a copolymer having a branching and/or alicyclic structure. At this time, the resin A has a constituent unit of the monomer represented by the above-described general formula (4) in the main chain.

The copolymerization composition ratio in the case where the aforementioned resin A is a copolymer can be determined by considering the glass transition temperature and the acid value. Although it cannot be generalized, it can be in the scope below.

The composition ratio (x) of the repeating unit having the branching and/or alicyclic structure in the resin A is preferably 10 to 70 mol%, more preferably 15 to 65 mol%, and 20 to 60 mol% is special. good. When the composition ratio (x) is within the above range, good developability can be obtained, and the development liquid resistance of the image portion 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 hardenability and developability can be obtained.

The composition ratio (z) of the repeating unit having an ethylenically unsaturated bond in the resin A is preferably 10 to 70 mol%, more preferably 20 to 70 mol%, and particularly preferably 30 to 70 mol%. When the composition ratio (z) is within the above range, the pigment dispersibility is excellent, and the sensitivity and the polymerization hardenability are good, and the liquid storage property after liquid adjustment and the dry film state after coating are maintained for a long period of time. The stability is getting good.

Further, the resin A composition ratio (x) is 10 to 70 mol% (more preferably 15 to 65 mol%, particularly preferably 20 to 50 mol%), and the composition ratio (y) is 5 to 70 m. Ear % (more preferably 10~60 mol%, especially good 30~70 mol%), composition ratio (z) is 10~70 mol% (more preferably 20~70 mol%, especially good The case of 30~70 mol%) is better.

In the above, a preferred embodiment of the resin A is described. In a preferred embodiment of the photosensitive resin composition of the present invention, the resin is preferably a resin A, and the polymerizable compound is specific to the structural formula (I). Exemplary compounds (3), exemplified compounds (10), exemplified compounds (M-5), exemplified compounds (M-6), exemplified compounds (M-7), and exemplified compounds (M-8) of the specific compound in the polymerizable compound The combination of the exemplary compound (M-14) and the like is preferred. When the photosensitive resin composition of the present invention is configured as described above, the effects of the present invention can be more effectively expressed.

In the case where the photosensitive resin composition of the present invention contains the resin A, the content ratio of the resin A in the photosensitive resin composition is preferably 5 to 50% by mass based on the total resin amount (mass) in the composition. 10 to 40% by mass is preferred.

The resin A may be used in combination with other resins, and it is preferable to use the resin A alone.

<Photopolymerization initiator>

The photosensitive resin composition of the present invention contains at least one type of photopolymerization initiator.

The photopolymerization initiator in the present invention is not particularly limited, and a well-known photopolymerization initiator can be used. The known photopolymerization initiators are, for example, those described in paragraph numbers [0010] to [0020] of JP-A-2006-23696, and paragraph numbers [0027] to [0053] of JP-A-2006-64921. Agent. In the case of a known photopolymerization initiator, an aminoacetophenone-based compound, a mercaptophosphine oxide-based compound, or an oxime ester-based compound other than the above is preferable.

Specific examples of the aminoacetophenone-based compound include, for example, IRGACURE (Irg) 907 (manufactured by Ciba Specialty Chemicals Co., Ltd.). Specific examples of the fluorenyl phosphine oxide-based compound include, for example, DAROCUR TPO and Irgacure (Irg) 819 (above, Ciba Specialty Chemicals Co., Ltd.). Further, specific examples of the oxime ester-based compound include, for example, IRGACURE (Irg) OXE01, CGI242, and the like (above, Ciba Specialty Chemicals Co., Ltd.). Hereinafter, the structure of these initiators is shown.

The total amount of the photopolymerization initiator in the photosensitive resin composition is preferably from 0.5 to 25% by mass, preferably from 1 to 20% by mass, based on the total solid content of the photosensitive resin composition.

<microparticle>

The photosensitive resin composition of the present invention preferably contains at least one kind of fine particles from the viewpoints of a resin, a polymerizable compound, a photopolymerization initiator, and a mechanical strength.

The fine particles are not particularly limited, and can be appropriately selected according to the purpose. For example, the extender pigments described in JP-A-2003-302639 [0035] to [0041] are preferred, and good development properties can be obtained. In terms of the optical spacer of the mechanical strength, colloidal vermiculite is preferred.

The average particle diameter of the fine particles is a point at which a high mechanical strength can be obtained in a structure in which an external force which easily absorbs a photo spacer or the like is formed, preferably 5 to 50 nm, preferably 10 to 40 nm, and 15 to 30 nm. It is especially good.

The content of the fine particles in the photosensitive resin composition (the photo spacer (or the photosensitive resin layer constituting the photosensitive spacer) is increased from the viewpoint of improving the mechanical strength (for example, a high mechanical strength can be obtained). The viewpoint of the photo-spacer is preferably 5 to 50% by mass, preferably 10 to 40% by mass, and 15 to 30% by mass based on the total solid content (mass) of the photosensitive resin composition. good.

<Other>

In addition to the resin, the specific polymerizable compound, the photopolymerization initiator, and the fine particles contained as needed, the photosensitive resin composition of the present invention may contain other components such as a photopolymerization initiation aid as needed.

The photosensitive resin composition can be used in combination with a photopolymerization initiation aid as another additive component. The photopolymerization initiation aid can be used in combination with a photopolymerization initiator because it promotes polymerization of a polymerizable compound which initiates polymerization by a photopolymerization initiator. The photopolymerization initiation aid is preferably at least one of an amine compound.

The amine compound may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-di Isoamyl methylamino benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4 , 4'-bis(dimethylamino)diphenyl ketone (commonly known as Michlerone), 4,4'-bis(diethylamino)diphenyl ketone, 4,4'-double (B More preferably, 4,4'-bis(diethylamino)diphenyl ketone is preferred. Further, a combination of an amine-based or other photopolymerization initiation aid may be used in combination.

Other photopolymerization initiation assistants other than the above may, for example, be an alkoxy ruthenium compound or oxygen sulphur A compound, a coumarin compound, or the like. The alkoxy oxime-based compound may, for example, be 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene or 2-B. Base-9,10-diethoxyanthracene, and the like. Oxygen and sulfur The compound is, for example, 2-isopropylthio Bismuth, 4-isopropylthio Bismuth, 2,4-diethylthio Bismuth, 2,4-dichlorooxysulfide 1-chloro-4-propoxythio Hey.

Further, a commercially available person can also be used as a photopolymerization starting aid. The commercially available photopolymerization starter is, for example, a product name "EAB-F" (manufactured by Hodogaya Chemical Industry Co., Ltd.).

The content of the photopolymerization initiator in the photosensitive resin composition is preferably 0.6 parts by mass or more and 20 parts by mass or less, and 1 part by mass or more and 15 parts by mass or less, based on 1 part by mass of the photopolymerization initiator. More preferably, it is preferably 1.5 parts by mass or more and 15 parts by mass or less.

Further, the other components may be selected and used as a component constituting a well-known composition, and the paragraph numbers of [0010] to [0020] and JP-A-2006-64921 of JP-A-2006-23696, for example, may be used. [0027] The components described in [0053].

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

"Photo spacers and their formation methods"

The photo spacer of the present invention is formed by using the photosensitive resin composition of the present invention described above. The details and preferred aspects of the photosensitive resin composition are as described above.

Since the photo-spacer of the present invention is formed by using the photosensitive resin composition of the present invention, it has a cross-sectional shape with high uniformity and can suppress height shift. Further, in the case where the photosensitive resin composition of the present invention contains the resin A, a photo spacer having a high compression modulus and deformation recovery property which is necessary for the photo spacer can be obtained.

Here, in the present invention, the pattern structure such as the photo spacer is described as having a "uniform cross-sectional shape".

In the state in which the pattern structure has a "uniform cross-sectional shape", it is preferable that the cross-sectional shape of the pattern structure is close to the shape of a rectangle in a plurality of places (preferably three or more) in the substrate. The above-mentioned "a shape close to a rectangle" is parallel to the normal direction of the substrate, and is cut in a plane perpendicular to the normal direction of the substrate of the pattern structure and the tight edge (the wiring of the edge of the cylindrical structure). In the cross section when the pattern structure is broken, the angle formed by the line corresponding to the side surface of the pattern structure and the line corresponding to the lower surface of the pattern structure (hereinafter also referred to as "taper angle") is 80° or more, 100. A shape below ° is preferred.

Here, the pattern structure is placed under the surface of the pattern structure, and is a contact surface with the base on which the pattern structure is formed. Further, the side surface of the pattern structure is formed on the surface of the pattern structure, and is not the lower surface of the pattern structure, and is not the upper surface of the pattern structure (the (for example, parallel) surface facing the lower surface of the pattern structure, and The face that is not in contact with the aforementioned lower ground).

The photo spacer of the present invention can be formed by any method by using the photosensitive resin composition of the present invention by using a method comprising the steps (A) to (c) shown below (the photointerval of the present invention). The method of preparation of matter can be most suitably formed.

The method for producing a photo spacer of the present invention comprises the steps of: (a) forming a film of the photosensitive resin composition of the present invention described above on a substrate (hereinafter, also referred to as "film formation step" And (b) an exposure step (hereinafter, also referred to as "exposure step") of exposing at least a portion of the film, and a development step of the film after exposure to (c) exposure (hereinafter also referred to as In the "development step", a heating step (hereinafter also referred to as "film heating step") of the film after heating and development, and other steps may be provided as needed.

(A) film formation step

The film forming step is a film on which a photosensitive resin composition of the present invention described above is formed on a substrate. The photosensitive resin layer in which the photosensitive resin layer is formed as a film can be formed into a photo spacer capable of uniformly maintaining a cell thickness by other steps such as an exposure step and a development step which will be described later. By using the photo spacer of the present invention, particularly in an image of a display device (particularly a liquid crystal display device) which is liable to cause display unevenness due to variations in cell thickness, display unevenness can be effectively eliminated.

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

(a) Coating method

The coating of the photosensitive resin composition can be carried out by a well-known coating method such as spin coating, curtain coating, slit coating, dip coating, blade coating, roll coating, metal bar coating, gravure It is carried out by a printing coating method or an extrusion molding method using a popper described in the specification of U.S. Patent No. 2,681,294. In particular, JP-A-2004-89851, JP-A-2004-17043, JP-A-2003-170098, JP-A-2003-164787, JP-A-2003-10767, JP-A-2002- A method of a slit nozzle or a slit coater described in JP-A-2001-310147 or the like is suitable.

(b) Transfer method

The transfer system uses a photosensitive transfer material, and the photosensitive resin layer formed into a film shape on the temporary support is bonded to a desired one by calendering or heating calendering using, for example, a heated or/or pressurized roll or flat plate. After the substrate surface, the temporary support is peeled off to transfer the photosensitive resin layer onto the substrate. Specifically, a laminator and a lamination method described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In view of the above, it is preferred to use the method described in Japanese Laid-Open Patent Publication No. H7-110575.

In the case of forming the photosensitive resin layer, an oxygen blocking layer (hereinafter also referred to as "oxygen interrupting film" or "intermediate layer") may be further provided between the photosensitive resin layer and the temporary support. Thereby, the exposure sensitivity can be improved. Moreover, in order to improve transferability, a thermoplastic resin layer having a cushioning property may be provided.

The temporary support, the oxygen barrier layer, the thermoplastic resin layer, and other layers constituting the photosensitive transfer material, and the method for producing the photosensitive transfer material can be applied to the paragraph number of JP-A-2006-23696 [ The structure and production method described in 0024]~[0030].

In the case where the photosensitive resin layer is formed together by the (a) coating method and the (b) transfer method, the layer thickness is preferably 0.5 to 10.0 μm, and preferably 1 to 6 μm. When the layer thickness is in the above range, the occurrence of pinholes can be prevented at the time of coating formation at the time of production, and the development of the unexposed portions without development does not require a long time.

Examples of the substrate on which the photosensitive resin layer is formed include a transparent substrate (for example, a glass substrate or a plastic substrate), a substrate with a transparent conductive film (for example, an ITO film), and a substrate with a color filter (also referred to as a color filter). A light sheet substrate), a drive substrate to which a driving element (for example, a thin film transistor [TFT]) is attached, or the like. The thickness of the substrate is generally preferably from 700 to 1200 μm.

(b) exposure step, (c) development step

At least a portion of the film formed in the film forming step described above is exposed in the exposure step to form a latent image. In the subsequent development step, the film exposed in the aforementioned exposure step is developed to form a spacer pattern of a desired shape.

Specific examples of such steps include, for example, the formation examples described in paragraphs [0071] to [0077] of JP-A-2006-64921, and the paragraph numbers [0040] to [0051] of JP-A-2006-23696. The steps and the like described in the above are taken as suitable examples in the present invention.

The photo spacer of the present invention may be provided with a heating process of a film described later, and the film heating step may not be provided by increasing the exposure amount during the exposure (hereinafter, also referred to as "no heating step"). It is also possible to form a photo spacer having a uniform cross-sectional shape and excellent height uniformity.

By the "no heating step", deterioration of the formed photo spacer, deterioration of the already formed pattern structure (coloring pattern, etc.), and the protective film can be more effectively suppressed.

The exposure amount in the case of "no heating step" is preferably 1 to 500 mJ/cm ^{2 and} preferably 10 to 300 mJ/cm ₂ .

(D) film heating step

The photo spacer of the present invention can also be provided with a film heating step of heating the film after the development of the developing step. By heating, the hardening of the film can be further promoted, and a photo spacer having high strength can be obtained. Further, in the case where the photosensitive resin composition contains the resin A, a photo spacer having a higher compression modulus and deformation recovery property can be obtained.

Here, the maximum temperature at the heating varies depending on the heating time, preferably 40 ° C to 145 ° C, and more preferably 40 ° C to 140 ° C. When the maximum temperature is in the range of 40 ° C to 145 ° C, deterioration of the formed photo spacer, deterioration of the formed pattern structure (coloring pattern, etc.), and the protective film can be more effectively suppressed.

Among them, the maximum temperature during heating is 80 ° C to 140 ° C, and the heating time is preferably 0.1 to 3.0 hours (particularly 0.2 to 1 hour).

As described above, a substrate for a display device including a photo spacer can be fabricated on a substrate. The photo spacer is preferably formed on a black light-shielding portion such as a black matrix formed on a substrate, or a driving element such as a TFT. In addition, a transparent conductive layer (transparent electrode) such as ITO or an alignment film such as polyimide may be present between a black light-shielding portion such as a black matrix or a driving element such as a TFT and a photo spacer.

For example, in the case where the photo spacer is provided on the black light-shielding portion or the driving element, a black light-shielding portion (black matrix or the like) of the substrate and a driving element may be coated in advance, for example, a photosensitive transfer material may be used. After the photosensitive resin layer is laminated on the support surface, and the photosensitive resin layer is formed by peeling and transferring, exposure, development, heat treatment, or the like is applied thereto to form a photo spacer, whereby a substrate for a display device can be produced.

In the substrate for a display device of the present invention, colored pixels of three colors of red (R), blue (B), and green (G) can be provided as needed.

The photo spacer of the present invention can be formed after forming a color filter including a black mask portion such as a black matrix or a colored portion such as a color pixel.

The black masking portion, the coloring portion, and the photo spacer may be arbitrarily combined: a coating method of applying a photosensitive resin composition, and a transfer method using a transfer material having a photosensitive resin layer composed of a photosensitive resin composition. And formed.

The black shielding portion, the colored portion, and the photo spacer may be formed of a photosensitive resin composition, and specifically, the photosensitive resin composition of the liquid is directly applied onto the substrate to form a photosensitive resin. After the layer, exposure and development are performed, and the black shielding portion and the colored portion are formed into a pattern, and then the photosensitive resin composition containing the other liquid is used on the other substrate different from the substrate (temporary support) a transfer material produced by forming a photosensitive resin layer, and after the transfer material is adhered to the substrate on which the black shielding portion and the colored portion are formed, and the photosensitive resin layer is transferred, exposure is performed. Development, the photo spacer can be formed into a pattern.

By doing so, a color filter in which a photo spacer is provided can be produced.

Protective film

The protective film of the present invention is formed by using the photosensitive resin composition of the present invention described above.

Since the protective film of the present invention is formed by using the photosensitive resin composition of the present invention, even when it is formed at a low heating temperature or without heat treatment, the film thickness uniformity is excellent.

The protective film of the present invention can be formed by any method using the method of the photosensitive resin composition of the present invention, and can be formed in the same manner as the above-described method for producing a photo spacer of the present invention. Here, in the case where the protective film is not patterned, that is, in the case where the protective film is formed into a so-called beta film, the above-described (b) exposure step is preferably a method of uniformly exposing the film.

Coloring Pattern

The colored pattern of the present invention is formed by using the photosensitive resin composition of the present invention described above. Here, the photosensitive resin composition is preferably in a form containing at least one of a coloring agent in addition to the components described above.

The coloring agent is not particularly limited and can be appropriately selected from among known coloring agents. The pigments and dyes described in JP-A-2005-17716 [0038] to [0054], and those described in JP-A-2004-361447 [0068] to [0072] are specifically mentioned. A coloring agent or the like described in JP-A-2005-17521 [0080] to [0088].

Since the colored pattern of the present invention is formed by using the photosensitive resin composition of the present invention, even in the case of forming at a low heating temperature or without heat treatment, a cross-sectional shape having high uniformity and a film thickness are obtained. Uniformity is also excellent.

Further, the coloring pattern of the present invention is a case where a color filter having a coloring pattern of a plurality of colors is used as one element, and at least one coloring pattern can be formed using the photosensitive resin composition of the present invention.

The colored pattern of the present invention can be formed by any method using the photosensitive resin composition of the present invention, and can be formed, for example, by the same method as the above-described method for producing a photo spacer of the present invention.

"Substrate for display device"

The substrate for a display device of the present invention comprises the above-described photo spacer of the present invention, the protective film of the present invention, and one or more selected from the colored pattern of the present invention.

The substrate for a display device of the present invention has a cross-sectional shape and uniformity of film thickness (height) formed by using the photosensitive resin composition of the present invention (the photo spacer of the present invention, the protective film of the present invention) Further, at least one of the color patterns of the present invention is used in the display device to suppress display unevenness when the image is displayed.

Here, the substrate for a display device refers to at least one of a pair of supports constituting the display device. The specific example of the display device substrate differs depending on the configuration of the display device and the display device, and may be, for example, a color filter substrate having a colored pattern (hereinafter also referred to as "colored pixel") and a driving means. A substrate (for example, a passive matrix substrate or an active matrix substrate) with a driving means, a substrate having a partition wall attached to the partition wall (for example, a substrate having a black matrix with a black matrix), and a colored pattern A color filter array (on array) substrate and a driving method, a glass substrate on which no pattern structure or film is provided, or the like.

The coloring pattern group (colored pixel group) of the color filter substrate may be composed of pixels of two colors that do not appear to be different colors, or may be composed of pixels of three colors or pixels of four or more colors. For example, in the case of three colors, it is composed of three kinds of hue of red (R), green (G), and cyan (B). In the case of arranging a pixel group of RGB three colors, it is preferable to arrange it in a mosaic type or a triangular type, and it is possible to arrange any of the four or more pixel groups. The color filter substrate can be formed, for example, by forming a pixel group of two or more colors in a manner as described above, or conversely, forming a pixel group after forming a black matrix. For the formation of RGB pixels, JP-A-2004-347831 and the like can be referred to.

Display component

The display element can be formed using the substrate for a display device of the present invention described previously.

In one of the display elements, for example, at least one of the light-transmitting pair of supports (including a substrate for a display device) includes at least a liquid crystal layer and a liquid crystal driving means (including a passive matrix driving method and The liquid crystal display element of the source matrix driving method).

In the case of the liquid crystal display device, the substrate for a display device can be used as a color filter substrate having a plurality of RGB pixel groups and each of the pixels constituting the pixel group is separated from each other by a black matrix. Since the color filter substrate is provided with a pattern structure having a uniform cross-sectional shape and uniformity of film thickness (height), the liquid crystal display element including the color filter substrate can be effectively suppressed: resulting from a color filter The variation in the cell pitch (cell thickness) between the substrate and the counter substrate occurs due to unevenness in color unevenness due to partial deviation of the liquid crystal material or low-temperature foaming. Thereby, the liquid crystal display element produced can display a clear image.

In a more detailed aspect of the liquid crystal display device, for example, at least one of the light-transmitting pair of supports (including a substrate for a liquid crystal display device) includes at least a liquid crystal layer and a liquid crystal driving means, and the liquid crystal The driving means has an active element (for example, a TFT), and a pair of substrates are formed by defining a predetermined width of the photo spacer.

Display device

The display device of the present invention includes the above-described substrate for a display device.

Since the display device of the present invention includes the substrate for a display device of the present invention having a cross-sectional shape and a uniform pattern thickness (height) uniformity, it is possible to suppress display unevenness.

The display device may be, for example, a display device such as a liquid crystal display device, a plasma display display device, an EL display device, or a CRT display device. The definition of the display device and the description of each display device are described in, for example, "Electronic display device (sasaki Sasaki, Industrial (stock) survey society issued in 1990)", "display device (Ibuki Shunzhang, industrial book (share) ) issued in the first year of Heisei).

Among the display devices, a liquid crystal display device is preferred.

The liquid crystal display device is configured by, for example, arranging a liquid crystal material with a predetermined width between one of the opposing surfaces of the optical spacer, and enclosing the liquid crystal layer (the sealed portion is referred to as a liquid crystal layer) in a predetermined gap. The thickness of the layer (cell thickness) is maintained to a desired uniform thickness.

The liquid crystal display mode in the liquid crystal display device may be, for example, an STN type, a TN type, a GH type, an ECB type, a ferroelectric liquid crystal, an antiferroelectric liquid crystal, a VA type, an IPS type, an OCB type, an ASM type, or the like. It is suitable. In the liquid crystal display device of the present invention, the display mode in which display unevenness is unlikely to occur due to fluctuations in the cell thickness of the liquid crystal cell is desired from the viewpoint of exhibiting the effect of the present invention most effectively. It is preferable to form a VA type display mode, an IPS type display mode, or an OCB type display mode in which the cell thickness is 2 to 4 μm.

Further, the liquid crystal used in the present invention may, for example, be a nematic liquid crystal, a cholesteric liquid crystal, a smectic liquid crystal or a ferroelectric liquid crystal.

In the basic configuration of the liquid crystal display device, for example, (a) a light-transmitting spacer is used, and a driving side substrate including a driving element such as a thin film transistor (TFT) and a pixel electrode (conductive layer) is arranged and aligned. The electrode (conductive layer) is disposed opposite to the opposite substrate, and the liquid crystal material is sealed in the gap portion; (b) the light-transmitting spacer is provided to have the driving substrate and the counter electrode (conductive layer) facing each other The liquid crystal display device of the present invention can be suitably used for various liquid crystal display devices in which the substrates are arranged in opposite directions and a liquid crystal material is sealed in the gap portions.

The liquid crystal display device is described in, for example, "Second Generation Liquid Crystal Display Technology (Edited by Uchida Natsuo, Side Industry Survey, issued in 1994)". In addition to the liquid crystal display element of the present invention, the liquid crystal display device of the present invention is not particularly limited, and the liquid crystal display device can be configured, for example, in various forms described in the "second-generation liquid crystal display technology". Among them, it is effective particularly in a liquid crystal display device constituting a color TFT system. A liquid crystal display device of a color TFT type is described, for example, in "Color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., issued in 1996)".

The liquid crystal display device can generally use an electrode substrate, a polarizing film, a retardation film, a backlight, a photo spacer, and the like, in addition to the above-described photo spacer, coloring pattern, protective film, substrate for liquid crystal display device, and liquid crystal display device. A wide variety of members such as a viewing angle compensation film, an antireflection film, a light diffusion film, and an antiglare film are used. These components are, for example, "'94 Liquid Crystal Display Peripherals, Chemicals Markets (Island Kentaro, CMC (shares), issued in 1994)", "2003 Liquid Crystal Related Market Status and Future Outlook (Volume 2)" It is described in "Bian Liangji, Fuji Chimera (share) general research, 2003, etc.). Japanese Patent Application No. 2008-092583, filed on March 31, 2008, and Japanese Patent Application No. 2008-092584, the priority of each of which is incorporated herein by reference. .

Example

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to the following examples as long as it does not exceed the gist thereof. In addition, "parts" are quality standards unless otherwise specified.

Further, the weight average molecular weight was measured by gel permeation chromatography (GPC). The GPC system uses HLC-8020GPC (manufactured by Tosoh Corporation), and the column system uses three TSKgels, Supermultipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm), and the eluent is THF (tetrahydrofuran). ). Further, the conditions were carried out using an IR detector with a sample concentration of 0.045 mg/mL, a flow rate of 0.35 mL/min, a sample injection amount of 10 μL, and a measurement temperature of 40 °C. In addition, the calibration line is made of Tosoh Corporation's "standard sample TSK standard, polystyrene"; "F-40", "F-20", "F-4", "F-1", "A-5000" Eight samples of "A-2500", "A-1000", and "n-propylbenzene" were produced.

<Synthesis of Resin A>

First, the synthesis of the exemplified compounds P-52, P-51, P-53, P-46, and P-47 exemplified as the specific examples of the resin A described above is carried out as a photosensitive resin composition. The resin used in the process. Further, the other resin A used in the present embodiment can also be synthesized by a similar method of changing the corresponding monomer.

(Synthesis of Compound P-52)

In the reaction vessel, 7.48 parts of 1-methoxy-2-propanol (MFG, manufactured by EMULSION, Japan) was added in advance, and the temperature was raised to 90 ° C, and 3.1 parts of styrene (St) and tricyclopentyl methacrylate were added. Ester ester (TCPD-M manufactured by Hitachi Chemical Co., Ltd.; x) 4.28 parts, methacrylic acid (MAA; y) 11.7 parts, azo polymerization initiator (Wako Pure Chemical Co., Ltd., V-601) A mixed solution of 2.08 parts and 55.2 parts of 1-methoxy-2-propanol was dropped into a reaction vessel at 90 ° C for 2 hours under a nitrogen atmosphere. After dropping, it was allowed to react for 4 hours to obtain an acrylic resin solution.

Next, 0.15 parts of hydroquinone monomethyl ether and 0.34 parts of tetraethylammonium bromide were added to the acrylic resin solution, and then glycidyl methacrylate (GLM, manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped for 2 hours. ) 26.4 parts (GLM-MAA; z). After dropping, the reaction was carried out at 90 ° C for 4 hours while blowing air, and then the solvent 1-methoxy-2-propyl acetate (MMPGAc, Daisy) was added so as to form a solid concentration of 45%. Prepared by the Chemical Industry Co., Ltd. to obtain a resin solution of the exemplified compound P-52 (Resin A) containing a structural unit derived from styrene in the previously described exemplified compound P-51 having an unsaturated group. (solid content acid value; 76.0 mg KOH / g, Mw; 25,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution) (x; y; z; St = 30 mol%; 27 mol%; 37 mol%; 6 mol%).

Here, GLM-MAA shows that glycidyl methacrylate is bonded to methacrylic acid (the same applies hereinafter).

Further, the molecular weight Mw of the exemplified compound P-52 represents a weight average molecular weight, and the measurement of the weight average molecular weight is carried out by gel permeation chromatography (GPC method) (the same applies hereinafter).

(Synthesis of Compound P-51)

In the synthesis of the aforementioned exemplified compound P-52, except that styrene was not used, x; y; z in the exemplified compound P-51 was 34 mol%; 27 mol%; 39 mol%, changed TCPD-M (x), methyl group In addition to the addition amount of the acrylic acid (y) and GLM-MAA (z), the synthesis was carried out in the same manner as in the synthesis of the above-exemplified compound P-52 to obtain an exemplified compound P-51 having an unsaturated group (resin Resin solution of A) (solid content acid value; 72.5 mg KOH/g, Mw; 22,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution).

(Exemplified synthesis of compound P-53)

In the synthesis of the above-exemplified compound P-52, methacrylic acid was replaced by dicyclopentenyloxyethyl methacrylate (FANCRYL FA-512M manufactured by Hitachi Chemical Co., Ltd.) without using styrene. Cyclopentene ester, such that x; y; z in the exemplified compound P-53 is 46.2 mol%; 24.3 mol%; 29.5 mol%, and the change of FA-512M (x), methacrylic acid (y), GLM-MAA In addition to the addition amount of (z), the synthesis was carried out in the same manner as in the synthesis of the above-exemplified compound P-52 to obtain a resin solution (solid component acid) of the exemplified compound P-53 (resin A) having an unsaturated group. Price; 71.2 mg KOH/g, Mw; 25,500, 1-methoxy-2-propanol/1-methoxy-2-propyl acetate 45% solution).

(Synthesis of Compound P-46)

In the synthesis of the above-exemplified compound P-52, in place of the substitution of ADMA (manufactured by Idemitsu Kosan Co., Ltd.) for tricyclopentenyl methacrylate, the composition of the structural unit derived from styrene is added to the exemplified compound P-1. x; y; z; St is 30 mol%; 24 mol%; 38 mol%; 8 mol%, by changing the addition amount of ADMA (x), methacrylic acid (y), GLM-MAA (z), and styrene, by The synthesis was carried out in the same manner as in the synthesis of the above-exemplified compound P-52 to obtain a resin in which an exemplary compound P-46 (resin A) derived from a structural unit of styrene was added to the exemplified compound P-1 having an unsaturated group. Solution (solid content acid value; 74.1 mg KOH/g, Mw; 29,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution).

(Synthesis of Compound P-47)

In the synthesis of the aforementioned exemplified compound P-52, except for methacrylic acid The base (IBXMA, manufactured by Wako Pure Chemical Industries, Ltd.) is substituted for tricyclopentenyl methacrylate, and the composition of the structural unit derived from styrene is added to the exemplified compound P-2. x; y; z; St is 34 mol% ; 24 mol%; 36 mol%; 6 mol%, modified IBXMA (x), methacrylic acid (y), GLM-MAA (z), and styrene added, by the same as the synthesis of the exemplified compound P-52 A method of synthesizing to obtain a resin solution of an exemplary compound P-47 (resin A) containing a structural unit derived from styrene in an exemplary compound P-2 having an unsaturated group (solid content acid value; 72.9 mgKOH/g) Mw; 29,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution).

[Example 1]: Coating method

<Production of Color Filter Substrate>

Color filter having black matrix, R (red) pixel, G (green) pixel, and B (blue) pixel is prepared according to the method described in paragraphs [0084] to [0095] of JP-A-2005-3861 A sheet (hereinafter, referred to as a color filter substrate). Here, the substrate size of the color filter substrate is 550 mm × 650 mm.

Next, on the R pixel, the G pixel, the B pixel, and the black matrix of the obtained color filter substrate, a transparent electrode of ITO (Indium Tin Oxide) was sputtered.

<Formation of photo spacers>

The ITO transparent electrode of the color filter substrate formed by sputtering the ITO transparent electrode prepared above was formed by a spinner and slit coating by the formulation shown in Table 1 below (Formulation 1 in Example 1). A coating liquid for a photosensitive resin layer. Then, using a vacuum dryer VCD (manufactured by Tokyo Ohka Co., Ltd.), a part of the solvent was dried for 30 seconds until the coating film had no fluidity, and then prebaked on a hot plate at 90 ° C for 3 minutes to form a film thickness. 5.2 μm photosensitive resin layer (film formation step).

Continuing, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Co., Ltd.) having an ultra-high pressure mercury lamp, a mask (a quartz exposure mask having a circular pattern of 15 μm in diameter), a mask and a photosensitive resin The color filter substrate disposed in the opposite direction is in an upright state that is approximately parallel and perpendicular, and the distance between the mask surface and the surface of the photosensitive resin layer is set to 100 μm, and the mask is passed through the mask at 365 nm. The intensity was 250 W/m ² and was irradiated with ultraviolet rays through an ultraviolet transmission filter (UV-35, manufactured by Toshiba Glass Co., Ltd.) (exposure amount: 200 mJ/cm ₂ ; exposure step).

Next, a Na carbonate-based developing solution (containing 0.38 mol/liter sodium hydrogencarbonate, 0.47 mol/liter sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, an anionic surfactant, an antifoaming agent, And stabilizer; trade name: T-CD1 (Fuji film (manufactured by Fujifilm)) diluted with pure water to a 10-fold dilution), at 29 ° C for 30 seconds, with a cone nozzle pressure of 0.15MPa for shower imaging, To form a pattern image (development step). Then, using a detergent (containing phosphate ‧ citrate ‧ nonionic surfactant ‧ defoamer ‧ stabilizer; trade name: T-SD3 (Fuji film (stock))) diluted 10 times with pure water The diluted solution was showered at 33 ° C for 20 seconds at a conical nozzle pressure of 0.02 MPa, and the residue around the formed pattern image was removed to form a cylindrical spacer pattern of 300 μm × 300 μm. The root spacers are spaced apart.

Next, the color filter substrate provided with the spacer pattern was subjected to heat treatment (heating step) at 140 ° C for 60 minutes to form a photo spacer on the color filter substrate. Here, 1000 pieces of the obtained photo spacers were measured using a three-dimensional surface structure analysis microscope (manufacturer; ZYGO Corporation, type: New View 5022), and the upper surface of the ITO transparent electrode (the two surfaces parallel to the substrate, The distance from the side of the substrate to the highest position of the photo spacer (hereinafter, this distance is also referred to as "the height of the photo spacer") is used, and the average value is taken as the average height of the photo spacer.

Further, the measurement of the bottom area of the obtained photo spacer was carried out using SEM photographing. The result was a cylindrical shape having a diameter of 15.1 μm and an average height of 4.7 μm.

<Production of Liquid Crystal Display Device>

Further, a glass substrate is prepared as a counter substrate, and a pattern for PVA mode is applied to each of the transparent electrode and the counter substrate of the color filter substrate obtained above, and a polyimide film is formed thereon. Alignment membrane.

Then, the sealing agent for the ultraviolet curable resin is applied by a dispenser method so as to surround the pixel group surrounding the color filter, and the liquid crystal for PVA mode is dropped and the counter substrate After the bonding, after the irradiated substrate is irradiated with UV, heat treatment is performed to harden the sealant. On both sides of the thus obtained liquid crystal cell, a polarizing plate HLC2-2518 manufactured by SANRITZ Co., Ltd. was attached.

Next, FR1112H (a substrate type LED made by STONELEY Electric Co., Ltd.) was used as a red (R) LED, and DG1112H (a substrate type LED made by STONELEY Electric Co., Ltd.) was used as a green (G) LED, and DB1112H (STONELEY) was used. The substrate type LED made of electric (share) is a blue (B) LED to constitute a backlight of the side light type, and the polarizing plate is disposed on the back side of the liquid crystal cell to be formed to form a liquid crystal display device.

<evaluation>

The following evaluation was performed about the obtained photo spacer and liquid crystal display device. The results of the measurement evaluation are shown in Table 2 below.

(cross-sectional shape of the photo spacer)

The heat-treated photo spacer obtained in the above-mentioned <formation of photo spacers> was cut by a plane parallel to the normal direction of the substrate, and the shape of the cross section was observed by a scanning electron microscope. The observation was performed on a total of five locations on the peripheral portion of the substrate and the central portion of the substrate, and the cross-sectional shape of the photo spacer was evaluated in accordance with the following criteria.

~ Evaluation benchmark ~

A; In all five places, a photo spacer having a cross-sectional shape having a taper angle of 45° or more and 90° or less is formed.

B; in all of the five places, although a light spacer having a cross-sectional shape having a taper angle of 45° or more and 95° or less is formed, compared with the above A, the angle from the taper is slightly larger. The words are getting worse.

C; a photo spacer having a cross-sectional shape having a taper angle of 40° or more and 100° or less is formed in all five places, but the angle from the taper angle is larger than the above-mentioned A and B. The words are getting worse.

D; at 1 to 4 places of 5, a photo spacer having a taper angle not in the range of 40° or more and 100° or less is formed.

E; a photo spacer having a taper angle not in the range of 40° or more and 100° or less is formed in all five places.

(high uniformity of photo spacers)

The difference between the maximum value and the minimum value was calculated from the results of the height of 1000 parts of the photo-spacer measured by the above-mentioned <formation of photo spacers>, and evaluated according to the following criteria. The degree of homogeneity indicates that the smaller the difference in values, the more excellent the uniformity.

~ Evaluation benchmark ~

A: The difference between the maximum value and the minimum value of the height of the photo spacer is less than 0.2 μm.

B: The difference between the maximum value and the minimum value of the height of the photo spacer is 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 photo spacer is 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 is 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 is 0.5 μm or more.

(Evaluation of heat treatment conditions)

The evaluation of the heat treatment conditions was carried out in the following order.

First, in the same manner as the above-mentioned <formation of photo spacers>, the exposure to the amount of exposure was changed to 250 mJ/cm ² , and the operation after the residue treatment and before the heat treatment was performed to prepare an evaluation having a spacer pattern. Use the sample.

With respect to the obtained sample for evaluation, the cross-sectional shape of the photo spacer and the height uniformity of the photo spacer when the heat treatment was performed without changing the heating temperature and the heat treatment was performed (the heat treatment time was fixed to 60 minutes) was evaluated. The method for evaluating the cross-sectional shape of the photo spacer and the height uniformity of the photo spacer is as described above.

Based on the evaluation results of the cross-sectional shape of the photo spacer and the height uniformity of the photo spacer, the evaluation of the heat treatment conditions was performed in accordance with the following criteria.

In addition, in the following evaluation criteria, the state in which the "cross-sectional shape excellent in uniformity" refers to the state of A, B, or C in the evaluation criteria of the cross-sectional shape of the photo spacer. In addition, in the following criteria, the state of "high degree of uniformity" means the state of A, B, or C in the evaluation criteria of the height uniformity of the photo spacer.

~ Evaluation benchmark ~

A; without a heat treatment, a spacer pattern having excellent cross-sectional shape uniformity and high uniformity was obtained.

B; a heating agent having a uniformity of cross-sectional shape and a spacer pattern excellent in height uniformity, which is lower than 80 °C.

C; The heating temperature is 80 ° C or more and less than 150 ° C, and a spacer pattern having excellent cross-sectional shape uniformity and high uniformity is obtained.

D; The heating temperature is 150 ° C or more and less than 200 ° C, and a spacer pattern having excellent cross-sectional shape uniformity and high uniformity is obtained.

E; The heating temperature is 200 ° C or more, and a spacer pattern having excellent cross-sectional shape uniformity and high uniformity is obtained.

(deformation recovery rate)

The obtained photo-spacer was measured and evaluated by a microhardness tester (DUH-W201, manufactured by Shimadzu Corporation) as follows. The measurement was carried out by using a 50 μm crucible round hammer press with a maximum load of 50 mN and a holding time of 5 seconds in accordance with the load-loading test method. From the measured values, the deformation recovery ratio [%] was determined according to the following formula, and the evaluation was performed based on the following evaluation criteria. The measurement was carried out in an environment of 22 ± 1 ° C and 50% RH.

Deformation recovery rate (%)

= (the amount of recovery after the load is opened [μm] / the amount of deformation at the load [μm]) × 100

~ Evaluation benchmark ~

A: The deformation recovery rate is 90% or more.

B: The deformation recovery rate is 87% or more and less than 90%.

C: The deformation recovery rate is 85% or more and less than 87%.

D: The deformation recovery rate is 80% or more and less than 85%.

E: The deformation recovery rate is 75% or more and less than 80%.

F: The deformation recovery rate is less than 75%.

(The display of the liquid crystal display device is uneven)

In the liquid crystal display device produced as described above, the gray scale display when the test signal of the gray scale was input was visually observed, and the presence or absence of display unevenness was evaluated in accordance with the following evaluation criteria. The evaluation results are shown in Table 2 below.

~ Evaluation benchmark ~

A: No unevenness was displayed, and a very good display image was obtained.

B: Although the edge portion of the glass substrate was slightly uneven, it did not affect the display portion and the display image was good.

C: A slight unevenness was observed on the display unit, but it was within the practical tolerance range.

D: Unevenness was observed on the display unit.

[Examples 2 to 13]: Coating method

In the first embodiment, a photo spacer and a liquid crystal display device were produced in the same manner as in the first embodiment except that the type of the polymerizable compound was changed as shown in the following Table 2. The same evaluation as in Example 1 was carried out on the obtained photo spacer and liquid crystal display device. The evaluation results are shown in Table 2 below.

[Examples 14 to 18]: Coating method

In the first embodiment, a photo spacer and a liquid crystal display device were produced in the same manner as in the first embodiment except that the type of the polymerizable compound and the resin were changed as shown in the following Table 2.

Further, the formulation of the photosensitive resin composition was the same as the above-mentioned Formulation 1 in Examples 14 to 17, and the above Formulation 2 in Example 18. Moreover, the same evaluation as in Example 1 was carried out on the obtained photo spacer and liquid crystal display device. The evaluation results are shown in Table 2 below.

[Example 19]: Coating method

In the first embodiment, a photo spacer and a liquid crystal display device were produced in the same manner as in Example 1 except that the formulation of the photosensitive resin composition was changed to the formulation 4 in Table 1. The same evaluation as in Example 1 was carried out on the obtained photo spacer and liquid crystal display device. The evaluation results are shown in Table 2 below.

[Example 20]: Transfer method

In the first embodiment, the formulation for the photosensitive resin layer is replaced by the formulation of the coating liquid for the photosensitive resin layer, and the coating liquid for the photosensitive resin layer is replaced by the coating for the use of the spacer shown below. A photo spacer and a liquid crystal display device were produced in the same manner as in Example 1 except that the transfer film was transferred to form a photosensitive resin layer. The resulting photo spacer is cylindrical in shape. The same evaluation as in Example 1 was carried out on the obtained photo spacer and liquid crystal display device. The evaluation results are shown in Table 2 below.

<Production of Photosensitive Transfer Film for Spacer>

The coating liquid for a thermoplastic resin layer composed of the following Formula A was applied onto a polyethylene terephthalate film temporary support (PET temporary support) having a thickness of 75 μm, and dried to form a dry layer thickness. It is a thermoplastic resin layer of 15.0 μm.

~Formulation A of coating liquid for thermoplastic resin layer~

‧Methyl methacrylate/2-ethylhexyl acrylate/Benzyl methacrylate/methacrylic acid copolymer 25.0 parts

(=55/11.7/4.5/28.8 [Morby], weight average molecular weight 90,000)

‧ Styrene / Acrylic Copolymer 58.4

(=63/37 [Morbi], weight average molecular weight 8,000)

‧2,2-bis[4-(methacryloxypolyethoxy)phenyl]propane 39.0 parts

‧The following surfactants 1 10.0 parts

‧Methanol 90.0 parts

‧1-methoxy-2-propanol 51.0 parts

‧ methyl ethyl ketone 700 parts

* surfactant 1

‧The following structures 1 30%

‧ methyl ethyl ketone 70%

Next, the coating liquid for an intermediate layer composed of the following Formula B was applied onto the formed thermoplastic resin layer, and dried to laminate an intermediate layer having a layer thickness of 1.5 μm.

~ Formulation of coating solution for intermediate layer B~

‧ polyvinyl alcohol 3.22 parts

(PVA-205 (saponification rate 80%), can be made by Pharmacy (share))

‧ polyvinylpyrrolidone 1.49 parts

(PVPK-30, ISB‧ Japan Co., Ltd.)

‧Methanol 42.3 parts

‧ distilled water 524

Then, the coating liquid for a photosensitive resin layer composed of the formulation 3 shown in Table 1 above was applied to the formed intermediate layer, and dried to laminate a photosensitive resin layer having a layer thickness of 5.0 μm.

As described above, the laminated structure of the PET temporary support/thermoplastic resin layer/intermediate layer/photosensitive resin layer (the total thickness of the three layers; 21.5 μm) is formed, and then the surface of the photosensitive resin layer is heated and pressurized. A polypropylene film as a cover film having a thickness of 12 μm was attached to obtain a photosensitive transfer film for a spacer.

<Production of Photo spacers>

The obtained spacer was peeled off with a cover film of a photosensitive transfer film, and the surface of the exposed photosensitive resin layer was superposed on the ITO transparent of the color filter substrate formed by sputtering the ITO transparent electrode formed in the same manner as in Example 1. On the electrode, a laminator type Lamic II type [manufactured by Hitachi Industrial Co., Ltd.] was used, and under pressure and heating conditions of 100 N/cm and 130 ° C were applied, and the bonding speed was 2 m/min. Subsequently, the PET temporary support is peeled off at the interface with the thermoplastic resin layer, and the photosensitive resin layer is transferred together with the thermoplastic resin layer and the intermediate layer (film formation step).

Continuing, a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Co., Ltd.) having an ultra-high pressure mercury lamp is used, and a mask (a quartz exposure mask having an image pattern) is opposed to the mask and the thermoplastic resin layer. The color filter substrate is disposed in a state of being substantially parallel and vertically erected, and a distance between the surface of the mask and the surface of the photosensitive resin layer on the side close to the intermediate layer is 100 μm, and is transmitted through the mask from the side of the thermoplastic resin layer. The exposure amount was 90 mJ/cm ² to perform the proximity exposure (exposure step).

Next, a triethanolamine-based developing solution (containing 30% of triethanolamine, trade name: T-PD2 (manufactured by Fujifilm Co., Ltd.) was diluted to 12 times with pure water (1 part with T-PD2 and 11 with pure water) The proportion of the mixture was mixed) at 30 ° C for 50 seconds, and shower development was carried out at a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer. Then, the air was blown on the upper surface of the glass substrate to be liquid-cut, and then pure water was showered for 10 seconds by showering, and pure water shower was washed, and air was blown to reduce the liquid on the substrate. Continuing, using a Na-carbonic acid imaging solution (0.38 mol/L sodium bicarbonate, 0.47 mol/L sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, an anionic surfactant, an antifoaming agent, and The stabilizer is contained; the product name: T-CD1 (manufactured by Fujifilm Co., Ltd.) diluted with pure water to a 10-fold dilution), and subjected to shower development at a cone nozzle pressure of 0.15 MPa at 30 ° C for 30 seconds. To form a pattern image (development step).

Next, use a detergent diluted with pure water (containing phosphate ‧ citrate ‧ nonionic surfactant ‧ defoamer ‧ stabilizer; trade name: T-SD3 (Fuji film)) 10 times The diluted solution was showered at 33 ° C for 20 seconds at a conical nozzle pressure of 0.02 MPa, and the surrounding residue of the formed pattern image was removed, and the columnar spacer pattern was set at an interval of 300 μm × 300 μm. The space formed by the object.

Next, the color filter substrate in which the spacer pattern was formed was subjected to heat treatment at 130 ° C for 60 minutes (film heating step) to form a photo spacer on the color filter substrate. The obtained photo spacer was a cylindrical shape having a diameter of 15.1 μm and an average height of 4.7 μm.

Further, a PVA mode liquid crystal display device was produced in the same manner as in Example 1 using a color filter substrate on which a photo spacer was formed.

[Comparative Example 1]

In the first embodiment, a photo spacer and a liquid crystal display device were produced in the same manner as in Example 1 except that the polymerizable compound was changed to the comparative compound W-1 described below. The same evaluation as in Example 1 was carried out for the photo spacer and the liquid crystal display device. The evaluation results are shown in Table 2 below.

[Comparative Example 2]

In Example 1, a light interval was produced in the same manner as in Example 1 except that the composition of the photosensitive resin composition was changed to Formulation 5 and the polymerizable compound was changed to DPHA (dipentaerythritol hexaacrylate). And liquid crystal display device. The same evaluation as in Example 1 was carried out for the photo spacer and the liquid crystal display device. The evaluation results are shown in Table 2 below.

As shown in the above Table 2, the photo spacer of the embodiment has high uniformity in cross-sectional shape and can suppress height shift. Further, the liquid crystal display device including the obtained photo spacer can suppress display unevenness.

[Example 21]

<Formation of Protective Film>

In the production of the color filter substrate of the eighth embodiment, after the black matrix, the R pixel, the G pixel, and the B pixel are formed, the photosensitive resin composed of the above formulation 1 is applied to the black matrix and each pixel. The composition is exposed (overall exposure) and heat-treated without passing through a mask to form a protective film. Here, the conditions of the coating, the exposure, and the heat treatment are the same as those of the coating, exposure, and heat treatment in the formation of the photo spacer of Example 8, except that the exposure is not performed through the mask.

Next, a transparent electrode of ITO (Indium Tin Oxide) was sputtered on the obtained protective layer to form.

<Formation of photo spacers>

On the ITO transparent electrode formed above, a photo spacer was formed in the same manner as in Example 1 except that the photosensitive resin composition used in Comparative Example 2 was used as the photosensitive resin composition.

<Production and evaluation of liquid crystal display device>

Next, a liquid crystal display device was produced in the same manner as in Example 1 using a color filter substrate on which the photo spacers were formed.

The obtained protective film and liquid crystal display device were evaluated in the same manner as in Example 1. Further, the evaluation of the film thickness uniformity was carried out in the same manner as in "the height uniformity of the photo spacer" of Example 1. The evaluation results are shown in Table 3.

[Comparative Example 3]

In the same manner as in Example 21 except that the polymerizable compound was changed to the comparative compound W-1, a protective film, a photo spacer, and a liquid crystal display device were produced, and the same evaluation was carried out. The evaluation results are shown in Table 3 below.

[Example 22]

<Formation of Colored Pattern>

In the production of the color filter substrate of Example 8, a color filter substrate was produced in the same manner as in Example 8 except that the R pixel was formed by the following method.

In other words, Pigment Red 254 (19.4 parts) and Pigment Red 177 (4.83 parts) were added to the above-mentioned Formulation 1 to prepare a photosensitive resin composition for R pixels.

R pixels were formed by the same method as the formation of the photo spacers of Example 1, except that the photosensitive resin composition for R pixels to be prepared and the photomask for R pixels were used as the photomask.

After the R pixel, the G pixel, and the B pixel of the color filter substrate to be formed are formed, a transparent electrode of ITO (Indium Tin Oxide) is formed by sputtering on each pixel.

<Formation of photo spacers>

A photo spacer was formed in the same manner as in Example 1 except that the photosensitive resin composition used in Comparative Example 2 was used as the photosensitive resin composition on the ITO transparent electrode formed as described above.

<Production and evaluation of liquid crystal display device>

Next, a liquid crystal display device was produced in the same manner as in Example 1 using a color filter substrate on which the photo spacers were formed.

The obtained protective film and liquid crystal display device were evaluated in the same manner as in Example 1. Further, the evaluation of the film thickness uniformity was carried out by the same method as the "height uniformity of the photo spacer" of Example 1. The evaluation results are shown in Table 3.

[Comparative Example 4]

In the same manner as in Example 22 except that the polymerizable compound was changed to the above-mentioned comparative compound W-1, a colored pattern, a photo spacer, and a liquid crystal display device were produced, and the same evaluation was carried out. The evaluation results are shown in Table 3 below.

As shown in the above Table 3, in the case where the protective film and the colored pattern were formed using the photosensitive resin composition of the present invention, the same results as in the case of forming the photo spacer were obtained.

According to the present invention, it is possible to provide a photosensitive resin composition which is excellent in polymerization hardenability at the time of exposure and which can form a pattern structure or a protective film under low-temperature heat treatment or without heating.

Moreover, according to the present invention, it is possible to provide a photo spacer having a high cross-sectional shape with high uniformity and excellent uniformity of height and a method for producing the same.

Moreover, according to the present invention, it is possible to provide a protective film having excellent film thickness uniformity or a colored pattern having a uniform cross-sectional shape and excellent film thickness uniformity.

Moreover, 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 capable of suppressing display unevenness.

The above description of specific aspects of the invention is provided for the purposes of illustration and description. The invention is not intended to be limited to the scope of the invention disclosed, or the scope of the invention. This aspect is selected to best illustrate the concepts of the present invention or its actual application, and therefore should be applicable to the particular use sought by others of the industry, and can be varied and varied. The manner in which the invention can be understood by others of the industry.

All journals and patent applications and technical standards described in this specification, especially in the case where their individual journals and patent applications, and technical standards are cited and individually specified, will be the same as the cited documents. The limited scope is incorporated in this specification. The details of the preferred embodiment of the present invention described above may of course be changed to a variety of application forms according to the manner in which the applicant applies. The scope of the invention is determined by the scope of the following patent claims and their equivalents.

Claims (8)

A method for producing a photo spacer, characterized in that it comprises at least the following steps (A) to (d): (a) forming a polymerizable compound containing a resin, having the following structural portion (I) on a substrate, and photopolymerization initiation a step of forming a film of the photosensitive resin composition of the agent, [In the structural part (I), X represents a hydrogen atom or a methyl group, * represents a bonding bond]; (B) an exposure step of exposing at least a part of the film; (c) the film after exposure exposure a developing step; (d) heating step of the film after heating and development; and a maximum temperature at the time of heating in the above step (d) is 40° C. or higher and 145° C. or lower. The method for producing a photo spacer according to claim 1, wherein the polymerizable compound has at least two of the aforementioned structural portions (I) in the molecule. The method for producing a photo-spacer according to the first aspect of the invention, wherein the polymerizable compound has a symmetrical structure in which two groups including the structural portion (I) are bonded. The method for producing a photo-spacer according to the first aspect of the invention, wherein the polymerizable compound having the structural portion (I) is a polymerizable compound represented by the following structural formula (II), [In the formula, R represents a linking group containing at least one ether bond between carbon and carbon of a divalent hydrocarbon group, and X represents a hydrogen atom or a methyl group]. The method for preparing a photo spacer according to claim 4, wherein in the above structural formula (II), R represents -CH ₂ -OR ^a -O-CH ₂ -, and R ^a represents a selected from alkyl The linking group of the group, the aryl group, and the group in which these are combined. The method of producing a photo-spacer according to claim 1, wherein the resin has a branch having a branching and/or alicyclic structure, an acidic group, and an ethylenically unsaturated bond in the side chain. The method for producing a photo spacer according to claim 6, wherein the acid value of the resin is 20 mgKOH/g or more. The method for producing a photo spacer according to claim 6, wherein the base having the branched and/or alicyclic structure is a group represented by the following formula (3), In the general formula (3), X' represents a divalent organic linking group, and may be unsubstituted or may have a substituent, and y represents 1 or 2, and n represents an integer of 0 to 15].