JP5030599B2 - PHOTOSPACER FOR LIQUID CRYSTAL DISPLAY, ITS MANUFACTURING METHOD, AND LIQUID CRYSTAL DISPLAY DEVICE - Google Patents

Description

  The present invention relates to a method of manufacturing a photo spacer for a liquid crystal display suitable for manufacturing a spacer constituting a display device in which fluctuations in the cell thickness of the liquid crystal cell tend to cause display unevenness, a photo spacer for a liquid crystal display manufactured by this method, and the liquid crystal The present invention relates to a liquid crystal display device including a photo spacer for display.

  Conventionally, liquid crystal display devices are widely used in display devices that display high-quality images. In general, a liquid crystal display device is provided with a liquid crystal layer capable of displaying an image with a predetermined orientation between a pair of substrates, and maintaining the spacing between the substrates, ie, the thickness of the liquid crystal layer, is an element that determines image quality. Therefore, a spacer for keeping the thickness of the liquid crystal layer constant is disposed between the substrates. The thickness between the substrates is generally referred to as “cell thickness”, and the cell thickness usually indicates the thickness of the liquid crystal layer, in other words, the distance between two electrodes applying an electric field to the liquid crystal in the display area. It is.

  Conventionally, the spacer has been formed by bead dispersion, but in recent years, a spacer with high positional accuracy has been formed by photolithography using a photosensitive composition. A spacer formed using such a photosensitive composition is called a photospacer.

  Photo spacers prepared by patterning, alkali development, and baking using a photosensitive composition have a weak compressive strength of the spacer dots, and tend to increase plastic deformation during panel formation. For high-quality image display, it is required that there is no problem that uniformity cannot be maintained because the thickness of the liquid crystal layer becomes smaller than the design value due to plastic deformation, or that there is no problem of image unevenness.

In relation to the above, as a spacer forming technique for finely adjusting the thickness (cell thickness) of the liquid crystal layer, a method of changing post-bake conditions at the time of spacer formation is disclosed (for example, see Patent Document 1).
JP 2003-330030 A

  Originally, a photo spacer used in a liquid crystal cell is required to have high deformation recovery. In order to achieve this, the crosslinking reaction rate of monomers and the like is increased, and the deformation recovery rate can be increased to some extent, but the improvement effect tends to reach its peak, and further improvement is required. It was.

  INDUSTRIAL APPLICABILITY The present invention has a high degree of deformation recovery and can provide a liquid crystal display photospacer that can eliminate display unevenness in a liquid crystal display device, a manufacturing method thereof, and display of high-quality images by preventing display unevenness. An object is to provide a liquid crystal display device and to achieve the object.

The present invention has the knowledge that the deformation recovery property of the photo spacer is dramatically improved by making the exposure amount in the post-exposure step within a predetermined range, and it is particularly effective for improving the display unevenness of the liquid crystal display device, This has been achieved based on such knowledge.
Specific means for achieving the above object are as follows.

<1> A resin layer forming step of forming a photosensitive resin layer containing at least a polymer compound having a crosslinkable group on a support, an exposure step of exposing the photosensitive resin layer in a pattern, and the photosensitive property A method for producing a photospacer for a liquid crystal display, comprising: a development step for removing an unexposed portion of a resin layer; and a post-exposure step for exposing the photosensitive resin layer from which an unexposed portion has been removed, wherein the post-exposure is performed. In the step, the exposure amount of the surface of the support on which the photosensitive resin layer is formed is an exposure amount that is 7.5 times or more the minimum exposure amount required to cure the photosensitive resin layer, An exposure amount on a surface opposite to the surface on which the photosensitive resin layer of the support is formed is 10 mJ / cm ² or less.

<2> In the post-exposure step, the exposure amount of the surface of the support on which the photosensitive resin layer is formed is an exposure that is 10 times or more the minimum exposure amount required to cure the photosensitive resin layer. Ryodea is, exposure of the surface opposite said formation to the surface of the photosensitive resin layer of the support is, for liquid crystal display according to <1>, wherein the 0 mJ / cm ² der Rukoto It is a manufacturing method of a photo spacer.
<3> The exposure amount in the exposure step is equal to or greater than the minimum exposure amount necessary to cure the photosensitive resin layer, and the minimum exposure amount necessary to cure the photosensitive resin layer. It is 1.5 times or less, The manufacturing method of the photo spacer for liquid crystal displays as described in <1> or <2>.

<4> light to be used for the post-exposure step is a method for producing the photo spacers for liquid crystal display according to any one of <1> to <3>, which is a parallel light.

< 5 > The polymer compound having a crosslinkable group is a repeating unit having at least one selected from a branched structure and a cyclic structure, a repeating unit having an acidic group, a repeating unit having an ethylenically unsaturated group, <1> thru | or < 4 >, The manufacturing method of the photo spacer for liquid crystal displays as described in any one of the above-mentioned.

< 6 > A liquid crystal display photospacer produced by the method for producing a liquid crystal display photospacer according to any one of <1> to < 5 >.

< 7 > A liquid crystal display device comprising the photo spacer for liquid crystal display according to < 6 >.

  According to the present invention, a photo spacer for a liquid crystal display that has a high degree of deformation recovery and can eliminate display unevenness in a liquid crystal display device, a manufacturing method thereof, and display of high-quality images by preventing display unevenness. A liquid crystal display device is provided.

  Hereinafter, the photospacer for a liquid crystal display of the present invention, a manufacturing method thereof, and a liquid crystal display device will be described in detail.

<Photo spacer for liquid crystal display and manufacturing method thereof>
The method for producing a photospacer for a liquid crystal display according to the present invention comprises: a resin layer forming step of forming a photosensitive resin layer containing at least a polymer compound having a crosslinkable group on a support; and the photosensitive resin layer is patterned. An exposure step for exposing the photosensitive resin layer, a development step for removing the unexposed portion of the photosensitive resin layer, and a post-exposure step for exposing the photosensitive resin layer from which the unexposed portion has been removed. In the step, the exposure amount of the surface of the support on which the photosensitive resin layer is formed is an exposure amount that is 5 times or more of the minimum exposure amount required to cure the photosensitive resin layer, and the support The exposure amount of the surface opposite to the surface on which the photosensitive resin layer is formed is 20 mJ / cm ² or less.

  In the post-exposure process, by setting the exposure amount of the surface on which the photosensitive resin layer of the support is formed to an amount specified in the present invention, the upper part of the structure (photo spacer) formed through the development process, that is, When the liquid crystal display device is constructed, the cross-linking of the portion where the pressure is concentrated to come into contact with the opposing substrate can be advanced, and the strength of the upper portion of the photo spacer can be improved. Further, by setting the exposure amount on the surface opposite to the surface on which the photosensitive resin layer of the support is formed to the amount specified in the present invention, the elasticity of the portion other than the upper portion of the photo spacer can be kept moderate. . As a result, it is possible to improve the elastic recovery force of the photo spacer, and display unevenness due to external pressure is less likely to occur when a liquid crystal panel is formed.

  The “minimum exposure amount required to cure the photosensitive resin layer” in the present invention will be described. “Minimum exposure amount required to cure the photosensitive resin layer” means that when the unexposed portion of the exposed photosensitive resin layer is removed by development, the exposed portion (cured portion) is removed by development. And the minimum exposure amount necessary to prevent the shape and size of the exposed portion from becoming uneven. When the exposure amount is insufficient, a portion cured by exposure of the photosensitive resin layer may fall off due to development. The minimum amount of exposure required to cure the photosensitive resin layer is a value that can vary depending on the photosensitive composition constituting the photosensitive resin layer, the pattern shape of the photo spacer, development conditions, etc. It cannot be defined uniquely. The “minimum exposure amount required to cure the photosensitive resin layer” may be the same as or different from the exposure amount for the photosensitive resin layer in the exposure step according to the present invention.

  The photosensitive resin layer according to the present invention contains at least a polymer compound having a crosslinkable group. The photosensitive composition constituting the photosensitive resin layer according to the present invention is not particularly limited as long as it contains at least a polymer compound having a crosslinkable group. For example, the photosensitive resin composition described in [0037] to [0085] of JP-A-2003-330030, or the spacer resin described in paragraph numbers [0009] to [0061] of JP-A-2003-207787. A known photosensitive composition such as a composition can be used.

  From the viewpoint of having a high degree of deformation recovery, the polymer compound having a crosslinkable group is a repeating unit having at least one selected from a branched structure and a cyclic structure, a repeating unit having an acidic group, and an ethylenic group. It is preferable to use a resin containing a repeating unit having an unsaturated group. For example, a resin (A) containing a repeating unit having at least one selected from a branched structure and a cyclic structure, a repeating unit having an acidic group, and a repeating unit having an ethylenically unsaturated group, a polymerizable compound ( B) Since the photospacer produced from the photosensitive composition containing at least the photopolymerization initiator (C) has a high degree of deformation recovery, display unevenness in the liquid crystal display device can be eliminated.

  Hereinafter, the detail of the photosensitive composition which can be used for this invention is demonstrated.

-Photosensitive composition-
The photosensitive composition is a resin (A) that contains a repeating unit having at least one selected from a branched structure and a cyclic structure, a repeating unit having an acidic group, and a repeating unit having an ethylenically unsaturated group. Hereinafter, it is also preferable to contain at least a “resin (A)”), a polymerizable compound (B), and a photopolymerization initiator (C). Moreover, it can comprise using other components, such as a coloring agent and surfactant, as needed.

-Resin (A)-
Resin (A) has a repeating unit having at least one selected from a branched structure and a cyclic structure: X (x mol%), a repeating unit having an acidic group: Y (y mol%), and an ethylenically unsaturated group. It has repeating unit: Z (z mol%), and may have other repeating unit as required. One repeating unit in the resin (A) may correspond to two or more of the above X, Y and Z. Furthermore, the repeating units X, Y and Z contained in the resin (A) may be one kind or two or more kinds.

-Repeating unit having at least one selected from branched and cyclic structures: X-
The “repeating unit having at least one selected from a branched structure and a cyclic structure” will be described.
First, as the branched structure, a branched alkyl group having 3 to 12 carbon atoms is shown, for example, i-propyl group, i-butyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group. 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, i-amyl group, t-amyl group, 3-octyl, t-octyl and the like. Among these, i-propyl group, s-butyl group, t-butyl group, isopentyl group and the like are preferable, and i-propyl group, s-butyl group, t-butyl group and the like are more preferable.

  Next, as the cyclic structure, an alicyclic hydrocarbon group having 5 to 20 carbon atoms or an aromatic group having 6 to 10 carbon atoms is shown. Examples of the alicyclic hydrocarbon group include a cyclopentyl group and a cyclohexyl group. Group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group, adamantyl group, tricyclodecyl group and the like. Among these, a cyclohexyl group, a norbornyl group, an isobornyl group, an adamantyl group, a tricyclodecyl group, and the like are preferable, and a cyclohexyl group, a norbornyl group, an isobornyl group, and the like are more preferable. Examples of the aromatic group include a phenyl group, a benzyl group, and a naphthyl group. Among these, a phenyl group and a benzyl group are preferable.

  Examples of the monomer that can be a repeating unit having at least one selected from a branched structure and a cyclic structure include styrenes, (meth) acrylates, vinyl ethers, vinyl esters, (meth) acrylamides, and the like ( (Meth) acrylates, vinyl esters and (meth) acrylamides are preferred, and (meth) acrylates are more preferred.

  Specific examples of the monomer that can be a repeating unit having a branched structure include i-propyl (meth) acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, and (meth) acrylic acid t. -Butyl, i-amyl (meth) acrylate, t-amyl (meth) acrylate, sec-iso-amyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate, Examples include t-octyl (meth) acrylate, among which i-propyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl methacrylate, and the like are preferable, and more preferably, i-methacrylic acid i. -Propyl, t-butyl methacrylate and the like.

  Next, specific examples of the monomer that can be a repeating unit having a cyclic structure include (meth) acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms, and styrenes. Specific examples include (meth) acrylic acid (bicyclo-2,2,1-heptyl-2), (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl, and (meth) acrylic. Acid-3-methyl-1-adamantyl, (meth) acrylic acid-3,5-dimethyl-1-adamantyl, (meth) acrylic acid-3-ethyladamantyl, (meth) acrylic acid-3-methyl-5-ethyl -1-adamantyl, (meth) acrylic acid-3,5,8-triethyl-1-adamantyl, (meth) acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl, (meth) acrylic acid octahydro- 4,7-methanoinden-5-yl, (meth) acrylic acid octahydro-4,7-methanoinden-1-ylmethyl, (meth) acrylic acid-1-menthyl (Meth) acrylic acid tricyclodecyl, (meth) acrylic acid-3-hydroxy-2,6,6-trimethyl-bicyclo [3,1,1] heptyl, (meth) acrylic acid-3,7,7-trimethyl -4-hydroxy-bicyclo [4,1,0] heptyl, (nor) bornyl (meth) acrylate, isobornyl (meth) acrylate, fuentyl (meth) acrylate, (meth) acrylic acid-2,2,5 -Trimethylcyclohexyl, styrene and the like. Among these compounds, cyclohexyl methacrylate, (nor) bornyl (meth) acrylic acid, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, (meth) acrylic acid-2-adamantyl, fuentyl methacrylate , 1-menthyl methacrylate, tricyclodecyl (meth) acrylate, and the like are preferable, and cyclohexyl methacrylate, (nor) bornyl methacrylate, isobornyl (meth) acrylate, and (meth) acrylate-2-adamantyl are particularly preferable.

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

  The monomer that can be a repeating unit having an acidic group is not particularly limited, and examples thereof include styrenes, (meth) acrylates, vinyl ethers, vinyl esters, (meth) acrylamides, and the like (meth) acrylates. , Vinyl esters and (meth) acrylamides are preferred, and (meth) acrylates are more preferred.

  Specific examples of the monomer that can be a repeating unit having an acidic group can be appropriately selected from known ones such as (meth) acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl ester, Fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid, acrylic acid dimer, addition reaction product of hydroxyl group-containing monomer and cyclic acid anhydride, ω-carboxy-polycaprolactone mono ( And (meth) acrylate. As these, those produced as appropriate may be used, or commercially available products may be used.

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

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

-Repeating unit having an ethylenically unsaturated group: Z-
There is no restriction | limiting in particular as said ethylenically unsaturated group, A (meth) acryloyl group is preferable. The connection between the ethylenically unsaturated group and the monomer is not particularly limited as long as it is a divalent linking group such as an ester group, an amide group, or a carbamoyl group. The method of introducing an ethylenically unsaturated group into the resin (A) can be appropriately selected from known ones. For example, a method of adding a (meth) acrylate having an epoxy group to a repeating unit having an acidic group, hydroxyl Examples include a method of adding a (meth) acrylate having an isocyanate group to a repeating unit having a group, and a method of adding a (meth) acrylate having a hydroxy group to a repeating unit having an isocyanate group.
Among these, the method of adding (meth) acrylate having an epoxy group to a repeating unit having an acidic group is most preferable because it is the easiest to produce and is low in cost.

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

In the Structural Formula (1), R ¹ represents a hydrogen atom or a methyl group. L ¹ represents an organic group.

However, in the structural formula (2), R ¹ represents a hydrogen atom or a methyl group. L ² represents an organic group. W represents a 4- to 7-membered aliphatic hydrocarbon group.

Of the compound represented by the structural formula (1) and the compound represented by the structural formula (2), the compound represented by the structural formula (1) is preferable. In the structural formula (2), L ₂ is The thing of a C1-C4 alkylene group is more preferable.

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

―Other repeating units―
The other repeating unit is not particularly limited, for example, (meth) acrylic acid ester, vinyl ether group, dibasic acid anhydride group, vinyl ester group, hydrocarbon alkenyl having no branched structure and / or alicyclic structure. Examples thereof include a repeating unit composed of a monomer having a group or the like.
There is no restriction | limiting in particular as said vinyl ether group, For example, a butyl vinyl ether group etc. are mentioned.

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

  As content rate of the other repeating unit in the said resin (A), it is preferable that molar composition ratio is 0-30 mol%, and it is more preferable that it is 0-20 mol%.

  Specific examples of the resin (A) include compounds represented by the following compounds P-1 to P-23.

-Manufacturing method of resin (A)-
The resin (A) includes a step of (co) polymerizing a monomer (monomer) to obtain a (co) polymerization reaction product, and a step of introducing an ethylenically unsaturated group into the (co) polymerization reaction product. Manufactured from a two-stage process.
First, the (co) polymerization reaction product is obtained by (co) polymerization reaction of various monomers. For example, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization and the like can be appropriately selected for the active species of polymerization. Among these, radical polymerization is preferable from the viewpoint of easy synthesis and low cost. Moreover, there is no restriction | limiting in particular also about the polymerization method, It can select suitably from well-known things. For example, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method and the like can be appropriately selected. Among these, the solution polymerization method is more desirable.

-Molecular weight-
The weight average molecular weight of the resin (A) is preferably 7,000 to 100,000, more preferably 8,000 to 80,000, particularly preferably 9,000 to 50,000. 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 (A).

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

-Acid value-
The preferred range of the acid value suitable as the resin (A) varies depending on the molecular structure that can be taken, but generally it is preferably 20 mgKOH / g or more, more preferably 50 mgKOH / g or more, and 70 to 130 mgKOH / g. It is particularly preferred that When the acid value is within the preferred range, a photospacer having good developability and mechanical strength can be obtained.

The resin (A) has a glass transition temperature (Tg) of 40 to 180 ° C. and a weight average molecular weight of 7,000 to 100,000, whereby a photospacer having good developability and mechanical strength can be obtained. This is preferable.
Furthermore, the preferable example of the said resin (A) has more preferable each combination of the said preferable molecular weight, glass transition temperature (Tg), and an acid value.

The copolymer composition ratio of the respective components of the resin (A) is determined in consideration of the glass transition temperature and the acid value, and cannot be generally stated, but “at least one selected from a branched structure and a cyclic structure. The “repeating unit having” is preferably 10 to 70 mol%, more preferably 15 to 65 mol%, particularly preferably 20 to 60 mol%. When the repeating unit having at least one selected from a branched structure and a cyclic structure is within the above range, good developability is obtained and the developer resistance of the image area is also good.
Further, the “repeating unit having an acidic group” is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, particularly preferably 20 to 50 mol%. When the repeating unit having an acidic group is within the above range, good curability and developability can be obtained.
Further, the “repeating unit having an ethylenically unsaturated group” is preferably 10 to 70 mol%, more preferably 20 to 70 mol%, particularly preferably 30 to 70 mol%. When the repeating unit having an ethylenically unsaturated group is within the above range, the pigment dispersibility is excellent, and the developability and curability are also good.

  As content of the said resin (A), 5-70 mass% is preferable with respect to the said photosensitive composition total solid, and 10-50 mass% is more preferable. The resin (A) can contain other resins described later, but only the resin (A) is preferable.

-Other resins-
As the resin that can be used in combination with the resin (A), a compound exhibiting swelling property with respect to an alkaline aqueous solution is preferable, and a compound that is soluble in an alkaline aqueous solution is more preferable.
As the resin exhibiting swellability or solubility with respect to an alkaline aqueous solution, for example, those having an acidic group are preferably mentioned. Specifically, an ethylenically unsaturated double bond and an acidic group are introduced into an epoxy compound. Compound (epoxy acrylate compound), vinyl copolymer having (meth) acryloyl group and acidic group in side chain, epoxy acrylate compound and vinyl copolymer having (meth) acryloyl group and acidic group in side chain And the like, and a maleamic acid copolymer are preferable.
The acidic group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, the availability of raw materials, etc. From the viewpoint, a carboxyl group is preferable.

-Ratio of resin (A) to other resins-
The total content of the resin (A) and the resin that can be used in combination is preferably 5 to 70% by mass and more preferably 10 to 50% by mass with respect to the total solid content of the photosensitive composition. When the solid content is 5% by mass or more, the film strength of the photosensitive resin layer can be increased, and the tackiness of the surface of the photosensitive resin layer can be improved. Moreover, if it is 70 mass% or less, exposure sensitivity can be improved. In addition, the said content has shown that solid content.

-Polymerizable compound (B), photopolymerization initiator (C), other components-
In the present invention, a polymerizable compound (B), a photopolymerization initiator (C), and other components that constitute a known composition can be suitably used. For example, paragraphs of JP-A-2006-23696 Examples include the components described in numbers [0010] to [0020] and the components described in paragraph numbers [0027] to [0053] of JP-A-2006-64921.

The mass ratio ((B) / (A) ratio) of the polymerizable compound (B) contained in the photosensitive composition to the resin (A) is preferably 0.3 to 1.5, preferably 0.4 to It is more preferable that it is 1.4, and it is especially preferable that it is 0.5-1.2. When the ratio (B) / (A) is within the preferred range, a photospacer having good developability and mechanical strength can be obtained.
As content in the photosensitive composition of the said photoinitiator (C), 0.1-20 mass% is preferable with respect to resin (A), and 0.5-10 mass% is more preferable.

-Fine particles (D)-
In the photosensitive composition, it is preferable to add fine particles. The fine particles (D) are not particularly limited and may be appropriately selected depending on the intended purpose. For example, extender pigments described in JP-A No. 2003-302039 [0035] to [0041] are preferable. Colloidal silica is preferred from the viewpoint of obtaining a photospacer having good developability and mechanical strength.

  The average particle diameter of the fine particles (D) is preferably 5 to 50 nm, more preferably 10 to 40 nm, and more preferably 15 to 30 nm from the viewpoint that a photospacer having high mechanical strength can be obtained. Is particularly preferred.

  The content of the fine particles (D) is 5 to 50% by mass with respect to the total solid content in the photosensitive composition of the present invention from the viewpoint that a photospacer having high mechanical strength is obtained. Is more preferable, 10 to 40% by mass is more preferable, and 15 to 30% by mass is particularly preferable.

In the method for producing a photospacer for a liquid crystal display of the present invention, a resin layer forming step of forming a photosensitive resin layer containing at least a polymer compound having a crosslinkable group on a support, and patterning the photosensitive resin layer An exposure process that exposes in a uniform manner, a development process that removes an unexposed portion of the photosensitive resin layer (hereinafter, the exposure process and the development process may be simply referred to as a “patterning process”), and unexposed. A photo-spacer is formed through a post-exposure step of exposing the photosensitive resin layer from which the portion has been removed.
Hereafter, each said process is demonstrated.

[Resin layer forming step]
The resin layer forming step in the present invention is a step of forming a photosensitive resin layer containing at least a polymer compound having a crosslinkable group on a support.
This photosensitive resin layer constitutes a photospacer that has a good deformation recovery property and can maintain a uniform cell thickness through a manufacturing process described later. By using the photo spacer, display unevenness in an image can be effectively eliminated particularly in a liquid crystal display device in which display unevenness is likely to occur due to variation in cell thickness.

  As a method of forming a photosensitive resin layer on a support, (a) a method of applying a solution containing the photosensitive composition described above by a known coating method, and (b) a transfer method using a photosensitive transfer film. A method of laminating is preferably mentioned. Each will be described below.

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

(B) Transfer method In the case of transfer, a photosensitive transfer film is used, and a photosensitive resin layer formed in a film shape on a temporary support is pressure-bonded or heated with a roller or flat plate heated and / or pressurized on the support surface. After bonding by pressure bonding, the photosensitive resin layer is transferred onto the support by peeling off the temporary support. Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From the viewpoint, it is preferable to use the method described in JP-A-7-110575.

When a photosensitive resin layer is formed on a temporary support, an oxygen blocking layer (hereinafter also referred to as “oxygen blocking film” or “intermediate layer”) is further provided between the photosensitive resin layer and the temporary support. it can. Thereby, the exposure sensitivity can be increased. Moreover, in order to improve transferability, you may provide the thermoplastic resin layer which has cushioning properties.
Regarding the temporary support, the oxygen blocking layer, the thermoplastic resin layer, and other layers constituting the photosensitive transfer film, and the method for producing the photosensitive transfer film, paragraph numbers [0024] to JP-A-2006-23696. This is the same as the configuration and the manufacturing method described in [0030].

  When the photosensitive resin layer is applied and formed by both (a) the coating method and (b) the transfer method, the layer thickness is preferably 0.5 to 10.0 μm, more preferably 1 to 6 μm. When the layer thickness is within the above range, the generation of pinholes during coating formation during production is prevented, and development and removal of unexposed portions can be performed without requiring a long time.

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

[Patterning process]
In the patterning step in the present invention, the photosensitive resin layer formed on the support is exposed and developed for patterning. Specific examples of the patterning process include the formation examples described in paragraphs [0071] to [0077] of Japanese Patent Application Laid-Open No. 2006-64921 and the paragraph numbers [0040] to [0051] of Japanese Patent Application Laid-Open No. 2006-23696. The described steps and the like are also preferable examples in the present invention.

In addition, as an exposure method in the patterning step, there are a proximity method, a mirror projection method, a stepper method, and the like, and any method may be used. In the mirror projection method, the exposure amount is calculated by the following: exposure amount (mJ / cm ² ) = illuminance (mV · mm / cm ² ) × SCAN speed (mm / s).

  Examples of the pattern of the photo spacer include (elliptical) cylinder, (elliptical) truncated cone, inverted (elliptical) truncated cone, polygonal column, polygonal truncated cone, and inverted polygonal cone.

[Post exposure process]
In the post-exposure step, the photosensitive resin layer from which the unexposed portion has been removed is exposed. Exposure in the post-exposure process (post-exposure) is performed by irradiating light (for example, 365 nm, 405 nm, etc.) in a wavelength region that can cure the photosensitive resin layer to the substrate on which the pattern after development is formed. Is called. The light source used for the post-exposure is not particularly limited, and specific examples include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and the like.

  In the post-exposure step according to the present invention, the exposure amount of the surface of the support on which the photosensitive resin layer is formed is an exposure amount that is 5 times or more the minimum exposure amount required to cure the photosensitive resin layer. It is necessary. If the exposure amount is less than 5 times, the upper portion of the photospacer cannot be sufficiently cured. The preferable exposure amount in the post-exposure step is 10 times or more the minimum exposure amount necessary for curing the photosensitive resin layer. By making the exposure amount 10 times or more, a high degree of deformation recovery can be imparted to the photo spacer.

In the post-exposure step according to the present invention, the exposure amount from the surface of the support opposite to the surface on which the photosensitive resin layer is formed needs to be 20 mJ / cm ² or less. When the exposure amount is more than 20 mJ / cm ² , sufficient mechanical property improvement effect may not be obtained.
In the post-exposure step, the exposure amount on the surface of the support opposite to the surface on which the photosensitive resin layer is formed is preferably as small as possible, and most preferably 0 mJ / cm ² .

  The light beam used in the post-exposure process is preferably parallel light. As a result, only the upper part of the photo spacer is post-exposed and a mechanical special effect is easily obtained.

-Post exposure illuminance-
In the present invention, the illuminance of post exposure is preferably 50 to 500 mW / cm ² . When the illuminance is 50 mW / cm ² or more, higher deformation recovery properties can be obtained. On the other hand, by being 500 mW / cm ² or less, the occurrence of reticulation during baking can be more efficiently suppressed.
Also more preferably the illuminance is 100 to 350 mW / cm ^2, and particularly preferably 150~250mW / cm ^2.

  The post-exposure amount (exposure energy) can be adjusted by selecting the exposure time after adjusting the post-exposure illuminance as described above.

  Here, the above-described exposure illuminance and exposure amount (exposure energy) in the present invention can be measured by using “UIT150” manufactured by USHIO INC. As a measuring device and setting the measurement wavelength to 365 nm.

  In this invention, you may have a baking process between the image development process and a post exposure process, or after a post exposure as needed. Although the heating temperature and heating time in the baking process depend on the composition and thickness of the photosensitive resin layer, heating may be performed at 200 to 250 ° C. for 20 to 100 minutes from the viewpoint of tact time and sufficient curing. preferable.

<Liquid crystal display substrate>
The substrate for a liquid crystal display device of the present invention is provided with a photospacer obtained by the method for producing a photospacer for a liquid crystal display of the present invention. The photospacer is preferably formed on a display light-shielding portion such as a black matrix formed on a support or on a driving element such as a TFT. Further, a transparent conductive layer (transparent electrode) such as ITO or a liquid crystal alignment film such as polyimide may exist between a light shielding portion for display such as a black matrix, a driving element such as TFT and a photo spacer.

For example, when the photo spacer is provided on the display light-shielding part or the driving element, the display light-shielding part (black matrix or the like) or the driving element previously disposed on the support is covered, for example, photosensitive transfer. The photosensitive resin layer of the film is laminated on the support surface, peeled and transferred to form a photosensitive resin layer, which is then exposed, developed, and post-exposed to form a photospacer. A device substrate can be manufactured.
The substrate for a liquid crystal display device of the present invention may further be provided with colored pixels of three colors such as red (R), blue (B), and green (G) as necessary.

<Liquid crystal display element>
A liquid crystal display element can be configured using the substrate for a liquid crystal display device of the present invention. As one of the liquid crystal display elements, a liquid crystal layer and liquid crystal driving means (simple matrix driving method and active matrix driving method) are provided between a pair of supports (including the substrate for a liquid crystal display device of the present invention) at least one of which is light transmissive. And at least).

  In this case, the substrate for a liquid crystal display device of the present invention can be configured as a color filter substrate having a plurality of RGB pixel groups and each pixel constituting the pixel group being separated from each other by a black matrix. Since this color filter substrate is provided with a photo spacer having a uniform height and excellent deformation recovery property, a liquid crystal display element equipped with the color filter substrate has a cell gap unevenness between the color filter substrate and the counter substrate ( Occurrence of cell thickness fluctuations) can be suppressed, and display unevenness such as color unevenness can be effectively prevented. Thereby, the produced liquid crystal display element can display a vivid image.

As another aspect of the liquid crystal display element, at least one of the liquid crystal display elements includes a liquid crystal layer and a liquid crystal driving unit between a pair of light transmissive supports (including the liquid crystal display device substrate of the present invention), and the liquid crystal The driving means has an active element (for example, TFT), and is configured to be regulated to a predetermined width by a photo spacer having a uniform height between a pair of substrates and excellent deformation recovery.
Also in this case, the substrate for a liquid crystal display device of the present invention is configured as a color filter substrate having a plurality of RGB pixel groups, and each pixel constituting the pixel group is separated from each other by a black matrix.

Examples of liquid crystals that can be used in the present invention include nematic liquid crystals, cholesteric liquid crystals, smectic liquid crystals, and ferroelectric liquid crystals.
In addition, the pixel group of the color filter substrate may be composed of two-color pixels exhibiting different colors, or may be composed of three-color pixels, four-color pixels or more. For example, in the case of three colors, it is composed of three hues of red (R), green (G), and blue (B). When arranging pixel groups of three colors of RGB, arrangement of mosaic type, triangle type, etc. is preferable, and when arranging pixel groups of four colors or more, any arrangement may be used. For producing the color filter substrate, for example, a black matrix may be formed after forming a pixel group of two or more colors, or conversely, a pixel group may be formed after forming a black matrix. Regarding the formation of RGB pixels, JP 2004-347831 A can be referred to.

<Liquid crystal display device>
The liquid crystal display device of the present invention comprises the photo spacer for liquid crystal display of the present invention. The liquid crystal display device of the present invention may comprise the liquid crystal display device substrate. The liquid crystal display device of the present invention may include the liquid crystal display element. As described above, the liquid crystal display device of the present invention regulates a predetermined width between a pair of substrates facing each other so as to face each other with the photo spacer produced by the method for producing a photo spacer for liquid crystal display of the present invention. The liquid crystal material is sealed in the regulated gap (the sealed portion is referred to as a liquid crystal layer), and the thickness (cell thickness) of the liquid crystal layer is maintained at a desired uniform thickness. .

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

  The basic configuration of the liquid crystal display device of the present invention includes: (a) a driving side substrate in which driving elements such as thin film transistors (TFTs) and pixel electrodes (conductive layers) are arranged; and a counter electrode (conductive layer). And (b) a driving substrate and a counter substrate provided with a counter electrode (conductive layer); and a counter substrate provided with a counter electrode (conductive layer). The liquid crystal display device of the present invention can be suitably applied to various liquid crystal display devices, and the like. .

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

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

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

(Synthesis Example 1)
In the reaction vessel, 5.11 parts of 1-methoxy-2-propanol and 5.11 parts of 1-methoxy-2-propylacetate were added in advance, and the temperature was raised to 90 ° C., and 5.10 parts of styrene and 9,84 parts of methacrylic acid were added. 1 part of an azo polymerization initiator (Wako Pure Chemical Industries, V-601), 5.11 parts of 1-methoxy-2-propanol, and 5.11 parts of 1-methoxy-2-propyl acetate The solution was dropped into a 90 ° C. reaction vessel over 2 hours under a nitrogen gas atmosphere. Reaction was performed for 4 hours after the dropwise addition to obtain an acrylic resin solution.
Next, 0.036 parts of hydroquinone monomethyl ether and 0.082 parts of tetraethylammonium bromide were added to the acrylic resin solution, and 9.28 parts of glycidyl methacrylate was added dropwise over 2 hours. After the dropwise addition, the mixture was reacted at 90 ° C. for 4 hours while blowing air, and then added by adding a solvent so that the solid concentration was 45%. The following compound P-24 (solid content acid value; 114 mgKOH / g, Mw; 15,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution). In the resin represented by the following compound P-24, x: y: z in the following compound P-24 was 30 mol%: 30 mol%: 40 mol%.

(Synthesis Example 2)
13.56 parts of 1-methoxy-2-propanol was added in advance to the reaction vessel and the temperature was raised to 90 ° C., and 8.24 parts of cyclohexyl methacrylate, 9.84 parts of methacrylic acid, an azo polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd.) , V-601) and a mixed solution consisting of 13.56 parts of 1-methoxy-2-propanol were dropped into a 90 ° C. reaction vessel over 2 hours under a nitrogen gas atmosphere. Reaction was performed for 4 hours after the dropwise addition to obtain an acrylic resin solution.
Next, 0.0415 part of hydroquinone monomethyl ether and 0.068 part of tetraethylammonium bromide were added to the acrylic resin solution, and then 9.28 parts of glycidyl methacrylate was added dropwise over 2 hours. Resin represented by the compound P-10 having an unsaturated group, which was prepared by adding a solvent so that the solid content concentration was 45% after reacting at 90 ° C. while blowing air after dropping. A solution (solid content acid value; 100 mg KOH / g, Mw; 18,000, 1-methoxy-2-propanol 45% solution) was obtained. In the resin represented by P-10, x: y: z in the compound P-10 was 30 mol%: 30 mol%: 40 mol%.
In addition, the molecular weight Mw of the resin obtained in Synthesis Example 1 and Synthesis Example 2 indicates a weight average molecular weight, and the molecular weight was measured using a gel permeation chromatograph (GPC).

(Example 1): Transfer method-Production of photosensitive transfer film for spacer-
On a 75 μm thick polyethylene terephthalate film temporary support (PET temporary support), a coating solution for a thermoplastic resin layer having the following formulation A is applied and dried to form a thermoplastic resin layer having a dry layer thickness of 6.0 μm. did.

[Prescription A for Coating Solution for Thermoplastic Resin Layer]
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (= 55 / 11.7 / 4.5 / 28.8 [molar ratio], weight average molecular weight 90,000) 25.0 parts Styrene / acrylic acid copolymer 58.4 parts (= 63/37 [molar ratio], weight average molecular weight 8,000)
2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane
39.0 parts ・ Surfactant 1 shown below 10.0 parts methanol 90.0 parts 1-methoxy-2-propanol 51.0 parts methyl ethyl ketone 700 parts

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

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

  Next, on the formed intermediate layer, a photosensitive resin layer coating solution having the formulation 1 shown in Table 1 below was applied and dried to laminate a photosensitive resin layer having a dry layer thickness of 4.1 μm.

  As described above, after forming a laminated structure of PET temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer (total thickness of the three layers is 11.6 μm), the surface of the photosensitive resin layer is formed. Further, a polypropylene film having a thickness of 12 μm was applied as a cover film by heating and pressing to obtain a photosensitive transfer film (1) for spacers.

-Production of color filter substrate (support according to the present invention)-
A color filter having a black matrix, an R pixel, a G pixel, and a B pixel was produced by the method described in paragraph Nos. [0084] to [0095] of JP-A-2005-3861. Next, a transparent electrode of ITO (Indium Tin Oxide) was further formed on the R pixel, G pixel, B pixel and black matrix of the color filter substrate by sputtering.

-Production of photo spacer-
The cover film of the obtained photosensitive transfer film for spacer (1) is peeled off, and the exposed surface of the photosensitive resin layer is superimposed on the ITO film of the color filter substrate on which the ITO film prepared above is sputtered. Then, using a laminator type Lamic II [manufactured by Hitachi Industries, Ltd.], the films were bonded at a conveyance speed of 2 m / min under pressure and heating conditions of a linear pressure of 100 N / cm and 130 ° C. Thereafter, the PET temporary support was peeled and removed at the interface with the thermoplastic resin layer, and the photosensitive resin layer was transferred together with the thermoplastic resin layer and the intermediate layer (resin layer forming step).

Next, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, the mask (quartz exposure mask having an image pattern) and the mask and the thermoplastic resin layer face each other. The distance between the mask surface and the surface of the photosensitive resin layer on the side in contact with the intermediate layer is set to 40 μm with the color filter substrate placed on the substrate in a state where the color filter substrate stands substantially parallel and vertically, and the thermoplastic resin layer is interposed through the mask. Proximity exposure was performed from the side with an exposure amount of 60 mJ / cm ² .

  Next, a triethanolamine developer (containing 30% by mass of triethanolamine, trade name: T-PD2, manufactured by Fuji Photo Film Co., Ltd., 12 times with pure water (1 part by mass of T-PD2 and pure water) The solution diluted to 11 parts by mass) was developed with shower at 30 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer. Subsequently, after air was blown off on the upper surface of the substrate, pure water was sprayed for 10 seconds by a shower, pure water shower cleaning was performed, and air was blown to reduce a liquid pool on the substrate.

  Subsequently, Na carbonate-based developer (0.38 mol / liter sodium hydrogen carbonate, 0.47 mol / liter sodium carbonate, 5% by weight sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, stabilizer included , Product name: T-CD1, manufactured by Fuji Photo Film Co., Ltd. diluted 5 times with pure water) and developed at 29 ° C. for 30 seconds at a cone type nozzle pressure of 0.15 MPa to develop the photosensitive resin layer Patterning images were obtained.

  Subsequently, a cleaning agent (trade name: T-SD3 manufactured by Fuji Photo Film Co., Ltd.) was diluted 10 times with pure water, sprayed at 33 ° C. for 20 seconds and a cone type nozzle pressure of 0.02 MPa, and further nylon hair was removed. Residues were removed by rubbing the image formed by the rotating brush, and a spacer pattern was obtained (patterning step).

In addition, at the time of exposure, the exposure amount is changed every 10 mJ from 10 mJ to 100 mJ, the shape of the patterned photo spacer and the presence or absence of dropping in the development process are confirmed, and at least necessary for curing the photosensitive resin layer The amount of exposure was examined. When the exposure amount was less than the required amount, the photo spacers dropped out, and the shapes and sizes became uneven. The minimum exposure amount required to cure the photosensitive resin layer was 40 mJ / cm ² .

Next, post-exposure was performed with a Hg lamp at 300 mJ / cm ² from the surface on which the photospacer was formed (surface on which the photosensitive resin layer was formed; table). At this time, the exposure amount of the surface opposite to the surface on which the photospacer was formed (the surface opposite to the surface on which the photosensitive resin layer was formed; the back) was 0 mJ / cm ² .

Next, the color filter substrate provided with the spacer pattern was subjected to heat treatment at 230 ° C. for 44 minutes (heat treatment step) to produce a photospacer.
The obtained spacer pattern was a cylindrical shape having a diameter of 24 μm and an average height of 3.6 μm. In addition, about the arbitrary 1000 pieces of the obtained photo spacer, the highest position from the transparent electrode formation surface of ITO is measured using a three-dimensional surface structure analysis microscope (manufacturer: ZYGO Corporation, model: New View 5022). The average was taken as the average height of the photo spacer.

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

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

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

[Example 2]
In Example 1, a photospacer and a liquid crystal display device were obtained in the same manner as in Example 1 except that the exposure amount on the surface on which the photospacer was formed was changed to 600 mJ / cm ² when performing the post-exposure.

[Example 3]
In Example 1, when performing the post-exposure, except the exposure amount of the surface forming the photo spacers and 600 mJ / cm ^2, the surface on which a photo-spacers that an exposure amount of the surface opposite the 10 mJ / cm ² Obtained a photospacer and a liquid crystal display device in the same manner as in Example 1.

[Example 4]
In Example 1, photo spacers and liquid crystals were used in the same manner as in Example 3 except that a patterning exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) capable of irradiating parallel light when performing post exposure was used. A display device was obtained.

[Example 5]
A photospacer and a liquid crystal display device were prepared in the same manner as in Example 2 except that the photosensitive resin layer coating solution consisting of formulation 2 in Table 1 was used instead of the photosensitive resin layer coating solution consisting of formulation 1 in Table 1. Got.

[Example 6]
A photospacer and a liquid crystal display device were used in the same manner as in Example 2 except that the photosensitive resin layer coating solution consisting of formulation 3 in Table 1 was used instead of the photosensitive resin layer coating solution consisting of formulation 1 in Table 1. Got.

[Comparative Example 1]
A photospacer and a liquid crystal display device were obtained in the same manner as in Example 1 except that post-exposure was not performed.

[Comparative Example 2]
A photo spacer and a liquid crystal display device were obtained in the same manner as in Example 1 except that post exposure was performed at 600 mJ / cm ² from the front and back surfaces of the color filter substrate.

[Comparative Example 3]
The exposure of the opposite surface and 600 mJ / cm ² and the photo-spacer formed surface, except that the 0 mJ / cm ² exposure amount of the surface forming a photo spacer in the same manner as in Example 1 by photo spacer and the liquid crystal A display device was obtained.

[Evaluation]
-Deformation recovery rate-
The photo-spacer was measured with a micro hardness tester (DUH-W201, manufactured by Shimadzu Corporation) as follows to determine the deformation recovery rate. The measurement was performed by a load-unloading test method using a frustum-type indenter with a diameter of 50 μm, a load speed of 3.1 mN / sec, and a holding time of 5 seconds. The maximum load was changed, and the elastic recovery rate at the maximum load at which the total deformation amount was 0.5 μm was measured. The measurement was performed in an environment of 22 ± 1 ° C. and 50% RH. Deformation recovery rates were determined for five arbitrary photospacers, and the average values are shown in Table 2.

Deformation recovery rate (%) =
(Deformation amount by weight [μm] / Recovery amount after weight release [μm]) × 100

  The deformation recovery rate is required to be 88% or more in the production of a liquid crystal display device, more preferably 90% or more, and particularly preferably 92% or more.

-Display unevenness-
About each liquid crystal display device, the load of 5 kg / cm < ² > was pressed for 5 second, and it was evaluated how much display nonuniformity of the part remained. The occurrence of display unevenness was evaluated according to the following evaluation criteria. Each evaluation result is shown in Table 2.

<Evaluation criteria>
5: No unevenness at all (very good)
4: The edge of the glass substrate is slightly uneven, but there is no problem with the display (good)
3: Slight unevenness on the display, but practical level (normal)
2: The display is uneven (somewhat bad)
1: Strong unevenness in display (very bad)

Claims (7)

A resin layer forming step of forming a photosensitive resin layer containing at least a polymer compound having a crosslinkable group on a support, an exposure step of exposing the photosensitive resin layer in a pattern, and the photosensitive resin layer A development process for removing an unexposed part, and a post-exposure process for exposing the photosensitive resin layer from which an unexposed part has been removed, a method for producing a photospacer for a liquid crystal display,
In the post-exposure step, the exposure amount of the surface of the support on which the photosensitive resin layer is formed is an exposure amount that is 7.5 times or more the minimum exposure amount required to cure the photosensitive resin layer. The exposure amount of the surface opposite to the surface on which the photosensitive resin layer of the support is formed is 10 mJ / cm ² or less. In the post-exposure step, the exposure amount of the surface of the support on which the photosensitive resin layer is formed is an exposure amount that is 10 times or more the minimum exposure amount required to cure the photosensitive resin layer. Ri, exposure of said opposite surface to the formed surface of the photosensitive resin layer of the support, the photo spacers for liquid crystal display according to claim 1, wherein 0 mJ / cm ² der Rukoto Production method. The exposure amount in the exposure step is not less than the minimum exposure amount necessary to cure the photosensitive resin layer, and the minimum exposure amount required to cure the photosensitive resin layer is 1.5. The method for producing a photospacer for a liquid crystal display according to claim 1 or 2, wherein the photospacer is twice or less. The method for producing a photospacer for a liquid crystal display according to any one of claims 1 to 3, wherein the light beam used in the post-exposure step is parallel light. The polymer compound having a crosslinkable group contains a repeating unit having at least one selected from a branched structure and a cyclic structure, a repeating unit having an acidic group, and a repeating unit having an ethylenically unsaturated group. method of manufacturing a photo spacer for a liquid crystal display according to any one of claims 1 to 4, characterized in that a resin. A liquid crystal display photospacer produced by the method for producing a liquid crystal display photospacer according to any one of claims 1 to 5 . A liquid crystal display device comprising the photo spacer for liquid crystal display according to claim 6 .