JP5127577B2 - Spacer and manufacturing method thereof, substrate for liquid crystal display device, liquid crystal display device - Google Patents

Description

  The present invention relates to a spacer, a manufacturing method thereof, a liquid crystal display substrate using the same, and a liquid crystal display device.

  In recent years, one drop fill technology (ODF method) has been proposed to increase the productivity of liquid crystal display elements. This method drops a predetermined amount of liquid crystal on the liquid crystal sealing surface of one of the two liquid crystal panel substrates constituting the liquid crystal display element, and maintains the predetermined cell gap under vacuum on the other substrate. This is a method of manufacturing a liquid crystal display element by facing and bonding them in a state where they can be produced. According to this method, since the liquid crystal display element has a larger area than the conventional method and the liquid crystal can be easily sealed even when the cell gap is narrowed, the ODF method will be a method for manufacturing a liquid crystal display element in the future. It will be mainstream.

  However, when fine particle spacers are used in the ODF method, the fine particle spacers dispersed when the liquid crystal is dropped or bonded to the opposite substrate are flowed along with the flow of the liquid crystal, and the distribution of the fine particle spacers present on the substrate is not good. There is a problem of uniformity. If the distribution of the spacers using the fine particles becomes non-uniform, there is a problem that the cell gap of the liquid crystal cell varies and color unevenness occurs in the liquid crystal display.

  To solve this problem, instead of conventional spacers using fine particles, a spacer (so-called photo spacer) in which a convex pattern is formed on a liquid crystal substrate to maintain a uniform cell gap by photolithography is proposed. Has been put to practical use. When this photo-spacer is used, the problem that the spacer is arranged inside the pixel and the problem that the spacer is uneven when the ODF method is used can be solved.

  However, in a large liquid crystal display device manufactured by an ODF method using a photo spacer, the liquid crystal in the liquid crystal cell flows downward of the display panel during use of the display device, so that the upper half surface and the lower half surface of the display panel In this case, a defect called “gravity failure” that causes color unevenness may occur, which is a serious problem. In order to eliminate such “gravity failure”, when the liquid crystal in the liquid crystal cell expands by the heat generated from the backlight and the cell gap is expanded, the compressed spacer is removed from the compression deformation. It is considered that this can be avoided by making it possible to follow the change in the cell gap by elastic recovery so that no gap is generated between the substrate and the spacer. However, in the conventional method, in order to give the spacer high deformation recovery force, it is necessary to highly crosslink the resin for forming the spacer to make it difficult to cause plastic deformation during compression. Resins having such a highly crosslinked structure generally have a high compression modulus and tend to be hard. In the case where the spacer is formed of such a hard resin, a large pressure is required in the process of compressing and deforming the spacer. In the liquid crystal display element, a large liquid crystal cell is pressed to spread the compressed cell. It will contain power. A phenomenon called "low-temperature foaming" in which, when the force of the spacer to push the liquid crystal cell is large, if the volumetric contraction of the liquid crystal in the liquid crystal cell occurs at low temperatures, the internal pressure in the liquid crystal cell suddenly decreases and bubbles are generated. This causes a display unevenness in the display image.

In view of this situation, in order to keep the gap between the two glass substrates of the liquid crystal display element constant, a technique for setting the elastic coefficient of the column spacer to 0.2 to 1.0 GPa is disclosed (for example, Patent Documents). 1).
JP 2005-258422 A

  However, if the compression modulus is too low and too soft, especially when the substrate size is large, for example, 19 inches or more, when the liquid crystal display device is formed and arranged in a direction intersecting the horizontal plane, The spacers that are positioned cannot withstand the weight of the liquid crystal and are separated from the substrate surface, and the liquid crystal accumulates downward due to gravity, which may cause display unevenness. Furthermore, a gap difference is likely to occur between two substrates sandwiching the liquid crystal material due to changes in the temperature environment. To make the spacer follow the gap change between the substrates, the spacer is softened and the amount of deformation and deformation are reduced. Although it is necessary to increase the rate, there are various problems in softening the spacer, such as increasing the column diameter, increasing the number of columns, or changing the columnar shape.

  The present invention has been made in view of the above, and provides a spacer having a large elastic recovery rate and a large amount of weight deformation, a manufacturing method thereof, a liquid crystal display device substrate and a liquid crystal display device capable of displaying a high-quality image. The purpose is to achieve the purpose.

Specific means for achieving the above object are as follows.
<1> At least on the side chain (A) , a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group, an adamantyl group, a tricyclodecyl group, a dicyclopentenyl group, a dicyclopentanyl group, tri cyclopentenyl group, and a alicyclic structure selected from tri-cyclopentadienyl group, an acidic group, a resin containing an ethylenically unsaturated bond, a, (B) a polymerizable compound, and (C) a photopolymerization initiator The elastic modulus at 15% compression at 25 ° C. is 0.5 GPa or more and 3.0 GPa or less, and the bottom area is more than 20 μm ² and 350 μm ² or less. Is a spacer having a thickness of 1.0 μm to 10.0 μm.
< 2 > The spacer according to <1 >, wherein the resin (A) has 10 or more carbon atoms.
< 3 > The spacer according to < 1 > or <2> , wherein the alicyclic structure has at least one selected from a tricyclopentenyl group, an adamantyl group, a norbornyl group, and an isobornyl group It is.
< 4 > The photopolymerization initiator (C) includes at least one selected from the group consisting of aminoacetophenone compounds, acylphosphine oxide compounds, and oxime ester compounds. > To < 3 > is the spacer according to any one of the above.

< 5 > The spacer according to any one of <1> to < 4 >, further comprising (D) fine particles.
< 6 > The average particle diameter of the fine particles (D) is 5 nm or more and 50 nm or less, and the mass ratio of the fine particles (D) to the total solid content is 5% by mass or more and 50% by mass or less. 5 >.
< 7 > The spacer according to any one of <1> to < 6 >, wherein the elastic modulus is 1.0 GPa or more and 3.0 GPa or less.
< 8 > Any one of <1> to < 7 >, wherein the bottom area is more than 20 μm ² and 180 μm ² or less, and the height is 1.5 μm or more and 5.0 μm or less. It is a spacer as described in above.
<9> The resin (A) is a repeating unit X having the alicyclic structure in the side chain, a repeating unit Y having the acidic group in the side chain, and a repeating unit having the ethylenically unsaturated bond in the side chain. The spacer according to any one of <1> to <8>, wherein the spacer is a copolymer having Z.
<10> The spacer according to <9>, wherein the resin (A) has a composition ratio (x) of a repeating unit having an alicyclic structure in the resin of 20 to 50 mol%.
<11> The spacer according to any one of <1> to <10>, wherein the alicyclic structure includes a group represented by the following general formula (a).

In general formula (a), x represents 1 or 2, and m and n each independently represent an integer of 0 to 15.

< 12 > The method for producing a spacer according to any one of <1> to < 11 >, wherein at least (A) a side chain includes a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, An alicyclic structure selected from a norbornyl group, an isobornyl group, an adamantyl group, a tricyclodecyl group, a dicyclopentenyl group, a dicyclopentanyl group, a tricyclopentenyl group, and a tricyclopentanyl group, an acidic group, and ethylene resins including sexual and unsaturated bonds, and forming a photosensitive resin layer on a support by applying the polymerizable compound (B), and (C) a photosensitive composition comprising a photopolymerization initiator, wherein the photosensitive It is a manufacturing method of the spacer which has the process of patterning the property resin layer and forming a spacer pattern.
< 13 > The method for producing a spacer according to any one of <1> to < 11 >, wherein a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group are provided at least on the side chain (A) on the temporary support. An alicyclic structure selected from a cyclooctyl group, a norbornyl group, an isobornyl group, an adamantyl group, a tricyclodecyl group, a dicyclopentenyl group, a dicyclopentanyl group, a tricyclopentenyl group, and a tricyclopentanyl group; and an acid group, a resin containing an ethylenically unsaturated bond, and with (B) a polymerizable compound, and (C) a photosensitive transfer material having a photosensitive resin layer containing a photopolymerization initiator, heating and / or Production of a spacer having a step of transferring the photosensitive resin layer onto a support by pressurization and patterning the photosensitive resin layer to form a spacer pattern. It is a method.
< 14 > A substrate for a liquid crystal display device, comprising the spacer according to any one of <1> to < 11 >.
< 15 > A liquid crystal display device comprising the substrate for liquid crystal display device according to < 14 >.

  According to the present invention, it is possible to provide a spacer having a large elastic recovery rate and a large amount of weight deformation, a manufacturing method thereof, a liquid crystal display device substrate and a liquid crystal display device capable of displaying a high-quality image.

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

<Spacer and manufacturing method thereof>
The spacer of the present invention has a cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group, adamantyl group, tricyclodecyl group, dicyclopentenyl group, dicyclopentyl group at least on the side chain (A). group, and alicyclic structure selected tri cyclopentenyl group, and a tri-cyclopentadienyl group, an acidic group, an ethylenically unsaturated bond and a resin containing, (B) a polymerizable compound, and (C) light It is formed using a photosensitive composition containing a polymerization initiator, has an elastic modulus at 15% compression at 25 ° C. in the range of 0.5 GPa or more and 3.0 GPa or less, and has a bottom area exceeding 20 μm ^{2 and} 350 μm ^2. The range is as follows, and the height is configured to be in the range of 1.0 μm to 10.0 μm.

  In the present invention, a structure having a predetermined bottom area and height is configured to have a constant elastic coefficient, so that a spacer having a large elastic recovery rate and a large amount of weight deformation can be obtained. When used as a spacer to keep the gap between substrates constant, due to the elastic recovery of the spacer and the small amount of deformation, for example, volume expansion / contraction due to changes in the weight of the liquid crystal material and temperature, and variations in liquid crystal injection amount The display unevenness caused by the above and the like can be effectively suppressed, and high-quality image display becomes possible. This is particularly effective in preventing display unevenness due to poor gravity caused by the space between the substrates being expanded when the elastic modulus of the spacer is too low, and when the substrate is large in size, the liquid crystal material between the substrates is For example, a large-sized substrate is likely to cause uneven display due to uneven distribution (gravity failure) near the bottom of the substrate due to the weight of the liquid crystal itself increasing when it is placed in a direction intersecting the horizontal plane, etc. This is particularly effective when using (preferably a substrate having a size of 400 mm × 300 mm or more).

  In the spacer of the present invention, the elastic modulus at 15% compression at 25 ° C. is in the range of 0.5 to 3.0 GPa. If the elastic modulus here is less than 0.5 GPa, the spacer is too soft, and the spacer is expanded when the substrate gap widens due to the volume expansion of the liquid crystal material or the liquid crystal injection amount exceeding a predetermined amount due to the temperature rise. When the liquid crystal material is partially extended or the like, for example, when the liquid crystal material is arranged in a direction intersecting the horizontal plane, the uneven distribution (gravity failure) occurs, resulting in display unevenness. On the other hand, when the elastic modulus exceeds 3.0 GPa, the spacer is too hard and the liquid crystal material undergoes volume shrinkage due to a decrease in temperature, thereby causing foaming (low temperature foaming) and causing display unevenness.

  In the present invention, the elastic modulus at the time of 15% compression at 25 ° C. controls the elastic recovery rate and the amount of weight deformation (softness) to a range that is not affected by temperature expansion / contraction of the liquid crystal material, variation in injection amount, etc. A range of 1.0 to 3.0 GPa is preferable, and a range of 1.3 to 2.4 GPa is more preferable.

“The elastic modulus at 15% compression at 25 ° C.” is a height H corresponding to 85% of the initial height H ₀ [mm] at a load application speed of 10 mN / s in a room adjusted to a temperature of 25 ° C. Compress until ₁ [mm], read the load F ₁ [N] at height H ₁ , and calculate from the following formula at 15% compression (strain amount = (H ₀ −H ₁ ) / H ₀ ) Is the value to be
Elastic modulus = (Load F ₁ / Spacer bottom area S [mm ² ]) / Strain amount In other words, the above equation shows that the strain amount when the load F ₁ is applied to the spacer of height H ₀ and bottom area S is ( It represents the elastic modulus when H ₀ −H ₁ ) / H ₀ .

  In order to adjust the elastic modulus at 15% compression (25 ° C.) within the above range, for example, (1) a method of changing the ratio of the monomer and the binder, (2) a method of changing the addition amount of particles such as silica, (3) A method of changing the type of initiator can be applied.

In the spacer of the present invention, the bottom area (S) is in the range of 20 μm ² <S ≦ 350 μm ² and the height (H) is in the range of 1.0 ≦ H ≦ 10.0 μm.
When the bottom area S is 20 μm ² or less, the spacer is easily separated from the substrate when the gap between the substrates is widened, and the liquid crystal material is unevenly distributed (gravity failure) when the liquid crystal material is arranged, for example, in a direction intersecting the horizontal plane. When the thickness exceeds 350 μm ² , it becomes impossible to follow, low-temperature foaming occurs, and display unevenness is also generated. Further, if the height H is less than 1.0 μm, it cannot follow when the gap between the substrates widens, and is unevenly distributed when the spacer is separated from the substrate and the liquid crystal material is arranged in a direction intersecting the horizontal plane, for example ( Inferior gravity) causes non-uniformity of display, and when it exceeds 10.0 μm, the elasticity decreases, and the liquid crystal material is unevenly distributed (defective gravity) when the liquid crystal material is arranged, for example, in a direction intersecting the horizontal plane. The shape may be deformed in the horizontal direction (side-down), resulting in display unevenness.

The bottom surface area S of the spacer, preferably 20 <a range of S ≦ 300 [mu] m ^2, more preferably in the range of 20 <S ≦ 180 [mu] m ^2, more preferably in the range of 50~180μm ^2. In addition, the height of the spacer is preferably in the range of 1.5 to 5.0 μm, more preferably in the range of 1.8 to 4.7 μm.

Among these, from the viewpoint of increasing the elastic recovery rate and the amount of load deformation of the spacer, the elastic modulus at 15% compression at 25 ° C. is in the range of 1.3 to 2.4 GPa, and the bottom area S of the spacer is 50 to 50%. The case where the height is in the range of 180 μm ² and the spacer height is in the range of 1.8 to 4.7 μm is particularly preferable.

The bottom area is the area of one of the end faces at both ends in the longitudinal direction of the spacer (for example, in the case of a cylindrical spacer, the area of a circular cross section perpendicular to the column length direction), and the height is the length of the spacer. This is an average value obtained by measuring a plurality of lengths in the direction (distance between one end of the spacer facing one of the two substrates and the other end of the spacer facing the other) and averaging the measured values.
The bottom area and height of the spacer are values after standing at 25 ° C. for 24 hours. For example, the bottom area is observed by SEM, and the height is a three-dimensional surface structure analysis microscope (manufacturer: ZYGO Corporation, model: New It can be measured by using View 5022).

  The spacer of the present invention includes at least two substrates, a liquid crystal material provided between the substrates, two electrodes for applying an electric field to the liquid crystal material, and a spacer for regulating a cell thickness between the substrates. Are formed using a photosensitive composition that includes at least (A) a resin, (B) a polymerizable compound, and (C) a photopolymerization initiator.

  The spacer of the present invention is a step of forming a photosensitive resin layer by applying a photosensitive composition containing at least the above (A) to (C) on one of the two substrates (hereinafter referred to as “layer”). This is referred to as a “forming step”). For the application of the photosensitive composition, a coating method of applying the photosensitive composition, the photosensitive resin layer of the photosensitive transfer material provided in advance with the photosensitive resin layer formed using the photosensitive composition is transferred. Any of the transfer methods can be applied.

-Layer formation process-
In the layer forming step in the present invention, the (A) side chain is formed on the support with a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group, an adamantyl group, a tricyclodecyl group, a dicyclodecyl group. A resin comprising an alicyclic structure selected from a pentenyl group, a dicyclopentanyl group, a tricyclopentenyl group, and a tricyclopentanyl group, an acidic group, and an ethylenically unsaturated bond , (B) a polymerizable compound And (C) a photosensitive resin layer is formed using a photosensitive composition containing at least a photopolymerization initiator.
This photosensitive resin layer constitutes the above-described spacer of the present invention capable of maintaining the cell thickness uniformly through other processes such as a patterning process described later. By using the spacer of the present invention, display unevenness in an image in a liquid crystal display device, in which display unevenness is likely to occur due to a change in cell thickness, is effectively eliminated.

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

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

(B) Transfer method Transfer is performed using a photosensitive transfer material, for example, a roller or a flat plate in which a photosensitive resin layer formed in a film shape on a temporary support is heated and / or pressurized on a desired support surface. Then, 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.

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

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

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

-Photosensitive composition-
Next, the photosensitive composition will be described.
The photosensitive composition contains at least (A) a resin, (B) a polymerizable compound, and (C) a photopolymerization initiator. (A) As a resin, a side chain includes a cyclopentyl group, a cyclohexyl group, a cyclohexane. An alicyclic structure selected from a heptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group, an adamantyl group, a tricyclodecyl group, a dicyclopentenyl group, a dicyclopentanyl group, a tricyclopentenyl group, and a tricyclopentanyl group When the acidic group, an ethylenically unsaturated bond, Ru is configuration using a resin having. Moreover, it can comprise using other components, such as a coloring agent and surfactant, as needed.

-(A) Resin-
As the resin, a resin having a reactive group and an acidic group in the molecule is preferable from the viewpoint that it can be arbitrarily selected from known resin components and used and has excellent elasticity recovery properties. Among them, from the viewpoint of increasing the elastic recovery property (that is, the deformation recovery rate) of the spacer, the side chain has a branched and / or alicyclic structure: X (x mol%), an acidic group: Y (y mol%), and ethylene. A resin having an unsaturated bond: Z (z mol%) is preferable, and may have another group (L) (1 mol%) as necessary. (A) A plurality of X, Y, and Z may be combined in one group in the resin.

  Here, the branched and / or alicyclic structure, the acidic group, and the ethylenically unsaturated bond may be contained in different side chains, or a part thereof may be combined and contained in the same side chain. Or all of them may be contained in the same side chain.

-Branched and / or alicyclic structure: X-
The “branched and / or alicyclic structure” will be described.
First, examples of the branched structure include branched alkyl groups having 3 to 12 carbon atoms. For example, i-propyl group, i-butyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group. Group, 2-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, i-amyl group, t-amyl group, 3-octyl, t-octyl and the like and groups having these. Among these, i-propyl group, s-butyl group, t-butyl group, isopentyl group and the like and groups having these are preferable, and i-propyl group, s-butyl group, t-butyl group and the like are further included. Groups are preferred.

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

  Furthermore, the form comprised by having group represented by the following general formula (a) as a group which has a branched and / or alicyclic structure is preferable.

  In general formula (a), x represents 1 or 2, and m and n each independently represent an integer of 0 to 15.

  Examples of the monomer for introducing a branched and / or alicyclic structure into the resin side chain 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 monomers for introducing a branched structure into the side chain of the resin include i-propyl (meth) acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, (meth ) T-butyl acrylate, i-amyl (meth) acrylate, t-amyl (meth) acrylate, sec-iso-amyl (meth) acrylate, 2-octyl (meth) acrylate, (meth) acrylic acid 3-octyl, t-octyl (meth) acrylate, and the like are mentioned. Among them, i-propyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl methacrylate, and the like are preferable, and more preferable. I-propyl methacrylate, t-butyl methacrylate and the like.

  Specific examples of the monomer for introducing the alicyclic structure into the side chain of the resin include (meth) acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. Specific examples include (meth) acrylic acid (bicyclo [2.2.1] heptyl-2), (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl, (meth) acrylic. Acid-3-methyl-1-adamantyl, (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-2 -Methyl-2-adamantyl, (meth) acrylic acid-2-ethyl-2-adamantyl, (meth) acrylic acid-3-hydroxy-1-adamantyl, (meth) acrylic Octahydro-4,7-mentanoinden-5-yl, (meth) acrylic acid octahydro-4,7-mentanoinden-1-ylmethyl, (meth) acrylic acid-1-menthyl, (meth) acrylic acid tricyclo Pentenyl, (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, cyclohexyl (meth) acrylate, and the like. Among these (meth) acrylic acid esters, (meth) acrylic acid cyclohexyl, (meth) acrylic acid (nor) bornyl, (meth) acrylic acid isobornyl, (meth) acrylic acid-1-adamantyl, (meth) acrylic acid- 2-adamantyl, fumedyl (meth) acrylate, 1-menthyl (meth) acrylate, tricyclodecyl (meth) acrylate, and the like are preferred, cyclohexyl (meth) acrylate, tricyclopentenyl (meth) acrylate, (meth ) (Nor) bornyl acrylate, isobornyl (meth) acrylate, and (meth) acrylate-2-adamantyl are particularly preferred.

  Furthermore, specific examples of the monomer for introducing the alicyclic structure into the side chain of the resin include compounds represented by the following general formula (1) or (2). Here, in the general formulas (1) and (2), x represents 1 or 2, and R represents hydrogen or a methyl group. m and n each independently represent 0-15. Among the general formulas (1) and (2), x = 1 or 2, m = 0 to 8, and n = 0 to 4 are preferable in terms of excellent developability and deformation recovery rate, and x = 1 or 2 , M = 1 to 4, and n = 0 to 2 are more preferable. Preferable specific examples of the compound represented by the general formula (1) or (2) include the following compounds D-1 to D-5 and T-1 to T-8.

As the monomer for introducing the alicyclic structure into the side chain of the resin, an appropriately produced monomer may be used, or a commercially available product may be used.
As said commercial item, Hitachi Chemical Co., Ltd. product: FA-511A, FA-512A (S), FA-512M, FA-513A, FA-513M, TCPD-A, TCPD-M,
H-TCPD-A, H-TCPD-M, TOE-A, TOE-M, H-TOE-A, H-TOE-M and the like can be mentioned. Among these, FA-512A (S) and 512M are preferable in terms of excellent developability and excellent deformation recovery rate.

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

  The monomer for introducing the acidic group into the resin 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 for introducing the acidic group into the resin can be appropriately selected from known ones such as (meth) acrylic acid, vinyl benzoic acid, maleic acid, and 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 (Meth) acrylate etc. are mentioned. As these, those produced as appropriate may be used, or commercially available products may be used.

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

  Commercially available products of the above-mentioned “monomer having an acidic group” are manufactured by Toagosei 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, Kyoeisha Yushi Chemical Co., Ltd .: HOA-MP, HOA-MS, Osaka Organic Chemical Industry Co., Ltd .: Biscote # 2100 and the like. Among these, (meth) acrylic acid and the like are preferable in terms of excellent developability and low cost.

-Ethylenically unsaturated bond: Z-
Although there is no restriction | limiting in particular as an ethylenically unsaturated bond, It is preferable to arrange | position by introducing a (meth) acryloyl group. The connection between the ethylenically unsaturated bond 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 bond into the side chain can be appropriately selected from known ones. For example, a method of adding (meth) acrylate having an epoxy group to a group having an acidic group, a hydroxyl group Examples include a method of adding a (meth) acrylate having an isocyanate group to a group having the same, a method of adding a (meth) acrylate having a hydroxy group to a group having an isocyanate group, and the like.
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.

  The (meth) acrylate having an ethylenically unsaturated bond and an epoxy group is not particularly limited as long as it has these. For example, in the compound represented by the following structural formula (1) and the following structural formula (2) The compounds represented are preferred.

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

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

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

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

-Other monomers-
The other monomer is not particularly limited, for example, (meth) acrylic acid ester, styrene, vinyl ether, dibasic acid anhydride group, vinyl ester group, hydrocarbon having no branched and / or alicyclic structure. And monomers having an alkenyl group.
There is no restriction | limiting in particular as said vinyl ether group, For example, a butyl vinyl ether group etc. are mentioned.

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

  As content rate of the other monomer in said (A) resin, 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 (A) resin include the following compounds (compounds P-1 to P-45).

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

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

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

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

<Acid value>
(A) Although the preferable range of the acid value of the resin varies depending on the molecular structure that can be taken, it is generally preferably 20 mgKOH / g or more, more preferably 50 mgKOH / g or more, and 70 to 130 mgKOH / g. It is particularly preferred. When the acid value is within the preferred range, a spacer 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 10,000 to 100,000 because a spacer having good developability and mechanical strength can be obtained. Preferably, the Tg is 45 to 140 ° C. (further 50 to 130 ° C.) and the weight average molecular weight is 12,000 to 60,000 (further 15,000 to 45,000). .
Furthermore, a preferable example of the (A) resin is more preferably a combination of the preferable molecular weight, glass transition temperature (Tg), and acid value.

The resin (A) in the present invention includes a repeating unit having a branched and / or alicyclic structure in the side chain: X (x mol%), a repeating unit having an acidic group in the side chain: Y (y mol%), It is a copolymer having at least ternary copolymer having a repeating unit having an ethylenically unsaturated bond in the side chain: Z (z mol%) in a separate copolymer unit, and the deformation recovery rate, development It is preferable from the viewpoint of residues and reticulation. Specifically, a copolymer obtained by copolymerizing at least one of the monomers constituting the X, Y, and Z is preferable.
Such a copolymer includes, for example, a monomer having a branched and / or alicyclic structure, a monomer having an acidic group, a monomer having an ethylenically unsaturated bond, and others as necessary. Can be obtained by copolymerizing the above monomer.

The copolymer composition ratio of the respective components of the (A) resin is determined in consideration of the glass transition temperature and the acid value. Although it cannot be generally stated, the following ranges can be adopted.
(A) The composition ratio (x) of the repeating unit having a branched and / or alicyclic structure in the resin is preferably 10 to 70 mol%, more preferably 15 to 65 mol%, particularly preferably 20 to 60 mol%. . When the composition ratio (x) is within the above range, good developability is obtained and the developer resistance of the image area is also good.
(A) As for the composition ratio (y) of the repeating unit which has an acidic group in resin, 5-70 mol% is preferable, 10-60 mol% is further more preferable, and 20-50 mol% is especially preferable. When the composition ratio (y) is within the above range, good curability and developability can be obtained.
(A) As for the composition ratio (z) of the repeating unit which has an ethylenically unsaturated bond in resin, 10-70 mol% is preferable, 20-70 mol% is still more preferable, 30-70 mol% is especially preferable. When the composition ratio (z) is within the above range, the pigment dispersibility is excellent, and the developability and curability are also good.
Further, as the (A) resin, the composition ratio (x) is 10 to 70 mol% (more preferably 15 to 65 mol%, particularly 20 to 50 mol%), and the composition ratio (y) is 5 to 5 mol%. 70 mol% (more 10 to 60 mol%, especially 30 to 60 mol%), and the composition ratio (z) is 10 to 70 mol% (more 20 to 70 mol%, especially 30 to 70 mol%). %) Is preferred.

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

-Other resins-
As the resin that can be used in combination with the resin (A), a compound that shows 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.

  When the (A) resin and other resin are used in combination, the total content (solid content) of the resin (A) that can be used in combination with the resin is based on the total solid content of the photosensitive resin layer. 5 to 70 mass% is preferable, and 10 to 50 mass% is more preferable. When the content is 5% by mass or more, the film strength of the photosensitive resin layer can be maintained, and the tackiness of the surface of the photosensitive resin layer can be maintained well. When the content is 70% by mass or less, the exposure sensitivity is good. become.

-(B) polymerizable compound, (C) photopolymerization initiator, other components-
The photosensitive composition in the present invention contains (B) a polymerizable compound and (C) a photopolymerization initiator together with the (A) resin, preferably (D) contains fine particles, and is further necessary. Depending on the above, other components such as a photopolymerization initiation assistant may be contained. The (B) polymerizable compound, (C) photopolymerization initiator, (D) fine particles, and other components can be selected from components constituting a known composition and used, for example, The components described in paragraph Nos. [0010] to [0020] of Japanese Patent No. 23696 and the components described in paragraph Nos. [0027] to [0053] of Japanese Patent Application Laid-Open No. 2006-64921 can be given.

As the photopolymerization initiator (C), aminoacetophenone compounds, acylphosphine oxide compounds, and oxime ester compounds are suitable in terms of sensitivity.
Specific examples of the aminoacetophenone compounds include IRGACURE (Irg) 369, IRGACURE (Irg) 379, IRGACURE (Irg) 907, etc. (above, manufactured by Ciba Specialty Chemicals Co., Ltd.).
Specific examples of the acylphosphine oxide compound include DAROCUR TPO, Irgacure (Irg) 819, etc. (above, manufactured by Ciba Specialty Chemicals Co., Ltd.).
Specific examples of the oxime ester compound include IRGACURE (Irg) OXE01, CGI242 and the like (above, manufactured by Ciba Specialty Chemicals Co., Ltd.).
The structures of these initiators are shown below.

  In the relationship with the (A) resin, the mass ratio ((B) / (A) ratio) of the (B) polymerizable compound to the (A) resin is preferably 0.5 to 2.0. It is more preferably 6 to 1.4, and particularly preferably 0.7 to 1.2. When the ratio (B) / (A) is within the above range, a spacer having good developability and mechanical strength can be obtained.

  Moreover, as content in the photosensitive resin layer of the said (C) photoinitiator, 0.5-25 mass% is preferable with respect to the total solid of the photosensitive resin layer, and 1-20 mass% is preferable. More preferred. When the content is within the above range, it is possible to prevent a decrease in photosensitivity and spacer strength, and it is possible to improve performance such as deformation recovery necessary as a spacer.

  When the photopolymerization initiation assistant is contained in the photosensitive composition, the photopolymerization initiation assistant is used in order to promote the polymerization of the photopolymerizable compound whose polymerization has been initiated by the photopolymerization initiator. It can be used in combination with a photopolymerization initiator. As the photopolymerization initiation assistant, it is preferable to use at least one amine compound.

  Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4 Examples include '-bis (ethylmethylamino) benzophenone, and 4,4'-bis (diethylamino) benzophenone is particularly preferable. Further, a plurality of amine-based and other photopolymerization initiation assistants may be used in combination.

Examples of other photopolymerization initiation assistants include alkoxyanthracene compounds, thioxanthone compounds, and coumarin compounds.
Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. It is done.
Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

Moreover, a commercially available thing can also be used as a photoinitiation auxiliary agent, As a commercially available photoinitiation auxiliary agent, a brand name "EAB-F" (made by Hodogaya Chemical Co., Ltd.) etc. are mentioned, for example. .
(D) As a usage-amount in the photosensitive composition of photoinitiator adjuvant, 0.6 mass part or more and 20 mass parts or less are preferable with respect to 1 mass part of said (C) photoinitiator, Furthermore, 1 mass The amount is preferably 15 parts by mass or more and 15 parts by mass or less, particularly preferably 1.5 parts by mass or more and 15 parts by mass or less.

-(D) Fine particles-
The photosensitive composition preferably contains fine particles in terms of mechanical strength.
(D) The fine particles are not particularly limited and may be appropriately selected depending on the purpose. For example, extender pigments described in JP-A-2003-302039 [0035] to [0041] are preferable, Colloidal silica is preferred from the viewpoint of obtaining a spacer 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 particularly preferably 15 to 30 nm in that a spacer having high mechanical strength is obtained. preferable.

  The content of the fine particles (D) in the photosensitive resin layer (that is, the spacer) is based on the total solid content (mass) in the photosensitive resin layer (spacer) from the viewpoint of obtaining a spacer having high mechanical strength. 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 15 to 30% by mass.

-Patterning process-
In the present invention, after the layer forming step, a step of patterning by exposing and developing the photosensitive resin layer formed on the support (hereinafter sometimes referred to as “patterning step”) may be provided. And a spacer having a desired shape can be manufactured.

  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 can be cited as preferable examples in the present invention.

The spacer of the present invention can be formed after forming a color filter including a black shielding part such as a black matrix and a colored part such as a colored pixel.
The black shielding part, the colored part and the spacer are formed by arbitrarily combining a coating method for applying a photosensitive composition and a transfer method using a transfer material having a photosensitive resin layer made of the photosensitive composition. Is possible.
The black shielding part, the colored part, and the spacer can each be formed from a photosensitive composition. Specifically, for example, after forming the photosensitive resin layer by directly applying the liquid photosensitive composition on a substrate, for example. Then, exposure / development is performed, the black shielding part and the colored part are formed in a pattern, and then the photosensitive composition of another liquid is placed on another substrate (temporary support) different from the substrate. The transfer material produced by forming the photosensitive resin layer is used, and after the photosensitive resin layer is transferred by bringing the transfer material into close contact with the substrate on which the black shielding portion and the colored portion are formed, exposure and By performing development, the spacer can be formed in a pattern. In this manner, a color filter provided with a spacer can be manufactured.

<Liquid crystal display substrate>
The substrate for a liquid crystal display device of the present invention includes the spacer of the present invention. The spacer is preferably formed on a black light shielding portion such as a black matrix formed on the 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 black light shielding portion such as a black matrix or a driving element such as a TFT and a spacer.

For example, when the spacer is provided on the black light shielding portion or the driving element, the black light shielding portion (black matrix or the like) or the driving element previously disposed on the support is covered so that, for example, the photosensitive transfer material The photosensitive resin layer is laminated on the support surface, peeled and transferred to form a photosensitive resin layer, and then subjected to exposure, development, heat treatment and the like to form a spacer, thereby forming the spacer for the liquid crystal display device of the present invention. A substrate can be produced. As described above, for example, after forming the photosensitive resin layer by directly applying the liquid photosensitive composition to the substrate, exposure and development are performed, and the black shielding portion and the colored portion are formed in a pattern, Thereafter, the transfer material prepared by placing the photosensitive composition of another liquid on another substrate (temporary support) different from the substrate to form a photosensitive resin layer is used. After the photosensitive resin layer is transferred by closely adhering to the substrate on which the black shielding portion and the colored portion are formed, the spacer can be formed in a pattern. In this manner, a substrate for a liquid crystal display device provided with a spacer 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 by providing 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. Including at least).

  In this case, the substrate for a liquid crystal display device of the present invention can be used as a color filter substrate having a plurality of RGB pixel groups and pixels constituting the pixel group being separated from each other by a black matrix. Since this color filter substrate is provided with a high deformation recovery spacer having an excellent elastic recovery rate and weighted deformation amount, a liquid crystal display element including the color filter substrate is provided between the color filter substrate and the counter substrate. It is possible to effectively prevent the occurrence of display unevenness such as color unevenness due to uneven distribution of liquid crystal material due to fluctuations in cell gap (cell thickness) and low temperature foaming. Thereby, the produced liquid crystal display element can display a vivid image.

  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 the pair of substrates is configured to be regulated to a predetermined width by a highly deformable spacer having excellent elastic recovery rate and weight deformation amount. Also in this case, the substrate for a liquid crystal display device of the present invention has a plurality of RGB pixel groups, and is used as a color filter substrate in which 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 as described above after forming a pixel group of two or more colors, or conversely, a pixel group may be formed after forming a black matrix. Good. Regarding the formation of RGB pixels, JP 2004-347831 A can be referred to.

<Liquid crystal display device>
The liquid crystal display device of the present invention is constituted by providing the liquid crystal display device substrate. In addition, the liquid crystal display device of the present invention can be configured by providing the liquid crystal display element. That is, as described above, the space between the pair of substrates arranged to face each other is regulated to a predetermined width by the spacer of the present invention, and the liquid crystal material is enclosed in the regulated gap (the enclosed portion is referred to as a liquid crystal layer). The thickness of the liquid crystal layer (cell thickness) is maintained at a desired uniform thickness.

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

  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). The liquid crystal display device of the present invention can be suitably applied to various liquid crystal display devices, such as a configuration in which a spacer is interposed and arranged opposite to each other and a liquid crystal material is sealed in the gap portion.

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

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

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

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

(Resin synthesis)
(A) The synthesis example of compound P-1 mentioned above as an example of resin is shown below.
-Synthesis Example 1
7.48 parts of 1-methoxy-2-propanol (MMPGAC, manufactured by Daicel Chemical Industries, Ltd.) was added in advance to the reaction vessel, the temperature was raised to 90 ° C., and 2-adamantyl methacrylate (ADMA, Hitachi Chemical ( Co., Ltd.) 6.35 parts, methacrylic acid 3.62 parts, azo polymerization initiator (Wako Pure Chemical Industries, Ltd., V-601) 0.22 parts, and 1-methoxy-2-propanol 7.48 The mixed solution consisting of parts was dropped into a 90 ° C. reaction vessel over 2 hours under a nitrogen gas atmosphere. After dripping, it was made to react for 4 hours and the acrylic resin solution was obtained.
Next, 0.020 part of hydroquinone monomethyl ether and 0.46 part of tetraethylammonium bromide were added to the acrylic resin solution, and then 3.53 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 prepared by adding a solvent so that the solid concentration was 45%. The compound P-1 [(( A) resin] (solid acid value; 70.6 mg KOH / g, Mw; 30,000, 1-methoxy-2-propanol 45% solution) (x: y: z is 41.0 mol%) : 24.0 mol%: 35.0 mol%).
In addition, molecular weight Mw of compound P-1 showed a weight average molecular weight, and the measurement of the weight average molecular weight was performed using the gel permeation chromatograph method (GPC method) (hereinafter the same).

  Hereinafter, Synthesis Examples (Synthesis Examples 2 to 10) for synthesizing the aforementioned compounds P-2 to P-10 as other compounds of the resin (A) will be shown.

-Synthesis Example 2-
The aforementioned compound P-2 was synthesized as follows.
In Synthesis Example 1, isobornyl methacrylate (x) was used so that ADMA was replaced with isobornyl methacrylate and x: y: z in compound P-2 was 48.0 mol%: 22.0 mol%: 30.0 mol%. Resin of Compound P-2 [(A) Resin] having an unsaturated group synthesized by the same method as in Synthesis Example 1 except that the addition amount of methacrylic acid (y) and glycidyl methacrylate (z) was changed. A solution (solid content acid value; 63.6 mg KOH / g, Mw; 30,000, and 10,000, 40,000, 1-methoxy-2-propanol 45% solution) was obtained.

-Synthesis Example 3-
Synthesis of the aforementioned compound P-3 was performed as follows.
In Synthesis Example 1, cyclohexyl methacrylate (x) was used so that x: y: z in compound P-3 was 45.0 mol%: 20.0 mol%: 35.0 mol% in place of ADMA in cyclohexyl methacrylate. Resin of Compound P-3 [(A) Resin] having an unsaturated group synthesized by the same method as in Synthesis Example 1 except that the addition amount of methacrylic acid (y) and glycidyl methacrylate (z) was changed. A solution (solid content acid value; 64.9 mg KOH / g, Mw; 30,000, 1-methoxy-2-propanol 45% solution) was obtained.

-Synthesis Example 4-
The aforementioned compound P-4 was synthesized as follows.
In Synthesis Example 1, ADMA was replaced with tricyclopentenyl methacrylate (TCPD-M, manufactured by Hitachi Chemical Co., Ltd.), and x: y: z in compound P-4 was 40.0 mol%: 25.0 mol%: The unsaturated compound was synthesized by the same method as in Synthesis Example 1 except that the addition amount of TCPD-M (x), methacrylic acid (y), and glycidyl methacrylate (z) was changed to 35.0 mol%. A resin solution (solid acid value: 65.2 mg KOH / g, Mw; 30,000, 1-methoxy-2-propanol 45% solution) of the compound P-4 [(A) resin] having a group was obtained.

-Synthesis Example 5-
Synthesis of the aforementioned compound P-5 was performed as follows.
In Synthesis Example 1, ADMA was replaced with tricyclopentanyl methacrylate (H-TCPD-M, manufactured by Hitachi Chemical Co., Ltd.), and x: y: z in compound P-5 was 42.0 mol%: 26. 0 mol%: By the same method as Synthesis Example 1 except that the addition amounts of H-TCPD-M (x), methacrylic acid (y), and glycidyl methacrylate (z) were changed so as to be 32.0 mol%. Resin solution of compound P-5 [(A) resin] synthesized and having an unsaturated group (solid content acid value: 67.6 mg KOH / g, Mw; 30,000, 1-methoxy-2-propanol 45% solution) Got.

-Synthesis Example 6
Synthesis of the aforementioned compound P-6 was carried out as follows.
In Synthesis Example 1, ADMA was replaced with tricyclopentenyloxyethyl methacrylate (TOE-M, manufactured by Hitachi Chemical Co., Ltd.), and x: y: z in compound P-6 was 40.0 mol%: 23.0 mol %: Synthesized by the same method as in Synthesis Example 1 except that the addition amount of TOE-M (x), methacrylic acid (y), and glycidyl methacrylate (z) was changed to 37.0 mol%. A resin solution of the compound P-6 [(A) resin] having an unsaturated group (solid content acid value: 54.8 mg KOH / g, Mw; 30,000, 1-methoxy-2-propanol 45% solution) was obtained. .

-Synthesis Example 7-
Synthesis of the aforementioned compound P-7 was performed as follows.
In Synthesis Example 1, ADMA was replaced with tricyclopentanyloxyethyl methacrylate (H-TOE-M, manufactured by Hitachi Chemical Co., Ltd.), and x: y: z in compound P-7 was 40.0 mol%: 25.0 mol%: The same as Synthesis Example 1 except that the addition amounts of H-TOE-M (x), methacrylic acid (y), and glycidyl methacrylate (z) were changed so as to be 35.0 mol%. Resin solution of compound P-7 [(A) resin] having an unsaturated group synthesized by the method (solid content acid value: 60.1 mg KOH / g, Mw; 30,000, 1-methoxy-2-propanol 45% Solution).

-Synthesis Example 8-
Synthesis of the aforementioned compound P-8 was carried out as follows.
In Synthesis Example 1, ADMA was replaced with dicyclopentenyloxyethyl acrylate (FA-512A, manufactured by Hitachi Chemical Co., Ltd.), and x: y: z in compound P-8 was 42.0 mol%: 23.0 mol% : Synthesized by the same method as in Synthesis Example 1 except that the addition amount of FA-512A (x), methacrylic acid (y), and glycidyl methacrylate (z) was changed to 35.0 mol%. A resin solution of a compound P-8 [(A) resin] having a saturated group (solid content acid value: 63.3 mg KOH / g, Mw; 30,000, 1-methoxy-2-propanol 45% solution) was obtained.

-Synthesis Example 9-
The aforementioned compound P-9 was synthesized as follows.
In Synthesis Example 1, ADMA was replaced with dicyclopentenyloxyethyl methacrylate (FA-512M, manufactured by Hitachi Chemical Co., Ltd.), and x: y: z in compound P-9 was 41.0 mol%: 24.0 mol. %: Synthesized by the same method as in Synthesis Example 1 except that the addition amount of FA-512M (x), methacrylic acid (y), and glycidyl methacrylate (z) was changed to 35.0 mol%. A resin solution of the compound P-9 [(A) resin] having an unsaturated group (solid content acid value: 64.7 mg KOH / g, Mw; 30,000, 1-methoxy-2-propanol 45% solution) was obtained. .

-Synthesis Example 10-
Synthesis of the aforementioned compound P-10 was carried out as follows.
In Synthesis Example 1, ADMA was replaced with dicyclopentanyl methacrylate (FA-513M, manufactured by Hitachi Chemical Co., Ltd.), and x: y: z in compound P-10 was 50.0 mol%: 24.0 mol%. : Synthesized by the same method as in Synthesis Example 1 except that the addition amount of FA-513M (x), methacrylic acid (y), and glycidyl methacrylate (z) was changed to 26.0 mol%. A resin solution (solid acid value: 70.8 mg KOH / g, Mw; 30,000, 1-methoxy-2-propanol 45% solution) of compound P-10 [(A) resin] having a saturated group was obtained.

(Example 1): Coating method <Preparation of color filter substrate>
A color filter having a black matrix, an R (red) pixel, a G (green) pixel, and a B (blue) pixel was produced by the method described in paragraph numbers [0084] to [0095] of JP-A-2005-3861. (Hereinafter, this is referred to as a color filter substrate). Here, the substrate size of the color filter substrate was 400 mm × 300 mm.
Next, a transparent electrode of ITO (Indium Tin Oxide) was further formed on the R pixel, G pixel, B pixel and black matrix of the obtained color filter substrate by sputtering.

<Formation of photo spacer>
On the ITO transparent electrode of the color filter substrate on which the ITO transparent electrode produced as described above was formed by sputtering, a glass substrate coater MH-1600 (manufactured by FS Asia Co., Ltd.) having a slit-shaped nozzle is shown in Table 1 below. A photosensitive resin layer coating solution having the formulation shown in (Prescription 1 in the Examples) was applied by slitting. Subsequently, after part of the solvent was dried for 30 seconds using a vacuum dryer VCD (manufactured by Tokyo Ohka Kogyo Co., Ltd.) to remove the fluidity of the coating film, it was pre-baked at 120 ° C. for 3 minutes, and a photosensitive film having a film thickness of 5.0 μm. A functional resin layer was formed (layer forming step).

Subsequently, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, the mask (quartz exposure mask having an image pattern) and the mask and the photosensitive resin layer face each other. The distance between the mask surface and the surface of the photosensitive resin layer is set to 100 μm in a state where the color filter substrate placed on the substrate is substantially parallel and vertical, and the proxy is used with an exposure amount of 300 mJ / cm ² through the mask. Mitty exposed.

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

  Next, the color filter substrate provided with the spacer pattern was subjected to heat treatment at 230 ° C. for 30 minutes (heat treatment step), thereby producing a photo spacer on the color filter substrate. Here, 1000 photo spacers obtained were measured using a three-dimensional surface structure analysis microscope (manufacturer: ZYGO Corporation, model: New View 5022) to measure the highest position of the highest spacer from the ITO transparent electrode forming surface side ( n = 20), and the average value when averaged was defined as the height (average height). Moreover, the measurement of the bottom area of the obtained photospacer was performed using the SEM photograph. As a result, it was a cylindrical shape having a diameter of 15.1 μm and an average height of 4.7 μm. The measured values are shown in Table 2 below.

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

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

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

<Evaluation>
The obtained photo spacer was subjected to the following measurements and evaluations. The results of measurement evaluation are shown in Table 2 below.

-Deformation recovery rate-
The obtained photo spacer was measured and evaluated by a micro hardness tester (DUH-W201, manufactured by Shimadzu Corporation) as follows. The measurement was performed by a load-unloading test method using a frustum-type indenter with a diameter of 50 μm, a maximum load of 50 mN, and a holding time of 5 seconds. From this measured value, the deformation recovery rate [%] was obtained by the following formula and evaluated according to the following evaluation criteria. The measurement was performed in an environment of 22 ± 1 ° C. and 50% RH.
Deformation recovery rate (%)
= (Recovery amount after release of load [μm] / Deformation amount under load [μm]) × 100
<Evaluation criteria>
5: Deformation recovery rate was 90% or more.
4: The deformation recovery rate was 87% or more and less than 90%.
3: The deformation recovery rate was 85% or more and less than 87%.
2: Deformation recovery rate was 80% or more and less than 85%.
1: The deformation recovery rate was 75% or more and less than 80%.
0: Deformation recovery rate was less than 75%.

−Elastic modulus at 15% compression at −25 ° C.−
In a room adjusted to a temperature of 25 ° C., the spacer is compressed to a height H ₁ [mm] corresponding to 85% of the initial height H ₀ [mm] at a load application speed of 10 mN / s, and the height H ₁ The load F ₁ [N] was read, and the elastic modulus at 15% compression (strain amount = (H ₀ −H ₁ ) / H ₀ ) was calculated from the following equation.
Elastic modulus = (load F ₁ / spacer bottom area S [mm ² ]) / strain amount

-Developability-
In the above-mentioned “-Production of Photo Spacer”, after the proximity exposure, development is performed in the same manner as the development conditions of each Example, SEM observation of the periphery of the formed photo spacer is performed, and the presence or absence of residues around the spacer is confirmed. did.
<Evaluation criteria>
5: A residue was not seen at all.
4: Some residue was observed around the pattern.
3: Residue was observed around the pattern.
2: Residues were observed on the periphery of the pattern and on the substrate in the vicinity of the pattern.
1: Residue was confirmed in several places on the substrate.

-Sensitivity-
With respect to the coating solution for the photosensitive resin layer used in each example, it was observed whether or not a spacer pattern could be formed when the exposure amount was variously changed, and evaluated according to the following evaluation criteria.
<Evaluation criteria>
A: Pattern formation was possible at 60 mJ or less.
Δ: Pattern formation was possible at 60 to 200 mJ.
X: The exposure amount of 200 mJ or more was required for pattern formation.

-Display unevenness-
(1) Display unevenness due to poor gravity The liquid crystal display device was allowed to stand at 60 ° C. for 2 days with the liquid crystal display device standing in parallel with the normal direction of the horizontal plane. After being allowed to stand, this liquid crystal display device was placed between crossed Nicols, and the display image was visually observed to evaluate the occurrence of defective gravity according to the following evaluation criteria.
<Evaluation criteria>
○: The displayed image was uniform.
Δ: Color unevenness occurred in a part of the display image.
X: There was color unevenness in the whole display image.
(2) Display unevenness due to low-temperature foaming After the liquid crystal display device is allowed to stand at 0 ° C for 24 hours, this liquid crystal display device is placed between crossed Nicols and visually observed to determine whether low-temperature foaming has occurred. Evaluation was performed according to the following evaluation criteria.
<Evaluation criteria>
○: No foaming was observed.
Δ: Color unevenness due to foaming was partially recognized.
X: Color unevenness due to foaming was observed.

(Examples 2 to 19 and Examples 21 to 23): Coating method In Example 1, the compound P-1 [(A) resin], fine particles, initiator, B used in the preparation of the coating solution for the photosensitive resin layer A photo spacer and a liquid crystal display device were produced in the same manner as in Example 1 except that / A, the formation method, and the like were changed as shown in Tables 2 to 3 below. The obtained photospacer was cylindrical.

(Comparative Examples 1 to 6): Coating Method In Example 1, the formulation 1 of the photosensitive resin layer coating solution was replaced with the formulation 2 or 3 described in Table 1 above, and the photosensitive resin layer coating solution was prepared. A photo spacer and a liquid crystal display device were prepared in the same manner as in Example 1 except that the compound P-1 [(A) resin], the fine particles, and the formation method used in the above were changed as shown in Table 3 below. Produced. The obtained photospacer was cylindrical.

Example 20: Transfer Method As shown in Table 3 below, the compound P-1 [(A) resin] used in the preparation of the coating solution for the photosensitive resin layer, the fine particles, the formation method, and the like in Example 1. In the same manner as in Example 1 except that the photosensitive resin layer was formed by changing and performing transfer using the photosensitive transfer film for spacer shown below instead of application of the coating solution for photosensitive resin layer. Thus, a photo spacer and a liquid crystal display device were produced. The obtained photospacer was cylindrical.

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

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

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

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

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

  Next, a photosensitive resin layer coating solution comprising the formulation 1 shown in Table 1 above ((A) resin is the compound in Table 3) is further applied onto the formed intermediate layer and dried to obtain a dry layer thickness of 5 A photosensitive resin layer of 0.0 μm was laminated.

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

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

Subsequently, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, the mask (quartz exposure mask having an image pattern) and the mask and the thermoplastic resin layer face each other. The distance between the mask surface and the surface of the photosensitive resin layer on the side in contact with the intermediate layer is set to 100 μm with the color filter substrate placed on the substrate in a state where the color filter substrate stands substantially parallel and vertically, and the thermoplastic resin layer is interposed through the mask. Proximity exposure was performed at an exposure amount of 90 mJ / cm ² from the side.

Next, a triethanolamine developer (containing 30% triethanolamine, trade name: T-PD2 (manufactured by Fujifilm Corporation) 12 times with pure water (1 part of T-PD2 and 11 parts of pure water) The mixture was diluted with a ratio at a flat nozzle pressure of 0.04 MPa for 30 seconds at 30 ° C. to remove the thermoplastic resin layer and the intermediate layer. Subsequently, after air was blown off on the upper surface of the glass substrate, pure water was sprayed for 10 seconds by a shower, pure water shower cleaning was performed, and air was blown to reduce a liquid pool on the substrate.
Next, a sodium carbonate-based developer (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, and stabilizer Contained; trade name: T-CD1 (manufactured by Fuji Film Co., Ltd.) diluted 10-fold with pure water) at 29 ° C. for 30 seconds, with a cone-type nozzle pressure of 0.15 MPa, shower developed, and a pattern image Formed. Subsequently, a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer; trade name: T-SD3 (Fuji Film Co., Ltd.)) diluted 10 times with pure water Sprayed with a shower at 33 ° C. for 20 seconds at a cone type nozzle pressure of 0.02 MPa, the residue around the formed pattern image is removed, and a cylindrical spacer pattern is formed with a spacer spacing of 300 μm × 300 μm. (Patterning process).
Next, the color filter substrate provided with the spacer pattern was subjected to heat treatment at 230 ° C. for 30 minutes (heat treatment step), thereby producing a photo spacer on the color filter substrate. The obtained photospacer had a cylindrical shape with a diameter of 15.1 μm and an average height of 4.7 μm.
And the PVA mode liquid crystal display device was produced like Example 1 using the color filter board | substrate with which the photo spacer was produced.

As shown in Tables 2 to 3, in the examples, compared with the comparative example, the deformation recovery performance is excellent, the gravity failure and low temperature foaming are suppressed, and the occurrence of display unevenness such as color unevenness is dramatically increased. I was able to improve. The sensitivity was also good.
On the other hand, when the predetermined elastic modulus, the bottom area, and the height are not satisfied (comparative example), the occurrence of poor gravity and low temperature foaming cannot be prevented, and the occurrence of display unevenness cannot be avoided.

Claims (15)

At least (A) on the side chain, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group, adamantyl group, tricyclodecyl group, dicyclopentenyl group, dicyclopentanyl group, tricyclopentenyl group photosensitive containing group, and the alicyclic structure selected from tri-cyclopentadienyl group, an acidic group, an ethylenically unsaturated bond and a resin containing, (B) a polymerizable compound, and (C) a photopolymerization initiator The elastic modulus at the time of 15% compression at 25 ° C. is 0.5 GPa or more and 3.0 GPa or less, the bottom area is more than 20 μm ² and 350 μm ² or less, and the height is 1 A spacer having a thickness of 0.0 μm or more and 10.0 μm or less. The spacer according to claim 1, wherein the resin (A) has 10 or more carbon atoms. The spacer according to claim 1 or 2 , wherein the alicyclic structure has at least one selected from a tricyclopentenyl group, an adamantyl group, a norbornyl group, and an isobornyl group. The (C) photopolymerization initiator contains at least one selected from the group consisting of aminoacetophenone compounds, acylphosphine oxide compounds, and oxime ester compounds. the spacer according to any one of the three. Furthermore, (D) microparticles | fine-particles are included, The spacer of any one of Claims 1-4 characterized by the above-mentioned. Wherein (D) an average particle diameter of the fine particles is at 5nm or 50nm or less, wherein (D) according to claim 5, wherein the weight ratio of the total solid content of the fine particles is not more than 5 wt% to 50 wt% Spacers. The spacer according to any one of claims 1 to 6 , wherein the elastic modulus is 1.0 GPa or more and 3.0 GPa or less. The spacer according to any one of claims 1 to 7 , wherein the bottom area exceeds 20 µm ² and is 180 µm ² or less, and the height is 1.5 µm or more and 5.0 µm or less. The (A) resin includes a repeating unit X having the alicyclic structure in a side chain, a repeating unit Y having the acidic group in a side chain, and a repeating unit Z having the ethylenically unsaturated bond in a side chain; The spacer according to any one of claims 1 to 8, wherein the spacer is a copolymer having. The spacer according to claim 9, wherein the (A) resin has a composition ratio (x) of a repeating unit having an alicyclic structure in the resin of 20 to 50 mol%. It has group represented by the following general formula (a) as said alicyclic structure, The spacer of any one of Claims 1-10 characterized by the above-mentioned.

[Wherein, x represents 1 or 2, and m and n each independently represents an integer of 0 to 15. ] A method for producing a spacer according to any one of claims 1 to 11,
At least (A) on the side chain, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group, adamantyl group, tricyclodecyl group, dicyclopentenyl group, dicyclopentanyl group, tricyclopentenyl group photosensitive containing group, and the alicyclic structure selected from tri-cyclopentadienyl group, an acidic group, an ethylenically unsaturated bond and a resin containing, (B) a polymerizable compound, and (C) a photopolymerization initiator The manufacturing method of the spacer which has the process of forming the photosensitive resin layer on a support body by apply | coating a photosensitive composition, and patterning the said photosensitive resin layer, and forming a spacer pattern. A method for producing a spacer according to any one of claims 1 to 11,
A cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group, an adamantyl group, a tricyclodecyl group, a dicyclopentenyl group, dicyclopentanyl at least on the temporary support (A) side chain groups, resins containing a alicyclic structure selected tri cyclopentenyl group, and a tri-cyclopentadienyl group, an acidic group, an ethylenically unsaturated bond, a, (B) a polymerizable compound, and (C) a photopolymerization Using a photosensitive transfer material having a photosensitive resin layer containing an initiator, the photosensitive resin layer is transferred onto a support by heating and / or pressurization, and the spacer pattern is formed by patterning the photosensitive resin layer. A method for manufacturing a spacer including a step of forming. The liquid crystal display device substrate provided with a spacer according to any one of claims 1 to 11. A liquid crystal display device comprising the substrate for a liquid crystal display device according to claim 14 .