JP2011095733A - Photosensitive resin composition for photospacer, photosensitive resin transfer material, photospacer and process for producing the same, substrate for liquid crystal display device, and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition for producing a photospacer that can also withstand vibrations having high frequencies. <P>SOLUTION: The photosensitive resin composition for a photospacer comprises a resin (A) having an acidic group in a side chain thereof, a polymerizable compound (B), a photopolymerization initiator (C), and surface-treating microparticles (D) that contain surface-treating double bonds in an amount of 0.02 mmol to 0.35 mmol per 1 g of the microparticles. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition for a photospacer, a photosensitive resin transfer material, a photospacer and a method for producing the same, and a substrate for a liquid crystal display and a liquid crystal display for producing a liquid crystal display.

  Conventionally, liquid crystal display devices are widely used in display devices that display high-quality images. In a liquid crystal display device, a liquid crystal layer capable of displaying an image with a predetermined orientation is disposed between a color filter substrate and a TFT substrate, and maintaining the thickness of the liquid crystal layer uniformly determines the image quality. One of the elements. For this purpose, a photospacer for keeping the thickness of the liquid crystal layer constant is disposed between these two substrates. Pixels used in color filters, black matrix and other liquid crystal alignment control protrusions, and photo spacers are conventionally patterned on a substrate through patterning, alkali development, and baking using a photosensitive resin composition and a photosensitive resin transfer material. It is produced by forming an image.

  In recent years, these liquid crystal display devices are required to have further durability against vibrations and shocks due to changes in usage environment such as outdoor use and the increase in the screen size of liquid crystal televisions. In particular, with respect to vibration, as the substrate for the liquid crystal display device becomes larger, distortion during vibration becomes larger, so that the photo spacers are sharpened and dents increased, and as a result, there is a concern that the display portion may be uneven.

  The photo-curable resin composition for photospacers having vibration resistance contains an acrylate copolymer resin, a polyfunctional monomer, a photopolymerization initiator, a solvent, and silica fine particles. There has been proposed a photocurable resin composition for a photospacer that is contained in an amount of 5% by mass or more and less than 10% by mass (see, for example, Patent Document 1).

  Further, a hydrophilic resin (A) containing a (meth) acryloyl group and a carboxyl group obtained by modifying an epoxy resin, inorganic fine particles (B) having a volume average particle diameter of 1 to 200 nm, and a radical photopolymerization initiator (C) And a use example of inorganic fine particles surface-treated with a compound having a (meth) acryloxy group is disclosed (for example, see Patent Document 2).

JP 2008-304322 A JP 2009-133961 A

However, when the composition for photo spacers described in Patent Documents 1 and 2 above is used, it can be applied to a liquid crystal display device having a small screen size, but it cannot be said to be sufficient for one having a large screen size. .
The photospacer compositions described in Patent Documents 1 and 2 have been proposed mainly for improving alkali developability, liquid crystal orientation of cured products, voltage holding characteristics, and elastic recovery characteristics having a relatively low frequency. It is a thing. For this reason, if the surface treatment amount of the inorganic fine particles is large, the development speed of the unexposed portion can be increased, but a component containing the hydrophilic resin (A) is extracted from the pattern contour portion of the exposed spacer, and the spacer having a particularly small size is extracted. In the case of forming a residue, a residue containing a large amount of inorganic fine particles was generated. Further, the photospacer compositions described in Patent Documents 1 and 2 do not take any consideration into vibration resistance against high frequencies.
The present invention has been made in view of the above, and a photosensitive resin composition for a photospacer for producing a photospacer excellent in vibration resistance and impact resistance that can withstand vibrations having a high frequency. , Photosensitive resin transfer material produced using the same, photospacer excellent in vibration resistance and impact resistance and manufacturing method thereof, substrate for liquid crystal display device including the photospacer, and liquid crystal display It is an object of the present invention to provide a liquid crystal display device including a device substrate.

The above object is achieved by the present invention described below.
That is, the photosensitive composition for spacers of the present invention is as follows.
<1> Resin (A) having an acidic group in the side chain, polymerizable compound (B), photopolymerization initiator (C), and surface treatment double bond amount are 0.02 mmol to 0.35 mmol per 1 g of fine particles. Photosensitive resin composition for photospacers containing surface-treated fine particles (D).
<2> The surface treated fine particles (D) have oxide fine particles containing at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, magnesium, indium, tin, antimony, and cerium on the surface. The photosensitive resin composition for photospacers according to <1>, comprising the treated fine particles.
<3> The photosensitive resin composition for a photospacer according to <1> or <2>, wherein the double bond includes at least one of a methacryloyl group and an acryloyl group.
<4> In any one of <1> to <3>, (B) / (A), which is a mass ratio of the polymerizable compound (B) to the resin (A), is 0.5 to 2. The photosensitive resin composition for photospacers of description.

The photosensitive resin transfer material of the present invention is as follows.
<5> a temporary support;
A photosensitive resin layer formed on the temporary support using at least the photosensitive resin composition for photospacers according to any one of <1> to <4>;
A photosensitive resin transfer material.
<6> The photosensitive resin transfer material according to <5>, which has at least one of an oxygen blocking layer and a thermoplastic resin layer between the photosensitive resin layer and the temporary support.

The manufacturing method of the photospacer of this invention is as follows.
<7> Production of a photospacer including a step of forming a photosensitive resin layer by applying the photosensitive resin composition for photospacer according to any one of <1> to <4> on a support. Method.
<8> At least using the photosensitive resin transfer material according to <5> or <6>, the photosensitive resin layer is transferred by either one of heating and pressurization to form a photosensitive resin layer on the support. A manufacturing method of a photospacer including a forming step.
<9> At least
A step of forming a photosensitive resin layer on a support using the photosensitive resin composition for a photospacer according to any one of <1> to <4>;
Exposing the photosensitive resin layer;
Developing the exposed photosensitive resin layer;
Heating the pattern formed by development;
A method for manufacturing a photospacer.
<10> At least
Using the photosensitive resin transfer material according to <5> or <6>, forming a photosensitive resin layer on a support;
Exposing the photosensitive resin layer;
Developing the exposed photosensitive resin layer;
Heating the pattern formed by development;
A method for manufacturing a photospacer.

The photo spacer of the present invention is as follows.
<11> Resin (A) having an acidic group in the side chain, polymerizable compound (B), light, produced by the method for producing a photospacer according to any one of <7> to <10> A photospacer comprising a polymerization initiator (C) and surface-treated fine particles (D) having a surface treatment double bond amount of 0.02 mmol to 0.35 mmol per 1 g of fine particles.

The substrate for a liquid crystal display device of the present invention is as follows.
<12> A substrate for a liquid crystal display device, comprising the photo spacer according to <11>.

The liquid crystal display device of the present invention is as follows.
<13> A liquid crystal display device comprising the liquid crystal display device substrate according to <12>.

  According to the present invention, a photosensitive resin composition for a photospacer for producing a photospacer excellent in vibration resistance and impact resistance capable of withstanding high frequency vibration, and produced using the same. Photosensitive resin transfer material, photospacer excellent in vibration resistance and impact resistance, and manufacturing method thereof, liquid crystal display device substrate including the photospacer, and liquid crystal display including the liquid crystal display device substrate An apparatus can be provided.

It is a schematic explanatory drawing of the shaking case and test board used for vibration resistance simulation evaluation. It is explanatory drawing of the shape of the TFT substrate patterned for PVA mode.

  Hereinafter, a photosensitive composition for a photospacer (hereinafter also referred to as “photosensitive composition”), a photosensitive resin transfer material, a photospacer, a method for producing the photospacer, a substrate for a liquid crystal display device, and a liquid crystal display according to the present invention. The apparatus will be described in detail.

<< Production Method of Photosensitive Composition and Photospacer >>
The photosensitive resin composition for photospacers of the present invention includes a resin (A) having an acidic group in the side chain, a polymerizable compound (B), a photopolymerization initiator (C), and surface-treated fine particles (D). By setting the surface treatment double bond amount of the fine particles within a specific range, it is possible to provide a photo spacer that can withstand vibrations having a large panel size and high frequency.

Moreover, the manufacturing method of the photospacer of this invention has the process (henceforth a layer formation process) which forms the photosensitive resin layer on the support body using the photosensitive resin composition for photospacers of this invention. .
More specifically, the method for producing a photospacer of the present invention has a photosensitive resin layer formed by applying the photosensitive composition of the present invention or using the photosensitive composition of the present invention. It has the process of transferring a photosensitive resin layer by heating and / or pressurization using a photosensitive resin transfer material, and forming a photosensitive resin layer on a support.

  According to the method for producing a photospacer of the present invention, a photospacer having resistance to vibration with a high frequency can be easily produced.

  Hereinafter, the manufacturing method of the photospacer of this invention is demonstrated, and the detail of the photosensitive composition of this invention is also described through this description.

<Layer formation process>
In the layer forming step in the present invention, a photosensitive resin layer (hereinafter also simply referred to as “photosensitive resin composition layer”) is formed on the support using the photosensitive composition or photosensitive resin transfer material of the present invention. It is a process.
This photosensitive resin layer constitutes a photospacer through a manufacturing process described later. By using the photo spacer, display unevenness caused by vibration is eliminated.

  As a method of forming a photosensitive resin layer on a support, (a) a method of applying a solution containing the photosensitive resin composition for a photospacer of the present invention by a known coating method, and (b) a photosensitive of the present invention. Any one of the methods of transferring the photosensitive resin layer by a transfer method using a photosensitive resin transfer material is preferable. Each will be described below.

(A) Coating method The photosensitive resin composition for the photo spacer is coated by a known coating method, for example, spin coating method, curtain coating method, slit coating method, dip coating method, air knife coating method, roller coating method, wire. It can be carried out by any one of a bar coating method, 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 In the transfer method, a photosensitive resin transfer material having a photosensitive resin layer on a temporary support is prepared in advance, and the photosensitive resin layer of the photosensitive resin transfer material is in contact with the support surface. Place and heat the roller with the roller heated from the back side of the photosensitive resin transfer material (that is, the temporary support surface side), applying the pressure as desired, or applying the pressure with the roller at room temperature. Alternatively, after bonding by pressing or thermocompression bonding using a flat plate, the photosensitive resin layer is transferred onto the support by peeling off the temporary support. Specifically, a method using a laminator and a laminating method described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794 are exemplified. From the viewpoint that foreign matter hardly adheres to the photosensitive resin layer, it is preferable to use the method described in JP-A-7-110575.

When forming the photosensitive resin layer in the transfer method, an oxygen blocking layer can be further provided between the photosensitive resin layer and the temporary support. Thereby, exposure sensitivity can be improved. It is also preferable to provide a thermoplastic resin layer having cushioning properties in order to improve transferability.
Regarding the temporary support, the oxygen blocking layer, the thermoplastic resin layer, and other layers constituting the photosensitive resin transfer material and the method for producing the photosensitive resin transfer material, paragraph number [0024] of JP-A-2006-23696 is disclosed. ] To [0030] may be employed.

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

  As the 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), Examples include a drive substrate with a drive element (for example, a thin film transistor [TFT]). The thickness of the support is generally preferably 700 μm to 1200 μm.

<< Photosensitive resin composition for photo spacer >>
Next, the photosensitive resin composition for photospacers will be described.
The photosensitive composition of the present invention has a resin (A) having an acidic group in the side chain, a polymerizable compound (B), a photopolymerization initiator (C), and a surface treatment double bond amount of 0.02 mmol to 1 g of fine particles. It contains at least surface-treated fine particles (D) of 0.35 mmol. Moreover, other components, such as a coloring agent and surfactant, may be included as needed.
The photosensitive resin composition for a photospacer is particularly preferably used for forming a photospacer.

<Resin (A)>
Resin (A) has an acidic group in the side chain. “Having an acidic group in the side chain” means that the resin (A) has a structural unit (group) having an acidic group in the side chain. Even if the acidic group is directly bonded to the main chain, it will be described later. As shown in specific examples of the monomer having an acidic group, the acidic group may be bonded via a linking group.
Similarly to the above, “having an ethylenically unsaturated group” means that the resin (A) has a structural unit (group) having an ethylenically unsaturated group in the side chain. Even if the group is directly bonded to the main chain, the ethylenically unsaturated group may be bonded via a linking group as shown in the specific example of the monomer having an ethylenically unsaturated group described later.
The resin (A) is more preferably a group having an acidic group (structural unit): Y (y mol%), and a group having a branched and / or alicyclic structure in the side chain (structural unit): X (x Mol%) and a group having an ethylenically unsaturated group (structural unit): Z (z mol%), and if necessary, other group (other structural unit): L (1 mol%). You may have. A plurality of X, Y, and Z may be combined in one group in the resin (A).

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

  The monomer used to have an acidic group in the side chain is not particularly limited, and examples thereof include styrenes, (meth) acrylates, vinyl ethers, vinyl esters, (meth) acrylamides, (Meth) acrylates, vinyl esters, and (meth) acrylamides are preferable, and (meth) acrylates are more preferable.

  Specific examples of the monomer having an acidic group in the side chain can be appropriately selected from known ones, such as (meth) acrylic acid, vinyl benzoic 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.
Among these, as the monomer having an acidic group in the side chain, (meth) acrylic acid or the like is preferable in terms of excellent developability and low cost.

The “ethylenically unsaturated group” is not particularly limited, but 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 side chain can be appropriately selected from known ones, for example, a method of adding a (meth) acrylate having an epoxy group to a group having an acidic group, or having a hydroxyl group Examples include a method of adding a (meth) acrylate having an isocyanate group to the group, 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.

The other monomer is not particularly limited. For example, (meth) acrylic acid ester having no branched and / or alicyclic structure, styrene, vinyl ether, dibasic acid anhydride group, vinyl ester group, carbonization And monomers having a hydrogen alkenyl group.
The vinyl ether is not particularly limited, and examples thereof include butyl vinyl ether.

The monomer having a dibasic acid anhydride group is not particularly limited, and examples thereof include maleic anhydride and itaconic anhydride.
The monomer having a vinyl ester group is not particularly limited, and examples thereof include vinyl acetate.
The monomer having a hydrocarbon alkenyl group is not particularly limited, and examples thereof include butadiene and isoprene.

  The content ratio of the other monomer in the resin (A) is preferably such that the molar composition ratio is 0 mol% to 30 mol%, and more preferably 0 mol% to 20 mol%.

    Specific examples of the resin (A) include compounds represented by the following compounds P-1 to P-35. In addition, the weight average molecular weights of these compounds are all 28,000-38,000.

  The resin (A) is produced from a two-step process including a (co) polymerization process of monomers and a process of introducing ethylenically unsaturated groups. First, in the (co) polymerization reaction, a (co) polymerization reaction of various monomers is performed. The (co) polymerization reaction 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.

  The weight average molecular weight of the copolymer suitable as the resin (A) 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 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 of the photo spacer shape in development.

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

  Although the preferable range of the acid value of the resin (A) 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 mgKOH / g to 130 mgKOH / g. Particularly preferred is g. When the acid value is within the preferable range, a photo spacer having good developability and mechanical strength can be obtained.

A photo spacer having good developability and mechanical strength is obtained when the glass transition temperature (Tg) of the resin (A) is 40 ° C. to 180 ° C. and the weight average molecular weight is 10,000 to 100,000. 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 resin (A) in the present invention comprises a group having a branched and / or alicyclic structure in the side chain: X (x mol%), a group having an acidic group: Y (y mol%), and ethylenically unsaturated. A group having a group: Z (z mol%) and a copolymer having at least ternary copolymer having different copolymer units, respectively, deformation recovery rate, development residue, vibration resistance, reticulation It is preferable from the viewpoint. Specifically, a copolymer obtained by copolymerizing at least one of the monomers constituting the X, Y, and Z is preferable.
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 “group having a branched and / or alicyclic structure in the side chain” "Is preferably 10 mol% to 70 mol%, more preferably 15 mol% to 65 mol%, and particularly preferably 20 mol% to 60 mol%. When the group having a branched and / or alicyclic structure in the side chain is within the above range, good developability is obtained and the developer resistance of the image area is also good.
The ratio of the “group having an acidic group in the side chain” is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, and particularly preferably 20 mol% to 50 mol%. When the group having an acidic group in the side chain is within the above range, good curability and developability can be obtained.
The ratio of “group having an ethylenically unsaturated group in the side chain” is preferably 10 mol% to 70 mol%, more preferably 20 mol% to 70 mol%, particularly preferably 30 mol% to 70 mol%. When the group having an ethylenically unsaturated group in the side chain is within the above range, the pigment dispersibility is excellent, and the developability and curability are also good.

  5 mass%-70 mass% are preferable with respect to the said photosensitive resin composition total solid, and, as for content of the said resin (A), 10 mass%-50 mass% are more preferable. The resin (A) can be used in combination with other resins described later, but it is preferable to use only the resin (A).

The resin that can be used in combination with the resin (A) is preferably a compound (resin) that shows swelling property with respect to an alkaline aqueous solution, and more preferably a compound (resin) that is soluble in the alkaline aqueous solution.
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.

  The total content of the resin (A) and the resin that can be used in combination with the resin is preferably 5% by mass to 70% by mass, and preferably 10% by mass to the total solid content of the photosensitive resin composition. 50 mass% is more preferable. When the solid content is less than 5% by mass, the film strength of the photosensitive layer described later tends to be weak, and the tackiness of the surface of the photosensitive layer may be deteriorated. Sensitivity may decrease. In addition, the said content represents solid content.

<Polymerizable compound (B)>
As the polymerizable compound (B) in the present invention, the components described in paragraph No. [0011] of JP-A-2006-23696 and the paragraph Nos. [0040] to [0049] of JP-A-2006-64921 are described. Can be used.

  The mass ratio ((B) / (A) ratio) of the polymerizable compound (B) to the resin (A) is preferably 0.5 to 2.0, and preferably 0.6 to 1.4. More preferred is 0.7 to 1.2. When ((B) / (A) ratio) is less than 0.5, the mechanical strength is lowered, or the developing speed of the unexposed area is decreased, which is not preferable. On the other hand, if the ratio is larger than 2.0, the developed photo spacers will drop off, and the preservability of the photosensitive resin layer after coating will decrease. When the ratio (B) / (A) is within the preferred range, a photo spacer having good developability and mechanical strength can be obtained.

  The photosensitive resin composition for a photospacer of the present invention preferably contains at least one of the following compounds B1 and B2 as the polymerizable compound (B).

In the formula, each X is a hydrogen atom or an H ₂ C═CR—CO— group, and four or more of the plurality of Xs are each an H ₂ C═CR—CO— group. R is a hydrogen atom or a lower hydrocarbon group having 4 or less carbon atoms. When multiple X represents each H _{2 C} = CR-CO- group, even each same or may differ from each other.

In the formula, each X is a hydrogen atom or an H ₂ C═CR—CO— group, and 6 or more of the plurality of Xs are each an H ₂ C═CR—CO— group. R is a hydrogen atom or a lower hydrocarbon group having 4 or less carbon atoms. When multiple X represents each H _{2 C} = CR-CO- group, even each same or may differ from each other.

  It is preferable that the contents W1 (mass%) and W2 (mass%) of the compound B1 and the compound B2 with respect to the total amount of the polymerizable compound (B) satisfy the following formulas (1) and (2). Here, the content of compound B1 with respect to the total amount of polymerizable compound (B) is W1 (mass%), and the content of compound B2 with respect to the total amount of polymerizable compound (B) is W2 (mass%). .

0.6 ≦ W2 / W1 ≦ 3.0 (1)
63% ≦ W1 + W2 ≦ 100% (2)

  By satisfying the above formulas (1) and (2), the photosensitive composition of the present invention can provide a resin pattern such as a photo spacer that can withstand vibrations having a high frequency.

Each X in the compound B1 represents a hydrogen atom or a H ₂ C═CR—CO— group, and at least 4, more preferably 5 or more, most preferably 5.5 or 6 of a plurality of X in the molecule. Each represents a H ₂ C═CR—CO— group.
R represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms, and most preferably a hydrogen atom or a methyl group. It is. Specific examples of compound B1 are specifically dipentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and their A mixture is mentioned. Of these, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and mixtures thereof are more preferred.

X in the compound B2 represents a hydrogen atom or a H ₂ C═CR—CO— group, and at least 6, more preferably 7 or more, most preferably 7.5 or more of X in the molecule Eight each represents a H ₂ C═CR—CO— group.
R represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms, and most preferably a hydrogen atom or a methyl group. is there. Specific examples of compound B2 are specifically tripentaerythritol hexamethacrylate, tripentaerythritol heptamethacrylate, tripentaerythritol octamethacrylate, tripentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate and their A mixture is mentioned. Of these, tripentaerythritol heptamethacrylate, tripentaerythritol octamethacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, and mixtures thereof are more preferable.

  The content W1 (%) and W2 (%) of the compounds B1 and B2 with respect to the total amount of the polymerizable compound (B) preferably satisfy the above (1) and (2) at the same time, but the content W1 (%) And W2 (%) is preferably 65% or more and 95%, more preferably 70% or more and 90% or less from the viewpoint of vibration resistance. When it is less than 63%, the vibration resistance deteriorates.

  On the other hand, the ratio W2 / W1 between the contents W1 (%) and W2 (%) is preferably 0.6 or more and 3.0 or less, more preferably 0.62 or more and 2.95 or less, and still more preferably 0.8. 7 or more and 2.6 or less. When it is less than 0.6, the adhesion between the photo spacer and the substrate is reduced, and at the same time, the vibration resistance is deteriorated. If it exceeds 3.0, the development residue is deteriorated and at the same time the vibration resistance is deteriorated.

<Photopolymerization initiator (C)>
The photosensitive resin composition of the present invention further contains a photopolymerization initiator (C). Examples of the photopolymerization initiator (C) include vicinal polyketaldonyl compounds disclosed in US Pat. No. 2,367,660, acyloin ether compounds described in US Pat. No. 2,448,828, US An aromatic acyloin compound substituted with an α-hydrocarbon described in Japanese Patent No. 2722512, a polynuclear quinone compound described in US Pat. Nos. 3,046,127 and 2,951,758, US Pat. No. 3,549,367 A combination of a triarylimidazole dimer and a p-aminoketone described in JP-A-51-48516, a benzothiazole compound and a trihalomethyl-s-triazine compound described in JP-B-51-48516, and U.S. Pat. No. 4,239,850 Trihalomethyl-triazine compounds, US Pat. No. 4,212 No. 76, a trihalomethyloxadiazole compound and the like, aromatic ketones described in paragraph numbers [0050] to [0051] of JP-A No. 2006-64921, lophine dimer, benzoin, Examples include benzoin ethers, polyhalogens, halogenated hydrocarbon derivatives, ketone compounds, ketoxime compounds, organic peroxides, thio compounds, hexaarylbiimidazoles, aromatic onium salts, ketoxime ethers, and the like.

  The said photoinitiator (C) may be used individually by 1 type, and may use 2 or more types together. 0.1-20 mass% is preferable with respect to resin (A), and, as for content of the said photoinitiator (C), 0.5-10 mass% is more preferable. If the amount is less than 0.1% by mass, sufficient sensitivity cannot be obtained. When it is more than 20% by mass, the preservability of the photosensitive resin layer after coating is lowered.

<Surface treatment fine particles (D)>
In the fine particles (D) of the present invention, the amount of double bonds formed by the surface treatment is 0.02 mmol to 0.35 mmol, preferably 0.025 mmol to 0.30 mmol, more preferably 0, per 1 g of fine particles. 0.03 mmol to 0.30 mmol, and more preferably 0.08 mmol to 0.18 mmol. If it is less than 0.02 mmol, the vibration resistance of the panel is deteriorated and the residue of the unexposed portion (non-pixel portion) of the photosensitive resin layer is deteriorated after development. If it exceeds 0.35 mmol, the followability (the thickness of the photosensitive resin layer at the spacer setting position / the original photosensitive resin layer thickness ratio) is reduced, and the height variation of the spacer is reduced, and the exposure of the photosensitive resin layer is reduced. The residue of the part (spacer outline) deteriorates.
The fine particles to be treated are preferably inorganic fine particles.

[Inorganic fine particles]
The inorganic fine particles contain at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, magnesium, indium, tin, antimony and cerium from the viewpoint of the colorlessness of the film obtained by the coating composition. Oxide fine particles are preferable.

  Examples of the oxide fine particles include particles of silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, cerium oxide, and the like. . Among these, silica, alumina, zirconia, titanium oxide, and antimony oxide particles are preferable from the viewpoint of the mechanical properties of the spacer. These can be used alone or in combination of two or more.

The oxide fine particles are preferably surface-treated in a state of being dispersed in a dispersion medium. From the viewpoint of compatibility with other components and dispersibility, the dispersion medium is preferably an organic solvent, such as methanol, ethanol, n-propyl alcohol, isopropanol, butanol, octanol, sec-butyl alcohol, tert-butyl. Alcohols such as alcohol, ethylene glycol, diethylene glycol, triethylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol Esters such as monoethyl ether acetate; Ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; benzene Toluene, xylene and the like aromatic hydrocarbons; dimethylformamide, dimethylacetamide, may be mentioned amides such as N- methylpyrrolidone.
Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.

  The number average particle diameter of the oxide fine particles is preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm, and particularly preferably 5 nm to 30 nm. When the number average particle diameter exceeds 200 nm, the transparency when the resin composition is a cured product tends to decrease, or the surface state when a photospacer is used tends to deteriorate. Various surfactants and amines may be added to improve the dispersibility of the oxide fine particles.

  More specifically, as the silica, a product commercially available as a silicon oxide fine particle dispersion (for example, silica particles) can be used. For example, as colloidal silica, methanol silica sol, MA-ST-MS, IPA-ST, IPA-ST-MS, IPA-ST-L, IPA-ST-ZL, IPA-ST-UP manufactured by Nissan Chemical Industries, Ltd. EG-ST, NPC-ST-30, MEK-ST, MEK-ST-L, MIBK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST -40, ST-C, ST-N, ST-O, ST-50, ST-OL (all trade names), hollow silica fine particles CS60-IPA (trade names) manufactured by Catalytic Chemical Industry Co., Ltd., etc. be able to. Examples of the powder silica include Aerosil (registered trademark) 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, and Sildex H31, H32, and H51 manufactured by Asahi Glass Co., Ltd. , H52, H121, H122 (all trade names), Nippon Silica Industry Co., Ltd. E220A, E220 (all trade names), Fuji Silysia Co., Ltd. SYLYSIA 470 (trade name), Nippon Sheet Glass Co., Ltd. SG Flakes Name).

  Further, as alumina, its water dispersion, Alumina Sol-100, -200, -520 (all trade names) manufactured by Nissan Chemical Industries, Ltd .; As isopropanol dispersion of alumina, AS-made by Sumitomo Osaka Cement Co., Ltd. 150 (trade name) I; AS-150T (trade name) manufactured by Sumitomo Osaka Cement Co., Ltd. is listed as the toluene dispersion of alumina; HXU- manufactured by Sumitomo Osaka Cement Co., Ltd. is used as the toluene dispersion of zirconia. 110JC (trade name); Examples of the aqueous dispersion of zinc antimonate powder include CELNAX (registered trademark) manufactured by Nissan Chemical Industries, Ltd .; alumina, titanium oxide, tin oxide, indium oxide Examples of powders and solvent dispersions such as zinc oxide include NANOTEK (trade name) manufactured by CI Kasei Co., Ltd. The antimony-doped tin oxide aqueous dispersion sol includes SN-100D (trade name) manufactured by Ishihara Sangyo Co., Ltd .; the ITO powder includes products manufactured by Mitsubishi Materials Corporation; cerium oxide water Examples of the dispersion include NEEDLAL (trade name) manufactured by Taki Chemical Co., Ltd.

The shape of the oxide fine particles is spherical, hollow, porous, rod-like, plate-like, fibrous, or indefinite, and preferably spherical, porous, or hollow (hollow fine particles). Particularly preferred is a spherical shape.
The specific surface area of oxide particles (by BET method using nitrogen) ^is preferably at 10m ² / g~1000m 2 / g, more ^preferably, is 100m ² / g~500m 2 / g . These oxide fine particles can be used after the powder in a dry state is dispersed in an organic solvent. For example, fine oxide fine particle dispersions known in the art as solvent dispersion sols of the above oxides can be used. The liquid can be used directly.

When silica is used as the inorganic fine particles, the average particle diameter of silica is preferably 5 nm to 100 nm, more preferably 7 nm to 50 nm, and still more preferably 8 nm to 20 nm.
When the particle size of the silica fine particles is too small, the silica fine particle aggregability increases. If the particle size of the silica fine particles is too large, the silica fine particles are transferred onto the glass substrate, the followability when the photosensitive resin layer is set is lowered, and the spacer height variation is reduced.
The silica fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape of the silica fine particles is most preferably a spherical diameter, but may be indefinite. Here, the average particle diameter of the inorganic fine particles is measured by a Coulter counter.

<Surface treatment of inorganic fine particles>
In the present invention, the surface treatment of the inorganic fine particles is carried out by treating the organosilane compound represented by the general formula (A), other organosilane compounds used in combination with the organosilane compound as necessary, inorganic fine particles, and if necessary. It is preferable to carry out the reaction by bringing water into contact with inorganic fine particles in the presence of a catalyst having a hydrolysis function and / or a metal chelate compound having a condensation function.

In general formula (A), R ₁ represents a substituted alkyl group or an aryl group having a polymerizable group having an unsaturated bond. R ₂ represents a substituted or unsubstituted lower alkyl group, and X represents a hydroxyl group or a hydrolyzable group. m represents an integer of 1 to 2, n represents an integer of 0 to 2, and p represents an integer of 2 to 3. The sum of m, n and p is 4.

In the reaction, the organosilane compound molecule may not be completely hydrolyzed, may be partially hydrolyzed, or may be partially condensed after hydrolysis. The organosilane compound molecule undergoes partial condensation following hydrolysis, and this modifies the surface of the inorganic fine particles, thereby improving dispersibility and obtaining a stable coating composition.
The polymerizable group contained in R ₁ is preferably a methacryloyl group, an acryloyl group, or a styryl group.
From the viewpoint of surface treatment speed and reactivity of unsaturated bonds, a methacryloyl group or an acryloyl group is more preferable.
The hydrolyzable group contained in X is preferably a lower alkoxy group having 1 to 3 carbon atoms, more preferably a methoxy group or an ethoxy group, and most preferably a methoxy group from the viewpoint of surface treatment speed.
R ₂ is preferably a substituted or unsubstituted lower alkyl group, from the viewpoint of steric hindrance, more preferably a methyl group and an ethyl group, and most preferably a methyl group.

  Specific examples of the organosilane compound include 3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM5103 (trade name), etc.), 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.). , KBM503 (trade name), etc.), 3-methacryloxypropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM502 (trade name), etc.), 3-methacryloxypropylethyldimethoxysilane, 3-methacryloxypropyltriethoxy Silane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE503 (trade name), etc.), 3-methacryloxypropylmethyldiethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE 502 (trade name), etc.), 3-methacryloxypropylethyl Diethoxysilane, p-styrylrotrimethoxysilane (Shin-Etsu Manabu Industry Co., Ltd., KBM1403 (trade name), etc.), acryloyl group-containing titanate coupling agent (Ajinomoto Fine-Tech Co., Ltd., PLENACT (PLENACT) KR5 (trade name))), and the like.

  The following values relating to the organosilane sol are values for the hydrolyzate of the compound represented by the general formula (A), a partial condensate thereof, or a mixture thereof. Even when other organosilane compounds having no unsaturated bond are used in combination, the following values described for the hydrolyzate, partial condensate, or mixture of the compound represented by formula (A) are satisfied. It is preferable.

  When the organosilane sol contains a condensate, the mass average molecular weight is preferably 1000 to 20000, more preferably 1000 to 10,000, even more preferably 1100 to 5000, and even more preferably 1200, when a component having a molecular weight of less than 300 is excluded. 3000 is more preferable, and 1200 to 2000 is particularly preferable.

  Of the components having a molecular weight of 300 or more in the organosilane sol, the component having a molecular weight of more than 20000 is preferably 20% by mass or less, more preferably 15% by mass or less, and more preferably 10% by mass or less. Is more preferably 6% by mass or less, and particularly preferably 4% by mass or less.

  Moreover, it is preferable that the component of molecular weight 1000-20000 is 80 mass% or more among the components of molecular weight 300 or more in organosilane sol. When there are too few components of molecular weight 1000-20000, panel vibration resistance will fall.

Here, the mass average molecular weight and the molecular weight were measured using a differential refractometer using THF as a solvent by a GPC analyzer using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation). The molecular weight is expressed in terms of polystyrene by detection, and the content is the area% of the peak in the molecular weight range when the peak area of a component having a molecular weight of 300 or more is defined as 100%.
The dispersity (mass average molecular weight / number average molecular weight) of the organosilane sol is preferably 3.0 to 1.1, more preferably 2.5 to 1.1, still more preferably 2.0 to 1.1. .5 to 1.1 is particularly preferable.

  An organosilane compound other than the general formula (A) can be used in combination, and the amount used in this case is preferably 0.5% by mass to 150% by mass, more preferably 1% by mass to 100% by mass, and most preferably Preferably it is 2 mass%-50 mass%. When the amount used is less than 0.5% by mass, the dispersibility is lowered, and when it is more than 150% by mass, the vibration resistance of the panel is further deteriorated.

  The hydrolysis and / or condensation reaction of the organosilane compound can be performed without a solvent or in a solvent. When a solvent is used, the concentration of the organosilane sol can be appropriately determined. As the solvent, an organic solvent is preferably used in order to uniformly mix the components. For example, alcohols, aromatic hydrocarbons, ethers, ketones, esters, amides and the like are preferable.

  The solvent preferably dissolves the organosilane and the catalyst. In addition, it is preferable in the process that an organic solvent is used as a coating solution or a part of the coating solution, and those that do not impair the solubility or dispersibility when mixed with other materials such as a fluorine-containing polymer are preferable.

  Among these, examples of the alcohols include monohydric alcohols and dihydric alcohols. Among these, monohydric alcohols are preferably saturated aliphatic alcohols having 1 to 8 carbon atoms. Specific examples of these alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol. Examples thereof include monobutyl ether and ethylene glycol monoethyl ether acetate.

  Specific examples of aromatic hydrocarbons include benzene, toluene, xylene and the like. Specific examples of ethers include tetrahydrofuran and dioxane. Specific examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, Specific examples of esters such as diisobutyl ketone include ethyl acetate, propyl acetate, butyl acetate, and propylene carbonate.

  Specific examples of amides include dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.

  These organic solvents can be used alone or in combination of two or more. The concentration of the solid content relative to the solvent in the reaction is not particularly limited, but is usually in the range of 1% by mass to 90% by mass, and preferably in the range of 20% by mass to 70% by mass.

  In the present invention, it is preferable to disperse the inorganic fine particles with an alcohol solvent and then perform a dispersibility improvement treatment, and subsequently replace the dispersion solvent with an aromatic hydrocarbon solvent or a ketone solvent. Substitution with a ketone solvent is preferable from the viewpoint of the affinity with the binder used at the time of coating and the improvement of the stability of the dispersion itself.

  The hydrolysis and / or condensation reaction of the organosilane compound is preferably performed in the presence of a catalyst.

  Examples of the catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid and toluenesulfonic acid; inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia; Examples include organic bases such as triethylamine and pyridine; metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium. From the viewpoint of the production stability of the sol solution and the storage stability of the sol solution, Acid catalysts (that is, inorganic acids and organic acids) are used. As the inorganic acid, hydrochloric acid and sulfuric acid are preferable, and as the organic acid, an acid dissociation constant in water (pKa value (25 ° C.)) of 4.5 or less is preferable. Among them, hydrochloric acid, sulfuric acid and organic acids having an acid dissociation constant of 3.0 or less in water are preferable, hydrochloric acid, sulfuric acid and organic acids having an acid dissociation constant in water of 2.5 or less are more preferable, and acid dissociation in water An organic acid having a constant of 2.5 or less is more preferable, specifically, methanesulfonic acid, oxalic acid, phthalic acid and malonic acid are more preferable, and oxalic acid is most preferable.

  When the hydrolyzable group of the organosilane is an alkoxy group and the acid catalyst is an organic acid, the amount of water added can be reduced because the carboxyl group or sulfo group of the organic acid supplies protons. The amount of water added relative to 1 mol of the alkoxide group of the organosilane is 0 mol to 2 mol, preferably 0 mol to 1.5 mol, more preferably 0 mol to 1 mol, and particularly preferably 0 mol to 0.5 mol. Is a mole. Further, when alcohol is used as a solvent, it is also preferable that water is not substantially added.

  When the acid catalyst is an inorganic acid, the amount used is 0.01 mol% to 10 mol%, preferably 0.1 mol% to 5 mol%, based on the hydrolyzable group. When the acid catalyst is an organic acid, the amount used varies depending on the amount of water added, but when water is added, 0.01 mol% to 10 mol% with respect to the hydrolyzable group, Preferably, it is 0.1 mol% to 5 mol%, and when substantially no water is added, it is 1 mol% to 500 mol%, preferably 10 mol% to 200 mol%, based on the hydrolyzable group. More preferably, it is 20 mol%-200 mol%, More preferably, it is 50 mol%-150 mol%, Most preferably, it is 50 mol%-120 mol%.

  The reaction is carried out by stirring at 25 ° C. to 100 ° C., but is preferably controlled by the reactivity of the organosilane compound.

The metal chelate compound that can be used in the production of the organosilane sol includes an alcohol represented by the general formula R ₃ OH (wherein R ₃ represents an alkyl group having 1 to 10 carbon atoms) and a general formula R ₄ COCH ₂ COR. _{5 wherein} R ₄ is an alkyl group having 1 to 10 carbon atoms, and R ₅ is an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. Any metal having a central metal selected from Zr, Ti, or Al as a child can be used without any particular limitation. Within this category, two or more metal chelate compounds may be used in combination. The metal chelate compound used in the present invention has the general formula Zr (OR ₃ ) p 1 (R ₄ COCHCOR ₅ ) p 2, Ti (OR ₃ ) q 1 (R ₄ COCHCOR ₅ ) q 2 and Al (OR ₃ ) r 1 (R ₄ COCHCOR ₅ ) What is chosen from the compound group represented by r2 is preferable, and it has the effect | action which accelerates | stimulates the condensation reaction of the said (A) component.

R ₃ and R ₄ in the metal chelate compound may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms. Specific examples thereof include an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. , Sec-butyl group, t-butyl group, n-pentyl group, phenyl group and the like. R ₅ represents an alkyl group having 1 to 10 carbon atoms as described above, or an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and n-butoxy. Group, sec-butoxy group, t-butoxy group and the like. Moreover, p1, p2, q1, q2, r1, and r2 in the metal chelate compound each represent an integer determined so as to be the tetradentate or hexadentate coordination.

  Specific examples of these metal chelate compounds include tri-n-butoxyethyl acetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetate). Zirconium chelate compounds such as acetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium, diiso Titanium chelate compounds such as propoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum, diisopropyl Poxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetonate bis (ethyl) An aluminum chelate compound such as acetoacetate) aluminum.

  Among these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxybis (acetylacetonato) titanium, diisopropoxyethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum are preferable. These metal chelate compounds can be used individually by 1 type or in mixture of 2 or more types. Moreover, as a metal chelate compound, the partial hydrolyzate of these metal chelate compounds can also be used.

  The metal chelate compound is preferably 0.01 to 50 parts, more preferably 0.1 to 50 parts, still more preferably 0.5 to 100 parts of the organosilane compound represented by the general formula (A). Used in a ratio of -10 parts. When the amount of the metal chelate compound component is too small, the condensation reaction of the organosilane compound represented by the general formula (A) is slow and the durability of the coating film may be deteriorated. On the other hand, when the amount is too large, the general formula (A) Storage stability of the composition containing the organosilane compound and metal chelate compound component represented may be deteriorated.

  By performing the surface treatment of the inorganic fine particles in this way, a film made of an organosilane sol is formed on the surface of the inorganic fine particles. For example, the surface state of particles containing Si can be quantitatively evaluated by measuring solid NMR of Si. Depending on the type of the surface treating agent and the selection of the reaction catalyst, fine particles having excellent stability when inorganic particles are dispersed in a solvent and excellent scratch resistance when a coating film is formed can be obtained.

<Other ingredients>
In the present invention, a component constituting a known composition can be suitably used as the other component, and examples thereof include components described in paragraph numbers [0014] to [0020] of JP-A-2006-23696. .

<< Photospacer manufacturing method >>
The manufacturing method of the photospacer of this invention has the exposure process which exposes the said photosensitive resin layer, and the image development process which develops the said exposed said photosensitive resin layer.
In the present invention, the exposure process and the development process are collectively described as a patterning process.

<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.

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

  The black shielding part, the colored part, and the photo 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 photospacer can each be formed from a photosensitive composition. Specifically, for example, after forming the photosensitive resin layer by directly applying the liquid photosensitive composition to the substrate, exposure and development are performed to form the black shielding portion and the colored portion in a pattern. Thereafter, the transfer material prepared by forming the photosensitive resin layer by placing the photosensitive composition of another liquid on another substrate (temporary support) different from the substrate is used for this transfer. After the material is brought into close contact with the substrate on which the black shielding portion and the colored portion are formed and the photosensitive resin layer is transferred, the photo spacer can be formed in a pattern by performing exposure and development. In this manner, a color filter provided with a photo spacer can be manufactured.

《Liquid crystal display device substrate》
The substrate for a liquid crystal display device of the present invention comprises a photospacer obtained by the method for producing a photospacer of the present invention. The photo spacer is preferably formed on a display light shielding part 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 with, for example, a photosensitive resin. The photosensitive resin layer of the transfer material is laminated on the support surface, peeled and transferred to form the photosensitive resin layer, and then subjected to exposure, development, heat treatment and the like to form a photo spacer, thereby forming the photo spacer of the present invention. A substrate for a liquid crystal display device 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 liquid crystal display elements, a liquid crystal layer and a liquid crystal driving means (simple matrix driving method or 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 transparent. 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 properties, a liquid crystal display element including 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.

Further, as another aspect of the liquid crystal display element, at least one of them includes a liquid crystal layer and a liquid crystal driving means between a pair of light transmissive supports (including the liquid crystal display device substrate of the present invention), and the liquid crystal drive The 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, when it consists of pixels 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. The liquid crystal display device of the present invention is configured by providing the liquid crystal display element. That is, as described above, the space between a pair of substrates facing each other so as to face each other is regulated to a predetermined width by the photo spacer produced by the photo spacer production method of the present invention, and the liquid crystal material is placed in the regulated gap. The liquid crystal layer is configured to be sealed (the liquid crystal layer 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). 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 includes the liquid crystal display device substrate of the present invention or the liquid crystal display element. For example, various types of liquid crystal displays described in the “Next Generation Liquid Crystal Display Technology” The device can be configured. 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 photo spacer, a viewing angle compensation film, a reflection, except that it includes the liquid crystal display device substrate or liquid crystal display element of the present invention described above. It can be generally configured using various members such as a prevention 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.

First, a synthesis example of surface-treated fine particles whose surface is modified with a double bond will be described.
(Synthesis Example 1)
A commercially available acidic aqueous silica sol (SNOWTEX-O (registered trademark), SiO ₂ concentration 20 mass%, particle size 10 to 20 nm) was concentrated under reduced pressure at a pressure of 150 Torr (0.020 MPa) with a rotary evaporator, and then subjected to atmospheric distillation with methanol. The solvent was replaced to obtain methanol silica sol (SiO ₂ concentration 40.6%, moisture 1.4%, pH 3.4 when methanol silica sol was diluted with an equal amount of distilled water). A solution prepared by dissolving 15.6 g of hexamethyldisiloxane (0.51 mmol / surface area of hydrophilic colloidal silica of 100 m ² ) in 250 g of methyl isobutyl ketone (MIBK) was added to 1560 g of this methanol sol under stirring, and this mixture was stirred. The mixture was heated with stirring and aged at a liquid temperature of 60 ° C. for 1 hour to obtain a silylated pretreated silica sol. Subsequently, atmospheric distillation was performed while adding MIBK to the silylated pretreated silica sol so that the SiO ₂ concentration was almost constant, and when the weight ratio of methanol to MIBK in the sol medium became 0.9. The atmospheric distillation was interrupted to obtain an alcohol-containing hydrophobic organosilica sol. While stirring this alcohol-containing hydrophobic organosilica sol, 7.8 g of hexamethyldisiloxane and 3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM5103 (trade name), molecular weight 234.3) 25 Then, a solution prepared by dissolving 3 g in 72 g MIBK was added, and the mixture was heated with stirring and aged at a liquid temperature of 60 ° C. for 1 hour to obtain a silylated silica sol. Subsequently, solvent substitution was performed by vacuum distillation at a pressure of 150 Torr (0.020 MPa) while adding MIBK to the resulting silylated silica sol, and MIBK-dispersed hydrophobic organosilica sol (SiO ₂ concentration 30.5%, surface The amount of treated double bonds was 0.171 mmol / g, the moisture was 0.05%, and the methanol concentration was 0.1%.

(Synthesis Examples 2 to 5)
In Synthesis Example 1, the value of the surface treatment double bond amount was changed from 0.171 mmol / g to 0.021 mmol / g (Synthesis Example 2), 0.043 mmol / g (Synthesis Example 3), and 0.086 mmol / g (Synthesis). Example 4), MIBK-dispersed hydrophobic organosilica sol (Synthesis Example 1) except that the amount of 3-acryloxypropyltrimethoxysilane added was changed to 0.341 mmol / g (Synthesis Example 5). to obtain a SiO ₂ concentration of 30.5%).

(Comparative Synthesis Examples 1 to 4)
In Synthesis Example 1, the value of the surface treatment double bond amount was changed from 0.171 mmol / g to 0 mmol / g (Comparative Synthesis Example 1), 0.017 mmol / g (Comparative Synthesis Example 2), and 0.370 mmol / g (Comparative). Synthesis Example 3), MIBK-dispersed hydrophobic organosilane in the same manner as in Synthesis Example 1 except that the amount of 3-acryloxypropyltrimethoxysilane added was changed to 2.13 mmol / g (Comparative Synthesis Example 4). Silica sol (SiO ₂ concentration 30.5%) was obtained.

(Synthesis Examples 6 to 10)
3-Acryloxypropyltrimethoxysilane used in Synthesis Example 1 (manufactured by Shin-Etsu Chemical Co., Ltd., KBM5103 (trade name), molecular weight 234.3, (R ₁ ) in the general formula (A) _m is 3-acryloyloxy Instead of using a propyl group, Xp is a trimethoxy group and n is 0), 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM503 (trade name), molecular weight 248.4, general formula (A (R ₁ ) _m is a 3-methacryloyloxypropyl group, Xp is a trimethoxy group, and n is 0) (Synthesis Example 6), 3-methacryloxypropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM502 ( trade name), molecular weight 232.4, formula (A) in _{(R 1) m} is methacryloyloxypropyl group, Xp Dimethoxy group, _{R 2:} methyl) (Synthesis Example 7), 3-methacryloxypropyl ethyl dimethoxy silane (molecular weight 246.4, double bonds: methacryloyl group, the general formula (A) X in: dimethoxy group, and _{(R 2} ) N is an ethyl group) (Synthesis Example 8), 3-methacryloxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE503 (trade name), molecular weight 290.4, (R ₁ ) in the general formula (A)) _m is a 3-methacryloyloxypropyl group, Xp is a triethoxy group, and n is 0) (Synthesis Example 9), p-styrylrotrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM1403 (trade name), molecular weight 224.3 formula in (a) _{(R 1) m} is p- styryl group, Xp is trimethoxy group, and n is 0) (synthesis example 10), surface treatment double bond Except that the values were respectively added equimolar to maintain the 0.171 mmol / g in the same manner as in Synthesis Example 1 to obtain a MIBK dispersed hydrophobic organosilica sol (SiO ₂ concentration 30.5%).

(Synthesis Example 11)
Zirconium oxide fine particle sol (methyl ethyl ketone zirconium sol, manufactured by Sumitomo Osaka Cement Co., Ltd., average particle size 10 nm, zirconium oxide concentration 30%), 333 g, 4.0 parts of 3-acryloxypropyltrimethoxysilane, and diisopropoxyaluminum After adding 0.20 g of ethyl acetate and mixing, 1.2 g of ion-exchanged water was added. The mixture was reacted at 60 ° C. for 8 hours, then cooled to room temperature, and 0.24 g of acetylacetone was added. Subsequently, while adding MIBK to the obtained zirconium oxide sol, solvent substitution was performed by vacuum distillation at a pressure of 150 Torr (0.020 MPa) to obtain a MIBK-dispersed zirconium oxide sol (ZrO ₂ concentration of 30.5%, surface treatment 2). The amount of heavy bonds was 0.171 mmol / g).

(Synthesis Example 12)
Alumina fine particle sol (IPA alumina sol AS-150I (trade name), manufactured by Sumitomo Osaka Cement Co., Ltd.) was diluted with IPA (isopropanol) so that the alumina fine particle sol concentration was 15%. To 667 g of this solution, 4.0 parts of 3-acryloxypropyltrimethoxysilane and 0.20 g of diisopropoxyaluminum ethyl acetate were added and mixed, and then 1.2 g of ion-exchanged water was added. The mixture was reacted at 60 ° C. for 8 hours, then cooled to room temperature, and 0.24 g of acetylacetone was added. Subsequently, while adding MIBK to the obtained zirconium oxide sol, solvent substitution was performed by vacuum distillation at a pressure of 150 Torr (0.020 MPa) to obtain a MIBK-dispersed zirconium oxide sol (ZrO ₂ concentration of 30.5%, surface treatment 2). The amount of heavy bonds was 0.171 mmol / g).

(Synthesis Example 13)
In the case of adding 3-acryloxypropyltrimethoxysilane in Synthesis Example 1, a MIBK-dispersed hydrophobic organosilica sol (SiO _{2) was} prepared in the same manner as in Synthesis Example 1 except that 1.26 g of diisopropoxyaluminum ethyl acetate was added as a catalyst. A concentration of 30.5% and a surface treatment double bond amount of 0.171 mmol / g) were obtained.

(Example 1: Transfer method)
Preparation of photosensitive transfer film for photospacer A 75 μm thick polyethylene terephthalate film temporary support (PET temporary support) was coated with a coating solution for a thermoplastic resin layer having the following formulation A1 and dried at 100 ° C. for 2 minutes. I let you. Thereafter, it was further dried at 120 ° C. for 1 minute to form a thermoplastic resin layer having a dry layer thickness of 18 μm. Here, the temperatures “100 ° C.” and “120 ° C.” in the drying conditions are both temperatures of the drying air. The same applies to the temperature under the following drying conditions.

Formulation A1 for coating solution for thermoplastic resin layer
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization ratio 55 / 11.7 / 4.5 / 28.8 [mol ratio], weight average molecular weight 90,000) 58.4 parts Styrene / acrylic acid copolymer (copolymerization ratio 63/37 [mol ratio], weight average molecular weight 8,000) 136 parts 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane
90.7 parts, MEGAFAC F-780-F (Dainippon Ink Chemical Co., Ltd.) 5.4 parts, methanol 111 parts, 1-methoxy-2-propanol 63.4 parts, methyl ethyl ketone 534 parts

  Next, on the formed thermoplastic resin layer, an oxygen barrier layer coating solution having the following formulation B is applied, dried at 80 ° C. for 1 minute, further dried at 120 ° C. for 1 minute, and a dry layer thickness of 1.6 μm. The oxygen barrier layer was laminated.

Formulation B for coating solution for oxygen barrier layer
Polyvinyl alcohol (PVA-205 (trade name), saponification rate 88%, manufactured by Kuraray Co., Ltd.)
3.22 parts · Polyvinylpyrrolidone (PVP K-30 (trade name), manufactured by IS Japan Co., Ltd.) 1.49 parts · 42.9 parts of methanol · 52.4 parts of distilled water

  Next, a photosensitive resin layer coating solution having the following formulation 1 was applied onto the formed oxygen barrier layer, followed by drying at 100 ° C. for 2 minutes, and further drying at 120 ° C. for 1 minute (drying conditions). A) A photosensitive resin layer having a dry layer thickness of 4.5 μm was laminated.

Formulation 1 of coating solution for photosensitive resin layer
1-methoxy-2-propyl acetate 389 parts Methyl ethyl ketone 189 parts Surface treatment fine particle 30.5% solution 75.1 parts of Synthesis Example 1 Solsperse (trade name) 20000 (manufactured by Ashibia Corporation (Avecia)) 3 .82 parts / 45% polymer solution (synthesized by the method described in paragraphs [0092] and [0106] of JP2008-146018; structural formula P-25 described in [0061], weight average molecular weight = 3.5 196 parts-polymerizable compound mixture B1-1: DPHA solution (dipentaerythritol hexaacrylate: 38), solid content 45%, 1-methoxy-2-propyl acetate 15%, 1-methoxy-2-propanol 40%) %, Dipentaerythritol pentaacrylate: 38%, 1-methoxy-2-propyl acetate: 24%) Mixture of 7.8 parts Polymerizable compound B 2 - 1 (n = 1: tripentaerythritol octaacrylate content of 85%, total 15% of the compound n = 2 and n = a 3 as an impurity)
35.0 parts urethane monomer (NK Oligo UA-32P (trade name), Shin-Nakamura Chemical Co., Ltd., nonvolatile content 75%, 1-methoxy-2-propyl acetate: 25%) 13.2 parts 2 , 4-Bis- (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl] -s-triazine 6.50 parts Hydroquinone monomethyl ether 0.125 parts Victoria 5% solution of pure blue NAPS (trade name) (made by Hodogaya Chemical Co., Ltd.) (solid content 5%, methanol 26%, methyl ethyl ketone 69%) 63.7 parts Megafak F-784-F (trade name) (Dainippon Ink Chemical Co., Ltd.) 1.03 parts

  In the formula, X represents an acryloyl group. A mixture of n = 1 to 3 is used.

  After forming the laminated structure of the PET temporary support / thermoplastic resin layer / oxygen barrier layer / photosensitive resin composition layer as described above, the surface of the photosensitive resin composition layer is further covered with a thickness of 12 μm as a cover film. The film made of polypropylene was heated and pressurized and pasted to obtain a photosensitive transfer film (1) for photospacers. It was wound around a 3 inch roll core of ABS resin, wrapped with a black polyethylene film and a transparent polyethylene film, and stored.

Production of color filter substrate Preparation of photosensitive dark color composition Preparation of carbon black dispersion (K-1) A carbon black dispersion (K-1) was prepared according to the following formulation.
・ Carbon black (Color Black FW2 (trade name) manufactured by Degussa Co., Ltd.) 26.7 parts ・ Dispersant (DISPARLON DA7500 (trade name) manufactured by Enomoto Kasei Co., Ltd., acid value 26, amine value 40) 3 .3 parts benzyl methacrylate / methacrylic acid (72/28 [mol ratio]) copolymer (molecular weight 30,000, 50% solution of propylene glycol monomethyl ether acetate)
10 parts ・ Propylene glycol monomethyl ether acetate 60 parts

  The above components were stirred for 1 hour using a homogenizer under the condition of 3000 rpm. The obtained mixed solution was finely dispersed for 8 hours with a bead disperser (trade name: DISPERMAT (trade name), manufactured by GETZMANN Co., Ltd.) using 0.3 mm zirconia beads, and carbon black. A dispersion (K-1) was obtained.

  Using the obtained carbon black dispersion liquid (K-1), a photosensitive dark color composition coating liquid CK-1 was prepared according to the formulation shown in Table 1 below. Numerical values in Table 1 indicate mass ratios.

Details of each component in Table 1 are as follows.
Resin solution C-2: benzyl methacrylate / methacrylic acid (= 85/15 mol ratio) copolymer (Mw 10,000, 50% solution of propylene glycol monomethyl ether acetate)
UV curable resin C-3: trade name CYCLOMER P ACA-250 manufactured by Daicel Chemical Industries, Ltd. [Acrylic copolymer having alicyclic, COOH and acryloyl groups in the side chain, propylene glycol Monomethyl ether acetate solution (solid content: 50%)]
Polymerizable compound C-5: Trade name: TO-1382, manufactured by Toagosei Co., Ltd. (mainly a monomer having a pentafunctional acryloyl group in which a part of the terminal OH group of dipentaerythritol pentaacrylate is substituted with a COOH group component.)
・ Initiator C-7: Trade name “OXE-02”, manufactured by Ciba Specialty Chemicals Co., Ltd. ・ Surfactant C-8: Trade name “Megafuck R30”, manufactured by Dainippon Ink & Chemicals, Inc.・ Solvent: PGMEA = propylene glycol monomethyl ether acetate EEP = 3-ethoxyethyl propionate

2. Formation of Black Matrix by Application Photosensitive Dark Color Composition Layer Formation Step The obtained photosensitive dark color composition CK-1 was applied to a washed glass substrate (Corning Corporation Millennium (trade name) 0.7 mm thickness). Using a slit coater (model number HC8000, manufactured by Hirata Kiko Co., Ltd.), adjusting the interval between the slit and the glass substrate and the discharge amount so that the film thickness after post-baking is 1.2 μm, and the coating speed is 120 mm / Application in seconds.

Prebaking step and exposure step Next, after heating (prebaking treatment) at 90 ° C. for 120 seconds using a hot plate, 100 mJ using a mirror projection type exposure machine (model number MPA-8800, manufactured by Canon Inc.) / Cm < ² >.

Development process Then, it developed with the inclination conveyance type developing device (model number SK-2200G, Dainippon Screen Mfg. Co., Ltd., inclination-angle 5 degrees). That is, a 1.0% developer of potassium hydroxide developer CDK-1 (trade name) (manufactured by FUJIFILM Electronics Materials Co., Ltd.) (1 part of CDK-1 and 99 parts of pure water diluted) , 25 ° C.), the shower pressure was set to 0.20 MPa, development was performed for 60 seconds, and washed with pure water to obtain a developed black matrix.

Baking process Next, post baking is performed for 40 minutes in a 220 ° C. clean oven, and a black matrix is formed in a grid pattern in which the color pixel formation region has an opening of 90 μm × 200 μm, a thickness of 1.2 μm, and a line width of about 25 μm. A black matrix substrate was formed.
When the optical density (OD) of the completed black matrix was measured using X-Rite 361T (V) (trade name) (manufactured by Sakata Inx Engineering Co., Ltd.), it was 4.2.

3. 3. Preparation of photosensitive coloring composition 3-1. Preparation of photosensitive coloring composition coating liquid CR-1 for red (R) A dispersion liquid (R-1) for red (R) was prepared according to the following formulation.
Pigment Red 254 (average particle diameter 43 nm in SEM observation) 11 parts Pigment Red 177 (average particle diameter 58 nm in SEM observation) 4 parts Solution 5 parts of following dispersion resin A-3 Dispersant (trade name: Disperbyk-161, manufactured by Big Chemie)
(30% solution of propylene glycol monomethyl ether acetate) 3 parts, alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer (75/25 [mol ratio] copolymer, molecular weight 30,000, propylene glycol monomethyl ether acetate solution ( Solid content: 50%)) 9 parts Solvent B: 68 parts of propylene glycol monomethyl ether acetate

  The above components were stirred for 1 hour using a homogenizer at 3000 rpm. The resulting mixed solution was finely dispersed for 4 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN Co., Ltd.) using 0.3 mm zirconia beads, and a red (R) dispersion (R- 1) was obtained. When the dispersed particles in the obtained red (R) dispersion (R-1) were observed with an SEM, the average particle size was 36 nm.

Using the obtained red (R) dispersion liquid (R-1), a photosensitive coloring composition coating liquid CR-1 for red (R) was prepared according to the following formulation.
-Red (R) dispersion (R-1) 100 parts-Epoxy resin: (trade name EHPE3150, manufactured by Daicel Chemical Industries) 2 parts-Polymerizable compounds: dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate 8 parts of a 63/37 (mass ratio) and polymerization initiator: 4- (o-bromo-pN, N-di (ethoxycarbonylmethyl) amino-phenyl) -2,6-di (trichloromethyl) ) -S-triazine 1 part-polymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 1 part-polymerization initiator: diethylthioxanthone 0.5 part-polymerization prohibited Agent: p-methoxyphenol 0.001 part, fluorine-based surfactant (trade name: MEGAFAC R30, manufactured by Dainippon Ink & Chemicals, Inc.) 0 .01 parts Nonionic surfactant (trade name: TETRONIC R150 ADEKA Co., Ltd.) 0.2 parts Solvent: 30 parts propylene glycol n-butyl ether acetate Solvent: 100 parts propylene glycol monomethyl ether acetate The components were mixed and stirred to obtain a photosensitive coloring composition coating liquid CR-1 for red (R).

3-2. Preparation of green (G) photosensitive coloring composition coating liquid CG-1 A green (G) dispersion liquid (G-1) was prepared according to the following formulation.
Pigment Green 36 (average particle diameter 47 nm in SEM observation) 11 parts Pigment Yellow 150 (average particle diameter 39 nm in SEM observation) 7 parts Solution 5 parts of following dispersion resin A-3 Dispersant (trade name: Disperbyk -161, manufactured by Big Chemie, 30% solution)
3 parts, alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer (85/15 [mol ratio] copolymer, molecular weight 30,000, propylene glycol monomethyl ether acetate solution (solid content: 50% by mass)) 11 parts Solvent: 70 parts of propylene glycol monomethyl ether acetate

  The above components were stirred for 1 hour using a homogenizer under the condition of 3000 rpm. The obtained mixed solution was finely dispersed for 8 hours using a bead disperser (trade name: Dispermat, manufactured by GETZMANN Co., Ltd.) using 0.3 mm zirconia beads, and a green (G) dispersion (G -1) was obtained. When the dispersed particles in the obtained green (G) dispersion liquid (G-1) were observed with an SEM, the average particle diameter was 32 nm.

Using the obtained green (G) dispersion liquid (G-1), a photosensitive coloring composition coating liquid CG-1 for green (G) was prepared according to the following formulation.
-Green (G) dispersion (G-1) 100 parts-Epoxy resin: (trade name EHPE3150, manufactured by Daicel Chemical Industries, Ltd.) 2 parts-Polymerizable compounds: dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate 8 parts of 63/37 (mass ratio) of polymerizable compound: tetra (ethoxy acrylate) of pentaerythritol
2 parts, polymerization initiator: 1,3-bistrihalomethyl-5-benzooxolantolyazine
2 parts Polymerization initiator: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 1 part Polymerization initiator: Diethylthioxanthone 0.5 part Polymerization inhibitor: p-methoxy 0.001 part of phenol / fluorine-based surfactant (trade name: MEGAFAC R08, manufactured by Dainippon Ink & Chemicals, Inc.) 0.02 part / nonionic surfactant (trade name: EMULGEN A-60, Kao ( 0.5 part ・ Solvent: Propylene glycol monomethyl ether acetate 120 parts ・ Solvent: Propylene glycol n-propyl ether acetate 30 parts The above composition is mixed and stirred, and a green (G) photosensitive coloring composition coating solution CG -1 was obtained.

3-3. Preparation of photosensitive coloring composition coating liquid CB-1 for blue (B) A dispersion (B-1) for blue (B) was prepared according to the following formulation.
Pigment Blue 15: 6 (average particle diameter 55 nm in SEM observation) 14 parts Pigment Violet 23 (average particle diameter 61 nm in SEM observation) 1 part 5 parts of the following dispersion resin A-3 Dispersant (Product) Name: Disperbyk-161, manufactured by Big Chemie, 30% solution)
3 parts, alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer (80/20 [mol ratio] copolymer, molecular weight 30,000, propylene glycol monomethyl ether acetate solution (solid content: 50%)) 4 parts, solvent : Propylene glycol monomethyl ether acetate 73 parts

  The above components were stirred for 1 hour using a homogenizer at 3000 rpm. The obtained mixed solution was subjected to a fine dispersion treatment for 4 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN Co., Ltd.) using 0.3 mm zirconia beads, and a blue (B) dispersion liquid (B -1) was obtained. When the dispersed particles in the obtained blue (B) dispersion liquid (B-1) were observed with an SEM, the average particle diameter was 39 nm.

Using the obtained blue (B) dispersion liquid (B-1), a blue (B) photosensitive coloring composition coating liquid CB-1 was prepared according to the following formulation.
-Blue (B) dispersion (B-1) 100 parts-Alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer (80/20 [mol ratio] copolymer, molecular weight 30,000), propylene glycol monomethyl ether Acetate solution (solid content: 50%) 7 parts-Epoxy resin: (trade name CELLOXIDE 2080, manufactured by Daicel Chemical Industries Ltd.) 2 parts-UV curable resin: (trade name Cyclomer P ACA-250, Daicel Chemical Industries, Ltd.) (acrylic copolymer having alicyclic, COOH and acryloyl groups in the side chain, propylene glycol monomethyl ether acetate solution (solid content: 50%)) 4 parts Polymerizable compound: Dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate 3/37 (mass ratio) mixture 12 parts Polymerization initiator: 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) -1- (o-acetyloxime) ethanone 3 parts ・ Polymerization inhibitor: p-methoxyphenol 0.001 part ・ Fluorine-based surfactant (trade name: MEGAFAC R08, manufactured by Dainippon Ink & Chemicals, Inc.) 0.02 part ・ Nonionic surfactant (product) Name: Emulgen A-60, manufactured by Kao Corporation) 1.0 parts Solvent: 20 parts ethyl 3-ethoxypropionate Solvent: 150 parts propylene glycol monomethyl ether acetate The above ingredients are mixed and stirred for blue (B) The photosensitive coloring composition coating liquid CB-1 was obtained.

4). Synthesis of Dispersing Resin A-3 4-1. Synthesis of chain transfer agent A3 Dipentaerythritol hexakis (3-mercaptopropionate) [DPMP; manufactured by Sakai Chemical Industry Co., Ltd.] (the following compound (33)), and having an adsorption site, and 4.55 parts of the following compound (m-6) having a carbon-carbon double bond was dissolved in 28.90 parts of propylene glycol monomethyl ether and heated to 70 ° C. under a nitrogen stream. To this, 0.04 part of 2,2′-azobis (2,4-dimethylvaleronitrile) [V-65, manufactured by Wako Pure Chemical Industries, Ltd.] was added and heated for 3 hours. Further, 0.04 part of V-65 was added and reacted at 70 ° C. for 3 hours under a nitrogen stream. By cooling to room temperature, a 30% solution of the mercaptan compound (chain transfer agent A3) shown below was obtained.

4-2. Synthesis of dispersion resin A-3 4.99 parts of a 30% solution of chain transfer agent A3 obtained as described above, 19.0 parts of methyl methacrylate, 1.0 part of methacrylic acid, propylene glycol monomethyl ether 66 parts of the mixed solution was heated to 90 ° C. under a nitrogen stream. While stirring this mixed solution, 0.139 part of dimethyl 2,2′-azobisisobutyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.], 5.36 parts of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate 9 40 parts of the mixed solution was added dropwise over 2.5 hours. After the completion of the dropwise addition, the mixture was reacted at 90 ° C. for 2.5 hours, and then a mixed solution of 0.046 parts of dimethyl 2,2′-azobisisobutyrate and 4.00 parts of propylene glycol monomethyl ether acetate was added, and further 2 hours. Reacted. To the reaction solution, 1.52 parts of propylene glycol monomethyl ether and 21.7 parts of propylene glycol monomethyl ether acetate were added and cooled to room temperature, whereby a solution of dispersion resin A-3 (polystyrene equivalent weight average molecular weight 24000) (dispersion resin 30) was obtained. Mass%, propylene glycol monomethyl ether 21 mass%, propylene glycol monomethyl ether acetate 49 mass%).
The acid value of this dispersion resin A-3 was 48 mgKOH / g. The structure of dispersion resin A-3 is shown below.

Preparation of Color Filter Photosensitive Colored Composition Layer Formation Step The obtained photosensitive coloring composition coating solution CR-1 for red (R) was applied to the black matrix forming surface side of the black matrix substrate. Specifically, as in the case of forming the photosensitive dark color composition layer, the interval between the slit and the black matrix substrate so that the layer thickness of the photosensitive coloring composition layer after post-baking is about 2.1 μm, Coating was performed at a coating speed of 120 mm / sec by adjusting the discharge amount.

Colored layer pre-baking step and colored layer exposing step Next, after heating (pre-baking treatment) at 100 ° C for 120 seconds using a hot plate, a mirror projection type exposure machine (model number MPA-8800, manufactured by Canon Inc.) is used. And exposed at 90 mJ / cm ² .
Further, the mask pattern and the exposure machine were set so that the overlap (exposure overlap amount) between the exposure pattern and the black matrix was 9.0 μm.

Colored layer developing step and colored layer baking step Thereafter, development was performed with an inclined conveyance type developing device (model number SK-2200G, manufactured by Dainippon Screen Mfg. Co., Ltd., inclination angle 5 °). That is, a 1.0% developer of a potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) (a solution obtained by diluting 1 part of CDK-1 and 99 parts of pure water, 25 ° C.) Then, the shower pressure was set to 0.2 MPa, development was performed for 45 seconds, and washed with pure water.
Next, post baking was performed for 30 minutes in a 220 ° C. clean oven to form heat-treated red pixels.

  Subsequently, in the said photosensitive coloring composition layer formation process, colored layer prebaking process, colored layer exposure process, colored layer development process, and colored layer baking process, the photosensitive coloring composition coating liquid CR-1 for red (R) is used. A green pixel was formed in the same manner except that the photosensitive coloring composition coating solution CG-1 for green (G) was used. Thereafter, a blue pixel was formed in the same manner except that the photosensitive coloring composition coating liquid CR-1 for red (R) was replaced with the photosensitive coloring composition coating liquid CB-1 for blue (B). A color filter was obtained.

  An ITO (Indium Tin Oxide) transparent electrode was further formed on the R pixel, G pixel, B pixel and black matrix of the color filter obtained above by sputtering to obtain a color filter substrate.

Preparation of Photospacer The black polyethylene film and the transparent polyethylene film are peeled off, the photosensitive transfer film for photospacer (1) is taken out, and a temporary support is removed from the cover film surface using a rotary cutter from above the cover film. A cut with a depth up to the part was made.
Next, it peeled at the interface of a cover film and a photosensitive resin layer using the tape, and removed the cover film.

  The exposed photosensitive resin layer is sputter-formed with the ITO film prepared above and superimposed on the ITO film of the color filter substrate heated to a surface temperature of 95 ° C. in advance to form a laminator Lamic II type [Hitachi Indust Were used, and bonded at a conveyance speed of 2 m / min under pressure and heating conditions of a linear pressure of 100 N / cm, an upper roll of 90 ° C., and a lower roll of 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 oxygen blocking layer (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 oxygen-blocking layer is set to 100 μm with the color filter substrate disposed on the substrate in a state where the color filter substrate stands substantially parallel and perpendicularly, and the thermoplastic resin is passed through the mask. Proximity exposure was performed from the layer side with an exposure amount of i-line of 50 mJ / cm ² .

Next, a triethanolamine developer (containing 30% triethanolamine, trade name: T-PD2 (manufactured by FUJIFILM Corporation) 10 times with pure water (1 part of T-PD2 and 9 parts of pure water). The mixture was diluted at a ratio), and shower development was performed at 30 ° C. for 60 seconds at a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the oxygen barrier layer.
Subsequently, after air was blown off on the upper surface of the glass substrate, pure water was sprayed for 10 seconds by a shower, pure water shower cleaning was performed, and air was blown to reduce a liquid pool on the substrate.
Subsequently, sodium carbonate developer (containing 0.38 mol / L sodium bicarbonate, 0.47 mol / L sodium carbonate, 5% sodium dibutylnaphthalene sulfonate, anionic surfactant, antifoaming agent, and stabilizer; Trade name: T-CD1 (manufactured by Fuji Film Co., Ltd.) diluted 10-fold with pure water, shower developed at 27 ° C. for 45 seconds with cone-type nozzle pressure of 0.15 MPa, and photo spacer pattern I got a statue.
Subsequently, a solution obtained by diluting a cleaning agent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer; trade name: T-SD3 (manufactured by Fuji Film Co., Ltd.)) 10 times with pure water Then, spraying was performed with a shower at a cone type nozzle pressure of 0.02 MPa at 33 ° C. for 20 seconds to remove residues around the formed pattern image, thereby obtaining a desired photospacer pattern.

Next, the color filter substrate provided with the photospacer pattern was subjected to heat treatment at 230 ° C. for 60 minutes (heat treatment step) to produce a photospacer.
Thus, a color filter substrate with a photo spacer was obtained.
The obtained photospacer pattern was a cylindrical shape having a diameter of 20 μm and an average height of 4.2 μm. For each of the 200 photo spacers obtained, the average height was determined by using a three-dimensional surface structure analysis microscope (manufacturer: ZYGO Corporation, model: New View 5022). The height to a high position was measured, and it was obtained by calculating the arithmetic average of 200 values.

Preparation of liquid crystal display device Separately, a TFT substrate having TFTs disposed on a glass substrate is prepared as a counter substrate, and the transparent electrode forming surface side of the color filter substrate with a photo spacer obtained above and TFT formation on the counter substrate are prepared. On the surface side, patterning for each PVA mode was performed, 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 around 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.
The above-described photo spacer and liquid crystal display device were subjected to the evaluation test described below, evaluated, and the results are shown in Table 3.

(Examples 2 to 5: transfer method)
In Example 1, instead of the surface-treated fine particles (surface treatment double bond amount: 0.171 mmol / g) of Synthesis Example 1 used for the preparation of the photosensitive resin layer coating solution (Formulation 1), Synthesis Example 2 was used. (Surface treatment double bond amount: 0.021 mmol / g), Synthesis example 3 (Surface treatment double bond amount: 0.043 mmol / g), Synthesis example 4 (Surface treatment double bond amount: 0.086 mmol / g) (Same as in Example 1 except that the surface-treated fine particles of Synthesis Example 5 (surface treatment double bond amount: 0.341 mmol / g) were used (configuration is shown in Table 2), and the results shown in Table 3 were obtained. Obtained.

(Comparative Examples 1-4: Transfer Method)
In Example 1, instead of the surface-treated fine particles of Synthesis Example 1 (surface treatment double bond amount: 0.171 mmol / g), Comparative Synthesis Example 1 (surface treatment double bond amount: 0 mmol / g) and Comparative Synthesis, respectively. Example 2 (surface treatment double bond amount: 0.017 mmol / g), comparative synthesis example 3 (surface treatment double bond amount: 0.370 mmol / g), comparative synthesis example 4 (surface treatment double bond amount: 2. The same procedure as in Example 1 was performed except that 13 mmol / g) of surface-treated fine particles were used (the composition is shown in Table 2), and the results shown in Table 3 were obtained. When the surface treatment double bond amount is smaller than 0.020 mmol / g, the panel vibration resistance and the development residue (unexposed portion: caused by the polymerizable compound (B)) are deteriorated, and when it is larger than 0.35 mmol / g, The followability deteriorated, and at 2.13 mmol / g, the development residue (outlined portion of the exposed portion) deteriorated.

(Examples 6 to 9: transfer method)
In Example 1, the height of the completed spacer was changed from 4.2 μm to 5.0 μm (Example 6), 4.7 μm (Example 7), 2.88 μm (Example 8), and 2.0 μm (Example). The procedure was the same as in Example 1 except that the coating thickness of the photosensitive resin layer was adjusted to 9) (the configuration is shown in Table 2), and the results shown in Table 3 were obtained.

(Examples 10 to 14: transfer method)
In Example 1, instead of the surface-treated fine particles in Synthesis Example 1, the same procedure as in Example 1 was performed except that the surface-treated fine particles in Synthesis Examples 6 to 10 were used (the composition is shown in Table 2). The results shown are obtained.

(Examples 15 to 17: transfer method)
In Example 1, while maintaining the height of the spacer after completion, the polymerizable compound (B) / resin (A) ratio, and the solid content concentration constant, the content of the surface-treated fine particles in the solid content from 0.12 respectively. Similar to Example 1 except that the formulation of the coating solution for the photosensitive resin layer was changed to 0.2 (Example 15), 0.1 (Example 16), and 0.05 (Example 17). (The composition is shown in Table 2) and the results shown in Table 3 were obtained.

(Examples 18 and 19: transfer method)
In Example 1, the ratio of the polymerizable compound (B) / resin (A) from 0.75, respectively, while keeping the height of the spacer after completion, the content of the surface treatment fine particles in the solid content, and the solid content concentration constant. The same procedure as in Example 1 was carried out except that the formulation of the photosensitive resin layer coating solution was changed to 0.52 (Example 18) and 1.9 (Example 19) (configuration is shown in Table 2). The results shown in Table 3 were obtained.

(Examples 20 and 21: transfer method)
In Example 1, in place of the surface-treated fine particles (silica) in Synthesis Example 1, the same procedure as in Example 1 was performed except that the surface-treated fine particles in Synthesis Example 11 (zirconia) and 12 (alumina) were used. The results shown in Table 3 were obtained.

(Example 22: Transfer method)
Example 1 was carried out in the same manner as in Example 1 except that the surface-treated fine particles in Example 1 (with catalyst) were used instead of the surface-treated fine particles (without catalyst) in Synthesis Example 1 (configuration is shown in Table 2). ) And the results shown in Table 3 were obtained. The results of panel vibration resistance simulation evaluation seemed to be slightly improved.

(Examples 23 to 26: transfer method)
In Example 1, instead of the structural formula P-25 described in Japanese Patent Application Laid-Open No. 2008-146018 used as the polymer solution of the coating solution for the photosensitive resin layer, paragraph [0058] of Japanese Patent Application Laid-Open No. 2008-146018, respectively. Structural formula P-10 (Example 23), the following structure 1 (Example 24), structure 2 (Example 25), and paragraph [0094] of JP-A-2004-240241, Synthesis Example 1 polymer (implementation) Example 26) was added in the same manner as in Example 1 except that the polymer solid content was equal, and the addition amount of 1-methoxy-2-propyl acetate was adjusted so that the coating liquid solid content was the same. (The composition is shown in Table 2) and the results shown in Table 3 were obtained.
In addition, the weight average molecular weights of the following structure 1 and structure 2 are 35,000 and 32,000, respectively.

(Example 27: Transfer method)
In Example 1, 2,4-bis- (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino)-used for the preparation of the photosensitive resin layer coating solution (formulation 1) The amount of 3-bromophenyl] -s-triazine was changed from 6.50 parts to 2.17 parts to produce a photosensitive transfer film for photospacers, and the photosensitive transfer film for photospacers was laminated to proxy The same procedure as in Example 1 was carried out except that the Mitie exposure amount was changed from 50 mj to 80 mj (the configuration is shown in Table 2), and the results shown in Table 3 were obtained.

(Examples 28 to 29: transfer method)
2,4-bis- (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl] used for the preparation of the coating solution for the photosensitive resin layer of Example 27 Instead of using -s-triazine, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole (Example 27) or 1- (9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl) (CGI242 manufactured by Ciba Specialty Chemicals Co., Ltd.) (Example 28) was used to prepare a photosensitive transfer film for photospacer, and photospacer Example 2 except that the photosensitive transfer film was laminated and the proximity exposure amount was changed from 80 mj to 60 mj (Example 28) or 40 mj (Example 29). 7 (the composition is shown in Table 2), and the results in Table 3 were obtained.

(Example 30: Transfer method)
In Example 1, 2,4-bis- (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino)-used for the preparation of the photosensitive resin layer coating solution (formulation 1) The amount of 3-bromophenyl] -s-triazine was changed from 6.50 parts to 2.17 parts, and 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadi 1.08 parts of azole was added to produce a photosensitive transfer film for photospacers, and the photosensitive exposure film for photospacers was further laminated to change the proximity exposure amount from 50 mj to 70 mj. (The composition is shown in Table 2), and the results in Table 3 were obtained.

(Example 31: Transfer method)
In Example 1, 2,4-bis- (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) used for the preparation of the coating solution for photosensitive resin layer (formulation 1) The amount of -3-bromophenyl] -s-triazine used was changed from 6.50 parts to 2.17 parts, and a new 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 was obtained. -Il) (CGI242 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.08 parts was added to produce a photosensitive transfer film for photospacers, and the photosensitive transfer film for photospacers was further laminated to expose the proximity exposure amount. Was performed in the same manner as in Example 1 except that 50 mj was changed from 50 mj to 60 mj (the configuration is shown in Table 2), and the results of Table 3 were obtained.

(Example 32: Coating method)
Photospacer fabrication (liquid registration method)
An example of the glass substrate coater MH-1600 (manufactured by FS Asia Co., Ltd.) having a slit-shaped nozzle on the ITO film of the color filter substrate on which the ITO film produced above was formed by sputtering. The coating solution for photosensitive resin layer containing the surface-treated fine particles of Synthesis Example 1 was applied. Subsequently, after part of the solvent was dried for 30 seconds using a vacuum dryer VCD (manufactured by Tokyo Ohka Kogyo Co., Ltd.) to eliminate the fluidity of the coating film, it was pre-baked at 120 ° C. for 3 minutes and the film thickness was 4.5 μm. A photosensitive resin composition layer was formed (layer forming step).

Subsequently, photo spacers were produced on the color filter substrate by the same patterning process and heat treatment process as in Example 1 (see Table 4). However, the exposure amount was 300 mJ / cm ² , and the development with the KOH developer was 23 ° C. for 60 seconds. The obtained photospacer pattern was a cylindrical shape having a diameter of 20 μm and an average height of 4.2 μm.

  After the production of the photospacer, the PVA mode liquid crystal display device of the present invention was produced using the color filter substrate in the same manner as in Example 1, and the results shown in Table 5 were obtained.

(Examples 33 to 36: coating method)
In Example 32, instead of the surface-treated fine particles (surface treatment double bond amount: 0.171 mmol / g) of Synthesis example 1, synthesis example 2 (surface treatment double bond amount: 0.021 mmol / g) and synthesis were performed, respectively. Example 3 (surface treatment double bond amount: 0.043 mmol / g), Synthesis example 4 (surface treatment double bond amount: 0.086 mmol / g), Synthesis example 5 (surface treatment double bond amount: 0.341 mmol / g) The same procedure as in Example 32 was performed except that the surface-treated fine particles of g) were used (configuration is shown in Table 4), and the results shown in Table 5 were obtained.

(Comparative Examples 7-9: Application method)
In Example 32, instead of the surface-treated fine particles (surface treatment double bond amount: 0.171 mmol / g) of Synthesis example 1, comparative synthesis example 1 (surface treatment double bond amount: 0 mmol / g) and comparative synthesis example, respectively. 2 (surface treatment double bond amount: 0.017 mmol / g) and Comparative Example 4 (surface treatment double bond amount: 2.13 mmol / g) were used in the same manner as in Example 27, except that the surface treatment fine particles were used. The results shown in Table 3 were obtained. When the surface treatment double bond amount is smaller than 0.020 mmol / g, the vibration resistance of the panel and the development residue (unexposed part: due to the polymerizable compound (B)) are deteriorated, and at 2.13 mmol / g, the development residue (Outline part of exposed part) deteriorated.

(Comparative Example 10: coating method)
In Example 32, instead of the surface-treated fine particles of Synthesis Example 1 (surface treatment double bond amount: 0.171 mmol / g), surface treatment of Comparative Synthesis Example 3 (surface treatment double bond amount: 0.370 mmol / g) The same procedure as in Example 32 was performed except that fine particles were used (the composition is shown in Table 4), and the results shown in Table 5 were obtained.

(Examples 38 to 41: Application method)
The height of the spacer completed in Example 32 was changed from 4.2 μm to 5.0 μm (Example 38), 4.7 μm (Example 39), 2.88 μm (Example 40), and 2.0 μm (Example 41). ) Was carried out in the same manner as in Example 32 except that the coating film thickness of the photosensitive resin layer was adjusted so that the composition was as shown in FIG.

(Examples 42 to 46: Application method)
In Example 32, the same procedure as in Example 32 was performed except that instead of the surface-treated fine particles in Synthesis Example 1, the surface-treated fine particles in Synthesis Examples 6 to 10 (Examples 42 to 46) were used, respectively. The results shown in Table 5 were obtained.

(Examples 47 to 49: Application method)
In Example 32, while maintaining the height of the spacer after completion, the polymerizable compound (B) / resin (A) ratio, and the solid content concentration constant, the content of the surface-treated fine particles in the solid content was 0.12 respectively. Similar to Example 32, except that the formulation of the coating solution for the photosensitive resin layer was changed to 0.2 (Example 47), 0.1 (Example 48), and 0.05 (Example 49). And the results shown in Table 5 were obtained.

(Examples 50 and 51: coating method)
In Example 32, while maintaining the height of the spacer after completion, the content of surface-treated fine particles in the solid content, and the solid content concentration, the ratio of the polymerizable compound (B) / resin (A) from 0.75, respectively. Performed in the same manner as in Example 32 except that the formulation of the photosensitive resin layer coating solution was changed to 0.52 (Example 50) and 1.9 (Example 51) (configuration is shown in Table 4). The results shown in Table 5 were obtained.

(Examples 52 and 53: Application method)
In Example 32, the same procedure as in Example 32 was performed except that instead of the surface-treated fine particles (silica) in Synthesis Example 1, the surface-treated fine particles in Synthesis Example 11 (zirconia) and 12 (alumina) were used, respectively. The results shown in Table 4 were obtained.

(Example 54: Coating method)
The same procedure as in Example 32 was performed except that the surface-treated fine particles in Synthesis Example 13 (with catalyst) were used instead of the surface-treated fine particles (without catalyst) in Synthesis Example 1 (the configuration is shown in Table 4). ) And the results shown in Table 5 were obtained. The results of the panel vibration resistance simulation evaluation were slightly improved.

(Examples 55 to 58: Application method)
In Example 32, instead of the structural formula P-25 described in Japanese Patent Application Laid-Open No. 2008-146018 used as the polymer solution of the coating solution for the photosensitive resin layer, paragraph [0058] of Japanese Patent Application Laid-Open No. 2008-146018, respectively. Structural formula P-10 (Example 55), the following structure 1 (Example 56), structure 2 (Example 57), and paragraph [0094] of JP-A-2004-240241, Synthesis Example 1 polymer (implementation) Example 58) was added in the same manner as in Example 32 except that the polymer solids were added in an equal amount and the addition amount of 1-methoxy-2-propyl acetate was adjusted so that the coating liquid solids were the same. And the results shown in Table 5 were obtained.

(Example 59: Coating method)
In the coating solution for photosensitive resin layer of Example 32, 2,4-bis- (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl] -s-triazine The amount was changed from 6.50 parts to 2.17 parts, and the proximity exposure amount at the time of producing the photospacer was changed from 300 mj to 480 mj (the configuration is shown in Table 4). ) And the results shown in Table 5 were obtained.

(Examples 60 and 61: coating method)
In the coating solution for photosensitive resin layer of Example 59, 2,4-bis- (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl] -s-triazine Instead of using 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole (Example 60), or 1- (9-ethyl-6- (2-methylbenzoyl) ) -9H-carbazol-3-yl) (CGI 242 manufactured by Ciba Specialty Chemicals Co., Ltd.) (Example 61), and further, the amount of proximity exposure during photospacer production was changed from 480 mj to 360 mj (Example 60). Alternatively, the same procedure as in Example 59 was performed except that the change was made to 240 mj (Example 61) (the structure is shown in Table 4), and the results shown in Table 5 were obtained.

(Example 62: Coating method)
In the coating solution for photosensitive resin layer of Example 32, 2,4-bis- (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl] -s-triazine Was changed from 6.50 parts to 2.17 parts, and newly added 1.08 parts 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole, Photosensitive transfer film for photospacer was prepared, and the same procedure as in Example 32 was performed except that the proximity exposure amount at the time of photospacer preparation was changed from 300 mj to 420 mj (configuration is shown in Table 4). The result was obtained.

(Example 63: Coating method)
In the coating solution for photosensitive resin layer of Example 32, 2,4-bis- (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl] -s-triazine Was changed from 6.50 parts to 2.17 parts, and 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) (Ciba Specialty Chemicals ( Co., Ltd. CGI242) 1.08 parts was added to produce a photosensitive transfer film for photospacers, and the proximity exposure amount at the time of photospacer production was changed from 300 mj to 360 mj, as in Example 32 And the results shown in Table 5 were obtained.

Evaluation vibration resistance simulation evaluation In the photo spacer production method of the example and the comparative example, a glass substrate on which ITO is vapor-deposited is used instead of the color filter substrate, and the substrate is developed and baked after uniform exposure without using a mask. Was cut into 2 cm square.
Separately, the following TFT substrate was prepared, and similarly cut into 2 cm square.

  The two types of substrates were laminated so that the TFT surface and the baked photosensitive resin layer overlapped, and a cellophane tape was wound around and fixed to obtain a substrate sample.

  Further, a SUS304 plate having a thickness of 1 cm is processed to produce a shaking case (inner diameter length 95 mm × width 45 mm × height 45 mm) shown in FIG. Pasted on. This shaking case was attached to a shaking bath model BW100 manufactured by Yamato Scientific Co., Ltd. so that the shaking direction and the vertical axis of the shaking case were in the same direction. A golf ball having a diameter of 4 cm and a weight of 45.7 g was put in a shaking case, and the golf ball was shaken to repeatedly give an impact to the TFT substrate.

  After completion of the test, the TFT substrate was peeled off, and the depression on the surface in contact with the TFT was measured using a three-dimensional surface structure analysis microscope (manufacturer: ZYGO Corporation, model: New View 5022). = 5 and averaged. The recess is preferably 0.1 μm or less.

Measurement conditions / shaking speed: 3 Hz (180 collisions / minute)
-Shaking time: 5 minutes-TFT substrate: TFT substrate patterned for PVA mode shown in Fig. 2 (7 TFTs with a height of 0.9 µm arranged in 600 µm x 300 µm)

Evaluation of Development Residue In “Preparation of Photospacer” in Examples and Comparative Examples, SEM observation was performed on the formed photospacer contour portion and the peripheral portion, and whether the residue remained on the contour and the periphery was evaluated according to the following criteria. The practical level is C or higher.

Evaluation criteria A: No residue is observed at all, and it is very good.
B: Residue is slightly seen only at the photo spacer outline, which is good.
C: A slight residue is seen in the photo spacer outline, and a slight residue is seen around the photo spacer, which is normal.
D: A lot of residue is seen in the photospacer outline, or the residue is seen not only around the photospacer but also between the photospacers.
E: Residue can be confirmed over the entire surface of the substrate, which is very bad.

Evaluation of Photospacer Residuality In “Production of Photospacers” in Examples and Comparative Examples, the laminate state of 1000 photospacers formed was observed with an optical microscope, and photospacer residual properties were evaluated according to the following criteria. The practical level is C or higher.

Evaluation criteria A: The number of photo spacers dropped out of 1,000 photo spacers was zero.
B: One to three photo spacers were dropped out of 1,000 photo spacers.
C: The number of photo spacers dropped out of 1000 photo spacers was 4 or more and 5 or less.
D: Six to ten photo spacers were dropped out of 1,000 photo spacers.
E: 11 or more photo spacers were dropped out of 1000 photo spacers.

Vibration resistance (uneven display)
For each of the liquid crystal display devices of Examples and Comparative Examples, vibration of 10 Hz to 100 Hz was continuously given for 15 minutes in the XYZ direction of the panel using a vibration tester F-16000BDH / LA16AW manufactured by EMIC, and repeated for 4 cycles. It was. The gray display when a gray test signal was input was observed visually and with a magnifying glass, and evaluated according to the following evaluation criteria. The practical level is C or higher.

Evaluation criteria A: Observed from the front, no display unevenness was observed over the entire display panel.
B: Display unevenness was slightly recognized at the center of the display panel only when observed from 45 degrees obliquely.
C: Observed from the front, display unevenness was slightly recognized at the center of the display panel.
D: Display unevenness was observed over the entire display panel as observed from the front.
E: Display unevenness was noticeable over the entire surface of the display panel as observed from the front.

Following the same transfer material as used in the examples and comparative examples, laminating and exposing on a flat substrate without preceding pixels under the same conditions, and then removing the thermoplastic resin layer and oxygen barrier layer by development The film thickness of the photosensitive resin layer measured with a surface roughness meter P-10 (manufactured by TENCOR) is T0. In the methods of Examples and Comparative Examples, after laminating, mask exposure is performed, and the film thickness at nine points in the substrate is similarly measured for the film thickness at the position where the spacer is to be prepared. The obtained values are T1 to T9, and the average value of T1 to T9 is T10.
A value obtained by dividing T10 by T0 × 100 (%) is defined as followability. The closer this value is to 100%, the more the photosensitive layer coating film of the transfer material is transferred to the substrate with good reproducibility when laminated on a stepped substrate. Evaluation was performed according to the following evaluation criteria. The practical level is 95% or more and 103% or less.

Apparently from the results of Tables 2 to 5, all of the examples according to the present invention are excellent in vibration resistance and follow-up property, there are few development residual residues, and excellent photo spacer residual property, and overall excellent performance. Was recognized. Corresponding to the results of the vibration resistance simulation, according to the present invention, the occurrence of vibration display unevenness was small and the vibration resistance was excellent.

Claims (13)

  Resin (A) having an acidic group in the side chain, polymerizable compound (B), photopolymerization initiator (C), and surface-treated fine particles having a surface treatment double bond amount of 0.02 mmol to 0.35 mmol per 1 g of fine particles A photosensitive resin composition for a photospacer comprising (D).   Fine particles obtained by subjecting the surface-treated fine particles (D) to oxide particles containing at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, magnesium, indium, tin, antimony and cerium. The photosensitive resin composition for photospacers of Claim 1 containing this.   The photosensitive resin composition for photospacers of Claim 1 or Claim 2 in which the said double bond contains at least 1 type of a methacryloyl group and an acryloyl group.   4. The photo according to claim 1, wherein (B) / (A), which is a mass ratio of the polymerizable compound (B) to the resin (A), is 0.5 to 2. 5. Photosensitive resin composition for spacers. A temporary support;
A photosensitive resin layer formed on the temporary support using at least the photosensitive resin composition for photospacers according to any one of claims 1 to 4,
A photosensitive resin transfer material.   The photosensitive resin transfer material according to claim 5, wherein at least one of an oxygen blocking layer and a thermoplastic resin layer is provided between the photosensitive resin layer and the temporary support.   The manufacturing method of the photo spacer including the process of apply | coating at least the photosensitive resin composition for photo spacers of any one of Claims 1-4 to a support body, and forming a photosensitive resin layer.   A step of forming a photosensitive resin layer on a support by transferring the photosensitive resin layer by at least one of heating and pressurization using at least the photosensitive resin transfer material according to claim 5. A method for manufacturing a photospacer. at least,
A step of forming a photosensitive resin layer on a support using the photosensitive resin composition for a photospacer according to any one of claims 1 to 4,
Exposing the photosensitive resin layer;
Developing the exposed photosensitive resin layer;
Heating the pattern formed by development;
A method for manufacturing a photospacer. at least,
Using the photosensitive resin transfer material according to claim 5 or 6 to form a photosensitive resin layer on a support;
Exposing the photosensitive resin layer;
Developing the exposed photosensitive resin layer;
Heating the pattern formed by development;
A method for manufacturing a photospacer.   A resin (A) having at least an acidic group in a side chain, a polymerizable compound (B), a photopolymerization initiator, produced by the method for producing a photospacer according to any one of claims 7 to 10. (C) and a photo-spacer containing surface-treated fine particles (D) having a surface-treated double bond amount of 0.02 mmol to 0.35 mmol per 1 g of fine particles.   A substrate for a liquid crystal display device, comprising the photospacer according to claim 11. A liquid crystal display device comprising the substrate for a liquid crystal display device according to claim 12.