JP2014232172A - Method for manufacturing patterned substrate, color filter, and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a patterned substrate, in which a photosensitive resin layer for patterning, formed on a substrate by a transfer process, is subjected to pattern exposure and developed to form a pattern, and a pattern having high adhesive force to the substrate is formed on the substrate.SOLUTION: The method for manufacturing a patterned substrate includes steps in the following order: a substrate surface treatment step which includes treating a surface of a substrate with a surface treating agent having a basic group, so as to prepare a substrate having a water contact angle of the surface of 42 degrees or more and 65 degrees or less; a photosensitive resin layer formation step of forming a photosensitive resin layer by a transfer process on the surface of the substrate; and a patterning step of forming a pattern by subjecting the photosensitive resin layer to pattern exposure and developing the resin layer.

Description

  The present invention relates to a method for manufacturing a substrate with a pattern, a color filter, and a display device.

Display devices are widely used in display devices that display high-quality images. In a liquid crystal display device which is widely used as a 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. Is one of the factors that determine image quality. For this purpose, a spacer is provided to keep the thickness of the liquid crystal layer constant.
The color filter includes a colored layer including a red, green, and blue pixel and a black matrix for shielding light that is embedded between the pixels on a support such as a glass plate. Since the colored layer has surface irregularities due to the pixels and the black matrix, an overcoat layer containing a resin (hereinafter referred to as “resin layer”) for the purpose of reducing the irregularities and protecting the colored layer, if necessary. Is also formed). In this case, the spacer is formed on the resin layer.
The spacer is advantageously formed on the colored layer of the color filter or on the resin layer by forming a photosensitive resin layer by a transfer method, pattern exposure, alkali development, and baking. (For example, see Patent Document 1). The method of forming the photosensitive resin layer by the transfer method is preferable in that the influence of the solvent can be avoided as compared with the method of forming the photosensitive resin layer by applying and drying a solvent solution of the photosensitive resin composition. It is.

Since the spacer has a small area in contact with the colored layer or the resin layer, the spacer is required to have excellent adhesion to the colored layer or the resin layer.
As in the case of the spacer, generally, when a pattern is formed on the substrate surface, it is required that the pattern be formed with high adhesion to the substrate surface. With the demand, the degree of adhesion demand is increasing.

As a method for improving the above-mentioned adhesion, a photopolymerizable monomer, a non-photosensitive resin and / or a photosensitive resin contained in a colored photosensitive composition for a color filter used for forming a pixel of a color filter It has been proposed to set the ratio in a specific range (see, for example, Patent Document 2). The surface of the colored layer formed using such a colored photosensitive composition for color filters, which has been subjected to UV cleaning at an exposure amount of 1000 mJ / cm ² , has a contact angle with pure water in the range of 75 ° to 100 °. In addition, it is described that when a resin layer is formed thereon, it has a high adhesive force. Furthermore, it is described that even when a spacer is formed in place of the resin layer, high adhesion is shown (see paragraph 0015 of Patent Document 2).
As another method for improving adhesion, for example, as described in Patent Document 3, it is conceivable to apply a method of treating with a coupling agent such as an aminosilane coupling agent. That is, a method of forming a spacer after treating the surface of the resin layer provided on the colored layer of the color filter with a coupling agent such as an aminosilane coupling agent can be considered.

JP 2010-55054 A JP 2009-300564 A JP-A-1-223416

However, even if a pattern such as a spacer is formed after treating the substrate surface as described above, it has been difficult to form a pattern having a sufficient adhesive force on the substrate surface. In other words, the pattern is formed after adjusting the contact angle by irradiating the surface of the substrate with ultraviolet light, and the case where the pattern is formed after treating the surface of the substrate with a coupling agent is sufficiently high. It has been difficult to form a pattern having an adhesive force on the substrate surface.
Furthermore, even if an attempt is made to form the photosensitive resin layer for pattern formation by the transfer method after treating the substrate surface as described above, it may be difficult to transfer the pattern itself.
Therefore, an object of the present invention is to provide a method for manufacturing a substrate with a pattern, in which when a pattern is formed on a substrate by a transfer method, a pattern having a high adhesion to the substrate can be obtained.
Furthermore, this invention makes it a subject to provide the color filter containing the said board | substrate with a pattern, and a display apparatus provided with the color filter.

The above object is achieved by the present invention described below.
<1> A substrate surface treatment step of preparing a substrate having a water contact angle of 42 degrees or more and 65 degrees or less, comprising treating the surface of the substrate with a surface treatment agent having a basic group, and the surface of the substrate In addition, a photosensitive resin layer forming step for forming a photosensitive resin layer by a transfer method and a pattern forming step for forming a pattern by pattern exposure and development of the photosensitive resin layer in this order are provided. Production method.

<2> The method for producing a substrate with a pattern according to <1>, wherein the substrate surface treatment step includes irradiating the surface of the substrate with ultraviolet rays before the treatment with the surface treatment agent.
<3> The photosensitive resin layer forming step uses a photosensitive resin transfer material having a photosensitive resin layer on a temporary support, and the surface of the substrate is treated with a surface treatment agent. <1> including stacking the photosensitive resin transfer material so that the photosensitive resin layer is in contact, and peeling the temporary support to transfer the photosensitive resin layer onto the surface of the substrate. Or the manufacturing method of the board | substrate with a pattern as described in <2>.
<4> The photosensitive resin layer in the photosensitive resin layer forming step includes a resin (A) having an acidic group in a side chain, a polymerizable compound (B), and a photopolymerization initiator (C). The manufacturing method of the board | substrate with a pattern as described in any one of <3>.
<5> The method for producing a patterned substrate according to any one of <1> to <4>, wherein the development in the pattern forming step is performed using an alkaline developer.

<6> The method for manufacturing a substrate with a pattern according to any one of <1> to <5>, wherein the substrate includes a support and a resin layer, and the surface is a surface of the resin layer.
<7> The substrate with a pattern according to any one of <1> to <6>, wherein the substrate is a color filter substrate having a colored layer including a plurality of colored pixels and a black matrix on a support. Method.
<8> The method for producing a patterned substrate according to <7>, wherein the pattern is a spacer.
<9> A color filter including a substrate with a pattern manufactured by the method for manufacturing a substrate with a pattern according to <7> or <8>.
<10> A display device comprising the color filter according to <9>.

  ADVANTAGE OF THE INVENTION According to this invention, when forming a pattern on a board | substrate by the transfer method, the manufacturing method of the board | substrate with a pattern from which the pattern which has high adhesive force with respect to a board | substrate is obtained is provided. Furthermore, according to the present invention, a color filter including the patterned substrate and a display device including the color filter are provided.

In the substrate with a pattern produced by the method for producing a substrate with a pattern according to the present invention, the reason that the pattern has a high adhesive force to the surface of the substrate is not necessarily clear, but is estimated to be due to the following reason. The
On the surface of the substrate treated with the surface treatment agent having a basic group, there is a basic group derived from the surface treatment agent. Furthermore, the water contact angle on the substrate surface is estimated to have a correlation with the amount per unit area of hydrophilic groups such as hydroxyl groups present on the substrate surface. It is estimated that the amount per unit area is specified. Accordingly, the amount of hydrophilic groups present on the substrate surface per unit area and the surface treatment agent having a basic group are determined by specifying that the water contact angle on the substrate surface is 42 degrees or more and 65 degrees or less. It is considered that the presence of the basic group on the substrate surface due to the combined effect brings about an effect that the pattern provided thereon has a high adhesive force.
In particular, when the surface of the substrate is irradiated with ultraviolet rays and then treated with a surface treatment agent having a basic group, the substrate surface and the basic group are firmly bonded, and the basic group is provided thereon. It is considered that the component constituting the pattern to be formed (for example, a resin having an acidic group such as a carboxyl group in the side chain) is firmly adhered by the interaction. This means that, on the substrate surface that has been subjected to the substrate surface treatment process according to the present invention, the adhesive force between the photosensitive resin layer formed by the transfer method and the substrate surface is high, and the photosensitive resin layer is formed by the transfer method. Can be satisfactorily transferred, and is also supported by the fact that the pattern does not fall off the substrate surface even during development in the pattern forming process according to the present invention.

  Hereinafter, a manufacturing method of a substrate with a pattern of the present invention, a color filter including a substrate with a pattern manufactured by the manufacturing method, and a display device including the color filter will be described in detail.

<Manufacturing method of substrate with pattern>
The method for producing a substrate with a pattern according to the present invention prepares a substrate having a surface with a water contact angle of 42 degrees or more and 65 degrees or less, including surface treatment of the surface of the substrate with a surface treatment agent having a basic group. A substrate surface treatment step, a photosensitive resin layer formation step for forming a photosensitive resin layer on the surface of the substrate by a transfer method, and a pattern formation step for pattern exposure and development of the photosensitive resin layer. , In this order.
[Substrate surface treatment process]
The substrate surface treatment step includes surface-treating the surface of the substrate with a surface treatment agent having a basic group, and the surface of the substrate surface-treated in this step has a water contact angle of 42 degrees or more and 65 degrees or less. .
The substrate to be processed in the substrate surface processing step may be any substrate as long as a pattern is formed on the surface thereof.
Particularly preferred substrates include color filter substrates.
The color filter substrate has a colored layer including a plurality of colored pixels and a black matrix on a support such as a glass plate. A resin layer is provided on the colored layer as desired.
The resin layer is provided as a flattening layer for flattening the surface of the colored layer, a protective layer for protecting the colored layer, or a layer for imparting other functions.
Such a resin layer is generally composed of an organic resin layer, and examples of the material include those obtained by thermosetting a thermosetting resin composition as described in Japanese Patent No. 5134982.

The substrate surface treatment step according to the present invention includes surface-treating the surface of the substrate with a surface treatment agent having a basic group, and the surface of the substrate subjected to the substrate surface treatment step has a water contact angle of 42 degrees or more and 65. Must be less than or equal to degrees.
For example, when the substrate is a color filter substrate having the resin layer as described above, the water contact angle on the surface of the resin layer is 42 simply by treating the surface of the resin layer with a surface treatment agent having a basic group. In many cases, it is difficult to prepare a product having a temperature of from 65 degrees to 65 degrees. In such a case, before the treatment with the surface treatment agent having a basic group, the surface of the resin layer is irradiated with ultraviolet rays and subsequently treated with the surface treatment agent having a basic group. Thereby, a color filter substrate having a water contact angle on the surface of the resin layer of 42 degrees or more and 65 degrees or less is obtained.
When the water contact angle on the surface of the resin layer is smaller than 42 degrees or larger than 65 degrees, it is difficult to transfer the photosensitive resin layer in the photosensitive resin layer transfer process, or transfer is possible. Even if it exists, the part which should remain as a pattern also lose | disappears by the image development in a pattern formation process, and a pattern is not formed.
The water contact angle is more preferably 53 ° to 65 °, and still more preferably 57 ° to 65 °.
In a preferred embodiment of the present invention, the above ultraviolet irradiation is performed. When the surface of the substrate, particularly the surface of the resin layer, is irradiated with ultraviolet rays and then treated with a surface treatment agent having a basic group, the adhesion of the pattern formed thereon is even higher. You can get things.

<UV irradiation>
As the light source for ultraviolet irradiation, a light source having a wavelength of 10 nm to 380 nm is used, a light source having a wavelength of 100 nm to 250 nm is preferable, and a light source having a wavelength of 150 nm to 200 nm is particularly preferable.
UV irradiation, irradiation intensity 33 mW / cm ² or more 200 mW / cm ² or less, preferably 40 mW / cm ² or more 100 mW / cm ² or less, more preferably conducted at 50 mW / cm ² or more 80 mW / cm ² or less.
The irradiation amount of the ultraviolet irradiation is selected so that the water contact angle of the surface treated with the subsequent surface treatment agent having a basic group is 42 degrees or more and 65 degrees or less. Preferably, the dose of ultraviolet irradiation is selected so that the water contact angle is in the range of 53 ° to 65 °, more preferably in the range of 57 ° to 65 °.
If Shimese a measure of dose energy of ultraviolet radiation, for example, a 300 mJ / cm ² or more 650 mJ / cm ² or less.
A preferred example of a light source that performs such ultraviolet irradiation is an excimer lamp.

<Surface treatment agent having basic group>
The substrate surface treatment step according to the present invention includes treating the surface of the substrate with a surface treatment agent having a basic group.
As the basic group of the surface treatment agent, an amino group is preferable.
The surface treatment agent having a basic group preferably has a functional group that reacts with the surface of the substrate in addition to the basic group. Examples of functional groups that react with the surface of the substrate include silanol groups.
A preferred group of surface treatment agents having a basic group includes, for example, silane coupling agents having a basic group. Specific examples of the silane coupling agent having such a basic group are listed below.

  Examples of the bifunctional silane coupling agent include N- [3- (meth) acryloxy-2-hydroxypropyl] -3-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldiethoxysilane, and γ-aminopropylmethyl. Dimethoxysilane, 4-aminobutylmethyldiethoxysilane, 11-aminoundecylmethyldiethoxysilane, m-aminophenylmethyldimethoxysilane, p-aminophenylmethyldimethoxysilane, 3-aminopropylmethyldis (methoxyethoxyethoxy) silane 3- (m-aminophenoxy) propylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, N -(6- Aminohexyl) aminomethylmethyldiethoxysilane, N- (6-aminohexyl) aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -11-aminoundecylmethyldimethoxysilane, (aminoethylaminomethyl) phenethylmethyl Examples include dimethoxysilane, N-3-[(amino (polypropyleneoxy))] aminopropylmethyldimethoxysilane, bis (2-hydroxyethyl) -3-aminopropylmethyldiethoxysilane, and the like.

  Examples of trifunctional silane coupling agents include N- [3- (meth) acryloxy-2-hydroxypropyl] -3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, and γ-aminopropyltrimethoxysilane. 4-aminobutyltriethoxysilane, 11-aminoundecyltriethoxysilane, m-aminophenyltrimethoxysilane, p-aminophenyltrimethoxysilane, 3-aminopropyltris (methoxyethoxyethoxy) silane, 3- (m -Aminophenoxy) propyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (6-aminohexyl) Aminomethyltriethoxysila N- (6-aminohexyl) aminopropyltrimethoxysilane, N- (2-aminoethyl) -11-aminoundecyltrimethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N-phenyl-γ -Aminopropyltrimethoxysilane, N-phenyl-γ-aminomethyltriethoxysilane, (cyclohexylaminomethyl) triethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, and the like.

As a method of treating the surface of a substrate with a surface treatment agent having a basic group, a solution obtained by dissolving a surface treatment agent having a basic group in a good solvent (for example, alcohol such as methanol) is applied to the surface of the substrate. Examples of the method include coating by a known coating method such as spin coating, roll coating, and spray coating, or immersing the substrate in the above solution.
The concentration of the surface treatment agent solution having a basic group is preferably such that the concentration of the surface treatment agent is 0.1% by mass or more and 0.5% by mass or less.
Moreover, the temperature at the time of a process has the preferable range of 5 to 40 degreeC.
In the case of the treatment by dipping, the dipping time is preferably 10 seconds or more and 3 minutes or less.
After immersion, it is preferable to wash with water at 5 to 40 degrees for 30 seconds to 5 minutes.
After washing with water, it is preferably dried at a temperature of 80 ° C. to 130 ° C. for 30 seconds to 5 minutes.

[Photosensitive resin layer forming step]
A photosensitive resin layer is provided on the surface of the substrate subjected to the substrate surface treatment process as described above by a transfer method. A pattern forming process to be described later is performed on the photosensitive resin layer, and a pattern is formed on the substrate.
A preferred example of the photosensitive resin layer for forming such a pattern includes a photo spacer. Hereinafter, although the case where the photosensitive resin layer is a photo spacer will be mainly described, the present invention is not limited to this.

<Photosensitive resin transfer material>
In order to provide the photosensitive resin layer on the surface of the substrate by transfer, it is preferable to use a separately manufactured photosensitive resin transfer material.
Such a photosensitive resin transfer material has a configuration in which a photosensitive resin layer is provided on a temporary support. It is preferable to include a thermoplastic resin layer and / or an intermediate layer between the temporary support and the photosensitive resin layer. When the thermoplastic resin layer and the intermediate layer are included, it is preferable to include the thermoplastic resin layer and the intermediate layer in this order from the temporary support side. Furthermore, it is preferable to provide a cover film on the surface of the photosensitive resin layer.
By using the photosensitive resin transfer material having the thermoplastic resin layer, even if the surface of the substrate has irregularities, it becomes easy to transfer the photosensitive resin layer in close contact along the irregularities.
As the intermediate layer, a layer having a function as an oxygen barrier layer is used. When the photosensitive resin transfer material having such an intermediate layer is used, the inhibition of curing of the photosensitive resin layer by oxygen can be reduced during pattern exposure in a pattern forming process described later.
Providing the above cover film reduces damage of the photosensitive resin layer when handling the photosensitive resin transfer material, and further reduces deterioration of the photosensitive resin layer of the photosensitive resin transfer material during storage. Is possible.
Regarding the temporary support, the thermoplastic resin layer, the intermediate layer, the cover film, and other layers constituting the photosensitive resin transfer material, and the method for producing the photosensitive resin transfer material, paragraph No. [ [0024] It is the same as the configuration and manufacturing method described in [0030].

(Photosensitive resin layer)
The photosensitive resin layer of the photosensitive resin transfer material may be anything as long as it is for forming a pattern, but development in the pattern forming process described later can be performed using an alkali developer. It is preferable. The photosensitive composition constituting such a photosensitive resin layer contains at least a resin (A) having an acidic group in the side chain, a polymerizable compound (B), and a photopolymerization initiator (C). Moreover, it can comprise using other components, such as a coloring agent and surfactant, as needed.

-Resin (A)-
Resin (A) has an acidic group in the side chain. Having an acidic group in the side chain means having 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 has an acidic group described later. As shown in the specific examples of the monomer, it includes that an acidic group may be bonded via a linking group.
Similarly to the above, the group having the following ethylenically unsaturated group means having a structural unit (group) having an ethylenically unsaturated group in the side chain, and the ethylenically unsaturated group is directly bonded to the main chain. Even if it is a form to do, as shown in the specific example of the monomer which has the ethylenically unsaturated group mentioned later, it includes that an ethylenically unsaturated group may couple | bond together through a coupling group.
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 having other groups (L) (1 mol%) as necessary. Also good. 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 carboxy group and a phenolic hydroxyl group are preferable from the viewpoint of excellent developability and water resistance of the cured film.

  The monomer used for having 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 preferred, and (meth) acrylates are more preferred.

  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, (meth) acrylic acid and the like are preferable in terms of excellent developability and low cost.

The “ethylenically unsaturated group in the side chain” is not particularly limited, and the ethylenically unsaturated group is preferably a (meth) acryloyl group. 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, styrene, vinyl ether, dibasic acid anhydride group, vinyl ester group, hydrocarbon having no branched and / or alicyclic structure. And monomers having an alkenyl group.
There is no restriction | limiting in particular as said vinyl ether group, For example, a butyl vinyl ether group etc. are mentioned.

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

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

  Specific examples of the resin (A) include compounds represented by compounds P-1 to P-35 described in paragraph numbers [0057] to [0063] of JP-A-2008-146018.

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

  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 less likely to be crushed, the crosslinking is less likely to be poor, and the spacer shape after development is good (there is no residue around the spacer).

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

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

The resin (A) has a glass transition temperature (Tg) of 40 to 180 ° C. and a weight average molecular weight of 10,000 to 100,000, whereby a photospacer having good developability and mechanical strength can be obtained. This is preferable.
Furthermore, the preferable example of the said resin (A) has more preferable each combination of the said preferable molecular weight, glass transition temperature (Tg), and an acid value.

The 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%, 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 “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 “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.

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

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

  The total content of the resin (A) and the resin that can be used in combination is preferably 5% by mass to 70% by mass with respect to the total solid content of the photosensitive composition, and is preferably 10% by mass to 50% by 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 has shown that solid content.

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

In the relationship with the resin (A), the mass ratio ((C) / (B) ratio) of the polymerizable compound (B) to the resin (A) is preferably 0.5 to 2.0, and It is more preferably 6 to 1.4, and particularly preferably 0.7 to 1.2. When the ratio (C) / (B) is within the preferred range, a photospacer having good developability and mechanical strength can be obtained.
As content of the said photoinitiator (C), 0.1 mass%-20 mass% are preferable with respect to resin (A), and 0.5 mass%-10 mass% are more preferable.

  In the present invention, it is particularly preferable that the photosensitive composition is for a photospacer because the effect of the present invention is most exhibited. Preferable examples of such a photosensitive composition for a photospacer include those described in Japanese Patent Application Laid-Open No. 2010-237589.

<Transfer of photosensitive resin layer using photosensitive resin transfer material>
Transferring the photosensitive resin layer of the photosensitive resin transfer material onto the surface of the substrate using the photosensitive resin transfer material is performed as follows.
First, when the photosensitive resin transfer material has a cover film, the cover film is peeled off to expose the surface of the underlying photosensitive resin layer.
Next, the substrate and the photosensitive resin transfer material are laminated by heating and / or pressing so that the exposed surface of the photosensitive resin layer is in contact with the surface of the substrate.
Next, the temporary support body of the photosensitive resin transfer material is peeled from the laminated body obtained by lamination. Thereby, the photosensitive resin layer of the photosensitive resin transfer material is transferred to the surface of the substrate. At this time, when the photosensitive resin transfer material has the above-described thermoplastic resin layer and / or intermediate layer, the thermoplastic resin layer and / or intermediate layer is also transferred to the surface of the substrate. That is, the photosensitive resin layer and the intermediate layer and / or thermoplastic resin layer thereon are transferred together on the surface of the substrate. In addition, when it has an intermediate | middle layer and a thermoplastic resin layer, it has a photosensitive resin layer, an intermediate | middle layer, and a thermoplastic resin layer in order from the surface of a board | substrate.
Specific examples of the laminate include laminators and lamination methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From the viewpoint of low foreign matter, it is preferable to use the method described in JP-A-7-110575.

[Pattern formation process]
The pattern forming process according to the present invention includes pattern exposure and development of the photosensitive resin layer transferred onto the surface of the substrate as described above.
Examples of the pattern forming step include formation examples described in paragraph numbers [0071] to [0077] of JP-A-2006-64921 and paragraph numbers [0040] to [0051] of JP-A-2006-23696. These processes are also suitable examples in the present invention.

For example, when forming a spacer on the surface of the color filter substrate, exposure is performed using a commercially available proximity type exposure machine (for example, manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) through a mask for forming the spacer. It is preferable. Examples of the plateau used for pattern exposure include medium to ultrahigh pressure mercury lamps, xenon lamps, metal halide lamps, and the like. The exposure amount is appropriately selected (for example, 300 mJ / cm ² ) according to the sensitivity of the photosensitive resin layer.
The pattern-exposed photosensitive resin layer is then developed.
Development can be performed by a known method. For example, a dilute aqueous solution of an alkaline substance is used as the developer, but it may be further added with a small amount of an organic solvent miscible with water. Prior to the development, pure water is preferably sprayed with a shower nozzle or the like to uniformly wet the surfaces of the photosensitive resin composition layer, the intermediate layer, and / or the thermoplastic resin layer.

  Examples of the alkaline substance used in the developer include alkali metal hydroxides (for example, sodium hydroxide, potassium hydroxide), alkali metal carbonates (for example, sodium carbonate, potassium carbonate), alkali metal bicarbonates ( For example, sodium hydrogen carbonate, potassium hydrogen carbonate), alkali metal silicates (for example, sodium silicate, potassium silicate), alkali metal metasilicates (for example, sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine Monoethanolamine, morpholine, tetraalkylammonium hydroxides (for example, tetramethylammonium hydroxide), trisodium phosphate, and the like. The concentration of the alkaline substance is preferably from 0.01 to 30% by mass, and the pH of the developer is preferably from 8 to 14.

  Examples of the “water-miscible organic solvent” used in the developer include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ethylene glycol mono n-butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone Etc. are preferable. The concentration of the organic solvent miscible with water is preferably 0.1 to 30% by mass. Furthermore, a known surfactant can be added, and the concentration of the surfactant is preferably 0.01 to 10% by mass.

The developer can be used as a bath solution or a spray solution. When removing the uncured portion of the photosensitive resin composition layer, methods such as rubbing with a rotating brush or wet sponge in the developer can be appropriately combined.
The temperature of the developing solution during development is usually preferably from about room temperature (20 ° C.) to 40 ° C. The development time depends on the composition of the photosensitive resin layer, the alkalinity and temperature of the developer, and the type and concentration when an organic solvent is added, but is usually from 10 seconds to 2 minutes.
In this way, a pattern is formed on the surface of the substrate.

When the intermediate layer and / or the thermoplastic resin layer are provided on the photosensitive resin layer transferred onto the substrate, the intermediate layer and / or the thermoplastic resin layer are removed prior to the above development. Preferably it is done. The treatment liquid used for such removal is preferably an aqueous solution containing an organic alkaline substance such as monoethanolamine or triethanolamine. Furthermore, the aqueous solution containing an organic alkaline substance may contain an organic solvent miscible with water such as benzyl alcohol and an anionic surfactant such as sodium n-butylnaphthalenesulfonate.
By showering the treatment liquid as described above into the intermediate layer and / or the thermoplastic resin layer, the intermediate layer and / or the thermoplastic resin layer is removed, and the underlying photosensitive resin layer is exposed.
Thereafter, air is blown to drain the treatment liquid adhering to the surface of the photosensitive resin layer, and then pure water is washed by a shower for 10 seconds, and air is further blown to leave the pure water remaining on the surface of the photosensitive resin layer. The above-described development is performed after draining the liquid. It is also possible to add a washing step after the development.

The pattern obtained by the development may be further subjected to heat treatment (also referred to as baking treatment). By this heat treatment, the strength of the pattern can be improved.
As a heat treatment method, various conventionally known methods can be used. That is, for example, a method of storing a plurality of substrates in a cassette and processing them with a convection oven, a method of processing one by one with a hot plate, a method of processing with an infrared heater, and the like.
Moreover, as baking temperature (heating temperature), it is 150-280 degreeC normally, Preferably it is 180-250 degreeC. The heating time varies depending on the baking temperature. When the baking temperature is 240 ° C., the heating time is preferably 10 to 120 minutes, and more preferably 30 to 90 minutes.

You may perform post exposure before the said heat processing.
As the light source used for the post-exposure, any light source that can irradiate light (eg, 365 nm, 405 nm) including the photosensitive wavelength of the photosensitive resin layer can be selected and used.
Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned.
The exposure may be an exposure to compensate for the exposure, usually at ^{50mJ / cm 2 ~5000mJ / cm 2} , preferably ^{200mJ / cm 2 ~2000mJ / cm 2} , more preferably 500 mJ / ^cm 2 ~ 1000 mJ / cm ² .
As described above, a pattern is formed on the substrate.

<Display device>
A display device using a color filter having the spacers manufactured as described above as a pattern will be described taking a liquid crystal display device as an example.
As one of liquid crystal display devices, a liquid crystal layer and liquid crystal driving means (simple matrix driving method and active matrix driving method) are provided between a pair of supports (including the substrate for a liquid crystal display device of the present invention) at least one of which is transparent. Including at least).

  In this case, the substrate for a liquid crystal display device of the present invention is a color filter substrate having the above spacer as a pattern. In the liquid crystal display device provided with this color filter substrate, the occurrence of cell gap unevenness (cell thickness fluctuation) between the color filter substrate and the counter substrate is suppressed, and the occurrence of display unevenness such as color unevenness is effectively prevented. be able to. Thereby, the produced liquid crystal display element can display a vivid image.

  As another embodiment of the liquid crystal display element, at least one of the pair of light-transmitting supports (at least one of which is a patterned substrate manufactured according to the present invention) is provided between the liquid crystal layer and the liquid crystal drive. And the liquid crystal driving means has an active element (for example, TFT), and is configured to be regulated to a predetermined width by a spacer having a uniform height between the pair of substrates and having excellent deformation recovery properties. is there.

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

  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). For example, the liquid crystal display device of the present invention can be suitably applied to various liquid crystal display devices.

  The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, side industry research committee, published in 1994)”. The liquid crystal display device of the present invention is not particularly limited except that it includes the liquid crystal display 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 spacer, and the like except that it includes the patterned substrate manufactured according to the present invention described above. It can be generally constructed using various members such as a viewing angle compensation film, an antireflection film, a light diffusion film, and an antiglare film. Regarding these members, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima, CMC Co., Ltd., published in 1994)”, “Current Status and Future Prospects of the 2003 Liquid Crystal Related Market (Part 2)” (Fuji Chimera Research Institute, Inc., 2003, etc.) ”.

  As mentioned above, although the manufacturing method of the substrate with a pattern of this invention demonstrated mainly the case where a board | substrate is a color filter board | substrate, manufacture of the substrate with a pattern of this invention is applicable also to board | substrates other than a color filter board | substrate. For example, a substrate used in a process for manufacturing a touch panel, a substrate used in a process for manufacturing an EL element, and the like can be given.

  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.

Example 1
<Preparation of photosensitive resin transfer material for spacer>
On a 75 μm thick polyethylene terephthalate film temporary support (PET temporary support), a coating solution for a thermoplastic resin layer having the following formulation A was applied, dried at 100 ° C. for 2 minutes, and further at 120 ° C. for 1 minute. It dried and formed the thermoplastic resin layer whose layer thickness after drying is 18 micrometers. 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 A] (Coating solution for thermoplastic resin layer)
・ Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (= 55 / 11.7 / 4.5 / 28.8 [molar ratio], weight average molecular weight 90,000) 58.4 parts Styrene / acrylic acid copolymer (= 63/37 [molar ratio], weight average molecular weight 8,000) ... 136 parts · 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane
... 90.7 parts-Surfactant solution 1 (below) ... 5.4 parts-Methanol ... 111 parts-1-methoxy-2-propanol ... 63.4 parts-Methyl ethyl ketone ... 534 parts

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

  Next, an intermediate layer coating solution comprising the following formulation B is applied onto the thermoplastic resin layer, dried at 80 ° C. for 1 minute, further dried at 120 ° C. for 1 minute, and the layer thickness after drying is A 1.6 μm intermediate layer was laminated.

[Prescription B] <Coating liquid for intermediate layer>
Polyvinyl alcohol <PVA-205, saponification rate 88%, manufactured by Kuraray Co., Ltd.>
... 3.22 parts ・ Polyvinylpyrrolidone <PVP K-30, manufactured by IS Japan Co., Ltd.>
... 1.49 parts · Methanol ... 42.9 parts · Distilled water ... 52.4 parts

  Next, a photosensitive resin layer coating solution having the following formulation C is applied onto the intermediate layer, followed by drying at 100 ° C. for 2 minutes, and further drying at 120 ° C. for 1 minute. A photosensitive resin layer of 3.0 μm was laminated.

[Prescription C] <Coating solution for photosensitive resin layer>
1-methoxy-2-propyl acetate 444.9 parts Methyl ethyl ketone 230.9 parts Solsperse 20000 (manufactured by Ashibia) 3.180 parts Resin solution <Structure unit of P-25 below (x: l: y : Z ratio is on a molar basis.) 45 parts of polymer (weight average molecular weight = 35,000), 15 parts of 1-methoxy-2-propylacetate and 40 parts of 1-methoxy-2-propanol> 190 .1 part-polymeric compound mixture solution B1-1 <dipentaerythritol hexaacrylate: 38%, dipentaerythritol pentaacrylate: 38%, and 1-methoxy-2-propyl acetate: 24%> ... 27.02 parts -Mixture of the following polymerizable compounds B2-1 <n = 1: Tripentaerythritol octaacrylate content 85%, The total of n = 2 and n = 3 is 15% as a pure product>
... 34.01 parts · Urethane monomer <NK Oligo UA-32P Shin-Nakamura Chemical Co., Ltd .: non-volatile content 75%, 1-methoxy-2-propyl acetate: 25%> ... 12.83 parts · Photopolymerization initiator <Irgacure 379EG (manufactured by BASF)> 3.157 parts ・ 5% solution of Victoria Pure Blue NAPS (Hodogaya Chemical Co., Ltd.) (solid content 5%, methanol 26%, methyl ethyl ketone 69%) ... 53.04 parts・ Megafac F-784F (Dainippon Ink Chemical Co., Ltd.) 0.85666 parts

  (In the above structural formula, X: an acryloyl group, a mixture of n = 1 to 3)

  After forming the laminated structure of the PET temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer as described above, a polypropylene film having a thickness of 12 μm is further applied to the surface of the photosensitive resin layer as a cover film. Affixed by heating and pressing to obtain a photosensitive transfer material (1) for photospacer. This photosensitive transfer material for photospacer (1) was wound around a cylindrical winding core made of ABS resin and having a diameter of 3 inches, packaged with a black polyethylene film and a transparent polyethylene film, and stored.

<Preparation of color filter substrate>
1. 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 manufactured by Degussa) 26.7 parts ・ Dispersant (Dispalon DA7500 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% by weight solution of propylene glycol monomethyl ether acetate) 10 parts propylene glycol monomethyl ether acetate ... 60 copies

  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, manufactured by GETZMANN) using 0.3 mm zirconia beads to obtain a carbon black dispersion (K-1). It was.

  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 wt% 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 propylene glycol, COOH group, and acryloyl group in the side chain, propylene glycol monomethyl ether acetate Solution (solid content: 50% by mass)]
Polymerizable compound C-5: trade name TO-1382 manufactured by Toagosei Co., Ltd. (The main component is 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. )
Initiator C-7: Trade name “OXE-02” Ciba Specialty Chemicals Co., Ltd. Surfactant C-8: Trade name “Megafac R30” Dainippon Ink & Chemicals, Inc. Solvent: PGMEA = Propylene glycol monomethyl ether acetate EEP = 3-Ethoxyethyl propionate

2. Formation of Black Matrix-Photosensitive Dark Composition Layer Formation Process-
The film after post-baking using the slit coater (model number HC8000, made by Hirata Kiko Co., Ltd.) to the glass substrate (Corning Millennium 0.7mm thickness) which washed the photosensitive dark color composition CK-1 obtained. Coating was performed at a coating speed of 120 mm / second by adjusting the interval between the slit and the glass substrate and the discharge amount so that the thickness was 1.2 μm.

-Pre-bake process, exposure process-
Next, after heating (prebaking treatment) at 90 ° C. for 120 seconds using a hot plate, exposure is performed at 100 mJ / cm ² using a mirror projection type exposure machine (model number MPA-8800, manufactured by Canon Inc.). did.

-Development process-
Then, it developed with the inclination conveyance type developing device (model number SK-2200G, Dainippon Screen Mfg. Co., Ltd., inclination angle 5 °). That is, a 1.0% developer of potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronics Materials) (a diluted solution of 1 part by weight of CDK-1 and 99 parts by weight of pure water), 25 ), 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 was performed in a clean oven at 220 ° C. for 40 minutes, and a black pixel provided with a black matrix having a grid pattern in which a color pixel formation region had an opening of 90 μm × 200 μm, a thickness of 1.2 μm, and a line width of about 25 μm. A matrix substrate was formed.
When the optical density (OD) of the completed black matrix was measured using X-Rite 361T (V) (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 size 43 nm in SEM observation) 11 parts Pigment Red 177 (average particle size 58 nm in SEM observation) 4 parts Solution 5 of the following dispersion resin A-3 Dispersant ( (Product 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% by mass) 9 parts Solvent B: Propylene glycol monomethyl ether acetate 68 parts

  The above components were stirred for 1 hour using a homogenizer at 3000 rpm. The obtained mixed solution was subjected to fine dispersion treatment for 4 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads, and a red (R) dispersion (R-1). Got. 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, Ltd. ... 2 parts-Polymerizable compound: dipentaerythritol penta-hexaacrylate ... 8 parts-Start of polymerization Agent: 4- (o-bromo-pN, N-di (ethoxycarbonylmethyl) amino-phenyl) -2,6-bis (trichloromethyl) -s-triazine ... 1 part-polymerization initiator: 2-benzyl -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 1 part polymerization initiator: diethylthioxanthone 0.5 parts polymerization inhibitor p-methoxyphenol 0.001 part fluorine Surfactant (trade name: Megafac R30, manufactured by Dainippon Ink & Chemicals, Inc.)
… 0.01 parts nonionic surfactant (trade name: Tetronic R150, manufactured by ADEKA)
0.2 parts, solvent: propylene glycol n-butyl ether acetate 30 parts, solvent: propylene glycol monomethyl ether acetate 100 parts The above components are mixed and stirred, and the photosensitive coloring composition coating liquid CR-1 for red (R) Got.

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, 30% solution manufactured by Big Chemie)
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 with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads, and a green (G) dispersion (G-1 ) 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) ... 2 parts-Polymerizable compound: Dipentaerythritol penta-hexaacrylate ... 8 parts-Polymerization 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 parts polymerization inhibitor: p-methoxyphenol 0.001 part fluorine-based surfactant (product) Name: Megafac R08 Dainippon Ink and Chemicals)
... 0.02 part nonionic surfactant (trade name: Emulgen A-60 manufactured by Kao Corporation) 0.5 part solvent: propylene glycol monomethyl ether acetate 120 parts solvent: propylene glycol n-propyl ether acetate 30 parts The above composition was mixed and stirred to obtain a photosensitive coloring composition coating solution CG-1 for green (G).

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 Solution 5 of the following dispersion resin A-3 5 dispersion Agent (trade name: Disperbyk-161, 30% solution manufactured by Big Chemie)
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% by mass)) 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 finely dispersed for 4 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads, and a blue (B) dispersion (B-1 ) 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% by mass) 7 parts / epoxy resin: (trade name Celoxide 2080 manufactured by Daicel Chemical Industries) 2 parts / UV curable resin: trade name Cyclomer P ACA-250 Daicel (Made by Chemical Industries)
(Acrylic copolymer having alicyclic, COOH and acryloyl groups in the side chain, propylene glycol monomethyl ether acetate solution (solid content: 50% by mass) ... 4 parts Polymerizable compound: Dipentaerythritol pentahexaacrylate 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 ・ Fluorosurfactant (trade name: Megafac R08, manufactured by Dainippon Ink & Chemicals, Inc.)
... 0.02 part nonionic surfactant (trade name: Emulgen A-60, manufactured by Kao Corporation) 1.0 part solvent: ethyl 3-ethoxypropionate 20 parts solvent: propylene glycol monomethyl ether acetate 150 Part The above components were mixed and stirred to obtain a photosensitive coloring composition coating solution CB-1 for blue (B).

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 Dispersing 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 mg / g. The structure of dispersion resin A-3 is shown below.

<Production of RGB pixels for color filter>
-Photosensitive coloring composition layer formation process-
The obtained red (R) photosensitive coloring composition coating liquid CR-1 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, colored layer exposure step-
Next, after heating (prebaking treatment) at 100 ° C. for 120 seconds using a hot plate, exposure was performed at 90 mJ / cm ² using a mirror projection type exposure machine (model number MPA-8800, manufactured by Canon Inc.). .
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 development process, colored layer post-baking process-
Then, it developed with the inclination conveyance type developing device (model number SK-2200G, Dainippon Screen Mfg. Co., Ltd., inclination angle 5 °). That is, a 1.0% developer of potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronics Materials) (a diluted solution of 1 part by weight of CDK-1 and 99 parts by weight of pure water), 25 The shower pressure was set to 0.2 MPa at 45 ° C., and development was performed for 45 seconds, followed by washing 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, a coloring layer prebaking process, a coloring layer exposure process, a coloring layer development process, and a coloring layer post-baking process, the photosensitive coloring composition coating liquid CR-1 for red (R). A green pixel was formed in the same manner except that the green (G) photosensitive coloring composition coating solution CG-1 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.

-Resin layer (OC layer) formation process-
On the colored layer including the R pixel, G pixel, B pixel, and black matrix of the color filter obtained above, an overcoat coating solution having the following composition was further provided as follows to obtain a color filter substrate.
-Copolymer of N-methylmaleimide and glycidyl methacrylate (former: mass ratio of the latter = 6: 4, polystyrene-equivalent weight average molecular weight 50000) ... 25 parts-(γ-glycidoxypropyl) -methyltrimethoxysilane 3 parts propylene glycol monomethyl ether acetate 72 parts The above components were mixed and stirred to prepare an overcoat coating solution.
This coating solution was applied onto the colored layer of the color filter, and dried and cured at 25 ° C. for 2 minutes under vacuum. The thickness of the resin layer was 1 μm.

-Spacer formation process-
The surface of the resin layer of the color filter substrate prepared above was irradiated with UV light having a wavelength of 172 nm for 9 seconds at an irradiation intensity of 35 mW / cm ² . Next, the surface of the resin layer was treated with a 0.3% aqueous solution of KBM-603 (a silane coupling agent N-2- (aminoethyl) -3-aminopropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.) at 20 ° C. for 30 seconds. And washed with water at 20 ° C. for 1 minute and dried at 110 ° C. for 5 minutes. The contact angle with water (pure water) on the surface of the resin layer of the color filter substrate thus treated and the contact angle with diiodomethane were measured and are shown in Table 2 described later.
The contact angle was measured as follows.
The measurement of the contact angle with water was performed using a surface contact angle measuring device FACE CONTACT-ANGLE METER CA-A manufactured by Kyowa Interface Science Co., Ltd. 1.7 μL of water was allowed to stand on a substrate that was kept horizontal with the surface contact angle measurement surface facing up, and the contact angle 20 seconds after the sample was left standing.
The contact angle with diiodomethane was also measured in the same manner as the water contact angle.
On the other hand, the photosensitive transfer material for photo spacer (1) is peeled off from the black polyethylene film and the transparent polyethylene film, taken out from the surface of the cover film by using a rotary cutter from the surface of 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 a tape, the cover film was removed, and the surface of the photosensitive resin layer was exposed.

  The surface of the exposed photosensitive resin layer of the photosensitive transfer material for photospacer (1) is in contact with the surface of the resin layer that has been subjected to the UV light irradiation and silane coupling agent treatment of the color filter substrate. At the same time, using a laminator Lamic II type (manufactured by Hitachi Industries, Ltd.), a linear pressure of 100 N / cm, an upper roll of 90 ° C., and a lower roll of 130 ° C. are applied at a conveying speed of 2 m / min. Combined.

  Thereafter, the PET temporary support was peeled and removed at the interface with the thermoplastic resin layer, and both the thermoplastic resin layer and the intermediate layer of the photosensitive transfer material for photospacer (1) were transferred to the surface of the resin layer.

Next, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, the mask (quartz exposure mask having an image pattern) and the mask and the thermoplastic resin layer face each other. The distance between the mask surface and the surface of the photosensitive resin layer on the side in contact with the intermediate layer is set to 100 μm with the color filter substrate placed on the substrate in a state where the color filter substrate stands substantially parallel and vertically, and the thermoplastic resin layer is interposed through the mask. Proximity exposure was performed from the side 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 rate of 30) at 30 ° C. for 60 seconds with a flat nozzle pressure of 0.04 MPa, and the thermoplastic resin layer and the intermediate layer were removed.
Subsequently, after air was blown off on the upper surface of the glass substrate, pure water was sprayed for 10 seconds by a shower, pure water shower cleaning was performed, and air was blown to reduce a liquid pool on the substrate.
Subsequently, a sodium carbonate developer (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, and stabilizer Contained; Trade name: T-CD1 (manufactured by Fuji Film Co., Ltd.) diluted 10 times with pure water) and developed at 28 ° C. for 50 seconds at a cone type nozzle pressure of 0.15 MPa. A pattern image was obtained.
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 Using this, brush development was performed while moving at a relative speed of 1.5 m / min at 33 ° C. to obtain a desired spacer pattern.

Finally, the color filter substrate provided with the spacer pattern was subjected to heat treatment at 230 ° C. for 60 minutes (heat treatment step) to obtain a color filter substrate with a spacer.
Each of the obtained spacers had a dome shape with a circular bottom surface.
For each of the 200 spacers obtained, using a three-dimensional surface structure analysis microscope (manufacturer: ZYGO Corporation, model: New View 5022), the height from the surface of the resin layer to the highest position of the spacer (hereinafter, “high” ”, A diameter of a cross section at 97% of the height (hereinafter also referred to as“ upper bottom ”), and a diameter of a cross section on the surface of the resin layer (hereinafter also referred to as“ lower bottom ”). ) Was measured. The “height”, “upper base” and “lower base” of the smallest spacer, and the mask diameter (diameter) on which the spacer is formed are shown in Table 2 below. When some or all of the formed spacers were dropped or removed during development, “no residue” was displayed.

(Examples 2 and 3, Comparative Examples 1 to 13)
As in Example 1, except that the drying conditions of the resin layer of the color filter substrate, the UV irradiation of the resin layer and / or the silane coupling agent treatment were changed as shown in Table 1, with spacers A color filter substrate was obtained.
In each of the examples and comparative examples, the contact angle with the water (pure water) on the surface of the resin layer after the surface of the resin layer of the color filter substrate was treated with UV light irradiation and / or a silane coupling agent, and The contact angle with diiodomethane was measured in the same manner as in Example 1 and is shown in Table 2 below. Further, in the same manner as in Example 1, the height of the minimum spacer, the upper and lower bases, and the mask diameter (diameter) on which the minimum spacer is formed are shown in Table 2 described later.
Table 2 also includes “transferability” indicating whether or not the thermoplastic resin layer and the intermediate layer of the photosensitive transfer material (1) for the photospacer could be transferred to the surface of the resin layer of the color filter substrate. It was described. The case where the transfer was successful was indicated as “OK”, and the case where the transfer was not successful was indicated as “NG”.

From the results in Table 2, the following can be understood.
As in Comparative Examples 2 and 4, when the surface of the resin layer was not subjected to both UV light irradiation and surface treatment with a silane coupling agent, the water contact angle of the surface of the resin layer was greater than 65 degrees, The surface of the resin layer cannot be transferred to the photosensitive resin layer of the photosensitive transfer material for the photospacer.
As in Comparative Examples 1 and 3, just by treating the surface of the resin layer with a silane coupling agent, the water contact angle cannot be reduced to 65 degrees or less. The surface of the resin layer cannot be transferred to the photosensitive resin layer.
As in Comparative Examples 5 to 11, can the surface of the resin layer be transferred to the photosensitive resin layer of the photosensitive transfer material for the photospacer only by irradiating the surface of the resin layer with UV light (Comparative Example 5)? Even if it can be transferred, both the exposed and unexposed portions at the time of pattern exposure, that is, the entire photosensitive resin layer are removed by development, and a spacer cannot be formed on the surface of the resin layer.
As in Comparative Examples 12 and 13, when both the UV light irradiation and the surface treatment with the silane coupling agent were performed on the surface of the resin layer, when the water contact angle on the surface of the resin layer was 42 degrees or less, And 65 ° or more, the surface of the resin layer can be transferred to the photosensitive resin layer of the photosensitive transfer material for the photospacer, but the entire photosensitive resin layer is removed by development, and the surface of the resin layer A spacer cannot be formed.
On the other hand, in Examples 1 to 3 according to the present invention, it is possible to form a spacer on the surface of the resin layer.

Example 4
In the same manner as in Example 1, a black matrix, a red pixel, a green pixel, and a blue pixel were formed on a cleaned glass substrate to obtain a color filter. The surface of the colored layer including the R pixel, G pixel, B pixel, and black matrix of this color filter was irradiated with UV light having a wavelength of 172 nm at an irradiation intensity of 35 mW / cm ² for 12 seconds. Next, the surface of the resin layer was treated with a 0.3% aqueous solution of KBM-603 (a silane coupling agent N-2- (aminoethyl) -3-aminopropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.) at 20 ° C. for 30 seconds. And washed with water at 20 ° C. for 1 minute and dried at 110 ° C. for 5 minutes. The contact angle with water (pure water) on the surface of the resin layer of the color filter substrate thus treated and the contact angle with diiodomethane were measured in the same manner as in Example 1, and are shown in Table 3 to be described later. .
Spacers were formed in the same manner as in Example 1 on the surface of the color filter substrate treated as described above.
Among the obtained spacers, “height”, “upper bottom” and “lower bottom” of the smallest spacer and the mask diameter (diameter) on which the smallest spacer is formed are shown in Table 3 below.
As shown in Table 3, it was confirmed that the effect of the present invention can be obtained even in a color filter substrate without a resin layer.

Example 5 (Liquid Crystal Display Device)
A liquid crystal display device was produced as follows using the color filter substrate with a spacer produced in Example 1. A glass substrate was prepared as a counter substrate, and the PVA mode was patterned on the transparent electrode and the counter substrate of the color filter substrate obtained in Example 1, and an alignment film made of polyimide was further provided thereon.

  After that, a UV curable resin sealant is applied by a dispenser method at a position corresponding to the outer periphery of the black matrix provided so as to surround the pixel group of the color filter, and a liquid crystal for PVA mode is dropped and attached to the counter substrate. Combined. 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 produced liquid crystal display device was subjected to 10 cycles to 100 Hz of vibration in the XYZ direction of the panel continuously for 15 minutes using a vibration tester F-16000BDH / LA16AW manufactured by EMIC, and repeated three cycles. The gray display when the gray test signal was input was observed visually and with a magnifying glass, and the evaluation result was A.

<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.

Claims (10)

Treating the surface of the substrate with a surface treatment agent having a basic group, and preparing a substrate having a surface water contact angle of 42 degrees to 65 degrees;
A photosensitive resin layer forming step of forming a photosensitive resin layer on the surface of the substrate by a transfer method;
A pattern forming step of forming a pattern by pattern exposure and development of the photosensitive resin layer; and
A method for manufacturing a substrate with a pattern that includes   The method for producing a substrate with a pattern according to claim 1, wherein the substrate surface treatment step includes irradiating the surface of the substrate with ultraviolet rays before the treatment with the surface treatment agent.   The photosensitive resin layer forming step uses a photosensitive resin transfer material having a photosensitive resin layer on a temporary support, and the photosensitive resin of the photosensitive resin transfer material on the surface treated with the surface treatment agent of the substrate. 3. The method includes: stacking the photosensitive resin transfer material so that the layers are in contact with each other; and peeling the temporary support to transfer the photosensitive resin layer to the surface of the substrate. A manufacturing method of a substrate with a pattern given in 2.   The photosensitive resin layer in the said photosensitive resin layer formation process contains resin (A) which has an acidic group in a side chain, a polymeric compound (B), and a photoinitiator (C). The manufacturing method of the board | substrate with a pattern as described in any one of these.   The manufacturing method of the substrate with a pattern as described in any one of Claims 1-4 which performs the image development in the said pattern formation process using an alkali developing solution.   The said board | substrate has a support body and a resin layer, The said surface is the surface of the said resin layer, The manufacturing method of the substrate with a pattern as described in any one of Claims 1-5.   The said board | substrate is a color filter board | substrate which has a colored layer containing a some colored pixel and black matrix on a support body, The manufacturing method of the board | substrate with a pattern as described in any one of Claims 1-6.   The method for producing a substrate with a pattern according to claim 7, wherein the pattern is a spacer.   A color filter comprising a patterned substrate manufactured by the method for manufacturing a patterned substrate according to claim 7. A display device comprising the color filter according to claim 9.