JP2011039404A - Photosensitive composition for forming barrier rib of optical element, black matrix using the same and manufacturing method of the same, as well as, method of manufacturing color filter - Google Patents

Abstract

An object of the present invention is to provide a photosensitive composition for forming a partition wall of an optical element which can form a partition wall having excellent adhesion durability with a substrate when used as an optical element and has good storage stability.
An alkali-soluble resin (A) having a photocurable ethylenically unsaturated double bond, a photopolymerization initiator (B), a phosphoric acid (meth) acrylate compound (C), and a photocurable functional group. A photosensitive composition for forming a partition wall of an optical element comprising a phosphoric acid compound (D) that is not present and a black pigment (E), wherein the phosphoric acid (meth) acrylate compound (C) with respect to the total solid content in the composition ) And 0.1 to 5% by mass, and the content of the phosphoric acid compound (D) having no photocurable functional group is 10 to 100 ppm. Photosensitive composition.
[Selection] Figure 1

Description

  The present invention relates to a photosensitive composition for forming partition walls of an optical element, a black matrix using the same, a method for producing the same, and a method for producing a color filter having the black matrix.

  In recent years, partition walls between pixels of a color filter, partition walls between pixels of an organic EL (Electro-Luminescence) display element, partition walls partitioning each TFT of an organic TFT (Thin Film Transistor) array, partition walls of an ITO electrode of a liquid crystal display element As a material for forming a permanent film such as a partition wall of a circuit wiring board, a photosensitive composition has attracted attention.

  When forming the partition of an optical element using such a photosensitive composition, a partition is pattern-formed by the photolithographic method on transparent substrates, such as glass. Then, an optical element is manufactured by forming a pixel in an opening between partition walls formed on the substrate.

  In the photosensitive composition for forming a partition wall used for the production of the optical element, when the partition wall is formed, photosensitive curability and developability are required, and when the optical element is manufactured after the partition wall formation, Properties such as heat resistance, solvent resistance not dissolved in ink, etc., partially required characteristics such as ink repellency on the upper surface and ink affinity on the wall near the substrate are required. Furthermore, when used as an optical element, durability in a use environment, particularly durability of adhesion between a partition wall and a substrate is required.

  Here, as a technique for improving the adhesion between the partition walls and the substrate in the optical element, it is known to add a phosphate ester to the partition wall forming photosensitive composition. Specifically, in Patent Document 1, a compound having a photopolymerization initiation system ethylenically unsaturated double bond, a color material, and a phosphoric acid (meth) acrylate compound are blended into a photopolymerizable composition for a color filter. Thus, it is described that a photopolymerizable composition having improved developability, sensitivity, image reproducibility, and adhesion can be obtained.

  However, phosphoric acid esters such as phosphoric acid (meth) acrylate compounds usually contain phosphoric acid and are difficult to purify, so that phosphoric acid esters are used in various applications while containing phosphoric acid. Yes. Therefore, the photosensitive composition also contains phosphoric acid (meth) acrylate compound and has a problem of affecting storage stability.

Japanese Patent No. 3577754

  The present invention has been made to solve the above-described problems, and can be used to form a partition wall having excellent adhesion durability to a substrate when used as an optical element, and the partition wall of an optical element having good storage stability. It aims at providing the photosensitive composition for formation. It is another object of the present invention to provide a black matrix having excellent adhesion durability with a substrate obtained thereby, a method for producing the same, and a method for producing a color filter having the black matrix.

  The photosensitive composition for forming a partition wall of the present invention comprises an alkali-soluble resin (A) having a photocurable ethylenically unsaturated double bond, a photopolymerization initiator (B), and a phosphoric acid (meth) acrylate compound (C). , A phosphoric acid compound (D) having no photocurable functional group, and a photosensitive composition for forming a partition wall of an optical element comprising a black pigment (E), wherein the phosphorus with respect to the total solid content in the composition Content of acid (meth) acrylate compound (C) is 0.1-5 mass%, and content of the phosphoric acid compound (D) which does not have the said photocurable functional group is 10-100 ppm. It is characterized by being.

  As used herein, “phosphoric acid (meth) acrylate compound” refers to both a phosphoric acid acrylate compound and a phosphoric acid methacrylate compound, and the term “(meth) acryloyloxy” refers to both acryloyloxy and methacryloyloxy. "(Meth) acrylic acid ester" is used to mean both acrylic acid ester and methacrylic acid ester.

  This invention provides the black matrix which consists of a coating-film hardened | cured material of the photosensitive composition for partition formation of the said invention.

  Further, the present invention provides a base material, a black matrix formed on the main surface of the base material so as to partition the main surface into a plurality of sections, and a region partitioned by the black matrix on the base material. A method for producing a black matrix of an optical element having a plurality of pixels, each of which is formed by coating the photosensitive composition for partition formation of the present invention on the substrate to form a coating film, An exposure process in which only a portion of the coating film that becomes the black matrix is exposed and photocured; a developing process in which the coating film other than the photocured portion is removed to form a black matrix of the photocured portion of the coating film; and And a post-baking step of heating the formed black matrix in order.

  Further, the present invention provides a base material, a black matrix formed on the main surface of the base material so as to partition the main surface into a plurality of sections, and a region partitioned by the black matrix on the base material. A method of manufacturing a color filter having a plurality of formed pixels, wherein a black matrix is formed on a substrate by the manufacturing method of the present invention, and then the region partitioned by the black matrix on the substrate. The method for producing a color filter is characterized by comprising a step of forming the pixel by an inkjet method or a photolithography method.

  When the photosensitive composition for forming a partition wall of an optical element of the present invention is used, a black matrix (partition wall) having excellent adhesion durability to a substrate can be produced when used as an optical element. Therefore, a color having this black matrix is produced. The filter has durability. Moreover, the photosensitive composition for partition formation of this invention has good storage stability.

It is a figure which shows typically an example of embodiment of the manufacturing method of the black matrix of this invention.

Embodiments of the present invention will be described below.
[Photosensitive composition for barrier rib formation]
The photosensitive composition for forming a partition wall of the present invention comprises an alkali-soluble resin (A) having a photocurable ethylenically unsaturated double bond, a photopolymerization initiator (B), and a phosphoric acid (meth) acrylate compound (C). : 0.1 to 5% by mass with respect to the total solid content of the composition, phosphoric acid compound having no photocurable functional group (D): 10 to 100 ppm with respect to the total solid content of the composition, and black pigment ( E).

(1) Alkali-soluble resin (A) having a photocurable ethylenically unsaturated double bond (hereinafter sometimes referred to simply as “alkali-soluble resin (A)”)
The alkali-soluble resin (A) contained in the photosensitive composition for forming a partition wall of the present invention is a photosensitive resin having a photocurable ethylenically unsaturated double bond and an alkali-soluble group, that is, an acidic group in one molecule. Resin. When the alkali-soluble resin (A) has a photocurable ethylenically unsaturated double bond, the exposure part of the photosensitive composition coating film for forming a barrier rib, which includes this at the time of exposure in photolithography at the time of barrier rib formation, Radical polymerization is promoted by the action of the photopolymerization initiator (B) described later, and curing is accelerated. In the development performed after the exposure, it remains on the surface of the coating film without being removed with an alkaline developer, and the partition walls of the optical element are formed. Can be formed. In addition, when the alkali-soluble resin (A) has an alkali-soluble group, that is, an acidic group, when the partition wall is formed, during development after exposure in photolithography, the photosensitive composition coating film for forming the partition wall including this is not exposed. The portion, that is, the uncured portion can be easily removed with an alkali developer. In addition, it is preferable that alkali-soluble resin (A) does not contain a perfluoroalkyl group substantially.

  Examples of the photocurable ethylenically unsaturated double bond of the alkali-soluble resin (A) include addition polymerization such as (meth) acryloyl group, allyl group, vinyl group, and vinyl ether group. And a group in which part or all of the hydrogen atoms of these addition polymerizable unsaturated groups are substituted with a hydrocarbon group. The hydrocarbon group is preferably a methyl group.

  Moreover, as an acidic group which the said alkali-soluble resin (A) has, one or more acidic groups chosen from the group which consists of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a phosphoric acid group are mentioned.

  As the alkali-soluble resin (A), specifically, a photocurable ethylenically unsaturated monomer having a functional group capable of binding to a photocurable ethylenically unsaturated monomer having an acidic group or a reactive group. A polymer (A1) having a side chain having an acidic group and a side chain having a photocurable ethylenically unsaturated double bond, a photocurable ethylenic epoxy resin Resin (A2) etc. which introduce | transduced the unsaturated double bond and the acidic group are mentioned.

  Examples of the polymer (A1) include a photocurable ethylenically unsaturated monomer having an acidic group and a photocurable ethylenically unsaturated monomer having a functional group capable of binding to a reactive group. It is obtained by forming a side chain having a photocurable ethylenically unsaturated double bond by reacting a reactive group with a compound having a double bond after synthesis by a normal radical polymerization method.

  The resin (A2) is obtained by further reacting a polybasic carboxylic acid or its anhydride with a reaction product of an epoxy resin and a carboxyl group and a compound having a photocurable ethylenically unsaturated double bond. Are preferred.

Specific examples of the epoxy resin used in the production of the resin (A2) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenolmethane type epoxy resin, and naphthalene. An epoxy resin having a skeleton, an epoxy resin having a biphenyl skeleton represented by the following formula (B21) (where s represents an integer of 1 to 50, preferably 2 to 10), and represented by the following formula (B22) Epoxy resin (wherein R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ independently represent any one of a hydrogen atom, a chlorine atom, and an alkyl group having 1 to 5 carbon atoms, which may be the same or different from each other) And t represents an integer of 0 to 10.) and the like.

  By reacting the epoxy resin with a compound having a carboxyl group and a photocurable ethylenically unsaturated double bond, a photocurable ethylenically unsaturated double bond is introduced into the epoxy resin. Subsequently, a carboxyl group can be introduced as an acidic group by reacting this with a polybasic carboxylic acid or its anhydride.

  In this invention, it is possible to use a commercial item as resin (A2) which introduce | transduced the acidic group and the photocurable ethylenically unsaturated double bond into the said epoxy resin. Commercially available products include KAYARAD PCR-1069, K-48C, CCR-1105, CCR-1115, CCR-1163H, CCR-1166H, CCR-1159H, TCR-1025, TCR-1064H, TCR-1286H, ZAR-1535H, ZFR-1122H, ZFR-1124H, ZFR-1185H, ZFR-1492H, ZCR-1571H, ZCR-1569H, ZCR-1580H, ZCR1581H, ZCR1588H (all are trade names, manufactured by Nippon Kayaku Co., Ltd.) and the like.

  In the photosensitive composition for forming a partition wall of the present invention, the alkali-soluble resin (A) preferably has 3 or more photocurable ethylenically unsaturated double bonds in one molecule, and 6 in one molecule. It is more preferable to have the above photocurable ethylenically unsaturated double bond. Thereby, it is easy to make a difference in the alkali solubility between the exposed portion and the unexposed portion of the coating film of the resulting photosensitive composition, and a fine pattern can be formed with a smaller exposure amount.

  In order to increase the crosslinking density of the cured film and to improve the heat resistance, the photosensitive composition for forming a partition wall of the present invention is heated with an alkali-soluble resin (A), specifically, as described later. May further contain a thermosetting resin (G) that undergoes a crosslinking reaction by heat treatment after development or the like. In that case, the alkali-soluble resin (A) is molecularly designed so as to have a group capable of undergoing a crosslinking reaction with the thermosetting resin (G).

  For example, as described later, in the photosensitive composition for forming a partition wall of the present invention, a resin having an epoxy group is preferably used as the thermosetting resin (G). In that case, the alkali-soluble resin (A) is The molecule is designed to have a group capable of undergoing a crosslinking reaction with an epoxy group, specifically, a carboxyl group, a hydroxyl group, an amino group, a phosphate group, and the like. At this time, when the alkali-soluble resin (A) already has a carboxyl group, a phenolic hydroxyl group or the like as an acidic group, since these act as groups capable of undergoing a crosslinking reaction, it is not particularly necessary to introduce a new group. When the alkali-soluble resin (A) has only a sulfonic acid group, a phosphoric acid group or the like as an acidic group, any one or more of a carboxyl group, a phenolic hydroxyl group, an alcoholic hydroxyl group and the like as a group capable of crosslinking reaction Is introduced.

  10-300 mgKOH / g is preferable and, as for the acid value of alkali-soluble resin (A), 30-150 mgKOH / g is more preferable. The developability of the photosensitive composition obtained as it is the said range is favorable. The acid value refers to the number of milligrams of potassium hydroxide necessary to neutralize resin acid in 1 g of a sample, and is a value that can be measured according to the measurement method of JIS K 0070.

  The weight average molecular weight of the alkali-soluble resin (A) is preferably 500 or more and less than 20,000, and more preferably 2,000 or more and less than 15,000. Within this range, the resulting photosensitive composition has good alkali solubility and developability. In addition, a weight average molecular weight says the value which measured polystyrene as the standard substance by the gel permeation chromatography method. Hereinafter, the weight average molecular weight described in the present specification is a value measured by the same measurement method as described above.

  The photosensitive composition for forming a partition of the present invention may contain one kind of compounds classified as this as an alkali-soluble resin (A), or may contain two or more kinds. Moreover, 5-80 mass% is preferable and, as for the ratio of alkali-soluble resin (A) with respect to the total solid of the photosensitive composition for partition formation of this invention, 10-60 mass% is more preferable. Within this range, the developability of the photosensitive composition is good.

(2) Photopolymerization initiator (B)
The photopolymerization initiator (B) contained in the barrier rib-forming photosensitive composition of the present invention is not particularly limited as long as it is a compound having a function as a photopolymerization initiator, but is composed of a compound that generates radicals by light. Is preferred.

  Examples of the photopolymerization initiator (B) include α-diketones such as benzyl, diacetyl, methylphenylglyoxylate, and 9,10-phenanthrenequinone; acyloins such as benzoin; benzoin methyl ether and benzoin ethyl ether Acyloin ethers such as benzoin isopropyl ether; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2,4 -Thioxanthones such as diisopropylthioxanthone and thioxanthone-4-sulfonic acid; benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzopheno Benzophenones such as acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2′-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl- [ Acetophenones such as 4- (methylthio) phenyl] -2-morpholino-1-propanone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; anthraquinone, 2-ethyl Quinones such as anthraquinone, camphorquinone, 1,4-naphthoquinone; ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), 4-dimethylaminobenzoic acid Isoamyl, 4-dimethylamino Aminobenzoic acids such as 2-ethylhexyl benzoate; halogen compounds such as phenacyl chloride and trihalomethylphenylsulfone; acyl phosphine oxides; peroxides such as di-t-butyl peroxide; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime), ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O— Oxime esters such as acetyloxime).

  In particular, the benzophenones, aminobenzoic acids and the like may be used together with other radical initiators to exhibit a sensitizing effect. In addition, aliphatic amines such as triethanolamine, methyldiethanolamine, triisopropanolamine, n-butylamine, N-methyldiethanolamine, and diethylaminoethyl methacrylate may also be used together with a radical initiator to exhibit a sensitizing effect. .

  In addition to the above, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 1,4-butanol bis (3-mercaptobutyrate), tris (2-mercaptopropanoyloxyethyl) isocyanate Thiol compounds such as nurate and pentaerythritol tetrakis (3-mercaptobutyrate) may also be used together with a radical initiator to exhibit a sensitizing effect.

  The photosensitive composition for forming a partition wall of the present invention may contain, as a photopolymerization initiator (B), one kind of compound classified as this alone, or a mixture of two or more kinds. Good. Moreover, 0.1-50 mass% is preferable and, as for the ratio of the photoinitiator (B) with respect to the total solid of the photosensitive composition for partition formation of this invention, 0.5-30 mass% is more preferable. The developability of the photosensitive composition obtained as it is the said range is favorable.

(3) Phosphoric acid (meth) acrylate compound (C)
The phosphoric acid (meth) acrylate compound (C) contained in the barrier rib-forming photosensitive composition of the present invention includes at least an O═P structure derived from phosphoric acid and ethylene derived from a (meth) acrylic acid compound in the molecule. Although it will not restrict | limit especially if it is a compound which has a (meth) acryloyl group which is an ionic unsaturated double bond, Specifically, the phosphoric acid (meth) acrylate compound shown by following General formula (2) is mentioned.

  The photosensitive composition for forming a partition wall of the present invention contains a phosphoric acid (meth) acrylate compound (C), and has excellent adhesion durability between the partition wall obtained using the phosphoric acid (meth) acrylate compound (C) and the substrate. It is. The phosphoric acid (meth) acrylate compound (C) is considered to have a phosphoric ester structure involved in the adhesion between the partition walls and the substrate. Further, since the phosphoric acid (meth) acrylate compound (C) has a (meth) acryloyl group, it can be radically polymerized with the alkali-soluble resin (A), and phosphoric acid (meth) can be obtained by this radical polymerization. The acrylate compound (C) is firmly fixed to the partition wall. Therefore, even when used as an optical element for a long period of time, it is possible to maintain the adhesion performance for a long time without eluting from the partition walls as the phosphoric acid (meth) acrylate compound (C).

In Formula (2), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and X is an integer of 1 to 3. Y represents an oxygen atom or a group represented by the following general formula (3).
—O— (CH ₂ ) _m — (OR ¹² ) ₁ —O— (3)
Here, OR ¹² is an oxyalkylene group having 2 to 6 carbon atoms or an oxycarbonylalkylene group having 4 to 6 carbon atoms, m is an integer of 1 to 15, and l is an integer of 0 to 10.

Examples of the phosphoric acid used in the present invention (meth) acrylate compound (C), is preferably a compound represented by the general formula (2), among these compounds, Y is _{-O- (CH} 2) m -O- A compound in which (1 in the above general formula (3) is 0) is more preferable, Y is —O— (CH ₂ ) ₂ —O—, R ⁴ is a hydrogen atom, and X is 1 to 1 Particularly preferred are mono (meth) acryloyloxyethyl phosphate, di (meth) acryloyloxyethyl phosphate and tris (meth) acryloyloxyethyl phosphate, respectively.

  The photosensitive composition for forming a partition wall of the present invention may contain, as the phosphoric acid (meth) acrylate compound (C), one kind of compound classified as such, or two or more kinds. Also good. Moreover, the ratio of phosphoric acid (meth) acrylate compound (C) with respect to the total solid of the photosensitive composition for partition formation of this invention is 0.1-5 mass%, and is 0.2-3 mass%. It is more preferable. When the content of the phosphoric acid (meth) acrylate compound (C) with respect to the total solid content of the barrier rib-forming photosensitive composition is less than 0.1% by mass, there is an advantage that the obtained partition wall and the substrate have excellent adhesion durability. If it exceeds 5% by mass, the storage stability of the photosensitive composition may be lowered.

(4) Phosphoric acid compound having no photocurable functional group (D)
The phosphoric acid compound (D) having no photocurable functional group contained in the photosensitive composition for forming a partition wall of the present invention has at least an O═P structure derived from phosphoric acid in the molecule and is photocurable. Although the phosphoric acid compound which does not have the functional group is specifically, a phosphoric acid compound represented by the following general formula (4) is exemplified.

(In Formula (4), R ⁵ is a hydrocarbon group having 1 to 15 carbon atoms in which an atom adjacent to a hydrogen atom or a phosphorus atom is a carbon atom. R ⁶ is a carbon atom in which an atom adjacent to a hydrogen or oxygen atom is a carbon atom. A certain C1-C4 hydrocarbon group, x is an integer of 1-3.)

  The phosphoric acid compound (D) having no photocurable functional group represented by the general formula (4) is a subcomponent usually contained in the phosphoric acid (meth) acrylate compound (C), and phosphoric acid. The (meth) acrylate compound (C) is an indivisible phosphate compound that is difficult to purify and separate. Specific examples of the phosphoric acid compound (D) having no photocurable functional group include phosphoric acid, trimethyl phosphate, and triethyl phosphate.

  The phosphoric acid compound (D) having no photocurable functional group is a component that decreases the storage stability of the barrier rib-forming photosensitive composition. Moreover, since it cannot couple | bond with the said alkali-soluble resin (A) like a phosphoric acid (meth) acrylate compound (C), when using as an optical element after partition formation, it is a component eluted from a partition.

  In the photosensitive composition for forming a partition wall of the present invention set from such a viewpoint, the allowable amount of the phosphoric acid compound (D) having no photocurable functional group is determined as follows. It is the quantity of 10-100 ppm with respect to the total solid of a thing. When the content of the phosphoric acid compound (D) having no photocurable functional group exceeds 100 ppm, the storage stability of the barrier rib-forming photosensitive composition cannot be sufficiently obtained.

(5) Black pigment (E)
The photosensitive composition for partition formation of this invention contains a black pigment (E). Thus, the partition walls of the optical element obtained using the photosensitive composition for forming a partition wall of the present invention are black. Such a black partition wall is usually called a “black matrix”. The black matrix is typically used as a grid-like black portion surrounding three color pixels of R (red), G (green), and B (blue) of a color filter in a liquid crystal display element.

  Specific examples of the black pigment (E) contained in the photosensitive composition for forming a partition wall of the present invention include carbon black, aniline black, anthraquinone black pigment, and perylene black pigment such as C.I. I. Pigment black 1, 6, 7, 12, 20, 31 etc. are mentioned. Moreover, in this invention, the mixture of organic pigments, such as a red pigment, a blue pigment, and a green pigment, and an inorganic pigment can also be used as a black pigment (E). Among such various pigments, carbon black is preferable as the black pigment (E) used in the present invention because of its price and light shielding properties. The carbon black may be surface-treated with a resin or the like, and a blue pigment or a violet pigment may be used in combination with the carbon black in order to adjust the color tone.

The carbon black used in the present invention is preferably one having a specific surface area of 50 to 200 m ² / g by the BET method from the viewpoint of the shape of the black matrix. When the specific surface area of the carbon black used is less than 50 m ² / g, the black matrix shape may be deteriorated. If the specific surface area of the carbon black is larger than 200 m ² / g, the dispersion aid is excessively adsorbed on the carbon black, and a large amount of dispersion aid needs to be blended in order to develop various physical properties. is there.

  The bon black used in the present invention preferably has a dibutyl phthalate oil absorption of 120 cc / 100 g or less from the viewpoint of sensitivity, and a smaller one is more preferable.

  Furthermore, as carbon black used for this invention, that whose average primary particle diameter by transmission electron microscope observation is 20-50 nm is preferable. If the average primary particle size is too small, it may be difficult to disperse at a high concentration, and it is difficult to obtain a photosensitive composition with good temporal stability. If the average primary particle size is too large, black This is because the matrix shape may be deteriorated. Moreover, as an average secondary particle diameter by transmission electron microscope observation, 80-200 nm is preferable.

  When the black pigment (E) is contained in the photosensitive composition for forming a partition wall of the present invention and used for forming a black matrix or the like, the ratio of the black pigment (E) to the total solid content of the photosensitive composition is 15 to 50 mass. % Is preferable, and 20 to 40% by mass is more preferable. The photosensitive composition obtained within this range has good sensitivity, and the partition walls, that is, the black matrix to be formed have excellent light shielding properties.

  In addition, although the OD (Optical Density) value is used as a value which shows the light-shielding property of a black matrix, the OD value of the black matrix obtained by using this for the photosensitive composition for partition formation of this invention is 3-6. It is preferable to prepare so that it may become the range. That is, the type, blending amount, and the like of the black pigment (E) to be blended with the photosensitive composition for forming a partition are appropriately selected as described above so that the OD value of the black matrix falls within the above preferable range.

(6) Optional Component The photosensitive composition for forming a partition wall of the present invention contains the above components (A) to (E) as essential components, but is optional as long as the effects of the present invention are not impaired as required. Various components described below can be contained as components.

(6-1) Silane coupling agent (F)
The photosensitive composition for partition formation of this invention can contain a silane coupling agent (F) as an arbitrary component. By blending a silane coupling agent, the adhesion of the partition formed using the resulting partition-forming photosensitive composition to the substrate is further improved, which is preferable.

  Specific examples of such a silane coupling agent (F) include tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, Examples include 3-chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, heptadecafluorooctylethyltrimethoxysilane, and polyoxyalkylene chain-containing triethoxysilane. These may be used alone or in combination of two or more.

  In the photosensitive composition for partition formation of this invention, 0.1-20 mass% is preferable and, as for the ratio of the silane coupling agent (F) in the total solid, 1-10 mass% is more preferable. If the content is too small, the effect of improving the adhesion of the partition walls to the base material formed from the photosensitive composition is small, and if the content is too large, a residue may be easily generated after development, which is not preferable.

(6-2) Thermosetting resin (G)
The photosensitive composition for forming a partition of the present invention may also contain a thermosetting resin (G) as an optional component. The thermosetting resin (G) is a resin that undergoes a crosslinking reaction with the alkali-soluble resin (A) by a heat treatment, specifically, a heat treatment after development, etc., and increases the crosslink density of the resin constituting the partition wall. And an optional component used for improving heat resistance.

  The thermosetting resin (G) depends on the type of the cross-linking reactive functional group of the alkali-soluble resin (A) to be cross-linked and cured. Depending on the type, for example, an amino resin, two or more epoxy groups A compound having two or more hydrazino groups, a polycarbodiimide compound, a compound having two or more oxazoline groups, a compound having two or more aziridine groups, a polyvalent metal, or two or more mercapto groups. Compounds, polyisocyanate compounds, and the like. These may be used alone or in combination of two or more.

  Among these, as the thermosetting resin (G) to be added to the photosensitive composition for forming a partition wall in the present invention, a compound having two or more epoxy groups is preferably used from the viewpoint of solvent resistance. Specific examples of compounds having two or more epoxy groups include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol / novolak type epoxy resins, cresol / novolac type epoxy resins, trisphenol methane type epoxy resins, and bromination. Glycidyl ethers such as epoxy resins, alicyclic epoxy resins such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (2,3-epoxycyclopentyl) ether, diglycidyl hexahydrophthalate, di Glycidyl esters such as glycidyl tetrahydrophthalate and diglycidyl phthalate, glycidyl amines such as tetraglycidyl diaminodiphenylmethane and triglycidyl paraaminophenol, triglycidyl And heterocyclic epoxy resins such as isocyanurate and the like.

  The blending ratio of the thermosetting resin (G) in the barrier rib-forming photosensitive composition of the present invention is 1 to 50 mass based on the total solid content of the composition, depending on the type and use of the optical element used. %, Preferably 5 to 30% by mass. Within such a range, the crosslink density of the cured resin constituting the partition obtained by using this increases, and a partition having excellent heat resistance can be obtained.

(6-3) Polymer containing fluorine atom and / or silicon atom The photosensitive composition for forming a partition wall of the present invention further contains, as an optional component, at least one hydrogen atom substituted with a fluorine atom. A polymer containing 20 alkyl groups (however, the alkyl group may have an etheric oxygen atom between carbon atoms) and / or a group represented by the following formula (1) may be contained.

(In Formula (1), R ¹ and R ² each independently represent a methyl group or a phenyl group. N represents an integer of 1 to 200.)

  The polymer containing a fluorine atom and / or a silicon atom acts as a surfactant. Moreover, when a partition is formed using the photosensitive composition for partition formation containing this, it also has a function as an ink repellent agent which provides ink repellency to the upper surface of a partition as needed.

  When the polymer containing the fluorine atom and / or silicon atom is used as a surfactant, the number average molecular weight is preferably 500 or more and less than 30000, and more preferably 1000 or more and less than 15000. When used as an ink repellent agent, the number average molecular weight of the polymer is preferably 500 or more and less than 15000, and more preferably 1000 or more and less than 10,000. Within this range, alkali solubility and developability are good.

  When the polymer containing fluorine atoms and / or silicon atoms is used as an ink repellent agent, the fluorine content of the polymer is preferably 5 to 35% by mass from the viewpoint of ink repellency and partition wall moldability. Yes, more preferably 12 to 30% by mass. Further, the silicon content in the polymer when the polymer contains a silicon atom is preferably 0.5 to 30% by mass, more preferably 0.5 to 10% from the viewpoints of ink repellency and partition wall moldability. % By mass.

  When the polymer is used as an ink repellent agent, the polymer is an ethylenic double chain in the side chain, preferably at a rate of 3 to 100 / molecule, more preferably at a rate of 6 to 30 / molecule. It is preferable to have a bond. By having an ethylenic double bond, the polymer can be radically polymerized to the alkali-soluble resin (A) in the barrier rib-forming photosensitive composition and fixed to the upper part of the barrier rib.

  Furthermore, the polymer preferably has an acidic group, for example, at least one acidic group selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group. The reason is that the polymer having the ink repellency hardly remains in the region (hereinafter also referred to as “dot”) partitioned by the partition wall on the base material because of alkali solubility, and the ink was injected. This is because the wet-spreading property of the ink becomes good. From such a viewpoint, the acid value of the polymer is preferably 10 to 400 mgKOH / g, and more preferably 20 to 300 mgKOH / g.

  The blending ratio of the polymer containing fluorine atoms and / or silicon atoms in the photosensitive composition for forming a partition wall of the present invention depends on the type and use of the optical element to be used. It is preferable to set it as 0.1-5 mass% with respect to the total solid of a thing, and it is more preferable to set it as 0.2-3 mass%. Further, the blending ratio when blending the polymer containing fluorine atoms and / or silicon atoms as an ink repellent agent in the barrier rib-forming photosensitive composition of the present invention depends on the type and use of the optical element used. It is preferable to set it as 0.1-5 mass% with respect to the total solid of a composition, and it is more preferable to set it as 0.2-3 mass%. Within such a range, good pixels can be obtained without color mixing or white spots of color inks formed by the ink jet method at the openings between the partition walls.

(6-4) Other optional components In the photosensitive composition for forming a partition wall of the present invention, a cross-linking agent, a curing accelerator, a thickener, a plasticizer, and an antifoam are optionally added as optional components other than the above. Agents, leveling agents, repellency inhibitors, ultraviolet absorbers, fillers, and the like.
The crosslinking agent is preferably a crosslinking agent having two or more ethylenic double bonds. Thereby, the sclerosis | hardenability of the photosensitive composition for partition formation improves, and the exposure amount at the time of forming a partition can be reduced. In addition, it is preferable that a crosslinking agent does not have an acidic group substantially.

Although it does not specifically limit as a crosslinking agent, Diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,9-nonanediol Di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethoxy Isocyanuric acid triacrylate, urethane acrylate and the like, and two or more of them may be used in combination.
It is preferable that content of the crosslinking agent in the total solid of the photosensitive composition for partition formation of this invention is 5-50 mass%, and 10-30 mass% is more preferable. Within this range, the developability of the photosensitive composition will be good.

The photosensitive composition for forming a partition wall of the present invention is appropriately selected from an alkali-soluble resin (A) having a photocurable ethylenically unsaturated double bond, a photopolymerization initiator (B), and a black pigment (E). Amount, 0.1 to 5% by mass relative to the total solid content of the phosphoric acid (meth) acrylate compound (C), phosphoric acid compound having no photocurable functional group (D ) In an amount of 10 to 100 ppm with respect to the total solid content of the composition, and for the other optional components, the appropriate amounts described above are arbitrarily weighed, and these are appropriately measured for an appropriate time by an appropriate method. Can be prepared by mixing and stirring for about 30 to 120 minutes.

  In the present invention, it is possible to form the coating film by applying the thus obtained photosensitive composition for forming a partition wall to a substrate as it is, but by adding a solvent described below, It is preferable to use it for coating film formation in the form of the coating liquid to contain. In addition, in this specification, a solvent means what is not reactive.

  Specific examples of such solvents include alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol and ethylene glycol; ketones such as acetone, methyl isobutyl ketone and cyclohexanone; 2-methoxyethanol, 2 Cell sorbs such as ethoxyethanol and 2-butoxyethanol; carbitols such as 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol and 2- (2-butoxyethoxy) ethanol; methyl acetate , Ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, Ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, ethyl-3-ethoxypropionate, cyclohexanol acetate, butyl lactate, γ Esters such as butyrolactone, 3-methyl-3-methoxybutyl acetate, glycerol triacetate; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl And ether, dibutyl ether, diethylene glycol methyl ethyl ether, and the like. Other examples include chain hydrocarbons such as n-butane and n-hexane, cyclic saturated hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as toluene, xylene, and benzyl alcohol. These may be used alone or in combination of two or more.

  The amount of the solvent to be added to the barrier rib-forming photosensitive composition of the present invention depends on the composition and use of the photosensitive composition, but may be 1 to 100% by mass with respect to the total solid content. preferable.

  The addition of the solvent can be performed on the obtained photosensitive composition for forming a partition wall, but when mixing and stirring the raw material components of the photosensitive composition for partition wall formation in the preparation, the solvent is used as a raw material. A method of adding to the components and mixing and stirring together with the raw material components is efficient and preferable.

[Black Matrix of the Present Invention and Method for Producing the Same]
The photosensitive composition for forming a partition wall of the present invention is used as a material for photolithography or the like in the same manner as a normal negative photosensitive composition, and the obtained black coating cured product is a black color for a normal optical element. Partition wall, black matrix, specifically, a base material, a black matrix formed on the main surface of the base material so as to partition the main surface into a plurality of sections, and a partition with the black matrix on the base material The present invention can be applied as a black matrix of an optical element having a plurality of pixels respectively formed in the formed region.

  The present invention also provides a method for producing the black matrix using the above-described photosensitive composition for forming a partition wall of the present invention. Below, the manufacturing method of the black matrix of this invention by the photolithographic process using the photosensitive composition for partition formation of this invention is demonstrated.

  The method for producing a black matrix according to the present invention includes a base material, a black matrix formed on the main surface of the base material so as to partition the main surface into a plurality of compartments, and the black matrix on the base material. A method for producing a black matrix of an optical element having a plurality of pixels each formed in a formed region, wherein the above-described photosensitive composition for forming a partition of the present invention is applied onto the substrate to form a coating film And an exposure process in which only the black matrix portion of the coating film is exposed to light and photocured, and development is performed to remove the coating film other than the photocured portion and form a black matrix comprising the photocured portion of the coating film. It has a process and a post-baking process which heats the formed black matrix in order.

  In this specification, “applying the photosensitive composition for forming a partition wall of the present invention onto a substrate” means, for example, forming the partition wall in addition to applying the photosensitive composition for partition wall formation of the present invention as it is. It also includes applying a coating solution containing the barrier rib-forming photosensitive composition in which a solvent is added to the photosensitive composition. Therefore, in the “coating film” before the exposure step described below, the “coating film comprising the barrier rib-forming photosensitive composition” includes the coating film comprising the coating solution.

  FIG. 1 is a diagram schematically showing an example of an embodiment of a method for producing a black matrix according to the present invention. FIG. 1A is a view showing a cross section in a state where a coating film 2 made of the photosensitive composition for forming a partition wall of the present invention is formed on a substrate 1. (B) is a figure which shows an exposure process typically. (C) is sectional drawing which shows the partition 1 (black matrix) 6 formed on the base material 1 and a base material after a image development process. Hereinafter, the production method of the present invention will be specifically described with reference to FIG.

(Coating film formation process)
In order to produce a black matrix, first, as shown in a cross section in FIG. 1 (a), the partition wall-forming photosensitive composition of the present invention is applied onto a substrate 1, and then the partition wall-forming photosensitive composition is used. A coating film 2 is formed.

  The material of the substrate 1 used in the production method of the present invention is not particularly limited, but is usually a material used for a substrate for an optical element, such as various glass plates; polyester (polyethylene terephthalate, etc.) , Thermoplastic sheets such as polyolefin (polyethylene, polypropylene, etc.), polycarbonate, polymethyl methacrylate, polysulfone, polyimide, poly (meth) acrylic resin; thermosetting plastic sheets such as epoxy resin, unsaturated polyester, etc. it can. Moreover, the board | substrate which formed the insulating film, such as a silicon nitride and a polyimide, in the said base material previously can be mentioned. In particular, a heat resistant plastic such as a glass plate or polyimide is preferable from the viewpoint of heat resistance. In addition, before forming the coating film 2 of the photosensitive composition for barrier rib formation on the base material 1, wash | cleaning the application surface of the photosensitive composition for barrier rib formation of the base material 1 by alcohol cleaning, UV ozone cleaning, etc. Is preferred.

  The method of forming the barrier rib-forming photosensitive composition coating film 2 is not particularly limited as long as a coating film having a uniform film thickness is formed. Spin coating, spraying, slit coating, roll coating , Spin coating, bar coating, and other methods used for normal coating formation. Moreover, the film thickness of the coating film 2 is determined in consideration of the height of the partition wall finally obtained. In general, the thickness is preferably 0.3 to 325 μm, more preferably about 1.3 to 65 μm.

  When manufacturing the black matrix, a pre-baking step may be provided as necessary before the following exposure step performed after the coating film forming step. In the pre-bake process, the coating film 2 formed on the substrate 1 in the coating film forming process is heated. By this heating, the volatile component contained in the barrier rib forming photosensitive composition constituting the coating film or the solvent added to the barrier rib forming photosensitive composition as needed is volatilized, and the coating film has no tackiness. Is obtained. Moreover, when the photosensitive composition for barrier rib formation contains an ink repellent agent, an ink repellent agent transfers to the coating-film surface vicinity. Examples of the heating method include a method in which the coating film 2 is heat-treated at 50 to 120 ° C. for about 10 to 2000 seconds with a heating device such as a hot plate and an oven together with the base material 1.

  In addition, when the coating liquid which added the solvent to the photosensitive composition for partition formation in the said coating-film formation process is used, removal of a solvent is needed. As described above, it is possible to remove the solvent by heating in the pre-baking step, but in order to remove the solvent, a drying step such as vacuum drying other than heating (drying) may be separately provided before the pre-baking step. Further, in order to efficiently dry the coating film without causing unevenness in the appearance of the coating film, it is more preferable to use heating combined with drying by the pre-baking step and vacuum drying in combination. The conditions for vacuum drying vary depending on the type of each component, the blending ratio, and the like, but preferably 500 to 10 Pa and a wide range of about 10 to 300 seconds.

(Exposure process)
Subsequent to the coating film forming step, an exposure step whose schematic diagram is shown in FIG. That is, the light 5 is irradiated through the mask 4 of a predetermined pattern to the coating film 2 of the photosensitive composition for partition formation after drying on the base material 1. Only the predetermined pattern portion cut in the mask 4 is transmitted by the light 5, reaches the photosensitive composition coating film for forming a partition wall on the substrate 1, and only that portion is photocured. Therefore, when the partition (black matrix) is formed, the predetermined pattern is provided in a shape that matches the shape of the partition (black matrix). For example, after the following post-baking step, the average width of the partition walls (black matrix) is preferably 100 μm or less, more preferably 20 μm or less, and the average distance between adjacent partition walls (black matrix) is preferably 300 μm or less. In the present invention, it is preferable to use a mask having a pattern formed so as to be 100 μm or less.

  The exposure is a step of irradiating a desired portion of the coating film with light, and the method is not particularly limited, but it is preferably performed through a mask having a predetermined pattern as shown in FIG. In FIG.1 (b), the exposed part of the coating film irradiated with light consists of a coating film hardened | cured material of the photosensitive composition for partition formation, On the other hand, an unexposed part is the photosensitive composition for uncured partition formation. In this state, the coating film 2 itself remains.

Specific examples of the light 5 to be irradiated include visible light; ultraviolet rays; far ultraviolet rays; excimer lasers such as KrF excimer laser, ArF excimer laser, F ₂ excimer laser, Kr ₂ excimer laser, KrAr excimer laser, Ar ₂ excimer laser; X-rays: electron beam and the like. The irradiation light 5 is preferably an electromagnetic wave having a wavelength of 100 to 600 nm, more preferably a light ray having a distribution in the range of 300 to 500 nm, particularly i-line (365 nm), h-line (405 nm), and g-line (436 nm). preferable.

As the irradiation device (not shown), a known ultra-high pressure mercury lamp, deep UV lamp, or the like can be used. The exposure dose is preferably in the range of 5 to 1000 mJ / cm ² , more preferably 50 to 400 mJ / cm ² . If the exposure amount is too low, curing of the barrier rib-forming photosensitive composition serving as the barrier ribs may be insufficient, and subsequent development may cause dissolution or peeling from the substrate 1. If the exposure amount is too high, high resolution tends not to be obtained. Further, the light irradiation (exposure) time depends on the exposure amount, the composition of the barrier rib-forming photosensitive composition, the thickness of the coating film, etc., but specifically 1 to 60 seconds, preferably 5 to 20 seconds. Can be mentioned.

(Development process)
After the exposure step, development is performed using a developer, and the unexposed portion 2 on the substrate 1 shown in FIG. Thereby, the structure of the partition (black matrix) 6 formed by the coating film cured product of the photosensitive composition for partition formation on the substrate 1 and the substrate as shown in the sectional view of FIG. Is obtained. A portion surrounded by the partition (black matrix) 6 and the substrate 1 is a portion called a dot 7 where a pixel is formed by ink injection or the like. The obtained base material with a black matrix becomes a substrate that can be used for optical element production by an inkjet method or a photolithography method through a post-bake process described later.

  As the developer used for development, for example, an alkaline aqueous solution containing alkalis such as inorganic alkalis, amines, alcohol amines, and quaternary ammonium salts can be used. In addition, an organic solvent such as a surfactant or alcohol can be added to the developer in order to improve solubility and remove residues.

  The development time (time for contacting with the developer) is preferably 5 to 180 seconds. Further, the developing method may be any of a liquid piling method, a dipping method, a shower method and the like. After development, water on the substrate 1 and the partition walls (black matrix) 6 can be removed by washing with high pressure water or running water and air-drying with compressed air or compressed nitrogen.

(Post bake process)
Subsequently, it is preferable to heat the partition (black matrix) 6 on the substrate 1. Examples of the heating method include a method in which the partition wall (black matrix) 6 is heated together with the base material 1 by a heating device such as a hot plate or an oven, preferably at 150 to 250 ° C. for 5 to 90 minutes. By this heat treatment, the partition wall (black matrix) 6 made of a cured coating film of the photosensitive composition for partition formation on the substrate 1 is further cured, and the dots 7 surrounded by the partition wall (black matrix) 6 and the substrate 1 are formed. The shape is also more fixed. The heating temperature is more preferably 180 ° C. or higher. When the heating temperature is too low, the partition wall (black matrix) 6 is not sufficiently cured, so that sufficient chemical resistance cannot be obtained. Thereafter, for example, when ink is injected into the dots 7 in the inkjet coating process, There is a possibility that the partition (black matrix) 6 swells or the ink oozes due to the solvent contained in the ink. On the other hand, if the heating temperature is too high, thermal decomposition of the partition walls (black matrix) 6 may occur.

The barrier rib-forming photosensitive composition of the present invention can be used for pattern formation in which the average width of the barrier rib (black matrix) is preferably 100 μm or less, more preferably 20 μm or less. Moreover, the average of the distance (dot width) between adjacent partition walls (black matrix) is preferably 300 μm or less, more preferably 100 μm or less. Further, the average height of the partition walls (black matrix) is preferably 0.05 to 50 μm, more preferably 0.2 to 10 μm.
[Method for Producing Color Filter of the Present Invention]

  The present invention also provides a base material, a black matrix formed on the main surface of the base material so as to partition the main surface into a plurality of compartments (a black matrix produced by the method of the present invention), and the base The present invention provides a method of manufacturing a color filter having a plurality of pixels respectively formed in a region partitioned by the black matrix on a material. Below, the manufacturing method of the color filter of this invention is demonstrated.

  The method for producing a color filter of the present invention includes a base material, a black matrix formed on the main surface of the base material so as to partition the main surface into a plurality of compartments, and the black matrix on the base material. Applied to the manufacture of a color filter having a plurality of pixels formed in each of the formed regions, and after forming a black matrix on the substrate by the manufacturing method of the present invention, partitioning with the black matrix on the substrate The method has a step of forming the pixel in the formed region by an ink jet method or a photolithography method.

  In the color filter, the shape of the pixel to be formed can be any known arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type. It is done according to the shape.

  Here, in the method for producing a color filter of the present invention, after the black matrix is formed by the above-described method of the present invention, before the ink is injected into the region (dot) partitioned by the black matrix on the substrate. In addition, the surface of the substrate exposed in the dots is subjected to an ink affinity treatment by, for example, an alkali aqueous cleaning process, a UV cleaning process, a UV ozone cleaning process, an excimer cleaning process, a corona discharge process, or an oxygen plasma process. May be.

(Pixel formation by inkjet method)
In order to form a pixel by an inkjet method in a region partitioned by a black matrix on a substrate, first, R (red) is applied to the dot after the ink-repellent treatment step is performed by the inkjet method as necessary. B (blue) and G (green) inks of three colors are injected. The ink can be injected in the same manner as a normal method using an ink jet apparatus generally used in the ink jet method. The ink jet device used for such ink injection is not particularly limited, but a method in which charged ink is continuously ejected and controlled by a magnetic field, and a method in which ink is intermittently ejected using a piezoelectric element. Ink jet apparatuses using various methods such as a method of heating ink and intermittently ejecting the ink by using the bubbling can be used.

  In the present specification, “ink” is a general term for liquids having optical and electrical functions after being dried and cured, and is not limited to conventionally used coloring materials. . Similarly, “pixels” formed by injecting the ink are also used to represent sections having optical and electrical functions, which are partitioned by partition walls (black matrix).

  Here, the ink used for forming the pixel of the color filter mainly includes a coloring component, a binder resin component, and a solvent. As the coloring component, it is preferable to use pigments and dyes excellent in heat resistance, light resistance and the like. As the binder resin component, a resin that is transparent and excellent in heat resistance is preferable, and examples thereof include an acrylic resin, a melamine resin, and a urethane resin. The water-based ink contains water and, if necessary, a water-soluble organic solvent, contains a water-soluble resin or a water-dispersible resin as a binder resin component, and contains various auxiliary agents as necessary. The oil-based ink contains an organic solvent as a solvent, a resin soluble in an organic solvent as a binder resin component, and various auxiliary agents as necessary.

  In the ink jet method, it is preferable to perform drying, heat curing, and ultraviolet curing as necessary after injecting ink into the dots by the ink jet apparatus.

(Pixel formation by photolithography)
In order to form a pixel by a photolithography method in a region partitioned by a black matrix on a base material, the substrate is first cleaned as necessary, and then a color ink composition is added as in the black matrix manufacturing method. Apply to substrate. The coating method is the same as the coating method in the black matrix manufacturing method. Thereafter, similarly to the above, a color layer is formed on the dots through the pre-bake process, the exposure process, the development process, and the post-bake process. This process is performed for each of the three ink colors R (red), B (blue), and G (green) (three times in total) to complete the pixel. As the ink, a composition mainly containing a coloring component, a binder resin, and a solvent is used. As the coloring component, it is preferable to use pigments and dyes excellent in heat resistance and light resistance. As the binder resin, those similar to the alkali-soluble resin (A) and the crosslinking agent can be used.

  Thus, after forming a pixel by the inkjet method or the photolithographic method in the area | region partitioned off with the black matrix on a base material, a protective film layer is formed as needed. The protective film layer is preferably formed for the purpose of increasing the surface flatness and for blocking the eluate from the ink in the partition walls and the pixel portion from reaching the liquid crystal layer. When forming the protective film layer, it is preferable to remove the ink repellency of the partition wall in advance. If the ink repellency is not removed, the overcoat coating solution is repelled, and a uniform film thickness cannot be obtained. Examples of the method for removing the ink repellency of the partition include plasma ashing and optical ashing.

  Further, if necessary, it is preferable to form a photo spacer on a black matrix composed of partition walls in order to improve the quality of a liquid crystal panel manufactured using a color filter.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In addition, "part" used as a compounding quantity of the compound in each example means "mass part".

Moreover, the symbol of the compound used for each following example is shown next.
(I) Compound used for preparation of ink repellent agent C6FMA: CH ₂ ═C (CH ₃ ) COOCH ₂ CH ₂ (CF ₂ ) ₆ F
MAA: methacrylic acid MMA: methyl methacrylate 2-HEMA: 2-hydroxyethyl methacrylate V-70: V-70 (trade name, manufactured by Wako Pure Chemical Industries, 2,2′-azobis (4-methoxy-2,4- Dimethylvaleronitrile))
2-ME: 2-mercaptoethanol MOI: Karenz MOI (trade name, manufactured by Showa Denko KK, 2-methacryloyloxyethyl isocyanate)
DBTDL: Dibutyltin dilaurate BHT: 2,6-di-t-butyl-p-cresol (ii) Component used for preparation of photosensitive resin composition coating solution OXE02: OXE02 (trade name, manufactured by Ciba Specialty Chemicals, Ethanon 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime)
ZCR1569: KAYARAD ZCR-1569H (trade name, manufactured by Nippon Kayaku Co., Ltd., a solution of a resin in which an ethylenically unsaturated double bond and an acidic group are introduced into an epoxy resin having a biphenyl skeleton; solid content: 70%, weight average molecular weight: 4710 )
DPHA: KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)
PGMEA: Propylene glycol 1-monomethyl ether 2-acetate CB: Carbon black dispersion (average secondary particle size 120 nm, dispersion medium PGMEA, carbon black 20%, polyurethane polymer dispersant 5% with an amine value of 18 mgKOH / g)
Silica dispersion: Silica dispersion (average particle size 20 nm, dispersion medium PGMEA, solid content 30%, silica is negatively charged)
157S70: 157S70 (trade name, manufactured by Japan Epoxy Resin, novolak epoxy resin)
KBM403: KBM-403 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltrimethoxysilane)
PA: 2: 1 (mass ratio) mixture of phosphoric acid, monomethacryloyloxyethyl phosphate and dimethacryloyloxyethyl phosphate (the concentration of phosphoric acid in the mixture is 0.3% by mass)

[Synthesis Example] Preparation of ink repellent agent To an autoclave having an internal volume of 1 L equipped with a stirrer, acetone (556 g), C6FMA (96 g), MAA (4.8 g), 2-HEMA (96 g), MMA (43.2 g). ), Chain transfer agent 2-ME (6.2 g) and polymerization initiator V-70 (4.5 g) were charged, and the mixture was polymerized at 40 ° C. for 18 hours with stirring in a nitrogen atmosphere. A solution was obtained. Water was added to the obtained acetone solution of the polymer (1) for reprecipitation purification, then reprecipitation purification with petroleum ether and vacuum drying to obtain 237 g of the polymer (1). The weight average molecular weight of the polymer (1) was 5600.

  Polymer (1) (100 g), MOI (47.7 g), DBTDL (0.19 g), BHT (2.4 g) and acetone (100 g) obtained above were added to a thermometer, stirrer and heating device. The solution was charged in a glass flask having an internal volume of 500 mL and polymerized at 30 ° C. for 18 hours with stirring to obtain a solution of the polymer (2). Water was added to the obtained acetone solution of the polymer (2) for reprecipitation purification, and then reprecipitation purification with petroleum ether and vacuum drying to obtain 135 g of the polymer (2). The weight average molecular weight was 8800. The obtained polymer (2) was used as an ink repellent agent in the production of the photosensitive composition for forming a partition wall in the examples.

[Example 1]
(Preparation of photosensitive composition dilution for partition wall formation)
ZCR1569 (13.37 parts) containing alkali-soluble resin (A), OXE02 (0.94 parts) as photopolymerization initiator (B), phosphoric acid (meth) acrylate compound (C) and phosphoric acid compound (D) As a dispersion liquid of PA (0.07 parts) containing phosphoric acid, phosphoric acid PGMEA solution (0.13 parts) containing phosphoric acid in a proportion of 1% by mass as phosphoric acid compound (D), and black pigment (E) CB (40.11 parts), KBM403 (1.34 parts) as a silane coupling agent (F), 157S70 (1.14 parts) as a thermosetting resin (G), DPHA (4. 01 part), a polymer (2) (0.05 parts) as an ink repellent agent, a silica dispersion (8.91 parts) containing silica as a filler, and PGMEA (29.94 parts) as a solvent. For the formation of barrier ribs To obtain a dilution of the composition (1).
Table 1 shows the composition (% by mass) of the solid content of the obtained photosensitive composition (1) for forming a partition wall. In addition, about phosphoric acid compound (D), content was shown by ppm. As shown in Table 1, the content of the phosphoric acid (meth) acrylate compound in the total solid content of the partition wall-forming photosensitive composition is 0.22% by mass, and the content of phosphoric acid is 51.3 ppm.

(Manufacture of black matrix)
After applying the diluted solution of the barrier rib forming photosensitive composition (1) prepared above on the glass substrate AN100 (manufactured by Asahi Glass Co., Ltd., 100 mm × 100 mm, 0.7 mm thickness) as a base material using a spinner, The coating was dried on a hot plate at 100 ° C. for 2 minutes to form a 2.0 μm barrier rib-forming photosensitive composition (1).

Using a super high pressure mercury lamp, a light of 100 mJ / cm ^{2 on} the basis of i-line (365 nm) is applied to the coating film of the photosensitive composition (1) for forming a partition wall on the glass substrate obtained above as a mask. Through and exposed. The mask has a lattice pattern with a light shielding part of 100 μm × 200 μm and a light transmission part of 20 μm, and the volume of the area partitioned by the partition formed on the glass substrate, that is, the opening (dot) is 40 pL. Met.

  The glass substrate after the exposure is developed by immersing it in a 10-fold diluted aqueous solution of an inorganic alkali type developer semi-clean DL-A4 (trade name, manufactured by Yokohama Yushi Kogyo Co., Ltd.), and the unexposed part is washed away with water. Dried.

  The glass substrate (1) on which the partition walls (black matrix) were formed was obtained by heating the glass substrate after development to drying on a hot plate at 220 ° C. for 30 minutes.

  Moreover, the glass substrate (2) used for the following adhesive evaluation was produced. That is, in the production of the glass substrate (1) on which the partition walls were formed, the cured coating film of the partition wall-forming photosensitive composition (1) was made of glass in the same manner as described above except that exposure was performed without using a mask. A glass substrate (2) formed on the entire surface of one side of the substrate was obtained.

<Evaluation>
The following evaluation was performed using the dilution liquid, the glass substrate (1), and the glass substrate (2) of the obtained photosensitive composition for partition formation (1). The results are shown in the lower column of Table 1.

(1) Developability In the glass substrate (1) obtained as described above, the case where the partition wall was completely developed was judged as ◯, and the case where there was a part that was not developed was judged as ×.

(2) PCT adhesion About the glass substrate (2) obtained above, the coating film cured product was scratched in a grid pattern so that the number of cells was 25 at intervals of 2 mm with a cutter. . Next, a PCT (pressure cooker) test was performed in which the glass substrate (2) was exposed to conditions of 121 ° C., 100 RH%, and 2 atmospheres for 24 hours. Adhesive tape (made by Nichiban Co., Ltd., trade name: cello tape (registered trademark)) is pasted on the cured part of the glass substrate (2) after the test on the part of the grid made by the cutter, and this adhesive tape is peeled off immediately afterwards. It was. By visual inspection, the case where the squares were not peeled off (the number of the squares that were peeled off was 0), and the case where the squares were almost peeled off (the number of the squares that were peeled off was 1 or more) was x. The adhesion state of was evaluated.

(3) Storage stability Photosensitive composition for partition wall formation (1) After preparing the diluted solution and storing it at 23 ° C. for 2 weeks, the partition wall (black matrix) is used in the same manner as the glass substrate (1). A glass substrate (4) having a coating film cured product of the photosensitive composition for partition wall formation (1) formed on the entire surface of one side of the glass substrate in the same manner as the glass substrate (2). ) Was produced.
The developability evaluation of the above (1) was performed on the glass substrate (3) and compared with the evaluation of the glass substrate (1). Moreover, said (2) PCT adhesiveness evaluation was performed about the glass substrate (4), and it compared with the evaluation of the glass substrate (2). Compared with the results of the glass substrate (1) and the glass substrate (2) prepared using the diluent for forming the barrier rib-forming photosensitive composition (1) before storage, those obtained with equivalent results What was not made was determined as x.

[Example 2]
ZCR1569 (13.16 parts) containing alkali-soluble resin (A), OXE02 (0.92 parts) as photopolymerization initiator (B), phosphoric acid (meth) acrylate compound (C) and phosphoric acid compound (D) PA (0.53 parts), a black pigment (E) dispersion liquid CB (39.49 parts), a silane coupling agent (F) KBM403 (1.32 parts), thermosetting Silica containing 157S70 (1.12 parts) as a resin (G), DPHA (3.95 parts) as a crosslinking agent, polymer (2) (0.05 parts) as an ink repellent agent, and silica as a filler The dispersion (8.78 parts) and PGMEA (30.68 parts) as a solvent were mixed to obtain a diluted solution of the barrier rib forming photosensitive composition (2). Although the composition (mass%) of solid content of the photosensitive composition (2) for partition formation obtained in Table 1 is shown, content of a phosphoric acid (meth) acrylate compound is 1.76 mass%, and phosphoric acid The content of was 52.7 ppm.

  Using the obtained diluted solution of the barrier rib forming photosensitive composition (2), a glass substrate on which barrier ribs (black matrix) were formed in the same manner as in Example 1, the barrier rib forming photosensitive composition (2) A glass substrate having a cured coating film formed on the entire surface of one side of the glass substrate was prepared, and the same evaluation as in Example 1 was performed. The results are shown in the lower column of Table 1.

[Comparative Example 1]
ZCR1569 (13.4 parts) containing an alkali-soluble resin (A), OXE02 (0.94 parts) as a photopolymerization initiator (B), and phosphoric acid (D) as a phosphoric acid compound (D) in a proportion of 1% by mass , PGMEA solution of phosphoric acid (0.15 parts), CB (40.2 parts) as a dispersion of black pigment (E), KBM403 (1.34 parts) as silane coupling agent (F), thermosetting 157S70 (1.34 parts) as an adhesive resin (G), DPHA (4.025 parts) as a crosslinking agent, a polymer (2) (0.05 parts) as an ink repellent agent, and silica as a filler Silica dispersion (8.93 parts) and PGMEA (29.83 parts) as a solvent were mixed to obtain a diluted liquid of the barrier rib-forming photosensitive composition (3). Although the composition (mass%) of solid content of the photosensitive composition (3) for partition formation obtained in Table 1 is shown, it does not contain a phosphoric acid (meth) acrylate compound, and the content of phosphoric acid is 48. 0.7 ppm.

  Using the obtained diluted solution of the barrier rib forming photosensitive composition (3), a glass substrate on which barrier ribs (black matrix) were formed in the same manner as in Example 1, the barrier rib forming photosensitive composition (3) A glass substrate having a cured coating film formed on the entire surface of one side of the glass substrate was prepared, and the same evaluation as in Example 1 was performed. The results are shown in the lower column of Table 1.

[Comparative Example 2]
ZCR1569 (12.83 parts) containing alkali-soluble resin (A), OXE02 (0.90 parts) as photopolymerization initiator (B), phosphoric acid (meth) acrylate compound (C) and phosphoric acid compound (D) PA (1.28 parts), a black pigment (E) dispersion as CB (38.38 parts), silane coupling agent (F) as KBM403 (1.28 parts), thermosetting Silica containing 157S70 (1.09 parts) as resin (G), DPHA (3.85 parts) as a crosslinking agent, polymer (2) (0.05 parts) as an ink repellent agent, silica as a filler The dispersion (8.55 parts) and PGMEA (31.69 parts) as a solvent were mixed to obtain a diluted solution of the barrier rib-forming photosensitive composition (4). Although the composition (mass%) of solid content of the photosensitive composition (4) for partition formation obtained in Table 1 is shown, content of a phosphoric acid (meth) acrylate compound is 4.28 mass%, and phosphoric acid The content of was 128.3 ppm.

  Using the obtained diluted solution of the barrier rib forming photosensitive composition (4), a glass substrate on which the barrier rib (black matrix) was formed in the same manner as in Example 1, the barrier rib forming photosensitive composition (4) A glass substrate having a cured coating film formed on the entire surface of one side of the glass substrate was produced, and the same evaluation as in Example 1 was performed. The results are shown in the lower column of Table 1.

＊表中の配合量（質量％）は、リン酸化合物（Ｄ）のみ質量％に替えてｐｐｍで示す。

* The compounding quantity (mass%) in a table | surface replaces only the phosphoric acid compound (D) with mass%, and shows it in ppm.

  As can be seen from Table 1, the barrier rib-forming photosensitive composition of Comparative Example that does not contain the phosphoric acid (meth) acrylate compound (C) or contains a large amount of the phosphoric acid compound (D) has a storage stability and a base. Compared to not satisfying both of the material adhesion, the photosensitive composition for forming a partition wall of the example has storage stability and the black matrix obtained by using this has a durability against adhesion to a substrate. Also excellent.

  The photosensitive composition for forming a partition wall of the present invention has storage stability and a black matrix obtained by using it is excellent in adhesion durability with a base material, and thus is useful for producing a color filter and the like.

DESCRIPTION OF SYMBOLS 1 ... Base material, 2 ... Layer of photosensitive composition for partition formation, 4 ... Mask, 5 ... Light, 6 ... Partition (black matrix), 7 ... Dot

Claims (7)

Alkali-soluble resin (A) having photocurable ethylenically unsaturated double bond, photopolymerization initiator (B), phosphoric acid (meth) acrylate compound (C), phosphorus having no photocurable functional group A photosensitive composition for forming partition walls of an optical element comprising an acid compound (D) and a black pigment (E),
Phosphoric acid compound having a content of the phosphoric acid (meth) acrylate compound (C) of 0.1 to 5% by mass with respect to the total solid content in the composition and having no photocurable functional group ( A photosensitive composition for forming a partition wall, wherein the content of D) is 10 to 100 ppm.   Furthermore, the photosensitive composition for partition formation of Claim 1 containing a silane coupling agent (F).   Furthermore, the photosensitive composition for partition formation of Claim 1 or 2 containing a thermosetting resin (G). Further, an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom (however, the alkyl group may have an etheric oxygen atom between carbon atoms) and / or the following formula The photosensitive composition for partition formation in any one of Claims 1-3 containing the polymer containing group shown by (1).

(In Formula (1), R ¹ and R ² each independently represent a methyl group or a phenyl group. N represents an integer of 1 to 200.)   The black matrix which consists of a coating-film hardened | cured material of the photosensitive composition for partition formation of any one of Claims 1-4   A base material, a black matrix formed on the main surface of the base material so as to partition the main surface into a plurality of compartments, and a plurality of regions formed respectively on the base material on the black matrix. It is a manufacturing method of the black matrix of the optical element which has a pixel, Comprising: The process of apply | coating the photosensitive composition for partition formation of any one of Claims 1-5 on the said base material, and forming a coating film. And an exposure process in which only a portion of the coating film that becomes the black matrix is exposed and photosensitively cured, and a developing process in which the coating film other than the photosensitively cured portion is removed to form a black matrix that includes the photosensitive cured portion of the coating film And a post-baking step of heating the formed black matrix in order.   A base material, a black matrix formed on the main surface of the base material so as to partition the main surface into a plurality of compartments, and a plurality of regions formed respectively on the base material on the black matrix. A method for producing a color filter having pixels, wherein after forming a black matrix on a substrate by the production method according to claim 6, an inkjet method or a region partitioned by the black matrix on the substrate A method for producing a color filter, comprising a step of forming the pixel by a photolithography method.

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