JP4954194B2 - Photosensitive resin laminate - Google Patents

Description

  The present invention relates to a photosensitive resin laminate useful for manufacturing a substrate with a black matrix, a substrate with color pixels, and a color filter.

  A liquid crystal display includes a member that colors backlight light, generally called a color filter. The color filter is composed of red, green, and blue color pixels and a black matrix that partitions them. Color pixels are necessary for colorization, but black matrix is usually arranged in a grid pattern between color pixels for the purpose of preventing malfunction of TFT, improving contrast, and preventing color mixing. .

  In recent years, liquid crystal displays have been required to have higher quality. For example, in order to improve the color reproducibility of a display, it is required to increase the color purity of color pixels. Increasing the color purity decreases the backlight transmittance and decreases the brightness. If the luminance of the backlight light is increased by compensating for the decrease in the transmittance of the backlight light, the black matrix that partitions the color pixels from the color pixels cannot completely block the backlight light, and part of the light is transmitted. Moreover, since it is necessary to design a large opening, that is, a color pixel portion in order to ensure the luminance of the panel, the black matrix tends to be thinned correspondingly. Conventionally, the black matrix has been produced by a metal thin film formed by sputtering, for example, chromium. However, considering the adverse effects on the environment, it is difficult to use chromium in the future, and a black matrix made of a resin containing a black pigment using a photolithography method (hereinafter referred to as a resin black matrix) is becoming mainstream.

  In addition, the production of liquid crystal displays requires improved productivity, and color filters are no exception. For example, although the exposure area of the color filter substrate increases as the liquid crystal display becomes larger, it is difficult to make the exposure mask the same size as the substrate. Therefore, one color filter substrate is divided and repeatedly exposed. In this case, the exposure time per time greatly affects the productivity, and a highly sensitive photolithography material is required. Furthermore, simplification of the photolithography process itself such as coating, drying, exposure, and development is considered as an important productivity improvement means.

  In particular, since the resin black matrix has an original function of high light shielding properties, it is very difficult to increase the sensitivity when it is manufactured using a photosensitive resin. Further, since the light shielding property is high and only a small amount of light reaches the bottom surface as compared with the surface, it is very difficult to ensure adhesion, particularly fine line adhesion, and line width stability during over-development. Similarly, although the color pixel is not as large as the black matrix, the color pigment has absorption at the exposure wavelength, so the sensitivity is remarkably lowered.

In view of such problems, several prior arts have been disclosed. For example, Patent Document 1 discloses a photopolymerizable black composition that has a high optical density and provides a good black matrix pattern. Patent Document 2 discloses a color filter forming material in which a specific photopolymerizable resin composition is laminated on a support film. However, in any case, there has been no disclosure of a resin black matrix forming material that has sufficient sensitivity, light-shielding property, fine wire adhesion, line width stability during over-development, and simultaneously satisfies productivity.
JP 2004-69754 A JP-A-2005-208480

  The present invention provides a photosensitive resin laminate excellent in sensitivity, light shielding property, fine wire adhesion, line width stability during over-development, transferability, and productivity in forming a resin black matrix, and It aims at providing the manufacturing method of the resin black matrix which used this. It is another object of the present invention to provide a highly sensitive photosensitive resin laminate and a method for manufacturing a color pixel using the same when forming color pixels.

  As a result of intensive studies to solve the above problems, the present invention has been made.

That is, the present invention is as follows.
(1) At least a support layer and a photosensitive resin layer are laminated, and the photosensitive resin layer is
3-40% by mass of an alkali-soluble polymer represented by the following formula (I),
From an alkali-soluble polymer copolymerized with benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 100,000 and an acrylic alkali-soluble polymer having a weight average molecular weight of 3,000 to 50,000 1 to 40% by mass of at least one alkali-soluble polymer selected from the group consisting of
3 to 25% by mass of a photopolymerizable compound having an ethylenically unsaturated double bond,
0.1-20% by mass of a photopolymerization initiator,
Containing 40 to 70% by weight of a color pigment, and
The alkali-soluble polymer represented by the formula (I): an alkali-soluble polymer obtained by copolymerizing benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 100,000 and a weight average molecular weight of 3, At least one alkali-soluble polymer (mass ratio) selected from the group consisting of acrylic alkali-soluble polymers of 000 to 50,000 = 1: 5 to 16: 1
A photosensitive resin laminate comprising the photosensitive resin composition.

(In the formula (I), X is a group represented by the following formula (II), Y is a residue excluding the acid anhydride group of dicarboxylic anhydride, Z is an acid anhydride group of tetracarboxylic dianhydride. And n is an integer of 1 to 20. R ₁ and R ₂ in the following formula (II) each independently represent H or CH ₃ group.)

(2) The photosensitive resin layer is
3 to 40% by mass of the alkali-soluble polymer represented by the above formula (I),
1 to 40% by mass of an alkali-soluble polymer obtained by copolymerizing benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 100,000,
3 to 25% by mass of a photopolymerizable compound having an ethylenically unsaturated double bond,
0.1-20% by mass of a photopolymerization initiator,
Containing 40 to 70% by weight of a color pigment, and
Alkali-soluble polymer represented by formula (I): Alkali-soluble polymer (mass ratio) copolymerized with benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 100,000 = 1: 5-16: 1
The photosensitive resin laminate according to (1), comprising the photosensitive resin composition.
(3) The photosensitive resin layer is
3 to 40% by mass of the alkali-soluble polymer represented by the above formula (I),
5-40% by mass of an alkali-soluble polymer obtained by copolymerizing benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 50,000,
5-25% by mass of a photopolymerizable compound having an ethylenically unsaturated double bond,
0.1-20% by mass of a photopolymerization initiator,
Containing 40 to 70% by weight of a color pigment, and
Alkali-soluble polymer represented by formula (I): Alkali-soluble polymer (mass ratio) = 1: copolymerized with benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 50,000 The photosensitive resin laminate according to (2), which is 5 to 5: 1.
(4) Alkali-soluble polymer represented by formula (I): alkali-soluble polymer and weight-average molecular weight obtained by copolymerizing benzyl methacrylate or benzyl acrylate having a weight-average molecular weight of 3,000 to 100,000 The photosensitive composition according to (1), wherein at least one alkali-soluble polymer (mass ratio) selected from the group consisting of acrylic alkali-soluble polymers having a 3,000 to 50,000 is 2: 1 to 16: 1. Resin laminate.
(5) The photosensitive resin laminated body as described in any one of (1)-(4) which contains an oxime ester compound as a photoinitiator in the photosensitive resin composition.
(6) In any one of (1) to (4), the photosensitive resin composition contains a compound represented by the following formula (III) as a photopolymerizable compound having an ethylenically unsaturated double bond. The photosensitive resin laminated body of description.

(In the formula (III), R ₃ , R ₄ and R ₅ each independently represent H or CH ₃ group. R ₆ is a divalent linking group, an alkylene group having 2 to 8 carbon atoms, This represents a kind of group selected from the group consisting of 3 to 10 cycloalkylene groups and C 6-10 phenylene groups.)
(7) The photosensitive resin laminate according to (1), wherein the color pigment is a black pigment.
(8) A method for producing a substrate with a color pixel, comprising at least a step of laminating the photosensitive resin laminate according to any one of (1) to (4) on a substrate, an exposing step, and a developing step. .
(9) A method for producing a substrate with a black matrix, comprising at least a step of laminating the photosensitive resin laminate according to (7) on a substrate, an exposing step, a step of peeling a support layer, and a developing step.
(10) A method for producing a substrate with a black matrix, comprising at least a step of laminating the photosensitive resin laminate according to (7) on a substrate, a step of peeling a support layer, a step of exposing, and a step of developing.
(11) At least a step of forming a black matrix on the substrate by the method according to (9) or (10), at least a part of the glass substrate not covered with the black matrix is heat sensitive or photosensitive. A method for producing a color filter, which in turn includes a printing step of printing the color ink by an inkjet method.
(12) A color filter produced by the method according to (11).

  When forming the resin black matrix, the photosensitive resin laminate of the present invention has the effect of being excellent in sensitivity, light shielding properties, fine wire adhesion, line width stability during over-development, transferability, and productivity. In addition, the photosensitive resin laminate of the present invention has an effect that sensitivity is very high when forming color pixels.

  Hereinafter, the present invention will be specifically described. In addition, the photosensitive resin layer in the photosensitive resin laminated body of this invention consists of a photosensitive resin composition. When describing about the compounding quantity of each component of the photosensitive resin composition, it describes by the mass% when the whole solid content in the photosensitive resin composition is 100%.

  The photosensitive resin laminate of the present invention contains 3 to 40% by mass of an alkali-soluble polymer (hereinafter sometimes simply referred to as a compound) represented by the following formula (I) in the photosensitive resin composition. The content is 3% by mass or more from the viewpoint of sensitivity, adhesion, and line width reproducibility, and 40% by mass or less from the viewpoint of transferability from the support layer to the substrate. Transferability refers to the ability to transfer the photosensitive resin layer to the substrate when the photosensitive resin laminate of the present invention is laminated to the substrate and the support layer is peeled off before or after exposure. When the transferability is not sufficient, the unexposed part or the exposed part is peeled off from the substrate together with the support layer when the support layer is peeled off. The content is preferably 5 to 30% by mass, more preferably 8 to 25% by mass, and still more preferably 8 to 20% by mass.

(In the formula (I), X is a group represented by the following formula (II), Y is a residue excluding the acid anhydride group of dicarboxylic anhydride, Z is an acid anhydride group of tetracarboxylic dianhydride. And n is an integer of 1 to 20. R ₁ and R ₂ in the following formula (II) each independently represent H or CH ₃ group.)

  Here, the “acid anhydride group” refers to a “—CO—O—CO— group”.

  Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyl Examples include tetrahydrophthalic anhydride and glutaric anhydride.

  Examples of tetracarboxylic dianhydrides include aromatic polycarboxylic anhydrides such as pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride. Things.

  The compound represented by the above formula (I) used in the present invention can be obtained, for example, by the method described in JP-A No. 2001-354735. The compound represented by the above formula (I) has substantially no dicarboxylic anhydride residue in the polymer chain, but has at its end. Therefore, unlike a compound having a dicarboxylic acid anhydride residue in the polymer chain, it is easy to control the solution viscosity even at the same solid content concentration, improving workability during coating, improving coating properties, and making the film thickness uniform. Can be achieved.

  The compound represented by the above formula (I) used in the present invention has at least two ethylenically unsaturated double bonds capable of addition polymerization. The photosensitive resin composition containing this compound is cured by addition polymerization by the action of the photopolymerization initiator even when the optical density is high, when irradiated with light of a predetermined wavelength that activates the photopolymerization initiator. be able to. For this reason, a color filter having a high display contrast and a beautiful color of R, G, B can be manufactured. In particular, when this compound is used for forming the black matrix, this effect is remarkable in the relationship between the light shielding property and the sensitivity. As shown in the examples below, when the amount of black pigment added is increased to increase the light shielding property, the light shielding property is usually increased and the sensitivity is decreased, but the compound represented by the above formula (I) is used. The sensitivity is kept low.

  The photosensitive resin laminate of the present invention has an alkali-soluble polymer obtained by copolymerizing benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 100,000 in the photosensitive resin composition and a weight average molecular weight. 1 to 40% by mass of at least one alkali-soluble polymer selected from the group consisting of acrylic alkali-soluble polymers of 3,000 to 50,000 is contained. In general, carbon black widely used as a black pigment has a large surface area, and when used in a pigment-dispersed photosensitive resin composition, it tends to be a liquid with poor thirotropic properties and poor fluidity. In order to improve the light-shielding properties, it is necessary to add a lot of such black pigments, but it is difficult to ensure coating uniformity with the manufacturing method that applies directly to the substrate (Akitoshi Taniguchi, “Latest Color Filter Technology Trends—Component Materials “Manufacturing / Evaluation / Overseas Trends”, First Printing, Information Organization Co., Ltd., May 31, 2005, p81-101). On the other hand, in the present invention, a compound represented by the above formula (I) having excellent patterning characteristics and the alkali-soluble polymer having excellent pigment dispersion, coating stability and transferability are blended together to form a photosensitive resin composition. Further, by forming a photosensitive resin laminate, a uniform photosensitive resin layer having a high light shielding property can be easily laminated on the substrate.

  The photosensitive resin laminate of the present invention includes an alkali-soluble polymer and a weight average molecular weight obtained by copolymerizing benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 100,000 in the photosensitive resin composition. 1 to 40% by mass of at least one alkali-soluble polymer selected from the group consisting of acrylic alkali-soluble polymers having a molecular weight of 3,000 to 50,000.

  The alkali-soluble polymer obtained by copolymerizing benzyl (meth) acrylate having a weight average molecular weight of 3,000 to 100,000 will be described. Here, (meth) acryl represents methacryl and acryl. The same applies hereinafter.

    The content of the alkali-soluble polymer obtained by copolymerizing benzyl (meth) acrylate is 1 to 40% by mass. The content is more preferably 5 to 40% by mass. The content is more preferably 5% by mass or more from the viewpoint of transferability from the support layer to the substrate and laminating properties, and more preferably 40% by mass or less from the viewpoint of sensitivity, adhesion, and line width stability. The content is more preferably 8 to 30% by mass, more preferably 10 to 25% by mass, and most preferably 10 to 18% by mass.

  It is preferable that 50 to 95% by mass of benzyl (meth) acrylate is copolymerized in the alkali-soluble polymer copolymerized with benzyl (meth) acrylate. The copolymerization ratio of benzyl (meth) acrylate is preferably 50% by mass or more from the viewpoint of dispersibility of the black pigment, development residue, and laminating property, and preferably 90% by mass or less from the viewpoint of development speed. The proportion of methacrylic acid benzyl copolymerization is more preferably 60 to 90% by mass and even more preferably 70 to 90% by mass.

  The alkali-soluble polymer obtained by copolymerizing benzyl (meth) acrylate is preferably copolymerized with a monomer having a carboxyl group or a carboxylic anhydride group in the side chain. Monomers having a carboxyl group or carboxylic anhydride group in the side chain include, for example, (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, maleic acid Examples include half esters. The proportion of copolymerization of the monomer having a carboxyl group in the side chain is preferably 5% by mass or more from the viewpoint of developability, from the viewpoint of suppressing the black pigment dispersibility and the black pigment from adhering to the substrate after development. 30 mass% or less is preferable. More preferably, it is copolymerized in an amount of 5 to 20% by mass.

The alkali-soluble polymer obtained by copolymerizing benzyl (meth) acrylate can also be copolymerized with other monomers. Alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate,
(Meth) acrylates having a hydroxyl group, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate,
(Meth) acrylate having a cycloalkyl group, for example, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, adamantyl (meth) acrylate,
Other examples include (meth) acrylamide, (meth) acrylonitrile, phenyl (meth) acrylate, glycidyl methacrylate, and styrene. In particular, 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate is preferable. The proportion of other monomers in the alkali-soluble polymer is preferably 5 to 30% by mass. In particular, when 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate is used as another monomer, the copolymerization ratio is 5% by mass or more from the viewpoint of dispersibility and laminating properties of the black pigment. From the viewpoint of heat resistance and chemical resistance, 30% by mass or less is preferable. The proportion of copolymerization is more preferably 5 to 15% by mass.

  The weight average molecular weight of the alkali-soluble polymer copolymerized with benzyl (meth) acrylate is more preferably 3,000 to 50,000. The molecular weight is more preferably 50,000 or less from the viewpoint of developability, and more preferably 3,000 or more from the viewpoint of adhesion. The weight average molecular weight is more preferably 10,000 to 40,000.

  The molecular weight was measured by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK (KF-807, KF-806M). , KF-806M, KF-802.5) in series, moving bed solvent: tetrahydrofuran, polystyrene standard sample (use of calibration curve by Shodex STANDARD SM-105 manufactured by Showa Denko KK) weight average molecular weight (polystyrene conversion) As required.

  The alkali-soluble polymer obtained by copolymerizing benzyl (meth) acrylate preferably has an amount of carboxyl group of 200 to 2,000 in terms of acid equivalent. An acid equivalent shows the mass of the linear polymer which has a 1 equivalent carboxyl group. The acid equivalent is preferably 2,000 or less from the viewpoint of developability, and the acid equivalent is preferably 200 or more from the viewpoint of suppressing the black pigment from adhering to the substrate after development. The acid equivalent is more preferably 400 to 900, and even more preferably 500 to 800. In addition, the measurement of an acid equivalent uses Hiranuma Sangyo Co., Ltd. Hiranuma automatic titration apparatus (COM-555), and is measured by a potentiometric titration method using 0.1 mol / L sodium hydroxide.

  An alkali-soluble polymer copolymerized with benzyl (meth) acrylate is obtained by diluting a mixture of the above-mentioned various monomers with a solvent such as acetone, methyl ethyl ketone, isopropanol, etc., into benzoyl peroxide, azobisisobutyro The synthesis is preferably carried out by adding an appropriate amount of a radical polymerization initiator such as nitrile and stirring with heating. In some cases, the synthesis is performed while a part of the mixture is dropped into the reaction solution. After completion of the reaction, a solvent may be further added to adjust to a desired concentration. As synthesis means, bulk polymerization, suspension polymerization, and emulsion polymerization may be used in addition to solution polymerization.

  An acrylic alkali-soluble polymer having a weight average molecular weight of 3,000 to 50,000 will be described. The content of the acrylic alkali-soluble polymer having a weight average molecular weight of 3,000 to 50,000 is 1 to 40% by mass. It is 1% by mass or more from the viewpoint of transferability from the support layer to the substrate and laminating property, and 40% by mass or less from the viewpoint of sensitivity, adhesion, and line width stability. 5-40 mass% is preferable, 8-20 mass% is more preferable, and 8-15 mass% is further more preferable. The weight average molecular weight is preferably 50,000 or less from the viewpoint of dispersion stability of the pigment, and 3,000 or more from the viewpoint of maintaining appropriate alkali developability and adhesion. The weight average molecular weight is more preferably 5,000 or more and 30,000 or less, and still more preferably 10,000 or more and 30,000 or less. The molecular weight can be determined by the same measurement method as described above.

  The acrylic alkali-soluble polymer having a weight average molecular weight of 3,000 to 50,000 preferably has a carboxyl group amount of 200 to 2,000 in terms of acid equivalent. An acid equivalent shows the mass of the linear polymer which has a 1 equivalent carboxyl group. The acid equivalent is preferably 2,000 or less from the viewpoint of developability, and the acid equivalent is preferably 200 or more from the viewpoint of suppressing the black pigment from adhering to the substrate after development. The acid equivalent is more preferably 300 to 900, and still more preferably 400 to 800. The acid equivalent can be determined by the same measurement method as described above.

An acrylic alkali-soluble polymer having a weight average molecular weight of 3,000 to 50,000 is an alkyl (meth) acrylate such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
(Meth) acrylate having a hydroxyl group in the side chain, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate,
(Meth) acrylates having alicyclic side chains, for example, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, adamantyl (meth) acrylate ,
In addition, for example, one or more compounds selected from (meth) acrylamide, (meth) acrylonitrile, phenyl (meth) acrylate, glycidyl (meth) acrylate, and styrene, and a compound having a carboxylic acid such as (meth) acrylic acid. Mention may be made of copolymerized alkali-soluble polymers. From the viewpoint of the cross-sectional shape when used as a black matrix, a polymer having a molecular weight of 10,000 to 30,000 obtained by copolymerizing styrene, methyl methacrylate and methacrylic acid is preferable.

  Alkali-soluble polymer represented by the above formula (I): an alkali-soluble polymer obtained by copolymerizing benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 100,000, and a weight average molecular weight of 3 , At least one alkali-soluble polymer (mass ratio) selected from the group consisting of acrylic alkali-soluble polymers in the range of 50,000 to 50,000 = 1: 5 to 16: 1. The mass ratio is 1: 5 or more from the viewpoints of sensitivity, adhesion, and line width reproducibility, and 16: 1 or less from the viewpoints of coatability to the support layer and transferability.

  The mass ratio is preferably 1: 5 to 5: 1. From the viewpoint of sensitivity, adhesion, and line width reproducibility, 1: 5 or more is preferable. 5: 1 or less is more preferable from a viewpoint of the coating property to a support layer, and transferability. A ratio of 1: 3 to 3: 1 is more preferable.

  Alkali-soluble polymer represented by the above formula (I): alkali-soluble polymer (mass ratio) = 1 copolymerized with benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 100,000 as described above : 5 to 16: 1. The mass ratio is 1: 5 or more from the viewpoints of sensitivity, adhesion, and line width reproducibility, and 16: 1 or less from the viewpoints of coatability to the support layer and transferability.

  The mass ratio is preferably 1: 5 to 5: 1. From the viewpoint of sensitivity, adhesion, and line width reproducibility, 1: 5 or more is preferable. 5: 1 or less is more preferable from a viewpoint of the coating property to a support layer, and transferability. A ratio of 1: 3 to 3: 1 is more preferable.

  Alkali-soluble polymer represented by the above formula (I): Acrylic alkali-soluble polymer (mass ratio) having a weight average molecular weight of 3,000 to 50,000 = 1: 5 to 16: 1. The mass ratio is preferably 1: 3 to 5: 1. From the viewpoint of sensitivity, adhesion, and line width stability, 1: 3 or more is preferable. 5: 1 or less is preferable from the viewpoint of coatability to the support layer and transferability. 1: 1 to 3: 1 is more preferable.

  In the photosensitive resin composition, an alkali-soluble polymer copolymerized with benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 100,000 and a weight average molecular weight of 3,000 to 50,000. In addition to at least one alkali-soluble polymer selected from the group consisting of acrylic alkali-soluble polymers, the heat resistance, the cross-sectional shape of the black matrix, the chemical resistance, the dispersibility of the color pigment, etc. Other alkali-soluble polymers can be used in combination. Examples of other alkali-soluble polymers include carboxymethyl cellulose, carboxyethyl cellulose, carboxypropyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, cellulose resin obtained by reacting a hydroxyl group of hydroxypropyl cellulose with a polybasic acid anhydride, and novolak resin. I can do it.

  The photosensitive resin laminated body of this invention contains 3-25 mass% of photopolymerizable compounds which have an ethylenically unsaturated double bond in the photosensitive resin composition. From the viewpoint of developability, it is 3% by mass or more, and from the viewpoint of adhesion, it is 25% by mass or less. By setting the content to 25% by mass or less, an appropriate development time can be secured and sufficiently stable adhesion can be secured. The content is more preferably 5 to 20% by mass, and further preferably 5 to 15% by mass.

  The photopolymerizable compound having an ethylenically unsaturated double bond preferably includes a compound represented by the following formula (III). The content is preferably 2% by mass or more based on the total solid content in the photosensitive resin composition from the viewpoint of adhesion, and preferably 20% by mass or less from the viewpoint of transferability.

(In the formula (III), R ₃ , R ₄ and R ₅ each independently represent H or CH ₃ group. R ₆ is a divalent linking group, an alkylene group having 2 to 8 carbon atoms, This represents a kind of group selected from the group consisting of 3 to 10 cycloalkylene groups and C 6-10 phenylene groups.)
Examples of the compound represented by the formula (III) include succinic acid-modified pentaerythritol tri (meth) acrylate, phthalic acid-modified pentaerythritol tri (meth) acrylate, isophthalic acid-modified pentaerythritol tri (meth) acrylate, and terephthalic acid-modified pentaerythritol. And tri (meth) acrylate. From the viewpoint of adhesion, succinic acid-modified pentaerythritol triacrylate is preferable.

  Examples of the photopolymerizable compound having an ethylenically unsaturated double bond other than the compound represented by the above formula (III) include, for example, an average of 2 mol of propylene oxide and an average of 6 mol of ethylene oxide at both ends of bisphenol A. Polyalkylene glycol dimethacrylate to which bisphenol A is added, and polyethylene glycol dimethacrylate to which bisphenol A is added with an average of 5 moles of ethylene oxide on both ends (NK ester BPE- manufactured by Shin-Nakamura Chemical Co., Ltd.) 500), 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-di ( p-hydroxyphenyl) propanedi (meta) Acrylate, Glycerol tri (meth) acrylate, Trimethylolpropane tri (meth) acrylate, Polyoxypropyltrimethylolpropane tri (meth) acrylate, Polyoxyethyltrimethylolpropane triacrylate, Pentaerythritol tetra (meth) acrylate, Di Pentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether-tertri (meth) acrylate, bisphenol A diglycidyl ether-terdi (meth) acrylate, and β-hydroxypropyl-β ′-(acryloyloxy) propyl Phthalate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyalkyl Glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate. From the viewpoint of adhesion, pentaerythritol tetra (meth) acrylate is preferable, and it is more preferable to use in combination with the compound of the above formula (III).

  Further, for example, a compound obtained by adding 1 to 3 mol of ethylene oxide to 2-hydroxyethyl (meth) acrylate and a half ester compound of hexahydrophthalic acid, and 1 to 3 mol of ethylene oxide to 2-hydroxyethyl (meth) acrylate Half-ester compound of added compound and succinic acid, compound obtained by adding 1 to 3 mol of ethylene oxide to 2-hydroxyethyl (meth) acrylate and half-ester compound of isophthalic acid, ethylene to 2-hydroxyethyl (meth) acrylate A half ester compound of a compound obtained by adding 1 to 3 moles of oxide and terephthalic acid may be mentioned.

  Further, for example, a diisocyanate compound such as hexamethylene diisocyanate, tolylene diisocyanate, or 2,2,4-trimethylhexamethylene diisocyanate, and a compound having a hydroxyl group and a (meth) acryl group in one molecule, such as 2- Examples thereof include urethane compounds obtained by reacting hydroxypropyl acrylate and oligopropylene glycol monomethacrylate. Specifically, the compound part obtained by making hexamethylene diisocyanate and oligo propylene glycol monomethacrylate (Nippon Yushi Co., Ltd. product, Blemma-PP1000) react can be mentioned.

  The photosensitive resin laminated body of this invention contains 0.1-20 mass% of photoinitiators in the photosensitive resin composition. It is 0.1% by mass or more from the viewpoint of sensitivity and adhesion, and 20% by mass or less from the viewpoint of line width reproducibility. The content is more preferably 1 to 10% by mass, and further preferably 1 to 5% by mass.

  The photopolymerization initiator is preferably an oxime ester compound. Specifically, oxime esters such as 1-phenyl-1,2-propanedione-2-O-benzoyloxime and 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime Alternatively, compounds described in JP-T-2004-534797 can be raised. Among these, a compound represented by the following formula (IV) is preferable.

  Specific examples of the compound represented by the formula (IV) include 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate (IRGACURE OXE-02 manufactured by Ciba Specialty Chemicals).

  The photosensitive resin laminate of the present invention may be used in combination with a photopolymerization initiator, a sensitizer, a chain transfer agent, etc. other than the above formula (IV) in the photosensitive resin composition.

  Examples of the photopolymerization initiator other than the above formula (IV) include the following. Thioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2-chlorothioxanthone, 2,4,5-triarylimidazole dimers, such as 2- (o-chlorophenyl) -4,5-diphenylimidazole Dimer, 2- (o-chlorophenyl) -4,5-bis- (m-methoxyphenyl) imidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole Dimer. Also, p-aminophenyl ketones such as p-aminobenzophenone, p-butylaminophenone, p-dimethylaminoacetophenone, p-dimethylaminobenzophenone, p, p′-bis (ethylamino) benzophenone, p, p ′ -Bis (dimethylamino) benzophenone [Michler's ketone], p, p'-bis (diethylamino) benzophenone, p, p'-bis (dibutylamino) benzophenone. Moreover, quinones, for example, 2-ethylanthraquinone, 2-tert-butylanthraquinone, aromatic ketones, for example, benzoin ethers such as benzophenone, benzoin, benzoin methyl ether, and benzoin ethyl ether. Acridine compounds such as 9-phenylacridine. Triazine compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2 , 4-Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphtho-) 1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4 ′ Methoxystyryl) -6-triazine. In addition, benzyldimethylketal, benzyldiethylketal, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide , 2-methyl-2-morpholino-1- (4- (methylthiophenyl) -propan-1-one, and the like.

  Examples of the sensitizer include N-arylglycine, mercaptotriazole derivatives, mercaptotetrazole derivatives, mercaptothiadiazole derivatives, and chain transfer agents such as hexanedithiol, decandithiol, and 1,4-butanediol bis. Thiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylol Propane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid Lis (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s- Well-known various compounds, such as polyfunctional thiol, such as a triazine, are mentioned.

  The photosensitive resin laminated body of this invention contains 40-70 mass% of color pigments in the photosensitive resin composition. It is 40% by mass or more from the viewpoint of light shielding properties, and is 70% by mass or less from the viewpoint of transferability, black matrix adhesion, line width stability, and shape. The content is preferably 45 to 65% by mass, and more preferably 50 to 65% by mass.

  Examples of the color pigment include organic pigments such as azo, phthalocyanine, indigo, anthraquinone, perylene, quinacridone, methine / azomethine, and isoindolinone, carbon blacks, titanium black, and titanium oxynitride. There are inorganic pigments such as black low-order titanium oxide, graphite powder, iron black, and copper oxide, which may contain a plurality of pigments. These pigments may be subjected to a surface treatment for enhancing the dispersibility in the photosensitive resin composition or for increasing the electric resistance value.

  Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index (C .. I.) Numbers can be mentioned. Listed below.

  C. I. Pigment red 9, C.I. I. Pigment red 97, C.I. I. Pigment red 105, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 215, C.I. I. Pigment red 216, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. Pigment Red 264, C.I. I. Pigment Red 265.

  Furthermore, C.I. I. Pigment orange 13, C.I. I. Pigment orange 31, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 42, C.I. I. Pigment orange 43, C.I. I. Pigment orange 51, C.I. I. Pigment orange 55, C.I. I. Pigment orange 59, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 65, C.I. I. Pigment orange 71, C.I. I. Pigment Orange 73.

  Furthermore, C.I. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment Yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 16, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 53, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 86, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 125, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 137, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 148, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 166, C.I. I. Pigment Yellow 173.

  Furthermore, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60, C.I. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38, C.I. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment black 1, C.I. I. Pigment Black 7.

  Examples of the dye include fuchsin, phthalocyanine green, auramin base, chalcoxide green S, paramadienta, crystal violet, methyl orange, nile blue 2B, Victoria blue, malachite green (Eizen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.). ), Basic Blue 20, Diamond Green (Eizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.), and the like.

  The photosensitive resin laminate of the present invention is useful as a black matrix forming material when the color pigment is a black pigment. Examples of black pigments include those that are black among the color materials listed above. That is, as an organic pigment, C.I. I. Pigment black 1, C.I. I. Examples of inorganic pigments such as CI Pigment Black 7 include carbon blacks, titanium black, titanium oxynitride, black low-order titanium oxide, graphite powder, iron black, and copper oxide. In addition, Cu, Fe, Mn, Cr, Co, Ni, V, Zn, Se, Mg, Ca, Sr, Ba, Pd, Ag, Cd, In, Sn, Sb, Hg, Pb, Bi, Si, and Al Inorganic pigments such as various metal oxides, composite oxides, metal sulfides, metal lead sulfates, metal carbonates, and the like can also be used. Carbon black is preferred from the viewpoints of light-shielding properties and sensitivity to black matrix, resolution, and adhesion. Titanium black is preferred from the viewpoint of black matrix insulation.

  As a preferable carbon black, at least one of the carbon blacks exemplified below can be used.

  For example, as carbon black manufactured by Mitsubishi Chemical Corporation, carbon black # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, MCF88, # 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40 , # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, Diamond Black LI, Diamond Black II, Diamond Black N33 Diamond Black SH, Diamond Black SHA, Diamond Black LH, Diamond Black H, Diamond Black HA, Diamond Black SF, Diamond Black N550M, Diamond Black E, Diamond Black G, Diamond Black R, Diamond Black N760M, Diamond Black LP I can do it.

  Examples of carbon blacks manufactured by Cancarb include Thermox N990, N991, N907, and N908.

  Asahi Carbon Corporation carbon blacks include Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 66HN, Asahi # 60H, Asahi # 60U, Asahi # 60, Asahi # 55 Asahi # 50H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15.

  The Degussa AG of carbon black, ColorBlack Fw200, ColorBlack Fw2, ColorBlack Fw2V, ColorBlackFw1, ColorBlack Fw18, ColorBlack S170, ColorBlack S160, SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, PrintexU, PrintexV, Printex140U, can be mentioned Printex140V.

  Carbon blacks manufactured by Cabot Corporation include Regal (registered trademark), Black Pearls (registered trademark), Elftex (registered trademark), Monarch (registered trademark), and Mogul ( Mogul; and carbon black sold under the Vulcan trademark name {eg Black Pearls® 2000, Black Pearls® 1400, Black Pearls® 1300, Black Pearls (registered trademark) 1100, Black Pearls (registered trademark) 1000, Black Pearls (registered trademark) 900, Black Pearls (registered trademark) 880, Black Pearls (registered trademark) 800, Black Pearls (registered trademark) 700, Black Pearls (registered trademark) L, Elftex (registered trademark) 8, Monarch (registered trademark) 1400, Monarch (registered trademark) 1300, Monarch (registered trademark) 1100, Monarch (registered trademark) 1000, Monarch (registered trademark) 900, Monarch (registered trademark) 880, Monarch (registered trademark) 800, Monarch (registered trademark) 700, Mogul (registered trademark) L, Regal (registered trademark) 330, Regal (registered trademark) 400, Vulcan (registered trademark) P}.

  Examples of carbon black manufactured by Colombian Chemical Corporation include Raven 780, Raven 890, Raven 1020, Raven 1040, Raven 1255, Raven 1500, Raven 5000, Raven 5250.

  In the photosensitive resin composition, a dispersing agent etc. can be included. As will be described later, the photosensitive resin laminate can be produced by coating the photosensitive resin composition on the support layer. However, the black pigment is dispersed in a solvent with a dispersant in advance, and this is added to the photosensitive layer. It can also be set as a resin composition, and it can also apply to a support layer to make a photosensitive resin layer.

  Examples of the dispersant include polyurethane, polycarboxylic acid ester such as polyurethane, unsaturated polyamide, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt, polysiloxane, hydroxyl group-containing polycarboxylic acid. Examples thereof include acid esters, modified products thereof, amides formed by the reaction of poly (lower alkyleneimine) and polyester having a free carboxylic acid group, and salts thereof. Moreover, the polymeric dispersing agent which has a basic functional group as described in Unexamined-Japanese-Patent No. 2005-25169 can be utilized. Specifically, Disperbyk160, Disperbyk161, Disperbyk162, Disperbyk163, Disperbyk164, Disperbyk166, and SOLSPERSE2SE, SE28500, SOLSPERSE24000, and SOLSPERSE24000, SERSPERSE24000, and SERSPERSE24000, SERSPERSE24000, SERSPERSE24000, and SERSPERSE24000, SERSPERSE24000 The alkali-soluble polymer used in the present invention, the alkali-soluble polymer obtained by copolymerizing the above-mentioned benzyl (meth) acrylate, and other alkali-soluble polymers also have a function as a pigment dispersant. As for content in the case of containing a dispersing agent, 0.1-15 mass% is preferable. From the viewpoint of dispersion stability of the pigment, 0.1% or more is preferable, and from the viewpoint of adhesion, 15% by mass or less is preferable. More preferably, it is 1-10 mass%.

  In addition, anionic activators such as polycarboxylic acid type polymer activators and polysulfonic acid type polymer activators, and nonionic activators such as polyoxyethylene and polyoxylene block polymers are dispersed together with the aforementioned dispersants. It can be used as an auxiliary agent.

  In addition, black pigments, particularly carbon black, can be coated with a resin or modified with a resin or a low-molecular compound in consideration of dispersibility, insulation, and the like. Examples of the resin used for the surface modification include polymers having a functional group capable of reacting with a carboxyl group on the surface of carbon black, such as polycarbodiimide and epoxy resin. Similarly, examples of the low molecular weight compound include a substituted benzenediazonium compound and a substituted allyldiazonium compound. Moreover, as a method of coating and modifying with a resin, JP-A No. 2004-219978, JP-A No. 2004-217785, JP-A No. 2004-360723, JP-A No. 2003-201381, JP-A No. 2004-292672 are disclosed. JP-A-2004-29745, JP-A-2005-93965, JP-A-2004-4762, US Pat. No. 5,554,739, US Pat. No. 5,922,118 Etc. can be used.

  The photosensitive resin composition may contain a coloring dye that develops color when irradiated with light. Examples of the coloring dye used include a combination of a leuco dye or a fluorane dye and a halogen compound. The coloring dye can be blended in an appropriate amount according to the desired OD value and color purity of the color pixel.

  Examples of the leuco dye include tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet].

  Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2, 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, triazine compounds and the like.

  Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine.

  Among such coloring dyes, a combination of tribromomethylphenylsulfone and a leuco dye or a combination of a triazine compound and a leuco dye is useful.

  In the photosensitive resin composition, in order to improve thermal stability and storage stability, a radical polymerization inhibitor can be contained. Examples of such radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p- Cresol, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), triethylene glycol-bis- [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] (IRGANOX245 manufactured by Ciba Specialty Chemicals), diphenylnitrosamine and the like. IRGANOX 245 is preferable because both the decrease in sensitivity is low and the storage stability is good.

  In the photosensitive resin composition, a plasticizer can also be contained as needed. Examples of such plasticizers include phthalates such as diethyl phthalate, p-toluenesulfonamide, polypropylene glycol, polyethylene glycol monoalkyl ether, polyalkylene oxide-modified bisphenol A derivatives such as ethylene oxide of bisphenol A. Examples include adducts and propylene oxide adducts. A preferable amount in the case of containing a plasticizer is 0.1 to 5% by mass. The amount is preferably 0.1% by mass or more from the viewpoint of suppressing the flexibility of the photosensitive resin layer and chip fly and cracking at the time of cutting after lamination, and preferably 5% by mass or less from the viewpoint of adhesion.

  A silane coupling agent can be included in the photosensitive resin composition. Silane coupling agents include vinyl groups, epoxy groups, styryl groups, methacryloxy groups, acryloxy groups, amino groups, ureido groups, chloropropyl groups, mercapto groups, sulfide groups, isocyanate groups, imidazolyl groups, and alkoxy groups. Compounds having a silyl group in the molecule can be raised. Specifically, Shin-Etsu Silicone Co., Ltd., KBM-1003, KBE-1003, KBM-403, KBE-403, KBM-502, KBE-502, KBM-503, KBE-503, KBM-603, KBE- Examples thereof include 603, KBM-903, KBE-903, KBE-585, KBM-802, KBE-846, KBE-9007 and the like, and imidazole silane compounds described in JP-A-2004-280057. The blending amount can be appropriately selected in consideration of the effect of adhesion and the adhesion of the residue to the substrate after development, but is preferably included in the range of 0.01 to 1% by mass.

  The photosensitive resin laminate of the present invention can be produced by coating a photosensitive resin layer made of a photosensitive resin composition on a support layer. The support layer used here is preferably a transparent layer that transmits active light. Support layers that transmit active light include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer. Examples thereof include a polymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, a cellulose derivative film, a triacetyl cellulose film, and a polypropylene film. As these films, those stretched as necessary can be used.

  Moreover, when applying to a support layer, a solvent can be added suitably and it can arrange in the optimal state for coating. Examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol monomethyl ether, propylene glycol. Monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether Ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2 -Ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxyb Acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate , 4-methyl-4-methoxypentyl acetate, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate, benzene, toluene, xylene, cyclohexanone, methanol, ethanol , Propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, and glycerin. Methyl ethyl ketone and methyl isobutyl ketone are preferred from the viewpoints of toxicity and drying properties when applied to the support layer. The dispersion stability of colored pigments, particularly black pigments, and the alkali solubility high represented by the above formula (I) used in the present invention are preferred. From the viewpoint of molecular solubility, propylene glycol monomethyl ether acetate (PGMEA) is preferred. In order to achieve the above-mentioned performance, methyl ethyl ketone, methyl isobutyl ketone, etc. and PGMEA may be mixed at an appropriate ratio. For example, PGMEA in which a black pigment is preliminarily dispersed, PGMEA in which the alkali-soluble polymer of the above formula (I) is preliminarily dissolved, and benzyl methacrylate or acrylic having a weight average molecular weight of 3,000 to 100,000 described above, respectively. At least one alkali-soluble polymer selected from the group consisting of an alkali-soluble polymer copolymerized with benzyl acid and an acrylic alkali-soluble polymer having a weight average molecular weight of 3,000 to 50,000; Photopolymerizable compound having a heavy bond, photopolymerization initiator, and other various additives are mixed and appropriately diluted with a solvent such as methyl ethyl ketone or PGMEA, and a photosensitive resin composition with good coatability and dryability to the support layer. It can be formulated as a physical solution.

  The haze of the support layer is preferably 5.0 or less. More preferably, it is 2.0 or less, More preferably, it is 1.0 or less. The haze here is a value representing turbidity, and the haze value H = the total transmittance T that is irradiated by the lamp and transmitted through the sample and the transmittance D of the light diffused and scattered in the sample. It is calculated as D / T × 100. These are defined by JIS-K-7105 and can be easily measured by a commercially available turbidimeter. A thinner support layer is advantageous in terms of image forming property and economy, but a thickness of 10 to 100 μm is common because it is necessary to maintain the strength.

  As for the photosensitive resin laminated body of this invention, a protective layer can also be laminated | stacked on the surface on the opposite side to the support layer of a photosensitive resin layer as needed. It is preferable that the adhesive force between the protective layer and the photosensitive resin layer is sufficiently smaller than the adhesive force between the support layer and the photosensitive resin layer and can be easily peeled off. Examples of such a protective layer include a polyethylene film, a polyethylene terephthalate film, a polypropylene film, a stretched polypropylene film (for example, E-200C, E-200A, etc. manufactured by Oji Paper Co., Ltd.), and release-treated polyethylene terephthalate. A film etc. are mentioned. The preferred thickness of the protective layer is 15 to 50 μm. 15 μm or more is preferable from the viewpoint of smooth surface production, and 50 μm or less is preferable from the viewpoint of stackability with the photosensitive resin layer and winding property.

  The photosensitive resin laminate of the present invention can be produced by the following method. As a photosensitive resin composition, an alkali-soluble polymer, a photopolymerizable compound having an ethylenically unsaturated double bond, a photopolymerization initiator, a color pigment, and the like, with an appropriate amount of solvent having a viscosity of 1 to several tens cps It mixes together and produces the photosensitive resin composition solution. The said photosensitive resin composition solution is apply | coated on the transparent polyester film of 20 micrometers in thickness used as a support layer, and it dries, and forms the photosensitive resin layer. Application is performed using an apparatus according to the application area, application speed, and the like. As a coating device, a blade coater, a bar coater, and a gravure coater can be mentioned as those useful for a small area. Examples of the sealed die method include a capillary coater, a lasing and rising coater, a slot die coater, and a lip coater, and examples of an open type include a comma coater and a gravure coater. The drying temperature can be appropriately selected according to the solvent. It is preferably at or above the temperature at which the solvent is sufficiently dried, and is preferably dried at or below the temperature at which the dimensional stability of the support layer can be ensured. 60-120 degreeC is preferable. The drying time is preferably longer than the degree that the solvent can be sufficiently dried, and is preferably dried at such a speed that the solvent can be uniformly evaporated from the coated surface. It is preferable that the dimensional stability of the support layer is not more than the extent that the dimensional stability cannot be ensured and the workability is not significantly impaired. If the drying means is a small area, a casting method or a hot air circulation type drying furnace can be used. In order to dry through a drying chamber of several meters or more, it can be dried by spraying hot air on the coating surface or the support layer, or by passing the upper support layer of a heated roll. The hot air nozzle includes a jet type, a positive pressure air floating type, a negative pressure air floating type, a negative pressure nozzle + roll type, a punching hole type, and a parallel flow type. Thereafter, a polyethylene film to be a protective layer is laminated and laminated. From the light shielding property of the black matrix and the film thickness accuracy at the time of application, the thickness of the photosensitive resin layer is preferably 0.3 μm or more. Moreover, it is preferable that it is 4.5 micrometers or less from flatness when it uses for a color filter. When creating a color filter using a resin black matrix, if the height of the black matrix is high, irregularities on the surface of the color filter will disturb the orientation of the liquid crystal, so a flattening film called an overcoat layer may be provided, It may be polished to make it flat. Since the influence on the orientation of the liquid crystal can be reduced, the overcoat layer can be made thin, and the thickness of the entire color filter can be made thin, the height of the black matrix is preferably 4.5 μm or less. The thickness of the photosensitive resin layer is more preferably 0.3 to 2 μm, still more preferably 0.3 to 0.8 μm.

  The black matrix described in the present invention can be formed by the following method using the above photosensitive resin laminate. First, after removing the protective layer, the photosensitive resin laminate is laminated (thermocompression bonding) to the glass substrate. At this time, the glass substrate is preferably preheated. The preheating temperature of the glass substrate is preferably 100 ° C. or higher from the viewpoint of laminating properties and air entrained during lamination to ensure sufficient adhesion, and preferably 150 ° C. or lower from the viewpoint of heat resistance of the support layer. More preferably, it is 110 degreeC or more and 140 degrees C or less.

  Next, image exposure is performed with active light through a mask film. When the exposure is increased, the support layer may be peeled off before exposure. However, when the support layer is peeled off and exposed, the amount of the initiator and the amount of the compound represented by the above formula (I) included in the present invention are appropriately adjusted and designed with high sensitivity. Is preferred. The influence of the support layer on the sensitivity is large, and it is preferable to design the sensitivity very high compared to the case of exposing through the support layer. That is, the step of laminating a photosensitive resin laminate containing 8 to 20% by mass of a photopolymerization initiator on the substrate in the photosensitive resin laminate according to (1) to (7) of the present invention, and peeling the support layer. It is preferable to manufacture a black matrix by a method for manufacturing a substrate with a black matrix, characterized in that a step, an exposing step, and a developing step are sequentially performed. As the substrate, a transparent substrate such as a glass substrate is preferable. In the said manufacturing method, since the problem of the transferability which an exposure part on a process sticks to a support layer, and peels from a base material is avoided, the above-mentioned weight average molecular weight in the photosensitive resin composition is 3000- At least one selected from the group consisting of an alkali-soluble polymer copolymerized with 100,000 benzyl methacrylate or benzyl acrylate and an acrylic alkali-soluble polymer with a weight average molecular weight of 3,000 to 50,000 The compounding ratio of the alkali-soluble polymer can be kept low, and the compounding amount of the compound represented by the above formula (I) can be increased. This is preferable from the viewpoint of sensitivity. However, since the unexposed portion strongly adheres to the support layer even in the production method, an alkali-soluble polymer copolymerized with benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 100,000 and The blending ratio of at least one alkali-soluble polymer selected from the group consisting of acrylic alkali-soluble polymers having a weight average molecular weight of 3,000 to 50,000 is 1% by mass or more, and 40% from the viewpoint of sensitivity. % Or less. Preferably it is 1-15 mass%, More preferably, it is 1-10 mass%, More preferably, it is 1-5 mass%. Similarly, since the unexposed portion strongly adheres to the support layer, the compounding amount of the compound represented by the formula (I) is 40% by mass or less, and 3% by mass or more from the viewpoint of sensitivity. Preferably it is 10-40 mass%, More preferably, it is 15-40 mass%, More preferably, it is 20-40 mass%.

  Next, when there is a support layer on the photosensitive resin layer, the support layer is removed if necessary, and then the photosensitive resin layer in the unexposed area is developed and removed using an alkaline aqueous solution. As the alkaline aqueous solution, a sodium carbonate aqueous solution, a potassium carbonate aqueous solution, a potassium hydroxide aqueous solution, a mixed aqueous solution of sodium hydrogen carbonate and sodium carbonate, an organic amine aqueous solution such as tetramethylammonium hydroxide, or the like is used. These alkaline aqueous solutions are selected according to the characteristics of the photosensitive resin layer. Generally, a 0.1 to 3% by mass aqueous sodium carbonate solution and a 0.03 to 0.1% by mass potassium hydroxide aqueous solution are used. In order to remove the photopolymerizable resin layer remaining undeveloped as necessary, further development may be performed in another developer. Another developer may be an alkaline aqueous solution having a different alkalinity from the developer used for developing the photosensitive resin layer first, an acidic developer, or a developer containing an organic solvent. Alternatively, the composition of the photosensitive resin layer can be appropriately selected according to the developer. In addition, the unexposed photosensitive resin layer, coloring pigment, and black pigment remaining undeveloped can be physically removed by a method such as high-pressure water washing. A water washing pressure of 0.2 MPa or more is effective.

  After forming the black matrix, the color filter of the present invention comprises the photosensitive resin laminate of the present invention and the heat-sensitive or photosensitive color on at least a part of the glass substrate with the black matrix that is not covered with the black matrix. It can be produced by forming red, blue and green color pixels with ink.

  The shape of the black matrix is generally a lattice shape surrounding the color pixels. In general, the pattern width of each side of the lattice is 5 to 50 μm, and the lattice point interval is 30 to 500 μm.

  Red, blue, and green color pixels can be produced by photolithography using a color resist such as the photosensitive resin laminate of the present invention or a liquid resist, or by an inkjet method or a printing method using a color ink. Various methods can be used. The ink jet method is a method of injecting color ink by an ink jet method using a black matrix formed on a glass substrate as a weir. The inkjet method does not require an exposure process that requires an expensive mask, does not require a development process, can form a pixel pattern regardless of unevenness, and improves yield, and is simple and low-cost. It is preferable because a pixel pattern can be formed. Since it can be cured without relying on photolithography, it may be heat sensitive, or it may be cured by full exposure so that it may be photosensitive. Known heat-sensitive or photosensitive color inks can also be used. Further, in the present invention, the composition includes a pigment and a dye exemplified as a coloring substance, a photopolymerizable compound having an ethylenically unsaturated double bond, a heat or a photopolymerizable initiator, and the viscosity is appropriately adjusted with a solvent. Can be used. For example, the color ink described in Example 1 of JP-A-2004-213033 can be used. The black matrix is preferably color repellent ink. Due to this property, due to the problem of ink landing accuracy, the color ink on the black matrix can also slide down the weir to fill the space for the color pixels.

  In the manufacturing method of the black matrix of this invention, the photosensitive resin laminated body laminated | stacked on the transparent support layer is used. The manufacturing method is a method of applying a photosensitive resin composition directly to a glass substrate, drying it, and then exposing and developing it through a photomask, and does not use a drying process. This is a preferable method from the standpoint that unevenness does not occur and the transparent support layer prevents contact between the photopolymerizable resin composition and the photomask, so that the photomask is not easily soiled.

  Furthermore, by exposing through a transparent support layer, very high sensitivity is obtained in order to prevent the photosensitive resin layer from coming into direct contact with oxygen. This indicates that it is useful in terms of sensitivity compared to a method in which a photosensitive resin composition is directly applied and dried on a glass substrate as disclosed in Patent Document 1, Comparative Example 8 of the present specification and the like. ing.

  As a method of forming a black matrix using a photosensitive resin laminate, a color pixel having a thickness of about 2 μm is formed on a glass substrate, and then the black photosensitive resin laminate is laminated on a glass substrate with a color pixel. A method of performing exposure from the side is also conventionally known (see Japanese Patent No. 3409925). When the black matrix is formed in this order, the black matrix is originally formed only between the pixels, so that there is an advantage that the alignment between the color pixels and the black matrix can be omitted. However, in such a method, in order to embed the photosensitive resin layer between the color pixels, a thermoplastic resin layer and an intermediate layer are laminated on a support layer having a thickness of 70 to 100 μm or more, and a photosensitive resin layer is further formed. It becomes a complicated layer structure such as stacking. Since the thermoplastic resin layer is embedded, the intermediate layer is considered to be provided to prevent contact between the photosensitive resin layer and oxygen when the thickened support layer and / or the thermoplastic resin layer is exposed after being peeled off. . If the photosensitive resin laminate of the present invention is used, it is possible to form a black matrix in advance because of excellent line width reproducibility and adhesion, so that the layer structure is simplified and the support layer is also 20 μm or less. Those having little absorption and scattering at the exposure wavelength can be used. By using a high-quality support layer, line width stability, pattern shape, linearity and the like are further improved.

The present invention will be described based on examples.
[Synthesis Example 1]
First, Compound 1 represented by the above formula (I) was synthesized according to the method described in JP-A No. 2001-354735.
That is, in a 500 ml four-necked flask, 235 g of bisphenolfluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tertbutyl-4-methylphenol and 72.0 g of acrylic acid were charged. It is. This was heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 ml / min. Next, the temperature was gradually raised while the solution was clouded, and the solution was heated to 120 ° C. to be completely dissolved. Here, although the solution gradually became transparent and viscous, stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 12 hours for the acid value to reach the target. And it cooled to room temperature and obtained the bisphenol fluorene type epoxy acrylate represented by the following formula (V) which is a colorless and transparent solid.

  Next, 600 g of propylene glycol monomethyl ether acetate (PGMEA) was added to 307.0 g of the bisphenolfluorene type epoxy acrylate thus obtained and dissolved. Thereafter, 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed, gradually heated to react at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to obtain Compound 1 corresponding to the above formula (I). It was. The disappearance of the acid anhydride group was confirmed by IR spectrum.

  Here, Compound 1 is a compound represented by the above formula (I), wherein X is a group represented by the above formula (II), and Y is an acid anhydride group from 1,2,3,6-tetrahydrophthalic anhydride. Residue excluding (—CO—O—CO—), Z is a residue obtained by removing acid anhydride from 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, and Y / Z The molar ratio corresponds to a compound of 50.0 / 50.0.

This compound 1 was made into an alkali-soluble polymer, adjusted so that the solid content concentration in PGMEA would be 40% by mass, and used to prepare the following photosensitive resin composition solution.
[Examples 1 to 9]
<Preparation of photosensitive resin composition solution>
Each component of the photosensitive resin composition was mixed at a ratio shown in Table 1 to obtain a photosensitive resin composition solution having a solid content of 10% by mass using methyl ethyl ketone as a solvent. In Table 1, components constituting the photosensitive resin composition represented by abbreviations (A-1 to F-1) are as follows.
A-1: PGMEA solution of compound 1 synthesized in Synthesis Example 1 (solid content concentration 40% by mass)
A-2: Methyl ethyl ketone solution of benzyl methacrylate / methacrylic acid copolymer (mass ratio 85/15, weight average molecular weight 30000, solid content concentration 40 mass%)
A-3: Methyl ethyl ketone solution of styrene / methyl methacrylate / methacrylic acid copolymer (mass ratio 25/50/25, weight average molecular weight 55000, solid content concentration 40 mass%). A-4: Methyl ethyl ketone solution of copolymer of styrene / methyl methacrylate / methacrylic acid (mass ratio 25/50/25, weight average molecular weight 20000, solid content concentration 40 mass%). B-1: Pentaerythritol tetraacrylate B-2: Succinic acid-modified pentaerythritol triacrylate (Aronix TO-756 manufactured by Toa Gosei Co., Ltd.)
C-1: 1- [9-Ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate (IRGACURE OXE-02 manufactured by Ciba Specialty Chemicals)
D-1: Carbon black <Preparation of photosensitive resin laminate>
The said photosensitive resin composition is uniformly apply | coated to a 20-micrometer-thick polyethylene terephthalate support layer using a bar coater, and is dried for 3 minutes in a 95 degreeC dryer. Subsequently, the 20-micrometer-thick stretched polypropylene protective layer was bonded together to the photosensitive resin layer, and the photosensitive resin laminated body of Examples 1-9 was obtained.

In addition, after application | coating of the photosensitive resin composition, it observed whether there was any nonuniformity and evaluated the coating property to a support layer as follows.
○: Uniform without uneven coating ×: Uneven with uneven coating <Formation of black matrix>
The protective layer of the photosensitive resin laminate of Examples 1 to 9 above was peeled off and laminated on a glass substrate. It took about 5 seconds to laminate the photosensitive resin laminate on a 10 cm square substrate. Then, it exposed at 40 mJ / cm < ² > with the ultrahigh pressure mercury lamp (HMW-801 by Corporation | KK Oku Seisakusho) through the glass mask of the matrix pattern of line width: space width 1: 9. At this time, the distance between the support layer and the glass mask was set to 100 μm. After peeling off the support layer, 0.05% by mass aqueous potassium hydroxide solution was sprayed at 23 ° C. to dissolve and remove the unexposed portion of the photopolymerizable resin layer. The spraying time at this time was 1.5 times the time (minimum development time) when the unexposed portion of the photopolymerizable resin layer was just removed from the glass substrate. Thereafter, post baking was performed at 240 ° C. for 60 minutes to form a black matrix.

In the black matrix formation step, when the support layer was peeled after exposure, the transfer of the photosensitive resin layer to the glass substrate was observed and the transfer property to the glass substrate was evaluated as follows. For the evaluation of transferability, a solid pattern was exposed in addition to a matrix pattern having a line width: space width of 1: 9, and evaluated simultaneously.
(Transferability to glass substrate)
○: The entire photosensitive resin layer is transferred to the glass substrate.
Δ: Part of the exposed portion of the solid pattern is peeled off together with the support layer, but the matrix pattern is transferred without any problem.
ΔΔ: A part of the exposed portion of the solid pattern is peeled off together with the support layer, and a part of the matrix pattern is peeled off together with the support layer.
X: It peels with a support layer irrespective of a matrix pattern and a solid pattern.
<Evaluation of black matrix>
(1) Film thickness About the black matrix on said glass substrate, the height of the pattern formed in the glass substrate was measured using the alpha step (AS200) by Tencor Instruments, and this was made into film thickness (micrometer) and did.
(2) Light-shielding property A solid pattern was prepared by the same method as the above black matrix, and the optical density was measured using an optical densitometer D200-II manufactured by Gretag Macbeth. The optical density is expressed by the relationship of optical density = log ₁₀ (I ₀ / I), where the incident light intensity is I ₀ and the transmitted light intensity is I with respect to light from a certain light source. A value obtained by dividing the optical density by the above film thickness was obtained, and this was regarded as a light shielding property. The light shielding property was evaluated according to the following rank.
○: 3 or more Δ: 2 or more and less than 3 x: Less than 2 (3) Sensitivity Laminating a photosensitive resin laminate on a glass substrate, and 21-step stove tablet (change of optical density 0.15 per tablet step) Through a mask film), the glass substrate exposed, developed and post-baked in the same manner as described above was visually read to see how many step tablet patterns remained. The sensitivity was evaluated according to the following rank.
○: 3 steps or more Δ: 2 steps or more and less than 3 steps ×: Less than 2 steps (4) Adhesiveness Line width: Space width = 1: 9 exposure at 40 mJ / cm ² through a matrix pattern mask of 1 and a minimum development time of 1 Developed for 5 times to form a matrix pattern. Whether or not the matrix pattern was formed was visually observed with an optical microscope, and the mask width (μm) corresponding to the smallest matrix pattern that could be formed was defined as adhesion. The evaluation of adhesion was according to the following rank.
○: Less than 5 μm Δ: 5 μm or more and less than 10 μm ×: 10 μm or more (5) Line width stability during over-development The photosensitive resin laminate used in Example 2 and Comparative Example 2 was laminated on a glass substrate, and 40 mJ / cm ^The black matrix was formed by exposing to ² and developing so that the values obtained by dividing the development time by the minimum development time were 1.1 (equivalent to around the minimum development time) and 1.6 (equivalent to over-development). The line width of the black matrix corresponding to the mask line width of 20 μm was measured with a length measuring microscope. The results are summarized in Table 2 as Examples 10 and 11 and Comparative Examples 8 and 9. It can be seen that the change in the line width of the photosensitive resin laminate of Example 2 is smaller than that of the photosensitive resin laminate of Comparative Example 2.
[Examples 12 to 13]
<Create color pixels>
In the above Example 1, D-2: C. I. Pigment Red 254 and D-3: Pigment Yellow 139 are mixed in the same manner as in Example 1 to prepare photosensitive resin composition solutions 14 and 15.
The photosensitive resin composition solutions 14 and 15 are uniformly applied to a polyethylene terephthalate base film having a thickness of 20 μm using a bar coater and dried in a dryer at 95 ° C. for 3 minutes. Next, a 25 μm-thick polyethylene protective film is laminated on the resulting photopolymerizable resin composition laminate, and the photosensitive resin laminates of Examples 12 and 13 can be obtained. The protective film of the photosensitive resin laminate of Examples 12 and 13 was peeled off and laminated on a glass substrate, and then passed through a mask film having a pattern with a line width / space width of 5 μm / 25 μm, and an ultrahigh pressure mercury lamp -Expose at 40 mJ / cm < ² > with HMW-801). After peeling off the support film, 0.05% by weight aqueous potassium hydroxide solution is sprayed at 23 ° C. for about 30 seconds to dissolve and remove the unexposed photosensitive resin layer and develop. Thereafter, post-baking is performed at 200 ° C. for 15 minutes to form color pixels.
[Examples 14 to 17 and Comparative Example 10]
Each component of the photosensitive resin composition was mixed in the proportions shown in Examples 14 to 17 and Comparative Example 10 in Table 1, and the photosensitive resin composition solutions 14 to 17 having a solid content of 10% by mass using methyl ethyl ketone as a solvent and the comparison. The photosensitive resin composition solution 10 was obtained. The photosensitive resin composition solutions 14 to 17 and the comparative photosensitive resin composition solution 10 were uniformly applied to a polyethylene terephthalate support layer having a thickness of 20 μm using a bar coater, and a 95 ° C. dryer. Dry for 3 minutes. Subsequently, the 20-micrometer-thick stretched polypropylene protective layer was bonded together to the photosensitive resin layer, and the photosensitive resin laminated body of Examples 14-17 and the comparative example 10 was obtained.

The protective layers of the photosensitive resin laminates of Examples 14 to 17 and Comparative Example 10 were peeled off and laminated on a glass substrate. Thereafter, the support layer was peeled off, and exposed at 100 mJ / cm ² with a super high pressure mercury lamp (HMW-801, manufactured by Oak Manufacturing Co., Ltd.) through a glass mask having a matrix pattern with a line width: space width of 1: 9. . At this time, the distance between the photosensitive resin layer and the glass mask was set to 100 μm. Subsequently, 0.05 mass% potassium hydroxide aqueous solution was sprayed at 23 degreeC, and the photopolymerizable resin layer of the unexposed part was melt | dissolved and developed. The spraying time at this time was 1.5 times the time (minimum development time) when the unexposed portion of the photopolymerizable resin layer was just removed from the glass substrate. Thereafter, post baking was performed at 240 ° C. for 60 minutes to form a black matrix. The results are shown in Table 3.

The transferability to the glass substrate was evaluated as follows because the support layer was peeled before the pattern was exposed.
○: The entire photosensitive resin layer is transferred to the glass substrate.
X: A part of the photosensitive resin layer is peeled off together with the support layer.
[Comparative Examples 1 to 7]
The components of the photosensitive resin compositions of Comparative Examples 1 to 7 were mixed at the ratio shown in Table 1 to obtain comparative photosensitive resin composition solutions 1 to 7 having a solid content of 10% by weight. Comparative Photosensitive Resin Composition Solutions 1 to 7 were applied on a 20 μm thick polyethylene terephthalate base film in the same manner as in Example, and a 20 μm thick stretched polypropylene protective layer was bonded to Comparative Example 1 The photosensitive resin laminated body of -7 was produced. Using the photosensitive resin laminates of Comparative Examples 1 to 7, a black matrix was formed on a glass substrate in the same manner as in the examples. Regarding the evaluation, the same items as in the examples were evaluated, and the results are shown in Table 1.
In addition, the photosensitive resin composition of Comparative Example 4 showed coating unevenness after coating and drying on the base film. Moreover, the adhesiveness of the photosensitive resin layer of an unexposed part and a support layer was high, and the exposed part was peeled from the board | substrate together when peeling a support layer. The photosensitive resin composition of Comparative Example 5 had a portion with a thin optical density, which was clearly visible after application, and could not be applied uniformly.

[Comparative Example 11]
The photosensitive resin composition solution 3 prepared in Example 3 was spin-coated on a 10 cm square glass substrate at 500 revolutions per minute using a spin coater (Mikasa spin coater 1H-360S). After coating, radial coating unevenness occurred from the center of the substrate toward the edge. In addition, coating unevenness of about 1 mm also occurred at the edge portion so as to border the substrate. In order to laminate the photosensitive resin layer on the glass substrate, it was necessary to further dry it in an oven at 80 ° C. for 10 minutes.
Furthermore, as in the case of Example 3, when an exposure development was performed to form a black matrix, no pattern was left on the substrate after development.

  The present invention can be used in the field of flat panel displays such as liquid crystal displays, organic EL displays and plasma displays, and color filters used in the liquid crystal displays and organic EL displays, and is particularly preferably used in the field of liquid crystal displays.

Claims (12)

At least a support layer and a photosensitive resin layer are laminated, and the photosensitive resin layer is
3-40% by mass of an alkali-soluble polymer represented by the following formula (I),
From an alkali-soluble polymer copolymerized with benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 100,000 and an acrylic alkali-soluble polymer having a weight average molecular weight of 3,000 to 50,000 1 to 40% by mass of at least one alkali-soluble polymer selected from the group consisting of
3 to 25% by mass of a photopolymerizable compound having an ethylenically unsaturated double bond,
0.1-20% by mass of a photopolymerization initiator,
Containing 40 to 70% by weight of a color pigment, and
The alkali-soluble polymer represented by the formula (I): an alkali-soluble polymer obtained by copolymerizing benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 100,000 and a weight average molecular weight of 3, At least one alkali-soluble polymer (mass ratio) selected from the group consisting of acrylic alkali-soluble polymers of 000 to 50,000 = 1: 5 to 16: 1
A photosensitive resin laminate comprising the photosensitive resin composition.

(In the formula (I), X is a group represented by the following formula (II), Y is a residue excluding the acid anhydride group of dicarboxylic anhydride, Z is an acid anhydride group of tetracarboxylic dianhydride. And n is an integer of 1 to 20. R ₁ and R ₂ in the following formula (II) each independently represent H or CH ₃ group.)

The photosensitive resin layer is
3 to 40% by mass of the alkali-soluble polymer represented by the above formula (I),
1 to 40% by mass of an alkali-soluble polymer obtained by copolymerizing benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 100,000,
3 to 25% by mass of a photopolymerizable compound having an ethylenically unsaturated double bond,
0.1-20% by mass of a photopolymerization initiator,
Containing 40 to 70% by weight of a color pigment, and
Alkali-soluble polymer represented by formula (I): Alkali-soluble polymer (mass ratio) copolymerized with benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 100,000 = 1: 5-16: 1
The photosensitive resin laminate according to claim 1, comprising the photosensitive resin composition. The photosensitive resin layer is
3 to 40% by mass of the alkali-soluble polymer represented by the above formula (I),
5-40% by mass of an alkali-soluble polymer obtained by copolymerizing benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 50,000,
5-25% by mass of a photopolymerizable compound having an ethylenically unsaturated double bond,
0.1-20% by mass of a photopolymerization initiator,
Containing 40 to 70% by weight of a color pigment, and
Alkali-soluble polymer represented by formula (I): Alkali-soluble polymer (mass ratio) = 1: copolymerized with benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 50,000 The photosensitive resin laminate according to claim 2, which is 5 to 5: 1. The alkali-soluble polymer represented by the formula (I): an alkali-soluble polymer obtained by copolymerizing benzyl methacrylate or benzyl acrylate having a weight average molecular weight of 3,000 to 100,000 and a weight average molecular weight of 3, The photosensitive resin laminate according to claim 1, wherein at least one alkali-soluble polymer (mass ratio) selected from the group consisting of acrylic alkali-soluble polymers of 000 to 50,000 is 2: 1 to 16: 1. body. The photosensitive resin laminated body as described in any one of Claims 1-4 which contains an oxime ester compound as a photoinitiator in the photosensitive resin composition. The photosensitive resin as described in any one of Claims 1-4 which contains the compound represented by following formula (III) as a photopolymerizable compound which has an ethylenically unsaturated double bond in the photosensitive resin composition. Laminated body.

(In the formula (III), R ₃ , R ₄ and R ₅ each independently represent H or CH ₃ group. R ₆ is a divalent linking group, an alkylene group having 2 to 8 carbon atoms, This represents a kind of group selected from the group consisting of 3 to 10 cycloalkylene groups and C 6-10 phenylene groups.) The photosensitive resin laminate according to claim 1, wherein the color pigment is a black pigment. The manufacturing method of the board | substrate with a color pixel which includes the process of laminating the photosensitive resin laminated body as described in any one of Claims 1-4 to a board | substrate at least, the process of exposing, and the process of image development in order. The manufacturing method of the board | substrate with a black matrix which includes the process of laminating the photosensitive resin laminated body of Claim 7 to a board | substrate at least, the process of exposing, the process of peeling a support layer, and the image development in order. A method for producing a substrate with a black matrix, comprising at least a step of laminating the photosensitive resin laminate according to claim 7 on a substrate, a step of peeling a support layer, a step of exposing, and a step of developing. At least a step of forming a black matrix on the substrate by the method according to claim 9 or 10, and ink jetting a heat-sensitive or photosensitive color ink on at least a part of the glass substrate not covered with the black matrix. A method for producing a color filter, which in turn includes a printing process for printing by a method. The color filter manufactured by the method of Claim 11.