JP2009084381A - Heat-curable resin, photosensitive resin composition containing the same, color filter using this photosensitive resin composition and liquid crystal display having the color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat-curable resin suitable for a photosensitive composition for forming a color filter and the like, which excels in long-term storage stability, development speed and photosensitivity and whose coating film after curing by irradiation of lights and/or baking excels in heat resistance, adhesion with a substrate, hardness, solvent resistance, alkali resistance and birefringence. <P>SOLUTION: The heat-curable resin is formed by the reaction of a melamine resin with a compound containing an isocyanate group and has a weight average mol.wt. of ≥2,500, or it is formed by the reaction of a melamine resin with a compound containing an isocyanate group and has a double bond equivalent of 100-2,000, or it is formed by the reaction of a melamine resin, a compound containing an isocyanate group and an acid anhydride and has a value of ≤60 mg KOH/g as the acid number of the solids content, or it is formed by the reaction of a melamine resin with an acid anhydride and has a value of ≤60 mg KOH/g as the acid number of the solid content. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a thermosetting resin, a photosensitive resin composition containing the thermosetting resin, a color filter using the photosensitive resin composition, and a liquid crystal display device including the color filter. And a photosensitive resin composition having excellent photosensitivity and excellent in heat resistance, adhesion to a substrate, hardness, solvent resistance, alkali resistance, and birefringence, after being cured by light irradiation and / or baking. And a color filter using the photosensitive resin composition.

  Thermosetting resins are excellent in transparency and heat resistance, and are used, for example, for forming colored layers of color filters used in liquid crystal displays, electronic paper displays, electroluminescent panels, and the like, and opposite substrate support layers. be able to. Furthermore, the present inventors have previously found that it is preferable to use the thermosetting resin as a birefringence adjusting agent by taking advantage of the property of developing the thickness direction retardation of the thermosetting resin. Therefore, it is considered that the thermosetting resin can be suitably used for forming a cell gap control raising layer and a retardation layer of a color filter for liquid crystal display.

In recent years, there has been a demand for higher image quality, lower power consumption, and lower prices for thin display devices such as liquid crystal displays. Color filters are compatible with various liquid crystal display modes with sufficient color purity, brightness, and contrast. Photosensitive resin composition capable of patterning a colored layer having a fine pattern, a counter substrate carrying layer, a cell gap control raising layer, and a retardation layer with high accuracy and low cost while exhibiting the above-described birefringence Is desired.
As such a photosensitive resin composition, for example, there is a technique of using a composition in which a melamine resin is blended as the above-described thermosetting resin in an alkali-developable photosensitive resin composition (for example, see Patent Document 1). However, when a large amount of the conventional melamine resin is blended, there is a problem that the sensitivity of the photosensitive resin composition is lowered, the exposure time necessary for sufficient curing is prolonged, and the productivity is deteriorated. Furthermore, the alkali developability of the photosensitive resin composition deteriorates, the development speed cannot be adjusted appropriately, the development time becomes longer, and conversely, the development speed is too high and the coating film is easily peeled off from the substrate. As a result, there is a limit to the amount of the melamine resin added, and the effect of a sufficient thermosetting resin could not be exhibited.
Patent No. 2937208

  The present invention has been made in view of the above circumstances, and is excellent in long-term storage stability, development speed and photosensitivity, and further, the coating film after being cured by light irradiation and / or baking is heat resistant, adhesion to a substrate, hardness , Photosensitive composition for forming an alkali developing type photosensitive color filter, a counter substrate carrying layer, a cell gap control raising layer, and a retardation layer having excellent solvent resistance, alkali resistance and birefringence An object of the present invention is to provide a thermosetting resin suitable for the above.

  Another object of the present invention is to provide a photosensitive composition containing the thermosetting resin, a color filter using the photosensitive composition, and a liquid crystal display device including the color filter.

  In order to solve the above problems, a first aspect of the present invention is a thermosetting resin obtained by reacting a melamine resin and a compound containing an isocyanate group, and having a weight average molecular weight of 2500 or more. provide.

  According to a second aspect of the present invention, there is provided a thermosetting resin obtained by reacting a melamine resin with an isocyanate group-containing compound and having a double bond equivalent of 100 to 2000.

  According to a third aspect of the present invention, there is provided a thermosetting resin obtained by reacting a melamine resin, a compound containing an isocyanate group, and an acid anhydride, and having a solid content acid value of 60 mgKOH / g or less. provide.

  According to a fourth aspect of the present invention, there is provided a thermosetting resin obtained by reacting a melamine resin with an acid anhydride and having a solid content acid value of 60 mgKOH / g or less.

In the thermosetting resins according to the first to fourth aspects of the present invention, those having the structural formula (I) shown below can be used as the melamine resin.

(Wherein R ^{1 to} R ⁶ each represent a hydrogen atom or CH ₂ OR (R represents a hydrogen atom or an alkyl group, and R ^{1 to} R ⁶ may be the same or different). , R ^{1 to} R ⁶ may be the same or different.
5th aspect of this invention contains the thermosetting resin mentioned above, a photopolymerizable monomer, a photoinitiator, and acrylic resin, and content of the said thermosetting resin is a photosensitive resin composition. Provided is a photosensitive resin composition characterized by being 3 to 60% of the solid content of the product.

  As the acrylic resin, one having an acid value of 50 to 130 mgKOH / g can be used. Moreover, what has a double bond equivalent of 100-2000 can be used as said acrylic resin.

  The photosensitive resin composition can further contain a pigment and a dispersant.

  According to a sixth aspect of the present invention, there is provided a substrate, a colored layer formed on the substrate and / or a counter substrate carrying layer formed on the substrate surface provided with the colored layer, and a cell gap control raising layer. , And a color filter comprising at least one of the retardation layers, wherein at least one of the colored layer, the counter substrate supporting layer, the cell gap control raising layer, and the retardation layer comprises: A color filter is provided that is a cured film of the photosensitive resin composition described in 1.

  According to a seventh aspect of the present invention, in the color filter including a substrate and a colored pixel formed on the substrate, the colored pixel is a cured film of the above-described photosensitive resin composition, and the position in the thickness direction. A color filter having a phase difference of 0 to 3 nm for a red pixel, 4 to 9 nm for a green pixel, and 5 to 10 nm for a blue pixel is provided.

  The eighth aspect of the present invention provides a liquid crystal display device comprising the above-described color filter.

  According to the present invention, the long-term storage stability, the development speed and the photosensitivity are excellent, and the coating film after being cured by light irradiation and / or baking is heat resistance, adhesion to the substrate, hardness, solvent resistance, Thermosetting suitable for a photosensitive composition for forming an alkali development type photosensitive color filter having excellent alkali resistance and birefringence, a counter substrate carrying layer, a cell gap control raising layer, and a retardation layer. A functional resin is provided.

  As a result of intensive studies on photosensitive compositions for forming a color filter coloring layer, a counter substrate carrying layer, a cell gap control raising layer, and a retardation layer, the present inventors have found that a melamine resin and an isocyanate group are present. It has been found that a photosensitive composition containing a thermosetting resin obtained by reacting a contained compound and / or an acid anhydride exhibits excellent performance for the above applications. That is, such a photosensitive composition is imparted with desired developability and photosensitivity, is excellent in long-term storage stability, development speed and photosensitivity, and further after being cured by light irradiation and / or baking. The coating film is excellent in heat resistance, adhesion to the substrate, hardness, solvent resistance, alkali resistance, and birefringence, and can solve the problems of the conventional techniques described above.

  The thermosetting resin according to the first aspect of the present invention is obtained by reacting a melamine resin and a compound containing an isocyanate group, and has a weight average molecular weight of 2500 or more.

  In such a thermosetting resin, several thermoreactive groups such as an imino group, a methylol group, and an alkoxymethyl group existing in the melamine resin skeleton are reacted with an isocyanate group of a compound containing an isocyanate group. Thus, a thermosetting resin having a weight average molecular weight of 2500 or more can be obtained.

  When a compound containing two or more isocyanate groups is used, a thermosetting resin having a larger weight average molecular weight can be obtained.

  Thus, when a photosensitive resin composition is prepared by blending a thermosetting resin having a weight average molecular weight controlled to 2500 or more, a conventional photosensitive resin composition containing a melamine resin having a weight average molecular weight of less than 2500 is used. In other words, the alkali developability of the photosensitive resin composition deteriorates, the development speed cannot be adjusted appropriately, the development time becomes longer, and conversely, the development speed is too high and the coating film peels off from the substrate. The effect of the thermosetting resin can be sufficiently exerted without causing the harmful effect of becoming easier.

  The thermosetting resin according to the second aspect of the present invention is obtained by reacting a melamine resin and a compound containing an isocyanate group, and has a double bond equivalent of 100 to 2000.

  In such a thermosetting resin, some of the thermoreactive groups such as imino group, methylol group and alkoxymethyl group present in the melamine resin skeleton contain an isocyanate group and a double bond group. Photosensitivity can be imparted to the thermosetting resin by reacting with the isocyanate group of the compound.

  When a photosensitive resin composition is prepared by blending a thermosetting resin imparted with photosensitivity in this way, the disadvantages when using a conventional non-photosensitive melamine resin, that is, the sensitivity of the photosensitive resin composition is reduced. The effect of the thermosetting resin can be sufficiently exerted without causing the adverse effect that the exposure time required for sufficient curing decreases and the productivity deteriorates.

  The thermosetting resin according to the third aspect of the present invention is obtained by reacting a melamine resin, an isocyanate group-containing compound and an acid anhydride, and has a solid content acid value of 3 to 60 mgKOH / g.

  The thermosetting resin according to the fourth aspect of the present invention is obtained by reacting a melamine resin and an acid anhydride, and has a solid content acid value of 3 to 60 mgKOH / g.

  In such thermosetting resins according to the third and fourth aspects of the present invention, some of the thermoreactive groups such as imino group, methylol group, alkoxymethyl group and the like which are present in the melamine resin skeleton and acid anhydrides are present. Thermosetting property by reacting with the acidic group of the product and / or reacting the isocyanate group of the compound obtained by reacting the compound containing the melamine resin and the isocyanate group with the acidic group of the acid anhydride. Carboxylic acid groups can be introduced into the resin, and alkali solubility, that is, developability can be imparted.

  Thus, by preparing a photosensitive resin composition by blending a thermosetting resin imparted with developability, a problem that has occurred with conventional melamine resins, that is, alkali developability of the photosensitive resin composition The effect of the thermosetting resin does not cause the adverse effect that the development speed cannot be adjusted appropriately and the development time becomes longer, or the development speed is too high and the coating film is easily peeled off from the substrate. Can be fully exhibited. In combination with the thermosetting resin having a weight average molecular weight of 2500 or more, the photosensitivity is further improved, that is, the alkali-soluble contrast of the exposed / unexposed area is clear, the pattern edge shape is good, It becomes possible to obtain a photosensitive resin composition excellent in fine workability that faithfully reproduces the mask shape.

  In the thermosetting resin according to the first to fourth aspects of the present invention, the melamine resin having the structural formula (I) described above can be used.

  The photosensitive resin composition which concerns on the 5th aspect of this invention contains the thermosetting resin mentioned above, the photopolymerizable monomer, the photoinitiator, and acrylic resin, and is solid of the photosensitive resin composition. It has a content of 3-60% thermosetting resin in the minutes.

  According to such a photosensitive resin composition, it contains 3 to 60% of the above-described thermosetting resin in the solid content of the photosensitive resin composition, so that the thermosetting resin has heat resistance and adhesion to the substrate. Properties having excellent properties, hardness, solvent resistance, alkali resistance, and birefringence can be sufficiently exhibited. That is, since these photosensitive resin compositions have been imparted with properties such as long-term storage stability, development speed and photosensitivity as described above, an alkali development type photosensitive color filter coloring layer and a counter substrate support are provided. It can be suitably used for forming a layer, a cell gap control raising layer, and a retardation layer.

  In the photosensitive resin composition according to the fifth aspect of the present invention, when the acid value of the acrylic resin is 50 to 130 mgKOH / g, the development speed cannot be adjusted appropriately, and the development time becomes longer. It is possible to adjust the alkali developability of the photosensitive resin composition to an optimum state without causing a problem that the developing speed is too high and the coating film is easily peeled off from the substrate.

  In addition, by setting the double bond equivalent of the acrylic resin to 100 to 2000, the sensitivity of the photosensitive resin composition is insufficient, and the exposure time necessary for sufficient curing becomes long, resulting in poor productivity. Without exposure, the exposure sensitivity of the photosensitive resin composition can be sufficiently maintained. Moreover, the photosensitive resin composition can contain a pigment and a dispersing agent further.

  Embodiments of the present invention will be described below.

  The thermosetting resin according to one embodiment of the present invention is obtained by reacting the following melamine resin and a compound containing an isocyanate group.

<Melamine resin>
Examples of the melamine resin used in the present invention include compounds having the structural formula (I) shown below and multimers thereof.

(Wherein R ^{1 to} R ⁶ each represent a hydrogen atom or CH ₂ OR (R represents a hydrogen atom or an alkyl group, and R ^{1 to} R ⁶ may be the same or different). , R ^{1 to} R ⁶ may be the same or different.
Two or more homopolymers or copolymers may be used in combination. In addition to the above, compounds having a 1,3,5-triazine ring, for example, those described in JP-A No. 2001-166144 can be used. In addition, compounds represented by the structural formula (II) shown below are also preferably used.

(R ⁷ to R ¹⁴ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, and particularly preferably a hydrogen atom.)
<Compound containing isocyanate group>
As the compound containing an isocyanate group used in the present invention, various known isocyanates such as aromatic, aliphatic or alicyclic can be used.

  For example, 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3- Aromatic polyisocyanates such as phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethyl Aliphatic polyisocyanates such as hexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate, etc. Examples thereof include alicyclic polyisocyanate and dimer isocyanate obtained by converting a carboxyl group of dimer acid into an isocyanate group.

  Moreover, when giving photosensitivity to this thermosetting resin, the compound containing an isocyanate group and a double bond group can be used suitably, 2-Athacryloyloxyethyl isocyanate, 2-methacryloyl Examples thereof include oxyethyl isocyanate, 1,1- (bisacryloyloxymethyl) ethyl isocyanate, monoisocyanate obtained by reacting pentaerythritol triacrylate and tolylene diisocyanate.

<Acid anhydride>
Examples of the acid anhydride used in the present invention include malonic acid anhydride, succinic acid anhydride, maleic acid anhydride, itaconic acid anhydride, phthalic acid anhydride, hexahydrophthalic acid anhydride, tetrahydrophthalic acid anhydride, Examples include methyltetrahydrophthalic anhydride and trimellitic anhydride.

  In the thermosetting resin which concerns on one Embodiment of this invention, the acid value needs to be 3-60 mgKOH / g in conversion of solid content, and if it is 20-50 mgKOH / g, it is more preferable. Therefore, the addition reaction of the acid anhydride is quantitatively reacted so that the acid value falls within this range.

If the acid value of the thermosetting resin is less than 3 mgKOH / g, there is a risk of developing failure in alkali development. If the acid value is greater than 60 mgKOH / g, the surface of the exposed part is eroded by the developer in alkali development. In addition, problems such as deterioration of long-term storage stability of the photosensitive resin composition are likely to occur.
[Method for preparing thermosetting resin]
The thermosetting resin according to an embodiment of the present invention can be prepared by any of the following methods.

(1) A method in which a compound containing a melamine resin and an isocyanate group is mixed and reacted under heating,
(2) A method in which a compound containing a melamine resin and an isocyanate group is mixed and reacted under heating, and further an acid anhydride is mixed and reacted under heating.

  (3) A method in which a melamine resin and an acid anhydride are mixed and reacted under heating.

  Moreover, you may include the process of distilling away unnecessary substances, such as a low boiling alcohol compound, using an evaporator etc. as a pretreatment, and the process of carrying out solvent substitution with the solvent suitable for the photosensitive resin composition.

  Thermosetting resins such as melamine resins have high thermal reactivity and are generally poor in long-term storage stability, so it has been difficult to use them in a large amount in a photosensitive resin composition. However, in the thermosetting resin according to one embodiment of the present invention, some of the plurality of thermoreactive groups present in the melamine resin skeleton are used for the reaction with the isocyanate group-containing compound or acid anhydride. For this reason, the thermal reactivity is moderately reduced, and the effect of improving the long-term storage stability of the photosensitive resin composition can be obtained. Further, as a result of the reaction with the isocyanate group-containing compound or acid anhydride, the polymer chain of the melamine resin becomes longer and the free movement of the melamine resin skeleton is constrained, so that the storage stability is improved. is there.

  The reaction with the isocyanate group-containing compound or acid anhydride makes it possible to impart alkali developability and / or photosensitivity necessary for the alkali development type photosensitive resin composition to the melamine resin. By providing alkali developability and / or photosensitivity in this way, adhesion with the substrate is improved, and a photosensitive resin composition having a good process margin that does not cause problems during the development process is realized. Can do.

 Furthermore, by including the thermosetting resin according to one embodiment of the present invention in the photosensitive resin composition, not only can the cured coating film be provided with sufficient heat resistance and hardness, but also solvent resistance. Further, an alkali resistance function can be imparted.

  In addition, birefringence can be controlled by adding an appropriate amount of the thermosetting resin according to an embodiment of the present invention. That is, the addition of the thermosetting resin makes it possible to increase the thickness direction retardation value further in the positive direction, so that the thermosetting used for each of the red, green, and blue pixels of the color filter. By appropriately setting the amount of the photosensitive resin to an optimal value, the thickness direction retardation value can be matched with the wavelength dispersion characteristics of the retardation value with other members such as liquid crystal and retardation plate of the liquid crystal display device. . As a result, it is possible to provide a liquid crystal display device with excellent visibility which has little phase difference between red, green and blue pixels even when viewed obliquely, and which is not colored in black display.

  The following can be illustrated as acrylic resin used for this invention.

  The material of the acrylic resin is, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) as a monomer. Alkyl (meth) acrylates such as acrylate, pentyl (meth) acrylate, lauryl (meth) acrylate, hydroxyl-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ethoxyethyl (meth) acrylate, Ether group-containing (meth) acrylates such as glycidyl (meth) acrylate and cyclohexyl (meth) acrylate, alicyclic (meth) acrylates such as isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Sulfonyl (meth) acrylate, benzyl (meth) acrylate, p- cumylphenyl (meth) using an aromatic-containing (meth) acrylates such as acrylate polymers.

  In addition, these monomers can be used individually or in combination of 2 or more types. Furthermore, compounds such as styrene, cyclohexylmaleimide, and phenylmaleimide that can be copolymerized with these (meth) acrylates can also be copolymerized.

  These resins can impart solubility by alkali, that is, alkali developability, by introducing a carboxyl group by copolymerizing a carboxylic acid having an ethylenically unsaturated group such as the above (meth) acrylic acid. The alkali developability can also be imparted by reacting the above-mentioned copolymer having a hydroxyl group with a polybasic acid anhydride. Acid anhydrides used in the above reaction include malon anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride trimellitic anhydride Thing etc. are mentioned.

  The solid content acid value of these carboxyl group-containing copolymers is preferably 50 to 130 mgKOH / g. When the acid value is less than 50 mgKOH / g, the time required for development becomes long, resulting in poor productivity. On the other hand, when the acid value is larger than 130 mgKOH / g, defects such as pattern peeling and pattern chipping occur.

  In addition, for example, a compound having an unsaturated double bond and an epoxy group such as glycidyl (meth) acrylate on the carboxyl group of the resin obtained by copolymerizing a carboxylic acid having an ethylenically unsaturated group such as (meth) acrylic acid By reacting, an unsaturated double bond can be introduced into the copolymer to impart photosensitivity.

  Similarly, a copolymer of an epoxy group-containing (meth) acrylate such as glycidyl (meth) acrylate is reacted with a carboxylic acid having an ethylenically unsaturated group such as (meth) acrylic acid, or hydroxyethyl (meth) acrylate. An unsaturated double bond is introduced into the copolymer by a method such as reacting an isocyanate having an ethylenically unsaturated group such as methacryloyloxyethyl isocyanate with a hydroxyl group-containing (meth) acrylate copolymer. Can be granted.

  The double bond equivalent of these photosensitive resins is preferably from 100 to 2000, more preferably from 100 to 1000. Within this range, improvement in photosensitivity can be expected.

[Photosensitive resin composition for forming color filter coloring layer, counter substrate carrying layer, and retardation layer]
Photosensitive resin composition capable of suitably forming a color filter coloring layer, a counter substrate carrying layer, a cell gap control raising layer, and a retardation layer using the thermosetting resin according to an embodiment of the present invention. Contains a photopolymerizable monomer, a non-photosensitive resin and / or a photosensitive resin, a photopolymerization initiator, and a solvent. For curing the photosensitive resin composition, any of curing methods such as UV exposure and deep UV exposure may be used.

  A thermosetting resin may be used individually by 1 type, and can also be used in combination of 2 or more type. Furthermore, the addition amount of the thermosetting resin is not particularly limited, but it is preferably 1 to 200% by weight and preferably 5 to 100% by weight with respect to 100% by weight of the pigment. More preferably, it is most preferable to set it as 10 to 70 weight%.

(Photopolymerizable monomer)
Examples of photopolymerizable monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylol Various acrylic and methacrylic acid esters such as propane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, melamine (meth) acrylate, epoxy (meth) acrylate, (meth) Examples include acrylic acid, styrene, vinyl acetate, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and acrylonitrile.

  Moreover, it is preferable to use the polyfunctional urethane acrylate which has the (meth) acryloyl group obtained by making polyfunctional isocyanate react with the (meth) acrylate which has a hydroxyl group. The combination of the (meth) acrylate having a hydroxyl group and the polyfunctional isocyanate is arbitrary and is not particularly limited. Moreover, one type of polyfunctional urethane acrylate may be used alone, or two or more types may be used in combination.

(Non-photosensitive resin and / or photosensitive resin)
In the photosensitive resin composition suitable using the thermosetting resin according to an embodiment of the present invention, preferably in the entire wavelength region of 400 to 700 nm in the visible light region, preferably 80% or more, more preferably 95% or more. A non-photosensitive transparent resin having a transmittance and / or a photosensitive transparent resin can be used in combination.

  Transparent resins include thermoplastic resins, thermosetting resins, and photosensitive resins. Examples of thermoplastic resins include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, and poly Vinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester resin, acrylic resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polybutadiene , Polyethylene, polypropylene, polyimide resin and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

(Pigment)
When the photosensitive composition layer is a colored layer of a color filter, it is necessary to further contain a pigment.

  Further, even in the case of a counter substrate supporting layer that is not a colored layer, a cell gap control raising layer, and a retardation layer, it can be used by containing a pigment in order to provide light shielding properties (hereinafter referred to as providing light shielding properties). ). Known pigments can be used for the photosensitive resin composition for forming the colored layer and for imparting light shielding properties. The blending amount of the pigment is not particularly limited, but is preferably about 5 to 70% by weight, more preferably about 5 to 50% by weight, with respect to 100% by weight of the total amount of the composition. More preferably, it is about 20 to 50% by weight, and the remainder consists essentially of a resinous binder provided by the pigment carrier.

  Also, a plurality of pigments can be used in combination for spectral adjustment of the color filter. The pigment is preferably contained in a proportion of 5 to 70% by weight based on the total solid content of the colored composition (100% by weight).

  In combination with the organic pigment, an inorganic pigment may be used in combination in order to ensure good coatability, sensitivity, developability and the like while balancing saturation and lightness. Inorganic pigments include yellow lead, zinc yellow, red pepper (red iron oxide (III)), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, and other metal oxide powders, metal sulfide powders, metal powders, etc. Can be mentioned. Furthermore, for color matching, a dye can be contained within a range that does not lower the heat resistance.

(Dispersant)
When the pigment is dispersed in the pigment carrier and the organic solvent, it is necessary to contain a dispersant and a surfactant for dispersing the pigment. Surfactants, pigment intermediates, dye intermediates, Solsperse, and the like are used as the dispersant, and have a pigment affinity part having a property of adsorbing to the pigment and a part compatible with the pigment carrier. It functions to adsorb to the pigment and stabilize the dispersion of the pigment on the pigment carrier.

  Specifically, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt, polysiloxane, long Oil-based dispersants such as chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) and polyesters having free carboxyl groups, and salts thereof , (Meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, and other water-soluble resins Molecular compound, polyester, modified polyacrylate , Ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.

  Although the addition amount of a dispersing agent is not specifically limited, It is preferable to set it as 1 to 10 weight% with respect to 100 weight% of compounding quantities of a pigment. Further, the coloring composition may be obtained by means of centrifugal separation, a sintered filter, a membrane filter, or the like, with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more and mixed dust. Is preferably removed.

(Surfactant)
Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more.

(Photopolymerization initiator)
Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1 Acetophenone compounds such as -hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Benzoin compounds such as benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl Benzophenone compounds such as 4′-methyldiphenyl sulfide, thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 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-pienyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6 -Styryl s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s- Riadin, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloro Triazine compounds such as methyl (4′-methoxystyryl) -6-triazine, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], O- (acetyl) Oxime ester compounds such as -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2, Phosphine compounds such as 4,6-trimethylbenzoyldiphenylphosphine oxide, 9,10-phenanthrenequinone, can Akinon, quinone-based compounds such as ethyl anthraquinone, borate compounds, carbazole compounds, imidazole compounds, titanocene compounds, and the like.

  These can be used singly or in combination of two or more.

(Photosensitizer)
Moreover, it is preferable to use together a polymerization initiator and a photosensitizer. As a sensitizer, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, A compound such as 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone may be used in combination.

  The sensitizer can be contained in an amount of 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.

(Multifunctional thiol)
The photosensitive resin composition can contain a polyfunctional thiol that functions as a chain transfer agent. The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercap -s- triazine, 2- (N, N- dibutylamino) -4,6-dimercapto -s- triazine.

  These polyfunctional thiols can be used alone or in combination. The polyfunctional thiol can be used in an amount of 0.2 to 150 parts by weight, preferably 0.2 to 100 parts by weight, with respect to 100 parts by weight of the pigment in the coloring composition.

(Storage stabilizer)
The photosensitive resin composition can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, triethylphosphine, and triphenylphosphine. Examples thereof include phosphine and phosphite. The storage stabilizer can be contained in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the pigment in the coloring composition.

(Adhesion improver)
In addition, the photosensitive resin composition may contain an adhesion improver such as a silane coupling agent in order to enhance the adhesion to the substrate. Examples of the silane coupling agent include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β ( Aminoethyl) γ-aminopro Lutriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N Examples include aminosilanes such as -phenyl-γ-aminopropyltriethoxysilane, thiosilanes such as γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane. The silane coupling agent can be contained in an amount of 0.01 to 100 parts by weight with respect to 100 parts by weight of the pigment in the coloring composition.

(solvent)
The photosensitive resin composition is mixed with a solvent such as water or an organic solvent in order to enable uniform coating on the substrate. When the composition of the present invention is a colored layer of a color filter, the solvent also has a function of uniformly dispersing the pigment. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether, toluene, Examples include methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent, and the like. These may be used alone or in combination. The solvent can be used in an amount of 800 to 4000 parts by weight, preferably 1000 to 2500 parts by weight with respect to 100 parts by weight of the pigment in the coloring composition.

[Method for Preparing Photosensitive Resin Composition]
The photosensitive resin composition can be prepared by a known method. For example, a photosensitive coloring composition containing a photopolymerizable monomer, a thermosetting resin, a pigment, a dispersant, and a solvent can be prepared by the following method.

 (1) A pigment composition prepared by mixing a pigment and a dispersant in advance in a photopolymerizable monomer and the thermosetting resin of the present invention, or a solution obtained by dissolving these in a solvent, is added and dispersed, and the remaining components Add.

  (2) A pigment and a dispersant are separately added and dispersed in a photopolymerizable monomer and the thermosetting resin of the present invention, or a solution in which these are dissolved in a solvent, and then the remaining components are added.

  (3) After the pigment is dispersed in the photopolymerizable monomer and the thermosetting resin of the present invention or a solution obtained by dissolving these in a solvent, a pigment dispersant is added, and the remaining components are added.

  (4) Prepare two types of photopolymerizable monomer and the thermosetting resin of the present invention, or a solution in which these are dissolved in a solvent, disperse the pigment and the dispersant separately in advance, and then mix these, Add ingredients. One of the pigment and the dispersant may be dispersed only in the solvent.

  Here, the dispersion of the pigment and the dispersant in the photopolymerizable monomer and the thermosetting resin of the present invention, or a solution in which these are dissolved in a solvent, is a three roll mill, a two roll mill, a sand mill, a kneader, a dissolver, a high speed. It can be performed using various dispersing devices such as a mixer, a homomixer, and an attritor. Moreover, in order to perform dispersion | distribution favorably, you may add and disperse | distribute various surfactants.

  In addition, when preparing a pigment composition by previously mixing a pigment and a dispersant, the powder pigment and the powder dispersant may be simply mixed, but (a) a kneader, a roll, an attritor, a super mill, etc. Mix mechanically with various pulverizers, (b) Disperse the pigment in the solvent, add a solution containing the dispersant, and adsorb the dispersant on the pigment surface. (C) Strong dissolving power such as sulfuric acid It is preferable to employ a mixing method in which the pigment and the dispersant are co-dissolved in the solvent that is held and then co-precipitated using a poor solvent such as water.

[Color filter]
Hereinafter, a method for forming a colored layer for a color filter will be described. A counter substrate carrying layer for uniformizing a cell gap of a liquid crystal display device formed on a substrate surface provided with the colored layer, for controlling a cell gap A similar forming method can be applied to the raised layer and the retardation layer.

  FIG. 1 is a schematic cross-sectional view of a color filter according to an embodiment of the present invention.

  As shown in FIG. 1, a black matrix 2 formed by patterning a metal such as chromium or a photosensitive black resin composition is formed on a substrate 1 by a known method. As the substrate 1 to be used, a transparent substrate is preferable, and specifically, a resin substrate such as a glass plate, polycarbonate, polymethyl methacrylate, polyethylene phthalate is preferably used. In addition, a transparent electrode made of a combination of metal oxides such as indium oxide, tin oxide, zinc oxide and antimony oxide is formed on the surface of the glass plate or resin plate for driving the liquid crystal after the liquid crystal panel is formed. Also good.

 First, the photosensitive composition containing the thermosetting resin according to an embodiment of the present invention is uniformly applied on the substrate 1 by a spray coating method, a spin coating method, a roll coating or the like, and dried. The layer formed in this step is referred to as “photosensitive composition layer”. Next, the formed photosensitive composition layer is patterned by photolithography. That is, exposure is performed by irradiating active energy rays such as ultraviolet rays and electron beams through a photomask having a desired light-shielding pattern, and then development is performed using a developer such as an organic solvent or an alkaline aqueous solution. Here, in the exposure step, the portion of the photopolymerizable monomer irradiated with the active energy ray is polymerized and cured. Further, when a photosensitive resin is contained, the resin is also crosslinked and cured.

  In order to improve the exposure sensitivity, after forming the photosensitive composition layer, a solution of a water-soluble or alkaline water-soluble resin (for example, polyvinyl alcohol or water-soluble acrylic resin) is applied and dried, so that oxygen Exposure may be performed after forming a film that suppresses polymerization inhibition due to.

 Next, in the development step, a desired pattern is formed by washing away the portion that has not been irradiated with the active energy ray with a developer. As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. As the developer, an alkaline developer such as an aqueous solution such as sodium carbonate or caustic soda, or an organic alkali solution such as dimethylbenzylamine or triethanolamine is mainly used. Moreover, as a developing solution, what added the antifoamer and surfactant was used as needed.

 Finally, it is baked and the same operation is repeated for other colors to produce a color filter. That is, a colored layer including red pixels 3R, green pixels 3G, and blue pixels 3B is formed on the substrate 1 on which the black matrix 2 is formed. Furthermore, the counter substrate carrying layer 4 for making the cell gap of the liquid crystal display device uniform can be formed on these colored pixels.

 Further, FIG. 2 shows a cell gap control raising layer 5 and a retardation layer 6 on a substrate surface provided with a colored layer, and a counter substrate carrying layer for making the cell gap of a liquid crystal display device uniform. The structure in which 4 was formed was illustrated.

Next, a liquid crystal display device including the color filter described above will be described.
FIG. 3 is a schematic cross-sectional view of a liquid crystal display device including a color filter according to an embodiment of the present invention.

  A liquid crystal display device 7 shown in FIG. 3 is a typical example of a TFT drive type liquid crystal display device for a notebook personal computer, and includes a pair of transparent substrates 8 and 9 disposed so as to be opposed to each other. Liquid crystal (LC) is enclosed.

  The liquid crystal (LC) is TN (twisted nematic), STN (super twisted nematic), IPS (in-plane switching), VA (vertical alignment), OCB (optically compensated alignment), etc. .

 A TFT (thin film transistor) array 10 is formed on the inner surface of the first transparent substrate 8, and a transparent electrode layer 11 made of, for example, ITO is formed thereon. An alignment layer 12 is provided on the transparent electrode layer 11. A polarizing plate 13 including a retardation film is formed on the outer surface of the transparent substrate 8.

  On the other hand, a color filter 14 as shown in FIG. 1 or 2 is formed on the inner surface of the second transparent substrate 9. The red, green and blue filter segments constituting the color filter 14 are separated by a black matrix (not shown). A transparent protective film (not shown) is formed so as to cover the color filter 14 and further, a transparent electrode layer 15 made of, for example, ITO is formed thereon, and the alignment layer 16 is covered so as to cover the transparent electrode layer 15. Is provided. A polarizing plate 17 is formed on the outer surface of the transparent substrate 9. A backlight unit 19 having a three-wavelength lamp 18 is provided below the polarizing plate 13.

  Next, although the Example and comparative example of this invention are shown and this invention is demonstrated concretely, this invention is not limited to these. Further, since the material used in the present invention is extremely sensitive to light, it is necessary to prevent exposure to unnecessary light such as natural light, and all operations are performed under a yellow or red light. In the examples and comparative examples, “parts” means “parts by weight”. The symbol of the pigment indicates a color index number. For example, “PG36” represents “CI Pigment Green 36” and “PY150” represents “CI Pigment Yellow 150”.

[Preparation of resin solution]
The acrylic resin solutions used in Examples and Comparative Examples are prepared as follows. The molecular weight of the resin is a polystyrene-reduced weight average molecular weight measured by GPC (gel permeation chromatography).

<Solvent substitution of melamine resin>
300 g of alkylated melamine resin / 1-butanol solution (Nippon Carbide Industries Co., Ltd., trade name: Nicalak MX-750) having a nonvolatile content of 73.5% by weight is contained in a flask having an internal volume of 500 ml, and an evaporator is used. Unnecessary substances such as 1-butanol were removed. To this alkylated melamine resin, 781.8 g of cyclohexanone was added, and a solvent-substituted melamine resin A was prepared so as to have a nonvolatile content of 22% by weight.

<Synthesis Example 1> Thermosetting resin 1
Into a five-necked reaction vessel having an internal volume of 1 liter, 596.2 g of the solvent-substituted melamine resin A (cyclohexanone) solution having a nonvolatile content of 22% by weight prepared above and 7.7 g of tolylene diisocyanate were charged and heated at 60 ° C. for 2 hours. Reacted.

It was confirmed by infrared spectroscopic analysis that no isocyanate group near 2280 cm ⁻¹ was present in the reaction organism.

  Next, the product was diluted with cyclohexanone so that the nonvolatile content of the product was 20% by weight, and a thermosetting resin 1 was obtained. The obtained thermosetting resin 1 had a weight average molecular weight of 11,200.

<Synthesis Example 2> Thermosetting resin 2
In a five-necked reaction vessel with an internal volume of 1 liter, 596.2 g of a solvent-substituted melamine resin A (cyclohexanone) solution having a nonvolatile content of 22% by weight prepared above, methacryloyloxyethyl isocyanate (manufactured by Showa Denko KK) 9.8 g of Karenz MOI) was charged and reacted at 60 ° C. for 2 hours to obtain a product. In addition, it was confirmed by infrared spectroscopic analysis that there was no absorption of an isocyanate group near 2280 cm ^{−1 in the} reaction organism.

  Next, the product was diluted with cyclohexanone so that the nonvolatile content of the product was 20% by weight, and a thermosetting resin 2 was obtained. The obtained thermosetting resin 2 had a weight average molecular weight of 4900.

<Synthesis Example 3>
A thermosetting resin 3 was obtained in the same manner as in Synthesis Example 1 except that 3.2 g of methacryloyloxyethyl isocyanate was used. The obtained thermosetting resin 1 had a weight average molecular weight of 6,700. The results are shown in Table 1 below.

<Synthesis Example 4> Thermosetting resin 4
In a five-necked reaction vessel with an internal volume of 1 liter, 596.2 g of the solvent-substituted melamine resin A (cyclohexanone) solution having a nonvolatile content of 22% by weight prepared above, butanetetracarboxylic dianhydride (Shin Nippon Rika Co., Ltd.) Product name: Ricacid BT-100) 6.3 g was charged and reacted at 60 ° C. for 24 hours to obtain a product. It was confirmed by infrared spectroscopic analysis that there was no absorption of an acid anhydride group in the vicinity of 1780 cm ^{−1 in the} product.

  Next, the product was diluted with cyclohexanone so that the nonvolatile content of the product was 20% by weight, and a thermosetting resin 4 was obtained.

<Synthesis Example 5> Thermosetting resin 5
A thermosetting resin 5 was obtained in the same manner as in Synthesis Example 4 except that 12.6 g of butanetetracarboxylic dianhydride was used.

<Synthesis Example 6> Thermosetting resin 6
Into a five-necked reaction vessel having an internal volume of 1 liter, 596.2 g of the solvent-substituted melamine resin A (cyclohexanone) solution having a nonvolatile content of 22% by weight prepared above and 7.7 g of tolylene diisocyanate were charged and heated at 60 ° C. for 2 hours. Reacted.

After confirming that the isocyanate group in the vicinity of 2280 cm ⁻¹ did not exist in the reaction organism by infrared spectroscopic analysis, 6.8 g of succinic anhydride was added and reacted at 60 ° C. for 24 hours to obtain a compound. In addition, it was confirmed by infrared spectroscopic analysis that there was no absorption of acid anhydride near 1780 cm ^{−1 in the} product.

  Next, the product was diluted with cyclohexanone so that the nonvolatile content of the product was 20% by weight, and a thermosetting resin 6 was obtained.

<Synthesis Example 7> Thermosetting resin 7
A thermosetting resin 7 was obtained in the same manner as in Synthesis Example 4 except that 14.6 g of succinic dianhydride was used.

<Synthesis Example 8> Acrylic resin 1
In a 5-neck reaction vessel with an internal volume of 2 liters, add 800 g of propylene glycol monomethyl ether acetate, 10 g of methacrylic acid, 40 g of methyl methacrylate, 80 g of butyl methacrylate, 40 g of hydroxyethyl methacrylate and 2 g of azobisisobutyronitrile, and add nitrogen gas. Was heated at 80 ° C. for 6 hours to obtain acrylic resin 1. The obtained acrylic resin 1 had a weight average molecular weight of 40,000.

<Synthesis Example 9> Acrylic resin 2
An acrylic resin 2 was obtained in the same manner as in Synthesis Example 8 except that 40 g of methacrylic acid was used. The resulting acrylic resin 2 had a weight average molecular weight of 40,000.

<Synthesis Example 10> Acrylic resin 3
In a five-necked reaction vessel with an internal volume of 2 liters, propylene glycol monomethyl ether acetate 800 g, methacrylic acid 30 g, butyl methacrylate 70 g, hydroxyethyl methacrylate 40 g, p-cumylphenoxyethyl acrylate 60 g and azobisisobutyronitrile 2 g In addition, while blowing nitrogen gas, it was heated at 80 ° C. for 6 hours to obtain an acrylic resin 3. The weight average molecular weight of the obtained acrylic resin 3 was 30000.

<Synthesis Example 11> Acrylic resin 4
An acrylic resin 4 was obtained in the same manner as in Synthesis Example 10 except that 33 g of methacrylic acid was used. The weight average molecular weight of the obtained acrylic resin 4 was 30000.

<Synthesis Example 12> Acrylic resin 5
In a five-necked reaction vessel with an internal volume of 2 liters, propylene glycol monomethyl ether acetate 800 g, methacrylic acid 40 g, butyl methacrylate 40 g, hydroxyethyl methacrylate 60 g, p-cumylphenoxyethyl acrylate 60 g and azobisisobutyronitrile 4 g In addition, while blowing nitrogen gas, it was heated at 80 ° C. for 6 hours to obtain an acrylic resin. The acrylic resin was further reacted with 45 g of methacryloyloxyethyl isocyanate at 60 ° C. for 8 hours to obtain an acrylic resin 5. The acrylic resin 5 had a weight average molecular weight of 25,000.

<Synthesis Example 11> Acrylic resin 6
An acrylic resin 5 was obtained in the same manner as in Synthesis Example 10 except that 15 g of methacryloyloxyethyl isocyanate was used. The acrylic resin 5 had a weight average molecular weight of 25,000. The results are shown in Table 2 below.

Example 1
[Preparation of colored composition 1]
The green coloring composition used for color filter preparation was prepared as follows.

<Green coloring composition>
A mixture having the following composition was uniformly stirred and mixed, then dispersed in a sand mill for 5 hours using a glass bead having a diameter of 1 mm, and then filtered through a 5 μm filter to prepare a green pigment dispersion.

Green pigment: C.I. I. Pigment Green 36 7.9 parts ("LIONOL GREEN 6YK" manufactured by Toyo Ink Manufacturing Co., Ltd.)
Yellow pigment: C.I. I. Pigment Yellow 150 5.8 parts ("FANCHON FAST YELLOW Y-5688" manufactured by BAYER)
Dispersant ("Ajisper PB821" manufactured by Ajinomoto Fine Techno Co., Ltd.) 1.8 parts Acrylic resin 2 (solid content 20%) 36.5 parts Cyclohexanone 48 parts Then, the mixture of the following composition was stirred and mixed to be uniform, It filtered with a 5 micrometers filter, and the green coloring composition 1 was obtained.

52 parts of the above dispersion Melamine resin 1 16 parts Trimethylolpropane triacrylate (Biscoat # 295, Osaka Organic Chemical Industry Co., Ltd.) 4.8 parts Photopolymerization initiator ("Irgacure-369" manufactured by Ciba Geigy) 2.8 parts Photosensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 part Cyclohexanone 40.2 parts (Examples 2-11, Comparative Examples 1-13)
Colored compositions 2 to 24 were obtained in the same manner as in Example 1 except that the resins described in Table 3 below were used as the pigment in the dispersion, the resin used in the dispersion, and the colored composition.

Example 12
[Preparation of Opposite Substrate Support Layer Photosensitive Resin Composition 1]
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 5 μm filter to prepare a photosensitive resin composition 1 for use in preparing the counter substrate carrying layer.

Thermosetting resin 2 16 parts Photopolymerizable monomer ("Aronix M-402" manufactured by Toa Gosei Co., Ltd.) 2.4 parts Photopolymerization initiator ("Irgacure-907" manufactured by Ciba Geigy Co., Ltd.) 2.8 parts Photosensitizer ( Nippon Kayaku "Diethylthioxanthone-S") 0.5 part Photosensitizer (Kanto Chemical "2-mercaptobenzothiazole") 0.5 part Cyclohexanone 40.2 parts (Example 13)
[Preparation of photosensitive resin composition 2 for raising layer for cell gap control]
A mixture having the composition shown below was stirred and mixed so as to be uniform, and then filtered through a 5 μm filter to prepare a photosensitive resin composition 2 used for preparing a raised layer for cell gap control.

Thermosetting resin 2 16 parts Trimethylolpropane triacrylate (Biscoat # 295, Osaka Organic Chemical Industry Co., Ltd.) 4.8 parts Photopolymerizable monomer (“Aronix M-402” manufactured by Toagosei Co., Ltd.) 2.4 parts Light Polymerization initiator ("Irgacure-907" manufactured by Ciba Geigy) 2.8 parts Photosensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts Cyclohexanone 40.2 parts (Example 14)
[Preparation of Photosensitive Resin Composition 3 for Retardation Layer]
A mixture having the composition shown below was stirred and mixed so as to be uniform, and then filtered through a 5 μm filter to prepare a photosensitive resin composition 3 used for preparing a retardation layer.

Thermosetting resin 2 16 parts Trimethylolpropane triacrylate (Biscoat # 295, Osaka Organic Chemical Industry Co., Ltd.) 4.8 parts Photopolymerizable monomer (“Aronix M-402” manufactured by Toagosei Co., Ltd.) 2.4 parts Light Polymerization initiator ("Irgacure-907" manufactured by Ciba-Geigy) 2.8 parts Photosensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts Cyclohexanone 40.2 parts (Comparative Examples 14-16)
Photosensitive resin compositions 4 to 6 were obtained in the same manner as in Examples 12 to 14 except that the melamine resin 2 was used as the resin.

  About the photosensitive resin composition which concerns on the said Example and comparative example, the following characteristics were measured and evaluated.

1. Long-term storage stability evaluation E type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.) It was measured under the condition of a rotation speed of 20 rpm at 25 ° C. From the values of the initial viscosity and the viscosity with time, the rate of change with time in viscosity was calculated by the following formula.

[Change in viscosity with time] = | ([initial viscosity] − [viscosity with time]) / [initial viscosity] | × 100
Long-term storage stability was evaluated according to the following criteria.

○: Viscosity change rate with time is 10% or less Δ: Viscosity change rate with time is 10% to 20%
X: Viscosity change rate with time exceeds 20%.

2. Thickness direction retardation value Rth
Each color coating film was prepared by the following procedure, and the thickness direction retardation value was measured.

  After coating each color resist shown in Table 3 on a glass substrate by spin coating, it was pre-baked at 70 ° C. for 20 minutes in a clean oven. Next, the substrate was cooled to room temperature, and then exposed to ultraviolet rays using an ultrahigh pressure mercury lamp. Thereafter, the substrate was spray-developed using a sodium carbonate aqueous solution at 23 ° C., washed with ion-exchanged water, and air-dried. Thereafter, post-baking was performed at 230 ° C. for 30 minutes in a clean oven to obtain each color coating film. The film thickness of the dried coating film was 1.8 μm in all cases. In addition, a coating film was formed in the same manner for the counter substrate carrying layer for uniformizing the cell gap of the liquid crystal display device, the cell gap control raising layer, and the photosensitive resin composition for the retardation layer. .

  Thickness direction retardation value is measured by using retardation measurement device ("RETS-100" manufactured by Otsuka Electronics Co., Ltd.) to measure retardation [Delta] ([lambda]) from the direction inclined 45 [deg.] From the normal direction of the substrate on which the coating film is formed. Then, the thickness direction retardation value (Rth) was calculated from the three-dimensional refractive index obtained by using this value, from Equation 1. However, measurement was performed at a wavelength of 610 nm for a red colored pixel, 550 nm for a green colored pixel, and 450 nm for a blue colored pixel.

Formula 1
Rth = {(Nx + Ny) / 2−Nz} × d
(Where Nx is the refractive index in the x direction in the plane of the colored pixel layer, Ny is the refractive index in the y direction in the plane of the colored pixel layer, and Nz is the refractive index in the thickness direction of the colored pixel layer. There is a slow axis where Nx is Nx ≧ Ny, and d is the thickness (nm) of the colored pixel layer.
Table 4 below shows the thickness direction retardation value Rth of each color coating film prepared from each color resist shown in Table 3 above. In addition, the retardation plate used in the liquid crystal display device, a combination of the thickness direction retardation value Rth of the liquid crystal material and the thickness direction retardation value Rth of the colored pixel layer, when viewed from an oblique direction during black display When the coloration of the liquid crystal display device is minimized, the thickness direction retardation value Rth of the colored pixel layer is 0 to 3 nm for red pixels, −4 to 9 nm for green pixels, and 5 to 10 nm for blue pixels, respectively. It was.

  The thickness direction retardation value was evaluated according to the following criteria.

  ○: 0 to 3 nm for red pixels, −4 to 9 nm for green pixels, and 5 to 10 nm for blue pixels.

  X: Not included in the above range.

  The evaluation results are shown in Table 4 below.

  Table 4 below shows the Rth values obtained for the cell gap control raising layer and the retardation resin composition.

3. Sensitivity evaluation The sensitivity of each photosensitive coloring composition, the cell gap control raised layer and the retardation resin composition shown in Table 3 was evaluated as follows.

That is, first, the obtained photosensitive composition was applied onto a glass substrate by spin coating, and then pre-baked at 70 ° C. for 15 minutes to form a coating film having a thickness of 2.3 μm. Next, UV exposure was performed through a photomask having a 50 μm fine line pattern by a proximity exposure method using UV as an exposure light source. The exposure amount was set to 8 levels of 30, 40, 50, 60, 70, 80, 90, and 100 mJ / cm ² .

  Next, after shower development using a 1.25 wt% sodium carbonate solution, washing was performed with water, and heat treatment was performed at 230 ° C. for 20 minutes to complete patterning.

  The film thickness of the obtained filter segment was divided by the film thickness (2.3 μm) of the unexposed / undeveloped portion to calculate the remaining film ratio. An exposure sensitivity curve was plotted with the horizontal axis representing the exposure amount and the vertical axis representing the remaining film ratio after development. From the obtained exposure sensitivity curve, the minimum exposure amount at which the residual film ratio reached 80% or more was defined as the saturation exposure amount, and the sensitivity was evaluated according to the following criteria.

○: Saturation exposure is 50 mJ / cm ² or less Δ: Saturation exposure exceeds 50 and 100 mJ / cm ² or less X: Saturation exposure exceeds 100 mJ / cm ²

4). Patterning property evaluation About each photosensitive coloring composition prepared in each Example and comparative example, the cell gap control raising layer, and the photosensitive resin composition for retardation layer, the patterning performance was evaluated as follows. Went.

  That is, first, the obtained black photosensitive composition was applied onto a glass substrate by spin coating, and prebaked at 70 ° C. for 15 minutes to form a coating film having a thickness of 2.3 μm. Next, ultraviolet exposure was performed through a photomask provided with a stripe pattern having a line width of 6 to 20 μm by a proximity exposure method using ultraviolet light as an exposure light source. The exposure amount was the saturation exposure amount described above.

  Next, shower development was performed using a 1.25 wt% sodium carbonate solution, followed by washing with water. The development time was set to an appropriate time for washing away the unexposed coating film. Next, heat treatment was performed at 230 ° C. for 20 minutes to produce a test substrate.

5). Resistance Evaluation In the same manner as the patterning evaluation, the glass substrate on which the stripe pattern was formed was exposed to the following conditions, and the appearance change of the pattern before and after that was observed with an optical microscope.

N-methyl-2-pyrrolidone solvent immersion 30 minutes (temperature 24 ° C)
Isopropyl alcohol solvent immersion 30 minutes (same as above)
γ-butyrolactone solvent immersion 30 minutes (same as above)
Resistance evaluation was performed according to the following criteria.

○: No change in appearance under all conditions ×: Problems such as pattern peeling, chipping, and cracks are observed.

The above results are shown in Table 4 below.

  From Table 4 above, the resin compositions according to Examples 1 to 14 using the thermosetting resin within the scope of the present invention are the long-term storage stability, sensitivity, patterning property, and further photosensitivity of the photosensitive resin composition. It can be seen that both the thickness direction retardation value and the resistance of the colored layer obtained by curing the conductive resin composition are good.

  On the other hand, it turns out that the resin composition which concerns on Comparative Examples 1-16 using the thermosetting resin outside the scope of the present invention is defective in at least one of the above characteristics.

  In particular, the color filter obtained from the photosensitive resin composition according to the above-described examples is excellent in heat resistance, adhesion to a substrate, hardness, solvent resistance, alkali resistance, and birefringence, and used in a liquid crystal display device. By using the color filter of the present invention by combining the retardation plate and the thickness direction retardation value of the liquid crystal material to be an optimum value, it is possible to visually recognize no color when viewed obliquely. It is possible to provide a liquid crystal display device having excellent properties.

It is a schematic sectional drawing which shows the color filter which concerns on one Embodiment of this invention. It is a schematic sectional drawing which shows the other example of the color filter which concerns on one Embodiment of this invention. It is a schematic sectional drawing which shows an example of the liquid crystal display device provided with the color filter of this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Glass substrate, 2 ... Black matrix, 3R, 3G, 3B ... Colored pixel, 4 ... Opposite substrate support layer, 5 ... Cell gap control raising layer, 6 ... Phase difference layer, 7 ... Liquid crystal display device, 8, DESCRIPTION OF SYMBOLS 9 ... Transparent substrate, 10 ... TFT array, 11, 15 ... Transparent electrode, 12, 16 ... Orientation layer, 13, 17 ... Polarizing plate, 14 ... Color filter, 18 ... Three wavelength lamp, 19 ... Backlight unit.

Claims (12)

  A thermosetting resin obtained by reacting a melamine resin with an isocyanate group-containing compound and having a weight average molecular weight of 2500 or more.   A thermosetting resin obtained by reacting a melamine resin with a compound containing an isocyanate group and having a double bond equivalent of 100 to 2000.   A thermosetting resin obtained by reacting a melamine resin, a compound containing an isocyanate group, and an acid anhydride, and having a solid content acid value of 60 mgKOH / g or less.   A thermosetting resin obtained by reacting a melamine resin with an acid anhydride and having a solid content acid value of 60 mgKOH / g or less. The thermosetting resin according to claim 1, wherein the melamine resin has a structural formula (I) shown below.

(Wherein R ^{1 to} R ⁶ each represent a hydrogen atom or CH ₂ OR (R represents a hydrogen atom or an alkyl group, and R ^{1 to} R ⁶ may be the same or different). , R ^{1 to} R ⁶ may be the same or different.   The thermosetting resin according to claim 1, a photopolymerizable monomer, a photopolymerization initiator, and an acrylic resin, wherein the content of the thermosetting resin is a photosensitive resin composition. A photosensitive resin composition characterized by being 3 to 60% of the solid content of the product.   The photosensitive resin composition according to claim 6, wherein the acrylic resin has an acid value of 50 to 130 mg KOH / g.   The photosensitive resin composition according to claim 6, wherein the acrylic resin has a double bond equivalent of 100 to 2,000.   Furthermore, it contains a pigment and a dispersing agent, The photosensitive resin composition in any one of Claims 6-8 characterized by the above-mentioned.   At least one of the substrate, the colored layer formed on the substrate and / or the counter substrate carrying layer formed on the surface of the substrate provided with the colored layer, the cell gap control raised layer, and the retardation layer 10. The photosensitive resin composition according to claim 6, wherein at least one of the colored layer, the counter substrate carrying layer, the cell gap control raising layer, and the retardation layer is a color filter comprising: A color filter which is a cured film.   A color filter comprising a substrate and a colored pixel formed on the substrate, wherein the colored pixel is a cured film of the photosensitive resin composition according to claim 6, and a thickness direction retardation is red. A color filter comprising 0 to 3 nm for a pixel, 4 to 9 nm for a green pixel, and 5 to 10 nm for a blue pixel.   A liquid crystal display device comprising the color filter according to claim 10.

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