JP5691362B2 - Thermosetting coloring composition and cured film obtained by firing the same - Google Patents

Description

  The present invention relates to a thermosetting coloring composition suitable for correcting defects such as bright spots of defective pixels formed in a liquid crystal display device or the like, a liquid crystal display element produced using the composition, and the like.

  The liquid crystal display panel is mainly composed of two substrates, front and back, and a liquid crystal material therebetween. Of the two substrates, a black matrix (BM), a color filter, a common electrode, and possibly a spacer are formed on the front substrate. As for the array substrate on the back side, active elements such as TFTs and electrodes to be sub-pixels are formed in an array on the liquid crystal side. Each of these substrates is manufactured by repeating a step of laminating a thin film on the substrate, a step of patterning the thin film, and the like.

  Therefore, in order to create a complete substrate without defects, a great effort is required to maintain and manage various setting conditions in each process. Therefore, a defect may occur in some cases.

  In addition, with the increase in the pattern area accompanying the increase in the screen size of liquid crystal display elements in recent years, defects are likely to occur, which has a great influence on the implementation of mass production with improved quality and yield. .

  Since these are directly related to the productivity of the liquid crystal display panel, the importance of solving these problems is increasing, and in order to solve the problems, respective repair techniques have been reported depending on the contents of the defects.

  For example, a pattern defect occurs with a certain probability due to a minute foreign substance or the like existing in the manufacturing process of the color filter substrate or in the material. Pattern defects are roughly classified into two types: black defects with protrusions and white defects with color loss. The generated pattern defects do not only affect the color characteristics of the liquid crystal display device, but particularly in the case of defects with protrusions, black defects formed on the color filter when the color filter is bonded to the TFT substrate and the display panel is assembled. This projection can reach the TFT substrate and cause a short path, which can cause a serious product failure.

  As these repair methods, for black defects, a method of removing foreign matters from the black defect portion with a laser has been reported. However, the laser irradiation is excessively performed, and not only the foreign matter but also the pixel is removed, and a white defect may occur.

  Regarding white defects, Patent Document 1 reports a repair method using ultraviolet curable black ink having sufficient light-shielding properties, in which three colorants of R (red), Y (yellow), and B (blue) are directly mixed. It was done. The color loss is visually recognized by the naked eye. However, when the color loss portion is colored black with black ink, the black portion is small and thus is not visually recognized by the naked eye. However, since the viscosity of the ink used in this method is high and it is difficult to fill the ink only in the missing color portion, the portion where the ink overlaps with the pattern of adjacent pixels or the like tends to be a new protrusion. .

  Further, as an example of the pattern defect, a defect generated during a process of forming a TFT (thin film transistor) on the array substrate can be mentioned. This is because the circuit formation pattern cannot be repaired, and when the array substrate is driven to display, the pixel corresponding to the pixel electrode connected to the TFT becomes a bright spot (bright spot defect) on the display screen. It is a recognized defect.

  As a method for repairing this defect, Patent Document 2 reported a method of irradiating a portion to be repaired with a laser and filling a recess to be formed with a UV curable light-shielding resin. However, in this method, in order to fill the light-shielding resin, a multi-step process such as masking the filling portion with a tape in advance is required.

  On the other hand, a method of directly filling the part to be repaired with light-shielding resin has been tried, but there is a problem that the filled resin is easily peeled off due to external factors such as wiping off the dirt on the substrate surface and washing with a solvent in the subsequent process. is there. This is because the resin has insufficient chemical resistance, solvent resistance, abrasion resistance, and adhesion to the substrate. In addition, the method has a problem that it is difficult to adjust the film thickness of the resin.

  In addition, since the TFT defect is repaired after the liquid crystal panel is formed, when the thermosetting light-shielding resin is used for the repair, it is necessary to bake the resin at a low temperature that does not affect the liquid crystal. . There are many resins that do not cure sufficiently at such low temperatures, and such resins cannot form cured products with excellent chemical resistance, wear resistance, and adhesion to the substrate, and effective repair is not possible. Can not.

  As the means for applying the resin for repairing to the defective part, the method of filling the repaired part with resin as described above, the method of dripping the required amount of paste with a dispenser (Patent Document 3), and the tip forming a flat surface For example, there is a method (Patent Document 4) in which resin is attached to the tip of a needle-like object and pressed against a defective portion.

  However, these coating means require a repair resin ink suitable for each method, and the coating means is difficult to apply to the repair of a finely colored pattern. There are problems such as difficult.

Japanese Patent No. 431551 JP-A-5-181099 JP 11-142635 A JP-A-8-182949

  The present invention is a novel composition capable of low-temperature firing, which can form a cured film having high light-shielding properties, excellent chemical resistance, abrasion resistance, and adhesion to a substrate, and also suitable for repairing fine colored pattern defects. The purpose is to provide.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have a thermosetting comprising a copolymer having a specific structure, a pigment, and a polymer having a free carboxylic acid group or an acid anhydride group. The present inventors have found that the coloring composition has excellent characteristics that can solve the above-mentioned problems, and have completed the present invention. That is, the present invention provides the following thermosetting coloring composition.

[1] (A) a copolymer obtained by polymerizing a radical polymerizable monomer (a1) represented by the general formula (I) and a radical polymerizable monomer (a2) other than the monomer (a1);
(B) a pigment;
(C) a thermosetting coloring composition containing a polymer having at least one structural unit selected from the group consisting of a structural unit derived from an unsaturated carboxylic acid and a structural unit derived from an unsaturated carboxylic anhydride. :

（式中、Ｒ¹は水素、又は任意の水素がフッ素で置き換えられてもよい炭素数１〜５のアルキルであり、
Ｒ²、Ｒ³およびＲ⁴はそれぞれ独立に、水酸基、炭素数１〜５のアルキル、炭素数１〜５のアルコキシ、または-O（Si(C_kH_2k+1)₂O）_mSi(C_pH_2p+1)₃であり（ｋは１〜５の整数であり、ｍは０〜１０の整数であり、ｐは１〜５の整数である）、ｎは１〜５の整数である。）。

(Wherein R ¹ is hydrogen or alkyl having 1 to 5 carbon atoms in which arbitrary hydrogen may be replaced by fluorine,
R ² , R ³ and R ⁴ are each independently a hydroxyl group, alkyl having 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, or —O (Si (C _k H _{2k + 1} ) ₂ O) _m Si ( C _p H _{2p + 1)} is ₃ (k is an integer from 1 to 5, m is an integer of 0, p is an integer of 1 to 5), n is an integer of 1 to 5 is there. ).

[2] The thermosetting coloring composition according to [1], wherein the radical polymerizable monomer (a2) includes a radical polymerizable monomer having an epoxy.
[3] In the formula (I), R ¹ is methyl;
R ² , R ³ and R ⁴ are each independently alkyl having 1 to 3 carbon atoms, alkoxy having 1 to 3 carbon atoms or —O (Si (C _k H _{2k + 1} ) ₂ O) _m Si (C _p H _{2p + 1} ) ₃ (k is an integer of 1-5, m is an integer of 0-10, p is an integer of 1-5),
n is an integer of 2-4, The thermosetting coloring composition as described in [1] or [2] characterized by the above-mentioned.

  [4] The above-mentioned radical polymerizable monomer (a1) is 3-methacryloxypropyltrimethoxysilane and / or 3-methacryloxypropyltris (trimethylsiloxy) silane. The thermosetting coloring composition in any one.

  [5] The epoxy-containing radical polymerizable monomer is glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, α-ethylacrylic acid glycidyl ester, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-methyl- 3- (meth) acryloxymethyl oxetane, 3-ethyl-3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane and 3-ethyl-3- (meth) acryloxyethyl The thermosetting coloring composition according to any one of [2] to [4], which is at least one compound selected from the group consisting of oxetanes.

[6] The unsaturated carboxylic acid is at least one selected from the group consisting of (meth) acrylic acid, itaconic acid, maleic acid, citraconic acid and fumaric acid,
The thermosetting according to any one of claims 1 to 5, wherein the unsaturated carboxylic acid anhydride is at least one selected from the group consisting of maleic anhydride, itaconic anhydride and citraconic anhydride. Coloring composition.

[7] The thermosetting coloring composition according to any one of [1] to [6], further comprising (D) a solvent.
[8] The method according to any one of [1] to [7], further comprising (E) at least one additive selected from the group consisting of a curing agent for epoxy resins, a coupling agent, and a surfactant. Thermosetting coloring composition.

[9] A cured film obtained by applying the thermosetting coloring composition according to any one of [1] to [8] on a substrate and baking the coating film formed on the substrate.
[10] having a pair of opposing substrates, a spacer separating the pair of substrates by a predetermined width, and a liquid crystal material sealed in a gap between the pair of substrates,
A liquid crystal display device, wherein the cured film according to [9] is formed on the substrate.

  The cured film obtained by curing the thermosetting coloring composition of the present invention has high light-shielding properties, excellent chemical resistance, abrasion resistance, and adhesion to the substrate. Suitable for various pattern defect repair. Furthermore, since the composition can be cured by low-temperature firing, it is suitable for repairing TFT defects after forming a liquid crystal panel.

[1. Thermosetting coloring composition]
The thermosetting coloring composition of the present invention is obtained by polymerizing (A) a radical polymerizable monomer (a1) represented by the above general formula (I) and a radical polymerizable monomer (a2) other than the monomer (a1). A copolymer obtained, (B) a pigment, (C) at least one structural unit selected from the group consisting of a structural unit derived from an unsaturated carboxylic acid and a structural unit derived from an unsaturated carboxylic anhydride. Containing polymer.

The thermosetting coloring composition of the present invention may contain additives such as (D) a solvent, (E) an epoxy resin curing agent, a coupling agent, and a surfactant, as necessary.
Although the suitable range of the viscosity of the thermosetting coloring composition of this invention is not specifically limited, It is preferable that the range of the viscosity in 25 degreeC is 3-200 mPa * s. More preferably, it is 5-100 mPa * s, Most preferably, it is 7-50 mPa * s.

  Moreover, when using this thermosetting coloring composition as an inkjet ink, it is preferable that the range of the viscosity is 5-40 mPa * s in an inkjet discharge temperature. More preferably, it is 7-30 mPa * s, Most preferably, it is 10-20 mPa * s.

  The viscosity of the thermosetting coloring composition of the present invention is such that the content of the (A) copolymer, (B) pigment and (C) polymer, (D) solvent content, or (A) copolymer weight. By adjusting the weight average molecular weight of the polymer or (C) polymer as appropriate, it can be within the above range.

[1.1 (A) Copolymer]
The copolymer (A) is a copolymer obtained by polymerizing a radical polymerizable monomer (a1) represented by the general formula (I) and a radical polymerizable monomer (a2) other than the monomer (a1). It is a coalescence. That is, this (A) copolymer is a copolymer obtained by polymerizing a mixture of monomers. Hereinafter, each of these monomers will be described.

<1.1.1 Radical polymerizable monomer (a1) represented by general formula (I)>
General formula (I) is again shown below.

当該式で表されるラジカル重合性モノマー（ａ１）を使用して得られた（Ａ）共重合体を用いると、低温での焼成によって十分に硬化した硬化膜が得られ、しかも耐薬品性、耐磨耗性および基板との密着性に優れた硬化膜を形成しうる熱硬化性着色組成物が得られる。さらに、後述するように一般に（Ｂ）顔料は溶剤に分散させた顔料分散液として、本発明の熱硬化性着色組成物を構成するその他の成分と混合するが、その際に、前記（Ａ）共重合体が顔料分散液に対して優れた安定性を示し、これらが均一に混合される。

When the (A) copolymer obtained by using the radically polymerizable monomer (a1) represented by the formula is used, a cured film sufficiently cured by baking at a low temperature is obtained, and further, chemical resistance, A thermosetting coloring composition capable of forming a cured film excellent in abrasion resistance and adhesion to the substrate is obtained. Further, as will be described later, in general, the (B) pigment is mixed with other components constituting the thermosetting coloring composition of the present invention as a pigment dispersion dispersed in a solvent. The copolymer exhibits excellent stability with respect to the pigment dispersion, and these are uniformly mixed.

In the above formula (I), R ¹ is hydrogen, or alkyl having 1 to 5 carbon atoms in which arbitrary hydrogen may be replaced by fluorine, preferably methyl.
R ² , R ³ and R ⁴ are each independently a hydroxyl group, alkyl having 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, or —O (Si (C _k H _{2k + 1} ) ₂ O) _m Si. (C _p H _{2p + 1} ) ₃ (k is an integer of 1 to 5, m is an integer of 0 to 10, and p is an integer of 1 to 5). R ² , R ³ and R ⁴ are preferably each independently alkyl having 1 to 3 carbon atoms, alkoxy having 1 to 3 carbon atoms or —O (Si (C _k H _{2k + 1} ) ₂ O) _m Si (C _p H _{2p + 1} ) ₃ (k is an integer of 1 to 5, m is an integer of 0 to 10, and p is an integer of 1 to 5).

Finally, n is an integer of 1-5, preferably an integer of 2-4.
Preferable specific examples of the radical polymerizable monomer (a1) represented by the general formula (I) include 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropyltris (trimethylsiloxy) silane.
In this invention, the said radically polymerizable monomer (a1) may be used individually by 1 type, or may mix and use 2 or more types.

<1.1.2 Radical polymerizable monomer other than monomer (a1) (a2)>
The radical polymerizable monomer (a2) other than the monomer (a1) used in the present invention does not correspond to the general formula (I) and is not particularly limited as long as it has radical polymerizability.

  Although details will be described later, considering the reactivity of the copolymer (A) with the polymer (C), the radical polymerizable monomer (a2) is preferably a radical polymerizable monomer having an epoxy. In the present specification, “epoxy” refers to a group having an oxirane ring and a group having an oxetane ring.

  Specific examples of the epoxy-containing radical polymerizable monomer include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, α-ethylacrylic acid glycidyl ester, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-methyl- 3- (meth) acryloxymethyl oxetane, 3-ethyl-3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane and 3-ethyl-3- (meth) acryloxyethyl Oxetane and the like.

  When the copolymer (A) obtained using these radical polymerizable monomers is used, a cured film sufficiently cured by baking at a low temperature can be obtained, and the chemical resistance, abrasion resistance, and substrate A thermosetting coloring composition capable of forming a cured film having excellent adhesion can be obtained.

Among the above specific examples, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate and 3-ethyl-3- (meth) acryloxymethyl oxetane are easily available. The cured film obtained from the thermosetting coloring composition of the present invention has excellent chemical resistance, adhesion to the substrate and abrasion resistance, (A) stability of the copolymer to the pigment dispersion, and the composition It is preferable from the viewpoint of improving the inkjet dischargeability and drawing performance.
Moreover, the radically polymerizable monomer (a2) demonstrated above may be used individually by 1 type, or may be used in mixture of 2 or more types.

<1.1.3 (A) Content of Copolymer>
In the thermosetting coloring composition of the present invention, the content of the copolymer (A) is 0.5 to 35% by weight of the entire composition from the viewpoint of the wear resistance of the cured film obtained from the composition. %, Preferably 1 to 20% by weight.

[1.2 (C) Polymer]
The polymer (C) used in the present invention is a polymer having at least one structural unit selected from the group consisting of a structural unit derived from an unsaturated carboxylic acid and a structural unit derived from an unsaturated carboxylic acid anhydride. It is a coalescence. Unsaturated carboxylic acid and unsaturated carboxylic acid anhydride are radically polymerizable monomers, and these polymerizable double bonds undergo radical polymerization to obtain (C) a polymer. As will be described later, the polymer (C) may have a constitutional unit derived from another monomer described later. Since the thermosetting coloring composition of the present invention contains such a polymer (C), the cured film obtained from the composition has excellent wear resistance and chemical resistance. .

  In addition, the copolymer (A) such as a copolymer obtained by polymerizing the radical polymerizable monomer (a1) represented by the general formula (I) and the unsaturated carboxylic acid (C) In this specification, a copolymer that can also correspond to a polymer shall be regarded as a copolymer (A).

Specific examples of the unsaturated carboxylic acid include (meth) acrylic acid, itaconic acid, maleic acid, citraconic acid, and fumaric acid.
Examples of the unsaturated carboxylic acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like.

  The polymer (C) may have a structural unit derived from hydroxystyrene or 4-hydroxyphenyl vinyl ketone. The use of the polymer (C) having these structural units is preferable from the viewpoint of high curability at low temperature of the thermosetting coloring composition of the present invention.

  Furthermore, the polymer (C) may have a structural unit derived from a radical polymerizable monomer containing N-substituted maleimide and dicyclopentanyl. When the polymer (C) having a structural unit derived from these monomers is used, the composition is excellent in dischargeability and drawing property when jetting the thermosetting coloring composition of the present invention as an ink jet ink. From the viewpoint that the cured film obtained from the above has excellent chemical resistance.

  Specific examples of the N-substituted maleimide include N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N- (4-acetylphenyl) maleimide, N -(2,6-diethylphenyl) maleimide, N- (4-dimethylamino-3,5-dinitrophenyl) maleimide, N- (1-anilinonaphthyl-4) maleimide, N- [4- (2-benz Oxazolyl) phenyl] maleimide and N- (9-acridinyl) maleimide.

Specific examples of the radical polymerizable monomer containing dicyclopentanyl include dicyclopentanyl acrylate and dicyclopentanyl methacrylate.
Furthermore, within the range that does not impair the effects of the present invention, the polymer (C) is a radical polymerization other than the radical polymerizable monomer containing the hydroxystyrene, 4-hydroxyphenyl vinyl ketone, N-substituted maleimide, and dicyclopentanyl. A structural unit derived from a functional monomer may be included.

  In the production of the polymer (C) used in the present invention, the above unsaturated carboxylic acid and unsaturated carboxylic acid anhydride may be used singly or as a mixture of two or more. Furthermore, when using the said other monomer, these monomers can be used individually by 1 type or in mixture of 2 or more types.

  In the thermosetting coloring composition of the present invention, the content of the polymer (C) is preferably 0.1 to 35% by weight of the entire composition, from 1 to 35% by weight, from the viewpoint of solvent resistance. % Is more preferable.

[1.3 (A) Copolymer and (C) Polymer Production Method]
The production method of the (A) copolymer and (C) polymer is not particularly limited, but the (A) copolymer is a mixture of the radical polymerizable monomer (a1) and the radical polymerizable monomer (a2). (C) The polymer is at least one selected from the group consisting of the unsaturated carboxylic acid and the unsaturated carboxylic acid anhydride, and, if necessary, other monomers mentioned above. It can be obtained by polymerizing the mixture.

  The polymerization is preferably radical polymerization in a solution using a solvent. The polymerization temperature is not particularly limited as long as radicals are sufficiently generated from the polymerization initiator to be used, but is usually in the range of 50 ° C to 150 ° C. The polymerization time is not particularly limited, but is usually in the range of 1 to 24 hours. Further, the polymerization can be carried out under any pressure of pressure, reduced pressure or atmospheric pressure.

  As the solvent used in the above polymerization reaction, a monomer to be used and a solvent capable of dissolving the produced (A) copolymer and (C) polymer can be used. Specific examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol, acetone, 2-butanone, ethyl acetate, propyl acetate, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, cyclohexanone, ethylene glycol monoethyl ether, Examples include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate and N, N-dimethylformamide.

  Further, as the solvent used in the polymerization reaction, in addition to the above-described solvents having high solubility such as monomers, the dischargeability and drawing performance when the thermosetting coloring composition of the present invention is jetted as an inkjet ink. Further, from the viewpoint of making nozzle clogging less likely, a high boiling point solvent can also be used. That is, (A) copolymer and (C) polymer are obtained in the state of a solution dissolved in a polymerization solvent, and this solution is prepared in the preparation of the thermosetting coloring composition of the present invention while containing the solvent. You may use for. In this case, the solvent corresponds to the solvent (D) described later.

  Specific examples of the solvent include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, Dipropylene glycol monomethyl ether acetate, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-methyl-2-pyrrolidone and N , N-dimethyl Acetamide, and the like.

The solvent used for the polymerization reaction can be used alone or as a mixed solvent of two or more.
(A) When producing the copolymer, the radically polymerizable monomer (a2) is usually used in an amount of 20 to 400 parts by weight, preferably 40 to 200 parts by weight, based on 100 parts by weight of the radically polymerizable monomer (a1). Then, these monomers are polymerized.

(C) When the polymer is produced, the amount used for the polymerization of the unsaturated carboxylic acid, the unsaturated carboxylic acid anhydride and the above-mentioned other radical polymerizable monomer is usually 1 to 50 weights of the unsaturated carboxylic acid. %, Unsaturated carboxylic acid anhydride is 0 to 50% by weight, and other radical polymerizable monomer is 0 to 99% by weight (however, the total amount of use of the three is 100% by weight),
Preferably, the unsaturated carboxylic acid is 5 to 30% by weight, the unsaturated carboxylic acid anhydride is 0 to 20% by weight, and the other radical polymerizable monomer is 50 to 95% by weight (however, the total amount used by the three members) Is 100% by weight).

  Examples of the polymerization initiator used when synthesizing the copolymer (A) and the polymer (C) include compounds that generate radicals by heat. Examples of such compounds include azo initiators such as azobisisobutyronitrile and 2,2'-azobis (methyl isobutyrate), and peroxide initiators such as benzoyl peroxide.

Moreover, in order to adjust the molecular weight of (A) copolymer and (C) polymer, you may add chain transfer agents, such as thioglycolic acid, in a suitable quantity.
For example, the (A) copolymer and the (C) polymer produced in this way have a weight average molecular weight determined by GPC analysis using polystyrene as a standard in the range of 1,000 to 100,000. The thermosetting coloring composition of the present invention is preferable because it is excellent in curability at low temperature, and has high ejection properties and drawing properties when jetted as an inkjet ink.

  Furthermore, the weight average molecular weight is preferably 1,000 to 50,000, and more preferably 1,000 to 10,000. If it exists in these ranges, the solubility with respect to the (D) solvent mentioned later of (A) copolymer and (C) polymer is excellent, and the viscosity of the thermosetting coloring composition of this invention containing them becomes lower. Therefore, when the composition is used as an inkjet ink and jetting, the discharge accuracy is improved and satellites are suppressed. The satellite is a minute droplet formed behind the main droplet when jetting.

  As the standard polystyrene when measuring the weight average molecular weight, for example, polystyrene having a molecular weight of 500 to 150,000 (for example, PL2010-0102 (S-M2-10) standard manufactured by Polymer Laboratories) can be used, As the column for the measurement, Shodex PLgel MIXED-D (manufactured by Polymer Laboratories) can be used, and as the mobile phase for the measurement, THF can be used. Under such conditions, the weight average molecular weight can be measured.

[1.4 (B) Pigment]
The (B) pigment contained in the thermosetting coloring composition of the present invention may be either an organic pigment or an inorganic pigment, and the low-temperature curability of the thermosetting coloring composition of the present invention, as well as the curing obtained from the composition. It is used to improve chemical resistance, abrasion resistance, adhesion to a substrate, light shielding properties, etc. in the film.

  Further, in the present invention, various organic pigments and inorganic pigments are used as the (B) pigment according to the required light shielding properties. Specific examples of such pigments include C.I. I. Pigment black 1, C.I. I. Pigment black 6, C.I. I. Pigment black 7, C.I. I. Pigment black 8, C.I. I. Pigment black 9, C.I. I. Pigment black 11, C.I. I. Pigment white 6, titanium black, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 202, C.I. I. Pigment red 209, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58, 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 16, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment violet 23, C.I. I. Pigment violet 37, C.I. I. Pigment orange 43, C.I. I. And CI Pigment Orange 71.

In the present invention, the (B) pigment may be a single type or a mixture of two or more types.
Since the (B) pigment is a powder, it is difficult to mix the (A) copolymer and (C) polymer, which are constituent components of the thermosetting coloring composition of the present invention, as it is. Therefore, in general, the (B) pigment is dispersed in a certain amount of solvent to obtain a pigment dispersion, and is mixed with the (A) copolymer and (C) polymer. As a solvent used here, the same solvent as mentioned as what is used in manufacture of said (A) copolymer and (C) polymer can be mentioned. Furthermore, in order to improve the dispersibility of (B) pigment, a pigment dispersant is generally used in combination.

  The average particle diameter (nm) of the (B) pigment in the thermosetting coloring composition of the present invention is usually 20 to 500 nm. More preferably, it is 30-200 nm, Most preferably, it is 30-100 nm. In addition, in this specification, the said average particle diameter is a volume average particle diameter measured using Otsuka Electronics Co., Ltd. zeta potential and particle size measurement system ELS-Zseries.

When the average particle size is within the above range, nozzle clogging of the inkjet head when the thermosetting coloring composition of the present invention is used as an inkjet ink can be effectively suppressed. Dispersion stability can also be kept good. In addition, when the average particle diameter is within the above range, specific optical characteristics such as desired light shielding properties can be obtained in a printed matter obtained by jetting the inkjet ink.
In the thermosetting coloring composition of the present invention, the content of the pigment (B) is preferably 1 to 30% by weight, more preferably 3 to 20% by weight based on the whole composition.

[1.5 (D) Solvent]
When the thermosetting coloring composition of the present invention is used as an inkjet ink, the composition preferably contains (D) a solvent in order to make it difficult to clog the nozzles of the inkjet head. (D) As an example of a solvent, the same solvent as mentioned in manufacture of the said (A) copolymer and (C) polymer is mentioned. (D) The solvent preferably has a boiling point of 180 ° C. or higher, more preferably 180 to 250 ° C., so that the nozzle surface of the inkjet head is difficult to dry and clogging does not occur.

  Specific examples of such a solvent (D) include ethyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol, ethylene glycol monomethyl ether acetate, ethylene glycol mono-t-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol. Monoethyl ether acetate, propylene glycol mono n-butyl ether, propylene glycol monophenyl ether, propylene glycol diacetate, diethylene glycol dimethyl ether acetate, diethylene glycol methyl ethyl ether, diethylene glycol methyl ethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate Diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono -N-butyl ether, dipropylene glycol mono-n-butyl ether acetate, dipropylene glycol mono-t-butyl ether acetate, tripropylene glycol monomethyl ether, tripropylene glycol mono-n-butyl ether, tripropylene glycol methyl ether acetate, tripropylene glycol Mono-n-propyl ether acetate, cyclo Xanone, cyclohexanol acetate, 1,3-butylene glycol diacetate, 3-methoxybutanol, 3-methoxybutyl acetate, 1,3-butylene glycol, triacetin, 1,3-dimethyl-2-imidazolidinone, 3-methoxy Examples thereof include ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, γ-butyrolactone and N-methyl-2-pyrrolidone.

In the present invention, the solvent (D) may be a single solvent or a mixed solvent of two or more.
The content of the solvent (D) in the thermosetting coloring composition of the present invention is preferably 95 to 50% by weight, more preferably 90 to 60% by weight, based on the total amount of the composition. Most preferably, it is 85 to 65% by weight.

  (D) If the content of the solvent is within the above range, nozzle clogging of the inkjet head caused by the high viscosity of the thermosetting coloring composition is suppressed, and continuous jetting is not hindered. Further, even when the amount of ink jetted at one time or the number of jettings is reduced, the ink jet coating film thickness necessary for repairing the defect of the liquid crystal display device can be obtained.

[1.6 (E) Additives]
The thermosetting coloring composition of this invention may contain (E) additives other than the component quoted above as needed.

  These (E) additives are obtained from the thermosetting coloring composition of the present invention when, for example, the radically polymerizable monomer (a2) having an epoxy is used as the synthetic monomer for the (A) copolymer. A curing agent for an epoxy resin used for further improving the heat resistance of the cured film obtained, a coupling agent used for improving the adhesion of the cured film, for example, to the substrate, and the cured film, For example, a surfactant used for improving wettability to the base substrate can be used.

<1.6.1 Curing agent for epoxy resin>
Examples of the epoxy resin curing agent include acid anhydrides, amines, quaternary onium salts, and crown ether complexes.

  Examples of acid anhydrides used as curing agents for epoxy resins include aromatic acid anhydrides such as trimellitic acid anhydride and phthalic acid anhydride; alicyclic acid anhydrides such as hexahydrophthalic acid anhydride, 4-methylhexahydrophthalic anhydride, 4-cyclohexene-1,2-dicarboxylic acid anhydride, Ricacid HNA100 (trade name; manufactured by Shin Nippon Rika Co., Ltd.), etc .; aliphatic acid anhydrides such as maleic anhydride Citraconic anhydride, etc .; aromatic tetracarboxylic dianhydrides such as 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride Anhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,2 ′, 3,3 ′ -Diphenylsulfone tetracarboxylic dianhydride, 2,3,3 ', 4'-diphenylsulfone tetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3', 4'-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexa Fluoropropane dianhydride or ethylene glycol bis (anhydrotrimellitate) etc .; alicyclic tetracarboxylic dianhydrides such as cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic Acid dianhydrides, or cyclohexanetetracarboxylic dianhydrides; and aliphatic tetracar Phosphate dianhydride, such as ethane tetracarboxylic acid dianhydride, or butane tetracarboxylic acid dianhydride and the like.

  Examples of amines used as curing agents for epoxy resins include aliphatic amines such as diethylenetriamine and triethylenetetramine; alicyclic amines such as isophoronediamine and 1,3-bisaminomethylcyclohexane; aromatic amines, For example, bisaminophenoxyphenylsulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, diaminodiphenylmethane, diaminodiphenylsulfone, etc .; and amine-modified products such as polyamide, ketamine, etc .; Secondary amines such as benzyldimethylamine, 2,4,6-trisdimethylaminophenol, diethylaminopropylamine, N-aminoethylpiperazine, 4- (N, N-dimethylamino) pyridine (DMAP), 4- ( , N- diethylamino) pyridine, and 1,8-diazabicyclo [5,4,0] - such undec-7-ene (DBU) and the like.

  Tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, tetraethylammonium bromide, tetraethylammonium chloride, tetraethylammonium iodide, n-dodecyltrimethylammonium used as a curing agent for epoxy resins Bromide, octadecyltrimethylammonium bromide, trimethylbenzylammonium bromide, cetyldimethylbenzylammonium chloride, cetyldimethylbenzylammonium bromide, cetylpyridium sulfate, tetraethylammonium acetate, trimethylbenzylammonium benzoate, trimethylbenzylammonium borate, 5-ben Fourth, such as ru-1,5-diazabicyclo [4,3,0] -5-nonenium chloride and 5-benzyl-1,5-diazabicyclo [4,3,0] -5-nonenium tetrafluoroborate Ammonium salts, and tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, tetraphenylphosphonium chloride, benzyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, triphenylmethoxymethylphosphonium chloride, triphenyl Phenylmethylcarbonylmethylphosphonium chloride, triphenylethoxycarbonylmethylphosphonium chloride, trioctylbenzylborophony Mukuroraido, trioctyl methyl phosphonium chloride, may be mentioned trioctyl ethyl phosphonium acetate, tetra-octyl phosphonium chloride, and quaternary phosphonium salts such as trioctyl ethyl phosphonium dimethyl phosphate and the like.

  Examples of crown ether complexes used as curing agents for epoxy resins include 12-crown-4, 15-crown-5, 18-crown-6, cis-dicyclohexano-18-crown-6, 21-crown-7. , Or 24-crown-8 and the like, such as KF, KCl, KBr, CsF, CsCl, CsBr, potassium thiocyanate, sodium phenoxide, potassium phenoxide, sodium benzoate, potassium benzoate, sodium acetate, or potassium acetate Mention may be made of complexes with inorganic salts or organic salts.

  Among these, 3,3′-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone that do not easily affect the curability and storage stability of the thermosetting coloring composition of the present invention are preferable. Furthermore, 3,3′-diaminodiphenyl sulfone and the like are particularly preferable.

  Moreover, content of the hardening | curing agent for epoxy resin in the thermosetting coloring composition of this invention is determined by content of the (A) copolymer to add. The content of the curing agent for epoxy resin is preferably 0.1 to 20 parts by weight, more preferably 100 parts by weight of the copolymer (A) contained in the thermosetting coloring composition of the present invention. Is 0.1 to 10 parts by weight, and most preferably 0.1 to 5 parts by weight.

<1.6.2 coupling agent>
As the coupling agent, for example, a silane-based, aluminum-based or titanate-based compound can be used.

Specifically, the silane compounds include 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyl. Trimethoxysilane etc. can be mentioned,
Examples of the aluminum-based compound include acetoalkoxyaluminum diisopropylate.
Examples of titanate compounds include tetraisopropyl bis (dioctyl phosphite) titanate.

  Among these, 3-glycidoxypropyltrimethoxysilane and the like are preferable because they have a large effect of improving the adhesion of the cured film obtained from the thermosetting coloring composition of the present invention to the substrate.

  When a coupling agent is used, the amount used is preferably 0.1 to 20 parts by weight, more preferably 0.1 to 100 parts by weight based on 100 parts by weight of the solid content of the thermosetting coloring composition of the present invention. The amount is 10 parts by weight, more preferably 0.1 to 5 parts by weight.

<1.6.3 Surfactant>
As the surfactant, for example, a silicon surfactant, an acrylic surfactant, a fluorine surfactant, or the like can be used.

Specifically, as the silicon-based surfactant, Byk-300, Byk-306, Byk-335, Byk-310, Byk-341, Byk-344, and Byk-370 (respectively trade names: Big Chemie Japan ( Etc.)
Examples of the acrylic surfactant include Byk-354, Byk-358, and Byk-361 (each trade name; manufactured by BYK Japan Japan Co., Ltd.).
Examples of the fluorosurfactant include DFX-18, Aftergent 250, or Aftergent 251 (each trade name; manufactured by Neos), F470, F475, F479, F553, F554, F477, and MCF350 (each trade name; DIC Corporation).

  When using the surfactant, the amount used is preferably 0.01 to 5% by weight, more preferably 0.01 to the total amount (100% by weight) of the thermosetting coloring composition of the present invention. The amount is 1% by weight, more preferably 0.01 to 0.5% by weight.

[1.7 Preparation Method of Thermosetting Coloring Composition]
The thermosetting coloring composition of the present invention comprises the above-described (A) copolymer, (B) pigment, and (C) polymer as essential components, and (D) a solvent and others as necessary. In order to adjust the particle diameter of the pigment, preferably (B), the mixture obtained by the above mixing is filtered with a filter having a pore diameter of 1.0 to 5.0 μm. It can be prepared.

[2 Cured film obtained by baking a coating film of thermosetting coloring composition]
The thermosetting coloring composition of this invention is suitable for the method of apply | coating on substrates, such as glass, by well-known methods, such as a spin coat, a roll coat, and a slit coat.

  Furthermore, when the thermosetting coloring composition of this invention contains (D) solvent, the said composition can be used as an inkjet ink excellent in the inkjet characteristics when jetting. Therefore, the composition is most suitable for a printing method in which the composition is applied only to a necessary portion, for example, an ink jet printing method.

  And a cured film is formed by baking the coating film of the thermosetting coloring composition of this invention apply | coated on the board | substrate by one of said methods. As a feature of the present invention, firing at 100 to 120 ° C. under a low temperature condition of 60 to 120 minutes is possible. Even if the firing conditions are changed to a higher temperature and a longer time, the properties of the obtained cured film are not particularly affected.

  The curing principle of the composition is not particularly limited. As an example, the (A) copolymer and (C) polymer in the composition are cured by heating. As a result, the light-shielding property, abrasion resistance, and chemical resistance of the cured film after film formation of the composition are excellent.

  Furthermore, the (A) copolymer and the (C) polymer react to form a three-dimensional structure by firing (heating) to form a crosslinked structure (however, the curing principle is not limited to this). While maintaining excellent ink jet characteristics, the light-shielding property, abrasion resistance, and chemical resistance of the cured film obtained by baking after film formation of the composition are further improved.

  In this case, the amount (B) of pigment used (B part by weight), the amount (A) of copolymer used (A part by weight), and the amount of polymer (C) used in the thermosetting coloring composition of the present invention. It is preferable that the following mathematical formula (1) and mathematical formula (2) are satisfied in the weight ratio of (C parts by weight). If the weight ratio is within this range, the ink jet characteristics when jetting the thermosetting coloring composition of the present invention, the light-shielding property and abrasion resistance of the cured film obtained by baking after film formation of the composition. Good balance between chemical resistance and adhesion to the substrate.

0.05 ≦ B / (A + C) ≦ 5.0 (1)
0.02 ≦ C / A ≦ 5.0 (2)
“B / (A + C)” in the formula (1) is more preferably 0.1 to 3.0, and further preferably 0.5 to 1.0. Moreover, “C / A” in the formula (2) is more preferably 0.05 to 5.0.

[3 Use of cured film formed from thermosetting coloring composition]
Since the cured film formed as described above contains a pigment, it has excellent light shielding properties. Therefore, the thermosetting coloring composition of the present invention is optimal for forming a cured film having a light-shielding property (a light-shielding cured film) as necessary depending on the pigment used. Here, the light-shielding cured film refers to, for example, a film provided for repairing (correcting) defects such as a bright spot of a defective pixel formed in a liquid crystal display device.

  As described in [Background Art], since the TFT defect is repaired after the liquid crystal panel is formed, it is required to fire the defect repair material at a low temperature that does not affect the liquid crystal. The thermosetting coloring composition of the present invention can be fired at a low temperature as described above.

  In the manufacturing process of liquid crystal display devices and the like, operations such as wiping off the surface of the substrate and cleaning with chemicals are performed. It is required to have excellent adhesion.

As described above, the cured film obtained from the thermosetting coloring composition of the present invention is excellent in all of these characteristics, so that the composition is widely suitable as a defect repair material for liquid crystal display devices and the like. .
Furthermore, since the thermosetting coloring composition of this invention can be apply | coated by an inkjet system, the said cured film is suitable also for the repair of a fine coloring pattern defect.

[4 Liquid crystal display element and solid-state image sensor]
The liquid crystal display element of the present invention comprises a pair of substrates disposed opposite to each other, a spacer for regulating the space between the substrates to a predetermined width, and a liquid crystal material sealed in the gap between the substrates (the sealed portion is a liquid crystal layer). The cured film of the present invention is formed on the substrate.

The spacer is formed using a photosensitive resin transfer material or the like in order to keep the thickness of the liquid crystal layer constant.
As the liquid crystal in the liquid crystal display element, STN type, TN type, GH type, ECB type, ferroelectric liquid crystal, anti-ferroelectric liquid crystal, VA type, MVA type, ASM type, IPS type, OCB type, AFFS type and others Are preferably mentioned. It is preferable to use a photo-spacer excellent in uniformity for systems that require cell gap uniformity, such as IPS type, MVA type, AFFS type, and OCB type.

As a basic configuration aspect of the liquid crystal display element of the present invention,
1) A color filter side including a drive side substrate in which drive elements such as thin film transistors (TFT) and pixel electrodes (conductive layers) are arranged, a color filter having a cured film of the present invention, and a counter electrode (conductive layer). The substrate is placed opposite to each other with a spacer in between, and a liquid crystal material is sealed in the gap.
2) A color filter-integrated driving substrate in which the color filter having the cured film of the present invention is directly formed on the driving side substrate and a counter substrate having a counter electrode (conductive layer) are arranged opposite to each other with a spacer interposed therebetween. In addition, a liquid crystal material sealed in the gap may be used. The liquid crystal display element of the present invention can be suitably applied to various liquid crystal display devices.

  Moreover, the cured film of this invention can be used also for the repair process in the manufacturing process of a solid-state image sensor, etc. The solid-state imaging device thus manufactured is, for example, a color on a silicon wafer provided with a transfer electrode and a photodiode, that is, on a transfer electrode or a photodiode having a higher height from the silicon wafer. A filter is provided (laminated) so as to cover the entire silicon wafer, and the cured film of the present invention is formed on at least a part of the color filter (for example, formed to repair defects generated in the color filter). Then, it can be manufactured by laminating microlenses. As the solid-state imaging device, both a contact-type or completely-contact type solid-state imaging device (image sensor) without an optical reduction system and a solid-state imaging device (CCD solid-state imaging device) with an optical reduction system can be adopted. .

  EXAMPLES Next, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these Examples.

[Synthesis Example 1] (A1) Synthesis of copolymer In a four-necked flask equipped with a stirrer, diethylene glycol mono-n-butyl ether acetate as a polymerization solvent, 3-methacryloxypropyltrimethoxysilane as a radical polymerizable monomer (a1), Glycidyl methacrylate as a radical polymerizable monomer (a2) and 2,2′-azobis (methyl isobutyrate) as a polymerization initiator were charged in the following weight, and polymerization was performed by heating at a polymerization temperature of 105 ° C. for 4 hours. .
Diethylene glycol mono-n-butyl ether acetate (DEGBEA) 150.0 g
3-Methacryloxypropyltrimethoxysilane 44.4g
55.6 g of glycidyl methacrylate
2,2'-azobis (methyl isobutyrate) 20.0 g.

The reaction solution was cooled to room temperature to obtain a copolymer solution (A1).
A part of the solution was sampled, and the weight average molecular weight of the (A1) copolymer was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight was 3,000.

[Synthesis Example 2] (A2) Synthesis of copolymer In the same manner as in Synthesis Example 1, the following components were charged in a four-necked flask equipped with a stirrer at the following weight and heated at a polymerization temperature of 90 ° C for 2 hours. Polymerization was performed.
Dipropylene glycol monomethyl ether acetate (DPMA) 150.0g
3-methacryloxypropyltrimethoxysilane 40.0 g
Glycidyl methacrylate 50.0g
4-hydroxyphenyl vinyl ketone 10.0 g
1,2'-azobis (methyl isobutyrate) 15.0 g.

  The same treatment as in Synthesis Example 1 was performed, and the weight average molecular weight determined by GPC analysis (polystyrene standard) of the obtained (A2) copolymer was 2,800.

[Synthesis Example 3] (A3) Synthesis of copolymer In the same manner as in Synthesis Example 1, the following components were charged in a four-necked flask with a stirrer at the following weight and heated at a polymerization temperature of 90 ° C for 2 hours. Polymerization was performed.

Diethylene glycol mono-n-butyl ether (DB) 150.0g
3-methacryloxypropyltris (trimethylsiloxy) silane 40.0 g
Glycidyl methacrylate 20.0g
4-hydroxyphenyl vinyl ketone 5.0 g
Dicyclopentanyl methacrylate 35.0g
2,2′-azobis (methyl isobutyrate) 8.0 g

  The weight average molecular weight calculated | required by GPC analysis (polystyrene standard) of the obtained (A3) copolymer was performed similar to the synthesis example 1, and was 6,600.

[Synthesis Example 4] (A4) Synthesis of copolymer In the same manner as in Synthesis Example 1, the following ingredients were charged in a four-necked flask equipped with a stirrer at the following weight and heated at a polymerization temperature of 90 ° C for 2 hours. Polymerization was performed.
Diethylene glycol mono-n-butyl ether acetate (DEGBEA) 150.0 g
3-methacryloxypropyltris (trimethylsiloxy) silane 30.0 g
3-methacryloxypropyltrimethoxysilane 39.0 g
Glycidyl methacrylate 25.0g
4-hydroxyphenyl vinyl ketone 6.0 g
1,2'-azobis (methyl isobutyrate) 15.0 g.

  The same treatment as in Synthesis Example 1 was performed, and the weight average molecular weight determined by GPC analysis (polystyrene standard) of the obtained (A4) copolymer was 4,800.

[Synthesis Example 5] (C1) Synthesis of Polymer In the same manner as in Synthesis Example 1, the following ingredients were charged in a four-necked flask equipped with a stirrer with the following weight and heated at a polymerization temperature of 105 ° C. for 2 hours for polymerization. Went. In the following monomers, methacrylic acid is an unsaturated carboxylic acid. The same applies to Synthesis Examples 6 to 8 below.
Diethylene glycol mono-n-butyl ether acetate (DEGBEA) 300.0 g
Dicyclopentanyl methacrylate 40.0g
N-cyclohexylmaleimide 35.0g
Methacrylic acid 25.0 g
2,2'-azobis (methyl isobutyrate) 20.0 g.

  The same treatment as in Synthesis Example 1 was performed, and the weight average molecular weight determined by GPC analysis (polystyrene standard) of (C1) polymer was 3,100.

[Synthesis Example 6] (C2) Synthesis of Polymer In the same manner as in Synthesis Example 1, the following components were charged in a four-necked flask equipped with a stirrer with the following weight and heated at a polymerization temperature of 110 ° C. for 2 hours for polymerization. Went.
Dipropylene glycol monomethyl ether acetate (DPMA) 200.0g
Dicyclopentanyl methacrylate 43.0g
N-cyclohexylmaleimide 33.0g
Methoxypolyethylene glycol methacrylate 2.0g
Methacrylic acid 22.0g
1,2'-azobis (methyl isobutyrate) 15.0 g.

  The same treatment as in Synthesis Example 1 was performed, and the weight average molecular weight determined by GPC analysis (polystyrene standard) of the (C2) polymer was 2,700.

[Synthesis Example 7] (C3) Synthesis of Polymer In the same manner as in Synthesis Example 1, the following components were charged in a four-necked flask with a stirrer at the following weights and heated at a polymerization temperature of 80 ° C. for 5 hours for polymerization. Went.
Diethylene glycol mono-n-butyl ether (DB) 200.0g
Styrene 60.0g
N-cyclohexylmaleimide 25.0g
Methacrylic acid 15.0g
4.0 g of 2,2′-azobis (methyl isobutyrate).

  The same treatment as in Synthesis Example 1 was performed, and the weight average molecular weight determined by GPC analysis (polystyrene standard) of the (C3) polymer was 3,600.

[Synthesis Example 8] (C4) Synthesis of Polymer In the same manner as in Synthesis Example 1, the following components were charged in a four-necked flask with a stirrer at the following weight and heated at a polymerization temperature of 80 ° C for 1.5 hours. Polymerization was performed.
Diethylene glycol methyl ethyl ether (EDM) 200.0g
Glycidyl methacrylate 92.0g
Methacrylic acid 8.0g
4.0 g of 2,2′-azobis (methyl isobutyrate).

  The same treatment as in Synthesis Example 1 was performed, and the weight average molecular weight determined by GPC analysis (polystyrene standard) of the (C4) polymer was 8,500.

[Comparative Synthesis Example 1] (M1) Copolymer Synthesis In the same manner as in Synthesis Example 1, the following components were charged in a four-necked flask with a stirrer at the following weight and heated at a polymerization temperature of 100 ° C for 3 hours. Polymerization was performed.
Diethylene glycol mono-n-butyl ether acetate (DEGBEA) 150.0 g
Glycidyl methacrylate 80.0g
Methacrylate-n-butyl 20.0g
10.0 g of 2,2′-azobis (methyl isobutyrate).

  The weight average molecular weight calculated | required by GPC analysis (polystyrene standard) of the obtained (M1) copolymer was performed in the same manner as in Synthesis Example 1, and was 3,300.

[Comparative Synthesis Example 2] (M2) Synthesis of copolymer In the same manner as in Synthesis Example 1, the following components were charged in the following weights, and polymerization was carried out by heating at a polymerization temperature of 100 ° C for 2 hours.
Dipropylene glycol monomethyl ether acetate (DPMA) 200.0g
Glycidyl methacrylate 40.0g
N-cyclohexylmaleimide 30.0g
N-Phenylmaleimide 30.0g
10.0 g of 2,2′-azobis (methyl isobutyrate).

  The weight average molecular weight calculated | required by GPC analysis (polystyrene standard) of the obtained (M2) copolymer was performed in the same manner as in Synthesis Example 1, and was 2,900.

[Comparative Synthesis Example 3] (M3) Synthesis of Polymer In the same manner as in Synthesis Example 1, the following components were charged in a four-necked flask equipped with a stirrer with the following weight and heated at a polymerization temperature of 100 ° C for 2 hours. Polymerization was performed.
Diethylene glycol mono-n-butyl ether (DB) 200.0g
Glycidyl methacrylate 100.0g
10.0 g of 2,2′-azobis (methyl isobutyrate).

  The same treatment as in Synthesis Example 1 was performed, and the weight average molecular weight determined by GPC analysis (polystyrene standard) of the obtained (M3) polymer was 4,100.

[Comparative Synthesis Example 4] (M4) Copolymer Synthesis In the same manner as in Synthesis Example 1, the following components were charged in a four-necked flask with a stirrer at the following weight and heated at a polymerization temperature of 90 ° C for 2 hours. Polymerization was performed.
Diethylene glycol mono-n-butyl ether acetate (DEGBEA) 150.0 g
Glycidyl methacrylate 30.0g
40.0 g of N-cyclohexylmaleimide
Benzyl methacrylate 10.0g
4-hydroxyphenyl vinyl ketone 20.0g
10.0 g of 2,2′-azobis (methyl isobutyrate).

  The weight average molecular weight calculated | required by GPC analysis (polystyrene standard) of the obtained (M4) copolymer was performed in the same manner as in Synthesis Example 1, and was 5,300.

<Preparation Example 1 of Pigment Dispersion> (B1) Carbon Black Dispersion 30 g of DEGBEA (diethylene glycol mono-n-butyl ether acetate) and styrene-maleic anhydride copolymer (acid value 175, weight average molecular weight 3500) as a pigment dispersant ) And styrene-α-methylstyrene-acrylic acid copolymer (acid value 200, weight average molecular weight 8000) in total were dissolved, and carbon black (CI pigment black 7, average primary particles) was dissolved in the resulting solution. After adding 20 g of a powder having a diameter of 0.030 μm and kneading with a three-roll mill, 44 g of DEGBEA and 400 g of zirconia beads having a diameter of 0.5 mm were added to the mixed solution, followed by stirring for 20 hours in a sand mill. The obtained liquid was filtered through a Teflon (registered trademark) membrane filter having a pore size of 1 μm to obtain a carbon black dispersion (B1).

<Preparation Example 2 of Pigment Dispersion> (B2) Carbon Black Dispersion 30 g of DPMA (dipropylene glycol monomethyl ether acetate) and styrene-maleic anhydride copolymer (acid value 175, weight average molecular weight 3500) as a pigment dispersant And 6 g of styrene-α-methylstyrene-acrylic acid copolymer (acid value 200, weight average molecular weight 8000) in total were dissolved, and carbon black (CI pigment black 7, average primary particle size) was dissolved in the resulting solution. After adding 20 g of 0.030 μm and powder) and kneading with a three-roll mill, 44 g of DPMA and 400 g of zirconia beads having a diameter of 0.5 mm were added to the mixed solution, and the mixture was stirred for 20 hours with a sand mill. The obtained liquid was filtered through a membrane filter made of Teflon (registered trademark) having a pore diameter of 1 μm (B2) to obtain a carbon black dispersion.

<Preparation Example 3 of Pigment Dispersion> (B3) Carbon Black Dispersion 30 g of DB (diethylene glycol mono-n-butyl ether) and styrene-maleic anhydride copolymer (acid value 175, weight average molecular weight 3500) as a pigment dispersant And 6 g of styrene-α-methylstyrene-acrylic acid copolymer (acid value 200, weight average molecular weight 8000) in total were dissolved, and carbon black (CI pigment black 7, average primary particle size) was dissolved in the resulting solution. After adding 20 g of 0.030 μm and powder) and kneading with a three-roll mill, 44 g of DB and 400 g of zirconia beads having a diameter of 0.5 mm were added to the mixed solution and stirred for 10 hours with a sand mill. The obtained liquid was filtered through a Teflon (registered trademark) membrane filter having a pore diameter of 1 μm (B3) to obtain a carbon black dispersion.

<Pigment Dispersion Preparation Example 4> (B4) Carbon Black Dispersion 30 g of DEGBEA (diethylene glycol mono-n-butyl ether acetate) and a styrene-maleic anhydride copolymer (acid value 175, weight average molecular weight 3500) as a pigment dispersant ) And styrene-α-methylstyrene-acrylic acid copolymer (acid value 200, weight average molecular weight 8000) in total were dissolved, and carbon black (CI pigment black 7, average primary particles) was dissolved in the resulting solution. After adding 20 g of a powder having a diameter of 0.030 μm and kneading with a three-roll mill, 44 g of DEGBEA and 400 g of zirconia beads having a diameter of 0.5 mm were added to the mixed solution, followed by stirring in a sand mill for 30 hours. The obtained liquid was filtered through a Teflon (registered trademark) membrane filter having a pore diameter of 1 μm (B4) to obtain a carbon black dispersion.

<Preparation example of thermosetting coloring composition and its evaluation>
(A) Copolymer (Synthesis Examples 1 to 4), (C) Polymer (Synthesis Examples 5 to 8), and (M) (Co) polymer (Comparative Synthesis Examples 1 to 4) obtained as described above. ) And (B) A thermosetting coloring composition (Examples 1 to 4 and Comparative Examples 1 to 5) is prepared using the pigment dispersion (Preparation Examples 1 to 4), and the thermosetting coloring composition is prepared. Various evaluations were performed.

[Example 1 (thermosetting coloring composition)]
The following components are mixed, and the mixture is filtered through a Teflon (registered trademark) membrane filter having a pore size of 2 μm, and a thermosetting coloring composition having a viscosity of 13.3 mPa · s, an average particle size of pigment of 79 nm, and a particle size distribution of 1.42. I got a thing. The viscosity of the composition was measured at 25 ° C. using an E-type viscometer (trade name; manufactured by VISCONIC END Co., Ltd., Tokyo Keiki Co., Ltd.) (hereinafter the same), and the average particle diameter of the pigment in the composition ( μm) and particle size distribution (Mv / Mn) were measured using a Zeta potential / particle size measurement system ELS-Zseries (Otsuka Electronics Co., Ltd.).
Diethylene glycol mono-n-butyl ether acetate (DEGBEA) 1.50 g
(A1) Copolymer (40% by weight solution) 1.00 g
(B1) Pigment dispersion 5.00 g
(C1) Polymer (25% by weight solution) 5.00 g
Byk-344 (trade name; manufactured by Big Chemie Japan Co., Ltd.) 0.05 g.

The parentheses provided for (A1) copolymer and (C1) polymer indicate the content (concentration) of the copolymer in each copolymer-containing solution. However, the weight of the polymerization initiator used during the synthesis is ignored and not included in the calculation. The same applies hereinafter.

  Inkjet characteristics (jetting characteristics) when jetting using this thermosetting coloring composition, chemical resistance of a cured film obtained by applying the composition to a substrate and baking the formed coating film The light shielding properties and the abrasion resistance were evaluated by the following evaluation methods. The evaluation results are shown in Table 1 below. Since the adhesion of the cured film to the substrate is a factor that greatly affects the chemical resistance and wear resistance of the cured film, the cured film having excellent chemical resistance and abrasion resistance is in close contact with the substrate. Excellent in properties.

(Evaluation method for jetting characteristics)
The thermosetting coloring composition was applied to a glass substrate with DMP-2831 manufactured by FUJIFILM Dimatix using a 10 pl head under a discharge voltage of 21 V and 30 ° C. to form a dot pattern. The case where the liquid column during jetting was discharged in the vertical direction and no satellite was generated was designated as “G”, and the case where the liquid column was in contact with the adjacent liquid column or a satellite was produced was designated as “NG”. “G” or “NG” is an abbreviation for “Good” or “No Good”, respectively (hereinafter the same).

(Chemical resistance evaluation method)
A transparent glass substrate is coated with a thermosetting coloring composition by spin coating, and a coating film formed on the substrate is pre-baked at 80 ° C. for 3 minutes and then baked at 120 ° C. for 60 minutes to obtain a film thickness of 1.5 μm. A cured film was formed. The cured film was subjected to the following treatments separately, and then the ratio of the film thickness after each treatment to the film thickness before each treatment (residual film ratio) was measured as chemical resistance. The case where the remaining film rate after each treatment was 95% or more was designated as “G”, and the case where the remaining film rate after each treatment was less than 95% was designated as “NG”. Note that the remaining film ratio after each treatment = (film thickness after each treatment / film thickness before each treatment) × 100.

IPA treatment: The cured film was immersed in isopropyl alcohol at 25 ° C. for 10 minutes without using an ultrasonic water bath.
IPA + US treatment: The cured film was immersed in isopropyl alcohol at 25 ° C. for 10 minutes using an ultrasonic water bath (output 100 W, oscillation frequency: 27 KHz).
The residual film ratio was measured using a step / surface roughness / fine shape measuring device (trade name: P-15, manufactured by KLA TENCOR Co., Ltd.).

(Light-shielding evaluation method)
A cured film having a film thickness of 1.5 μm was formed on the transparent glass substrate in the same manner as in the above (chemical resistance evaluation method). When the cured film is irradiated with light, the brightness (Y) of transmitted light is measured, and the optical density (OD value) is calculated according to the formula OD = −log ₁₀ (Y / 100). Was set to “G”, and the case where the OD value was less than 3 was set to “NG”. The brightness (Y) was measured using JASCO Corporation UV-Vis Near-Infrared Spectrophotometer V-670.

(Abrasion resistance evaluation method)
A cured film having a film thickness of 1.5 μm was formed on the transparent glass substrate in the same manner as in the above (chemical resistance evaluation method). EtOH was attached to a cotton swab and the cured film formed on the transparent glass substrate was rubbed. Thus, the case where the number of times until the film disappeared was 50 times or more was designated as “G”, and the case where the number was less than 50 was designated as “NG”.

[Example 2 (thermosetting coloring composition)]
The following components are mixed, and the mixture is filtered through a Teflon (registered trademark) membrane filter having a pore size of 2 μm. The thermosetting coloring composition has a viscosity of 12.8 mPa · s, an average particle size of pigment of 73 nm, and a particle size distribution of 1.26. I got a thing.
Dipropylene glycol monomethyl ether acetate (DPMA) 2.70 g
(A2) Copolymer (40% by weight solution) 1.00 g
(B2) Pigment dispersion 5.00 g
(C2) Polymer (33.3% by weight solution) 4.00 g
Byk-344 (trade name; manufactured by Big Chemie Japan Co., Ltd.) 0.05 g.

  Using this thermosetting coloring composition, in the same manner as in Example 1, the jetting properties, chemical resistance, light shielding properties and abrasion resistance were evaluated. The evaluation results are shown in Table 1 below.

[Example 3 (thermosetting coloring composition)]
The following components are mixed, and the mixture is filtered through a Teflon (registered trademark) membrane filter having a pore size of 2 μm, and a thermosetting coloring composition having a viscosity of 14.5 mPa · s, an average particle size of pigment of 110 nm, and a particle size distribution of 1.57. I got a thing.
Diethylene glycol mono-n-butyl ether (DB) 2.50 g
(A3) Copolymer (40% by weight solution) 1.30 g
(B3) Pigment dispersion 5.00 g
(C3) Polymer (33.3% by weight solution) 4.00 g
F-475 (trade name; manufactured by DIC Corporation) 0.05 g.

  Using this thermosetting coloring composition, in the same manner as in Example 1, the jetting properties, chemical resistance, light shielding properties and abrasion resistance were evaluated. The evaluation results are shown in Table 1 below.

[Example 4 (thermosetting coloring composition)]
The following components are mixed, and the mixture is filtered through a Teflon (registered trademark) membrane filter having a pore size of 2 μm. The thermosetting coloring composition has a viscosity of 11.9 mPa · s, an average particle size of pigment of 50 nm, and a particle size distribution of 1.73. I got a thing.
Diethylene glycol mono-n-butyl ether acetate (DEGBEA) 2.50 g
(A4) Copolymer (40% by weight solution) 1.10 g
(B4) Pigment dispersion 5.00 g
(C4) Polymer (33.3% by weight solution) 4.00 g
F-475 (trade name; manufactured by DIC Corporation) 0.05 g.

  Using this thermosetting coloring composition, in the same manner as in Example 1, the jetting properties, chemical resistance, light shielding properties and abrasion resistance were evaluated. The evaluation results are shown in Table 1 below.

[Comparative Example 1 (thermosetting coloring composition)]
The following components are mixed, and the mixture is filtered through a Teflon (registered trademark) membrane filter having a pore size of 2 μm, and a thermosetting coloring composition having a viscosity of 13.2 mPa · s, an average particle size of pigment of 79 nm, and a particle size distribution of 1.42. I got a thing.
Diethylene glycol mono-n-butyl ether acetate (DEGBEA) 1.50 g
(M1) Copolymer (40% by weight solution) 1.00 g
(B1) Pigment dispersion 5.00 g
(C1) Polymer (25% by weight solution) 5.00 g
Byk-344 (trade name; manufactured by Big Chemie Japan Co., Ltd.) 0.05 g.

  Using this thermosetting coloring composition, in the same manner as in Example 1, the jetting properties, chemical resistance, light shielding properties and abrasion resistance were evaluated. The evaluation results are shown in Table 1 below.

[Comparative Example 2 (thermosetting coloring composition)]
The following components are mixed, and the mixture is filtered through a Teflon (registered trademark) membrane filter having a pore size of 2 μm. The thermosetting coloring composition has a viscosity of 12.8 mPa · s, an average particle size of pigment of 73 nm, and a particle size distribution of 1.26. I got a thing.
Dipropylene glycol monomethyl ether acetate (DPMA) 2.70 g
(M2) Copolymer (33.3% by weight solution) 1.00 g
(B2) Pigment dispersion 5.00 g
(C2) Polymer (33.3% by weight solution) 4.00 g
Byk-344 (trade name; manufactured by Big Chemie Japan Co., Ltd.) 0.05 g.

  Using this thermosetting coloring composition, in the same manner as in Example 1, the jetting properties, chemical resistance, light shielding properties and abrasion resistance were evaluated. The evaluation results are shown in Table 1 below.

[Comparative Example 3 (thermosetting coloring composition)]
The following components are mixed, and the mixed solution is filtered through a Teflon (registered trademark) membrane filter having a pore size of 2 μm. The thermosetting coloring composition has a viscosity of 13.8 mPa · s, an average particle size of pigment of 110 nm, and a particle size distribution of 1.57. I got a thing.
Diethylene glycol mono-n-butyl ether (DB) 2.50 g
(M3) Polymer (33.3% by weight solution) 1.30 g
(B3) Pigment dispersion 5.00 g
(C3) Polymer (33.3% by weight solution) 4.00 g
F-475 (trade name; manufactured by DIC Corporation) 0.05 g.

  Using this thermosetting coloring composition, in the same manner as in Example 1, the jetting properties, chemical resistance, light shielding properties and abrasion resistance were evaluated. The evaluation results are shown in Table 1 below.

[Comparative Example 4 (thermosetting coloring composition)]
The following components are mixed, and the mixture is filtered through a Teflon (registered trademark) membrane filter having a pore size of 2 μm, and a thermosetting coloring composition having a viscosity of 12.4 mPa · s, an average particle size of pigment of 50 nm, and a particle size distribution of 1.73. I got a thing.
Diethylene glycol mono-n-butyl ether acetate (DEGBEA) 2.50 g
(M4) Copolymer (40% by weight solution) 1.10 g
(B4) Pigment dispersion 5.00 g
(C4) Polymer (33.3% by weight solution) 4.00 g
F-475 (trade name; manufactured by DIC Corporation) 0.05 g.

  Using this thermosetting coloring composition, the jetting characteristics, chemical resistance, light-shielding property and abrasion resistance were evaluated. The evaluation results are shown in Table 1 below.

[Comparative Example 5 (thermosetting coloring composition)]
The following components are mixed, and the mixture is filtered through a Teflon (registered trademark) membrane filter having a pore size of 2 μm, and a thermosetting coloring composition having a viscosity of 11.8 mPa · s, an average particle size of pigment of 50 nm, and a particle size distribution of 1.73. I got a thing.
Diethylene glycol mono-n-butyl ether acetate (DEGBEA) 3.50 g
(M4) Copolymer (40% by weight solution) 4.10 g
(B4) Pigment dispersion 5.00 g
F-475 (trade name; manufactured by DIC Corporation) 0.05 g.

  Using this thermosetting coloring composition, the jetting characteristics, chemical resistance, light-shielding property and abrasion resistance were evaluated. The evaluation results are shown in Table 1 below.

表１に示した結果から明らかなように、実施例１〜４の熱硬化性着色組成物はジェッティング特性が良好であり、その硬化膜は耐薬品性、遮光性および耐磨耗性のすべてに優れていることが判る。一方、比較例１〜５の熱硬化性着色組成物の硬化膜は耐磨耗性が不良であり、組成物のジェッティング特性および硬化膜の耐薬品性が不良であるものも散見される。特に比較例５は、（Ｃ）重合体を含有しない熱硬化性着色組成物を使用した例であるが、耐薬品性および耐磨耗性が極めて不良である。

As is apparent from the results shown in Table 1, the thermosetting coloring compositions of Examples 1 to 4 have good jetting characteristics, and the cured film has all of chemical resistance, light shielding property and abrasion resistance. It turns out that it is excellent in. On the other hand, the cured films of the thermosetting coloring compositions of Comparative Examples 1 to 5 have poor wear resistance, and some have poor composition jetting characteristics and cured film chemical resistance. In particular, Comparative Example 5 is an example using a thermosetting coloring composition containing no (C) polymer, but the chemical resistance and abrasion resistance are extremely poor.

  By using the thermosetting coloring composition of the present invention, a cured film excellent in chemical resistance, light shielding property and abrasion resistance can be produced. The cured film is suitable for repairing defects in a liquid crystal display device.

Claims (11)

(A) Copolymer obtained by polymerizing 100 parts by weight of the radically polymerizable monomer (a1) represented by the general formula (I) and 20 to 400 parts by weight of a radically polymerizable monomer (a2) other than the monomer (a1) 0.5% to 35% by weight of coalescence,
(B) 1 to 30% by weight of a pigment having an average particle size of 30 to 200 nm ;
(C) 1 to 50% by weight of structural units derived from unsaturated carboxylic acid, 0 to 50% by weight of structural units derived from unsaturated carboxylic acid anhydride and 0 to 99% by weight of structural units derived from other monomers (however, , the sum of 3's usage to 100 wt%.) polymer having a except (the copolymer (a).) containing a 0.1 to 35 wt%,
A thermosetting coloring composition for forming a light-shielding cured film, wherein the radical polymerizable monomer (a2) includes a radical polymerizable monomer having an epoxy :

(Wherein R ¹ is hydrogen or alkyl having 1 to 5 carbon atoms in which arbitrary hydrogen may be replaced by fluorine,
R ^2, R ³ and R ⁴ are each independently, hydroxyl, alkoxy having a carbon number of 1-5 or _{-O (Si (C k H 2k} + 1) 2 O), m Si (C p H 2p + 1) 3 (K is an integer of 1-5, m is an integer of 0-10, p is an integer of 1-5), and n is an integer of 1-5. ). In the formula (I), R ¹ is methyl,
The R ^2, R ³ and R ⁴ are each independently of the carbon number 1-3 alkoxy or _{-O (Si (C k H 2k} + 1) 2 O) m Si (C p H 2p + 1) is ₃ ( k is an integer of 1 to 5, m is an integer of 0 to 10, and p is an integer of 1 to 5).
n is an integer of 2-4, The thermosetting coloring composition of Claim 1 characterized by the above-mentioned. The radically polymerizable monomer (a1) is 3-methacryloxypropyltrimethoxysilane and / or 3-methacryloxypropyltris (trimethylsiloxy) silane, according to any one of claims 1-2 . Thermosetting coloring composition. The radical polymerizable monomer having the epoxy is glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, α-ethylacrylic acid glycidyl ester, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-methyl-3- ( Composed of (meth) acryloxymethyl oxetane, 3-ethyl-3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane and 3-ethyl-3- (meth) acryloxyethyl oxetane The thermosetting coloring composition according to any one of claims 1 to 3 , wherein the thermosetting coloring composition is at least one compound selected from the group. The unsaturated carboxylic acid is at least one selected from the group consisting of (meth) acrylic acid, itaconic acid, maleic acid, citraconic acid and fumaric acid;
The thermosetting according to any one of claims 1 to 4 , wherein the unsaturated carboxylic acid anhydride is at least one selected from the group consisting of maleic anhydride, itaconic anhydride, and citraconic anhydride. Coloring composition. The polymer (C) is composed of 5 to 30% by weight of structural units derived from an unsaturated carboxylic acid, 0 to 20% by weight of structural units derived from an unsaturated carboxylic acid anhydride, and 50 to 50 of structural units derived from other monomers. 95% by weight (provided that the total amount used by the three members is 100% by weight), and the other monomer contains an N-substituted maleimide. The thermosetting coloring composition described in 1.   Furthermore, (D) The thermosetting coloring composition in any one of Claims 1-6 containing a solvent. Additionally, (E) mosquitoes coupling agent and at least one additive selected from the group consisting of surfactants, thermosetting colored composition according to any one of claims 1 to 7. The light-shielding cured film obtained by apply | coating the thermosetting coloring composition in any one of Claims 1-8 on a board | substrate, and baking the coating film formed on this board | substrate. A pair of opposing substrates, a spacer separating the pair of substrates by a predetermined width, and a liquid crystal material sealed in a gap between the pair of substrates,
A liquid crystal display element, wherein the light-shielding cured film according to claim 9 is formed on the substrate.   An ink-jet ink comprising the thermosetting coloring composition according to claim 1.