JP2014199342A - Photocurable resin composition, color filter and method for manufacturing the same, liquid crystal display device, and organic light-emitting display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable composition from which a high-precision color filter can be manufactured without inducing a void even when a line width of a light-shielding part is decreased.SOLUTION: A photocurable resin composition is provided, comprising a photocurable resin having two or more ethylenically unsaturated bonds in one molecule and an initiator. A heat of reaction in exposure Q(=Q-Q) [J/g] of the photocurable resin composition is obtained, which is defined by a difference between a heat of reaction prior to exposure Q[J/g] and a heat of reaction after exposure Q[J/g]: Qis calculated from an area value of a DSC curve (A) in a temperature range from 100 to 250°C, the DSC curve (A) obtained by differential scanning calorimetry of the photocurable resin composition; and Qis calculated from an area value of a DSC curve (B) in a temperature range from 100 to 250°C, the DSC curve (B) obtained by differential scanning calorimetry of the resin composition after exposure which is prepared by exposing the photocurable resin composition to light with luminous energy E [mJ/cm] by use of a high-pressure mercury lamp. A ratio (Q/E) of Qto the exposure luminous energy E is 0.85 or less. A ratio (Q/T) of the heat of reaction after exposure Qto a reaction peak temperature T [°C], which is defined by a temperature where a heat flow reaches the maximum in the DSC curve (B) in the temperature range from 100 to 250°C, is 0.5 or less.

Description

  The present invention relates to a photocurable resin composition, a color filter and a method for producing the same, a liquid crystal display device, and an organic light emitting display device.

In recent years, a display device such as a liquid crystal display device or an organic electroluminescence display device has been required to have more excellent optical performance. In order to perform color display, the display device usually includes a color filter having a colored layer. Even in such a color filter, further improvement in optical performance is required.
In order to improve the optical performance of the color filter, for example, the brightness is improved by widening the opening by narrowing the line width of the light shielding part (black matrix), and the pigment concentration in the photocurable resin composition is increased. High color purity of color filters by increasing the density has been studied.

  FIG. 5 is a schematic view showing an example of a conventional color filter manufacturing method. When forming a colored layer using a photocurable resin composition, first, the photocurable resin composition is applied onto the transparent substrate 1 on which the light shielding portion 2 is formed as shown in FIG. A coating film 14 of the composition is formed. Next, after exposure 11 through a mask 13 having a predetermined pattern, development with a developer is performed to form a cured coating film 15. The cured coating film 15 is subjected to a heat treatment after the development process to form a sufficiently cured colored layer 16. When the colored layer is exposed from above, the upper side of the colored layer undergoes more curing reaction, and the lower side is less likely to proceed with the curing reaction, so the lower side is easily dissolved during development. It tends to be in reverse taper shape

When the color filter opening is widened by narrowing the line width of the light shielding portion, there is a problem that a cavity as shown in the example of FIG. 7 is generated between the light shielding portion 2 and the colored layer 16. . Such a cavity causes panel unevenness such as glare of the display device.
FIG. 6 is a schematic diagram illustrating an example of a method for manufacturing a color filter in the case where the opening is widened by narrowing the line width of the light-shielding portion 2. As shown in the example of FIG. 6, when the opening is widened by narrowing the line width of the light shielding part 2, it is difficult for exposure light to reach near the base of the light shielding part 2, and the curing reaction of the coating film does not proceed easily. In addition, since the overlap between the light-shielding portion and the coating film pattern is small, the developing solution may enter the opening during development to dissolve the coating film, resulting in the formation of cavities 17. And the cavity 18 may remain as it is after heat-curing.
Such a cavity 18 is difficult to be exposed and hardened to be exposed to the lower side of the coating film when the concentration of the pigment in the photocurable resin composition is increased or when the coating film is thickened. It is particularly likely to occur.

As a result of intensive studies, the present inventors can form a coating film that does not generate cavities even if the line width of the light shielding portion is reduced by using a photocurable resin composition having specific physical properties. And gained knowledge.
The present invention has been completed based on such findings.

  The present invention provides a photocurable composition capable of producing a high-definition color filter without producing a cavity even if the line width of the light-shielding portion is reduced, and a high-brightness and high-definition using the photocurable composition. An object is to provide a color filter, a high-luminance and high-definition liquid crystal display device using the color filter, and an organic light-emitting display device.

The photocurable resin composition according to the present invention is a photocurable resin composition containing a photocurable resin having two or more ethylenically unsaturated bonds in one molecule, and an initiator,
In the DSC curve (A) obtained by differential scanning calorimetry of the photocurable resin composition, the pre-exposure reaction heat calculated from the area value of the DSC curve (A) in the temperature range of 100 to 250 ° C. Differential scanning was performed on Q ₁ [J / g] and the exposed resin composition obtained by exposing the photocurable resin composition to an exposure amount E [mJ / cm ² ] using a high-pressure mercury lamp. In the DSC curve (B) obtained by calorimetric measurement, the difference from the post-exposure reaction heat Q ₂ [J / g] calculated from the area value of the DSC curve (B) in the temperature range of 100 to 250 ° C. The value (Q ₃ / E) of the reaction heat Q ₃ (= Q ₁ −Q ₂ ) [J / g] defined for the exposure amount E is 0.85 or less,
The value (Q ₂ / T) of the post-exposure reaction heat Q ₂ with respect to the reaction peak temperature T [° C.] defined by the temperature at which the heat flow takes the maximum value in the temperature range of 100 to 250 ° C. of the DSC curve (B). It is 0.5 or less.

  In the photocurable resin composition of the present invention, it is preferable that the absorption spectrum of the initiator has a maximum value in a wavelength range of 310 to 400 nm from the viewpoint of hardly generating a cavity.

  The photocurable resin composition of the present invention may further contain a color material, and the color material may contain a green color material.

  In the photocurable resin composition of the present invention, the content ratio of the coloring material is 30 parts by mass or more with respect to 100 parts by mass of the total solid content of the photocurable resin composition. It is preferable from the point that can be achieved.

  The color filter according to the present invention is a color filter including at least a transparent substrate and a colored layer provided on the transparent substrate, and at least one of the colored layers includes the photocurable resin composition according to the present invention. It has a colored layer formed by curing.

  In the color filter of the present invention, at least one chromaticity coordinate of the colored layer can achieve y = 0.620 to 0.710.

The method for producing a color filter according to the present invention is a method for producing a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate,
A photocurable resin composition comprising a photocurable resin having two or more ethylenically unsaturated bonds in one molecule and an initiator, wherein the photocurable resin composition is subjected to differential scanning calorimetry. In the DSC curve (A) obtained by the above, the pre-exposure reaction heat Q ₁ [J / g] calculated from the area value of the DSC curve (A) in the temperature range of 100 to 250 ° C., and the photocurability DSC curve (B) obtained by differential scanning calorimetry of the resin composition after exposure obtained by exposing the resin composition with an exposure amount E [mJ / cm ² ] using a high-pressure mercury lamp , The reaction heat at the time of exposure Q ₃ (= Q ₁₎ defined by the difference from the post-exposure reaction heat Q ₂ [J / g] calculated from the area value of the DSC curve (B) in the temperature range of 100 to 250 ° C. -Q ₂₎ of [J / g], the exposure amount E Against values _(Q 3 / E) is not less than 0.85, with respect to the DSC curve (B) heat flow reaction peak temperature T [° C.] defined at a temperature which takes the maximum value in the temperature range of 100 to 250 ° C. of the post-exposure value of the heat of reaction Q ₂ (Q _{2 / T)} is 0.5 or less, a step of preparing a photocurable resin composition,
On the transparent substrate, the step of coating the photocurable resin composition to form a coating film,
Exposure with an exposure dose E [mJ / cm ² ] using a high-pressure mercury lamp;
And a step of firing in a temperature range of 100 to 250 ° C.

The present invention provides a liquid crystal display device comprising the color filter according to the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
In addition, the present invention provides an organic light emitting display device comprising the color filter according to the present invention and an organic light emitter.

  According to the present invention, a photocurable composition capable of producing a high-definition color filter without producing a cavity even if the line width of the light-shielding portion is reduced, and a high brightness and high intensity using the photocurable composition. A fine color filter, a high-brightness and high-definition liquid crystal display device using the color filter, and an organic light-emitting display device can be provided.

FIG. 1 is a schematic cross-sectional view showing an example of the color filter of the present invention. FIG. 2 is a schematic cross-sectional view showing an example of the liquid crystal display device of the present invention. FIG. 3 is a schematic cross-sectional view showing an example of the organic light emitting display device of the present invention. FIG. 4 is a schematic view showing an example of a method for producing a color filter of the present invention. FIG. 5 is a schematic view showing an example of a conventional method for producing a color filter. FIG. 6 is a schematic view showing an example in which the opening is widened by narrowing the line width of the light shielding portion in the conventional method for manufacturing a color filter. FIG. 7 is an enlarged photograph showing an example of a cross section of a colored layer having a cavity.

Hereinafter, the photocurable resin composition, color filter, liquid crystal display device and organic light emitting display device according to the present invention will be described in order.
In the present invention, light includes electromagnetic waves having wavelengths in the visible and invisible regions, and further includes radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam. In the present invention, (meth) acryl means either acryl or methacryl, and (meth) acrylate means either acrylate or methacrylate.

[Photocurable resin composition]
The photocurable resin composition according to the present invention is a photocurable resin composition containing a photocurable resin having two or more ethylenically unsaturated bonds in one molecule, and an initiator,
In the DSC curve (A) obtained by differential scanning calorimetry of the photocurable resin composition, the pre-exposure reaction heat calculated from the area value of the DSC curve (A) in the temperature range of 100 to 250 ° C. Differential scanning was performed on Q ₁ [J / g] and the exposed resin composition obtained by exposing the photocurable resin composition to an exposure amount E [mJ / cm ² ] using a high-pressure mercury lamp. In the DSC curve (B) obtained by calorimetric measurement, the difference from the post-exposure reaction heat Q ₂ [J / g] calculated from the area value of the DSC curve (B) in the temperature range of 100 to 250 ° C. The value (Q ₃ / E) of the reaction heat Q ₃ (= Q ₁ −Q ₂ ) [J / g] defined for the exposure amount E is 0.85 or less,
The value (Q ₂ / T) of the post-exposure reaction heat Q ₂ with respect to the reaction peak temperature T [° C.] defined by the temperature at which the heat flow takes the maximum value in the temperature range of 100 to 250 ° C. of the DSC curve (B). It is 0.5 or less.

In the photocurable resin composition according to the present invention, the value (Q ₃ / E) of the reaction heat upon exposure Q ₃ [J / g] calculated by the above specific method with respect to the exposure amount E (Q ₃ / E) is 0.85 or less. In addition, in the post-exposure resin composition obtained by exposing the photocurable resin composition according to the present invention, the post-exposure reaction with respect to the reaction peak temperature T [° C.] defined by the above specific method By having a specific physical property that the value of the heat Q ₂ (Q ₂ / T) is 0.5 or less, it is difficult to form a cavity when manufacturing a color filter.

The use of the specific photocurable resin composition as described above is not yet elucidated as the effect of exerting the above effects, but is estimated as follows.
The photocurable resin composition of the present invention, since the exposure amount E is relatively small exposure during the heat of reaction Q _3, at the time of exposure, it is presumed that the curing reaction proceeds relatively mildly. Such a photocurable resin composition of the present invention can easily control the progress of the curing reaction by adjusting the exposure amount. Therefore, it is easy to adjust the resin composition after exposure to a resin composition having appropriate fluidity during heating while decreasing the solubility in the developer.
Further, the obtained resin composition after exposure has a value (Q ₂ / T) of the post-exposure reaction heat Q ₂ with respect to the reaction peak temperature T [° C.] of 0.5 or less, and the heating temperature is relatively high. It is difficult for the curing reaction to proceed until Therefore, when the heating temperature at the time of baking is less than the reaction peak temperature T [° C.], the curing reaction of the resin composition after exposure hardly progresses, but it is estimated that the fluidity is increased by heating. Alternatively, the reaction peak temperature T even when relatively low, since the reaction heat Q ₂ relatively small, the curing reaction proceeds gently, is presumed to be cured while flowing.
Since the photocurable resin composition of the present invention has such properties, the resin composition after exposure having improved fluidity at the time of firing is formed in the cavity even when a cavity is generated during development. It is estimated to be easy to enter. Therefore, it is presumed that the cavity is filled after firing, and the obtained colored layer does not have a cavity.
The reason why the temperature range is 100 to 250 ° C. is that the reaction of the curable resin having an ethylenically unsaturated bond is usually completed in the range of 100 to 250 ° C.

In the present invention, the pre-exposure reaction heat Q ₁ [J / g] is calculated as follows.
The photocurable resin composition to be measured is applied onto a substrate and dried to form a dry coating film having a thickness of 3.5 μm. The dried coating film is scraped off and 5 mg is enclosed in a sample pan. Next, a DSC curve (A) in a temperature range of 100 to 250 ° C. is obtained by a differential scanning calorimeter in accordance with the plastic transition temperature measurement method described in JIS K7121. In the DSC curve, the horizontal axis x is temperature [° C.] and the vertical axis y is heat flow [W / g]. The pre-exposure reaction heat Q ₁ [J / g] is calculated from the area value of the region formed by the obtained DSC curve (A) and y = 0. The temperature raising condition is 10 ° C./min. As the suggested scanning calorimeter, for example, DSC-60 manufactured by Shimadzu Corporation can be used.

In the present invention, the post-exposure reaction heat Q ₂ [J / g] is calculated as follows.
The photocurable resin composition to be measured is applied onto a substrate and dried to form a dry coating film having a thickness of 3.5 μm. Subsequently, the resin composition after exposure is obtained by exposing with the exposure amount E [mJ / cm < ² >] using a high pressure mercury lamp. The resin composition after the exposure is scraped off, sealed in a 5 mg sample pan, and measured with a differential scanning calorimeter in the same manner as described above to obtain a DSC curve (B) in a temperature range of 100 to 250 ° C. In the DSC curve, the horizontal axis x is temperature [° C.] and the vertical axis y is heat flow [W / g]. The post-exposure reaction heat Q ₂ [J / g] is calculated from the area value of the region formed by the obtained DSC curve (B) and y = 0.

The exposure amount E is not particularly limited, but the exposure amount E is preferably set in a range of ²⁰ to 300 mJ / cm ² in terms of a wavelength of 365 nm, and further, E is preferably set to 30 to 200 mJ / cm ^2. . As a criterion for selecting the resin composition, E is preferably 40 mJ / cm ² from the viewpoint of patterning property and productivity. By setting E within the above range, the colored layer is less likely to form cavities.

Exposure time reaction heat _{Q 3} are the difference in the exposure prior to reaction heat _{Q 1} and post-exposure heat of reaction _{Q 2 (= Q 1 -Q 2} ) obtained by [J / g]. Q ₃ are or not be maintained the shape during development too small, since the adhesiveness may be deteriorated, Q ₃ is preferably at 2.0 [J / g] or more.
The reaction peak temperature T [° C.] is defined as the temperature at which the heat flow takes the maximum value in the temperature range of 100 to 250 ° C. of the DSC curve (B). If the reaction peak temperature T is too low, the curing reaction tends to proceed before the exposed resin composition flows. Therefore, T is preferably 150 ° C. or higher, and more preferably 170 ° C. or higher.
From these values, the value (Q ₃ / E) of the reaction heat at the time of exposure Q ₃ (= Q ₁ −Q ₂ ) [J / g] with respect to the exposure amount E and the post-exposure reaction with respect to the reaction peak temperature T [° C.]. The value of heat Q ₂ (Q ₂ / T) can be determined.

In the photocurable resin composition of the present invention, (Q ₃ / E) calculated by the above method is 0.85 or less. The photocurable resin composition of the present invention as described above, since the exposure amount E is relatively small exposure during the heat of reaction Q _3, at the time of exposure, it is presumed that the curing reaction proceeds relatively gently . Especially, it is preferable that (Q < ₃ > / E) is 0.05-0.85, and it is more preferable that it is 0.15-0.85. If it is below the said upper limit, it will be easier to control the progress of the curing reaction during exposure. Then, by adjusting the exposure amount in the vicinity of the exposure amount E, it is possible to achieve a degree of curing that can flow during post-exposure heating while reducing the solubility in the developer. On the other hand, if it is more than the said lower limit, the sensitivity of a photocurable resin composition will be ensured.

In the photocurable resin composition of the present invention, the value of the post-exposure reaction heat Q ₂ (Q ₂ / T) with respect to the reaction peak temperature T [° C.] of the resin composition after exposure is 0.5 or less. is there. Thus, since the resin composition after exposure of the photocurable resin composition of the present invention has a relatively high curing reaction temperature, the fluidity of the resin composition after exposure is improved at a moderate heating temperature. . Also when a relatively low reaction peak temperature T is also because the reaction heat Q ₂ relatively small, the curing reaction proceeds gently and cured while flowing. For this reason, even when a cavity is generated during development, the cavity is filled and a high-definition colored layer having no cavity can be obtained. Among these, (Q ₂ / T) is preferably 0.10 to 0.50, and more preferably 0.20 to 0.50. If it is below the said upper limit, the hardening reaction rate at the time of a heating is low, and it is easy to ensure the fluidity | liquidity of a resin composition. On the other hand, if it is more than the said lower limit, it is excellent in sclerosis | hardenability.

The photocurable resin composition according to the present invention contains a photocurable resin having two or more ethylenically unsaturated bonds in at least one molecule and an initiator, and impairs the effects of the present invention. In the absence, other components may be contained as necessary.
Hereafter, each component of such a photocurable resin composition of this invention is demonstrated in detail in order.

<Photocurable resin having two or more ethylenically unsaturated bonds in one molecule>
In the photocurable resin composition of the present invention, the photocurable resin having two or more ethylenically unsaturated bonds in one molecule may be any one that can be polymerized by a photoinitiator described later, and is conventionally known. What is necessary is just to select suitably from things. Among these, polyfunctional (meth) acrylates having two or more acryloyl groups or methacryloyl groups in one molecule are preferable.

Examples of such polyfunctional (meth) acrylates include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, long chain aliphatic di (meth) acrylate, and neopentyl glycol. Bifunctional (meth) acrylates such as di (meth) acrylate polyethylene glycol di (meth) acrylate and polypropylene di (meth) acrylate may be mentioned.
Examples of the trifunctional or higher polyfunctional (meth) acrylate include, for example, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, succinic anhydride-modified pentaerythritol tetra (meth) acrylate, tri (meth) acrylate phosphate, tris (acryloxyethyl) isocyanurate, tris ( Methacryloxyethyl) isocyanurate, dipentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate, alkyl-modified dipentaerythritol Tora (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, succinic anhydride-modified dipentaerythritol penta (meth) acrylate, urethane tri (Meth) acrylate, ester tri (meth) acrylate, urethane hexa (meth) acrylate, ester hexa (meth) acrylate and the like.

These polyfunctional (meth) acrylates may be used individually by 1 type, and may be used in combination of 2 or more type. Further, when the photocurable resin composition of the present invention requires excellent photocurability (high sensitivity), the polyfunctional monomer has three (trifunctional) or more polymerizable double bonds. Preferred are poly (meth) acrylates of polyhydric alcohols having a valence of 3 or more and their dicarboxylic acid modified products. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meta) ) Acrylate, modified succinic acid of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate Dipentaerythritol modified from succinic acid Hexa (meth) acrylate are preferable.
The photocurable resin having two or more ethylenically unsaturated bonds in one molecule may be used alone or in combination of two or more.

From the viewpoint of ensuring fluidity during heating of the resin composition after exposure, a photocurable resin having two or more ethylenically unsaturated bonds in one molecule having a relatively large double bond equivalent is selected. It is preferable. As a standard, the double bond equivalent of the photocurable resin having an ethylenically unsaturated bond is preferably 100 to 300 g / mol, more preferably 120 to 250 g / mol. Double bond equivalent as the amount is small after the exposure reaction heat Q _2, and the exposure time of the heat of reaction Q ₃ tends to increase.
In addition, a double bond equivalent means the mass (g / mol) of the photocurable resin per 1 mol of double bonds.

<Initiator>
The initiator used in the photocurable resin composition of the present invention usually contains a photoinitiator. As a photoinitiator, it can select from a conventionally well-known thing suitably, and can use it. For example, benzophenone derivatives such as benzoin and benzophenone or derivatives thereof; xanthone and thioxanthone derivatives; halogen-containing compounds such as chlorosulfonyl, chloromethyl polynuclear aromatic compounds, chloromethyl heterocyclic compounds, chloromethyl benzophenones; Fluorenones; haloalkanes; oximes such as oxime ester compounds; redox couples of photoreducing dyes and reducing agents; organic sulfur compounds; peroxides. Preferably, Irgacure 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure 369 (2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone), Irgacure 651 (2, 2-dimethoxy-2-phenylacetophenone), Irgacure 907 (2- [4- (methylthio) benzoyl] -2- (4-morpholinyl) propane) (all manufactured by Ciba Specialty Chemicals), Darocur (Merck) Manufactured by Asahi Denka Kogyo Co., Ltd.), 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole (black gold) Such as ketone-based and biimidazole-based compounds such as Kasei Co., Ltd. Examples include oxime ester compounds. These initiators can be used alone or in combination of two or more. When two or more kinds are used in combination, it is preferable not to inhibit the absorption spectral characteristics.

The photoinitiator is decomposed by heating and can also function as a thermal initiator. Such a photoinitiator preferably has a 50% thermal decomposition temperature of 150 ° C. or higher when the photoinitiator is heated, and more preferably 170 ° C. or higher. By using such a photoinitiator, the reaction peak temperature T can be easily set to 150 ° C. or higher.
The 50% pyrolysis temperature is measured by the differential thermothermal gravimetric simultaneous measurement method, for example, using the following measuring apparatus and conditions.
Measuring device: "Differential thermo-thermogravimetric simultaneous measuring device TG / DTA6200 type" manufactured by SII Nano Technology
Measurement conditions: sample amount (14 ± 0.5 mg), nitrogen gas flow rate (200 ml / min), measurement start / end temperature (40-500 ° C.), heating rate (40-100 ° C. → 20 ° C./min, 100-500 ℃ → 10 ℃ / min)
Heat treatment: Measured in a nitrogen atmosphere within the above temperature range without heat treatment.

In the present invention, it is particularly preferable to use a photoinitiator having an absorption spectrum having a maximum value in the wavelength range of 310 to 400 nm because it is less likely to cause cavities and has excellent development adhesion. A photoinitiator having a maximum value in the range of 400 nm is more preferred. By using a photoinitiator having a maximum wavelength within the above range, the absorption of irradiation light becomes appropriate, and a polymerization reaction of a photocurable resin having two or more ethylenically unsaturated bonds in one molecule. In addition, since the irradiation light easily reaches the inside of the photocurable resin composition, the reverse taper shape is suppressed, and as a result, cavities are hardly generated and the adhesion is excellent.
Specific examples of the photoinitiator having a maximum value in the wavelength range of 310 to 400 nm include, for example, 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone, 2- [4 -(Methylthio) benzoyl] -2- (4-morpholinyl) propane, oxime ester compounds and the like.

Moreover, it is preferable that it is a photoinitiator whose molar absorption coefficient in wavelength 365nm is 0.10 or more from the point which is excellent in sclerosis | hardenability.
The molar extinction coefficient is dissolved in a solvent (for example, acetonitrile) that has no absorption in the measurement wavelength region and can uniformly dissolve the initiator, and is appropriately diluted to obtain an appropriate absorbance. (For example, UV-2550 (made by Shimadzu Corporation)) is measured by measuring the absorbance.

  In this invention, you may contain the thermal-polymerization initiator which generate | occur | produces a radical or a cation with a heat | fever as an initiator further. By using a thermal polymerization initiator, the curability during firing can be easily adjusted, and the physical properties of the present invention can be easily adjusted. Such a polymerization initiator may be appropriately selected from conventionally known initiators. Specifically, an azo polymerization initiator etc. are mentioned, for example.

The thermal polymerization initiator can be used in a range where the value (Q ₂ / T) of the post-exposure reaction heat Q ₂ with respect to the reaction peak temperature T [° C.] of the resin composition after the exposure satisfies 0.5 or less. Using a thermal polymerization initiator, the reaction peak temperature T tends to decrease, because the post-exposure heat of reaction Q ₂ there is a tendency to increase, thermal polymerization initiator is preferably in a small amount of use. The content ratio of the thermal polymerization initiator is appropriately adjusted depending on the polymerization initiator, the type of the photocurable resin having two or more ethylenically unsaturated bonds in one molecule, but as a guideline. Is preferably 8 parts by mass or less and more preferably 5 parts by mass or less with respect to 100 parts by mass of the total amount of the initiator.

  The content of the initiator used in the photo-curable resin composition of the present invention is such that the photo-curing property has two or more ethylenically unsaturated bonds in one molecule from the viewpoint of having the specific physical properties. It is preferable to set it as 1-50 mass parts with respect to 100 mass parts of resin, and it is more preferable to set it as 2-40 mass parts. If the content of the initiator is not less than the above lower limit, the hardness of the colored layer can be made sufficient.

The photocurable resin composition of the present invention can be suitably used as a photocurable resin composition for forming a so-called white pixel of a color filter. In addition, the photocurable resin composition of the present invention is preferably used as a resin composition to be mixed with a colorant when preparing a photocurable resin composition for forming a colored layer of a color filter. it can.
The photocurable resin composition of the present invention may further contain other components as long as the effects of the present invention are not impaired. The photocurable resin composition of the present invention may be a photocurable colored resin composition further containing a coloring material.

<Other ingredients>
Other components include, for example, colorants, dispersants, solvents, alkali-soluble resins, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, antifoaming agents, silane coupling agents, and ultraviolet rays. Examples include absorbents, adhesion promoters, and the like.
Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, Examples include sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and the like. In addition, a fluorosurfactant can also be used.
Furthermore, examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl. Examples of the antifoaming agent and leveling agent include silicon-based, fluorine-based, and acrylic compounds.

(Color material)
In the present invention, the color material is not particularly limited as long as it can produce a desired color, and various organic or inorganic colorants can be used alone or in admixture of two or more. As the color material, for example, organic pigments, inorganic pigments, dyes, and the like can be used. Among these, organic pigments are preferably used from the viewpoint of color developability and heat resistance.
Specific examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyer's and Colorists).

In the photocurable resin composition of this invention, you may contain a green color material as a color material.
Examples of the green color material include C.I. I. Pigment Green 58 (PG58), C.I. I. Pigment green 7 (PG7).
Conventionally, in order to achieve a green target chromaticity with a high color density using PG58 or PG7, it has been necessary to make the green colored layer thicker than before or to increase the pigment density. In the present invention, even when such a green pigment is used, a high-definition color filter can be obtained without generating a cavity.

In the present invention, the content ratio of the color material may be adjusted as appropriate so as to achieve the target color purity, and is not particularly limited. The photocurable resin composition of the present invention does not form a cavity even when the content ratio of the coloring material is 30 parts by mass or more with respect to 100 parts by mass of the total solid content of the photocurable resin composition. A high-definition color filter can be obtained.
In the case of a green color material, it is preferably 30 to 60 parts by mass with respect to 100 parts by mass of the total solid content of the photocurable resin composition, from the point that high color purity can be achieved without generating voids. It is more preferable that it is 35-55 mass parts.
The chromaticity coordinates of the colored layer formed using the photocurable resin composition by setting the green color material to 30 parts by mass or more with respect to 100 parts by mass of the total solid content of the photocurable resin composition Can be easily adjusted to y = 0.620 to 0.710.

(Dispersant)
When the color material is used by being dispersed in a solvent described later, it is preferable to use a dispersant in order to disperse the color material satisfactorily. The dispersant can be appropriately selected from those conventionally used as dispersants. Examples of the dispersant that can be used include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. Among the surfactants, a polymer surfactant (polymer dispersant) is preferable because it can be uniformly and finely dispersed.

  Examples of the polymer dispersant include polysulfonic acid type polymer dispersions such as polystyrene sulfonic acid (salt), styrene-styrene sulfonic acid (salt) copolymer, polyvinyl sulfonic acid (salt), and dodecylbenzene sulfonic acid (salt). Agents; (Co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts, (partial) ammonium salts of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid ( Partially) alkylamine salts; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylic acid esters and their modified products; polyurethanes; tertiary amine-modified polyurethanes; unsaturated polyamides; Long-chain polyaminoamide phosphates; polyethyleneimine derivatives (poly (lower alkyleneimine) Amides and their bases obtained by reaction with polyesters containing a boxyl group); polyallylamine derivatives (polyallylamine and polyesters having free carboxyl groups, polyamides or co-condensates of esters and amides (polyesteramides) Reaction products obtained by reacting one or more compounds selected from among compounds); polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene alkyl phenyl ethers such as oxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; polyethylene glycol dilaurate, polyethylene glycol distearate and the like Ethylene glycol diesters; sorbitan fatty acid esters; polymeric surfactants such as fatty acid-modified polyesters are preferably used. Examples of commercially available polymer dispersants include Polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), Megafac F171, F172, F173 (manufactured by Dainippon Ink and Chemicals), Florard Fc430, Fc431 (manufactured by Sumitomo 3M), Solsperse 13240, 20000, 24000, 26000, 28000, etc. Agents (manufactured by Avicia), Dispersic 111, 161, 162, 163, 164, 182, 2000, 2001 (manufactured by BYK Chemie), Azisper PB711, PB411, PB111, PB821, PB822 (manufactured by Ajinomoto Fine Techno) and the like can be used. .

In this invention, said dispersing agent can be used individually by 1 type or in combination of 2 or more types.
The blending ratio of the dispersant is usually 1 to 100 parts by mass with respect to 100 parts by mass of the colorant, and among them, from the viewpoint of dispersibility and dispersion stability, it is used at a ratio of 10 to 60 parts by mass. preferable.

(Alkali-soluble resin)
The photocurable resin composition of the present invention preferably has an alkali-soluble resin from the viewpoint of developability to an alkali developer, and among them, a resin having a carboxyl group is preferable. Specific examples include an acrylic copolymer having a carboxyl group and an epoxy (meth) acrylate resin having a carboxyl group. Among these, particularly preferred are those having a carboxyl group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved. These acrylic copolymers and epoxy acrylate resins may be used as a mixture of two or more.

The acrylic copolymer having a carboxyl group is obtained by copolymerizing a carboxyl group-containing ethylenically unsaturated monomer and an ethylenically unsaturated monomer.
The acrylic copolymer having a carboxyl group may further contain a structural unit having an aromatic carbocyclic ring. The aromatic carbocycle functions as a component that imparts coating properties to the photocurable resin composition.
The acrylic copolymer having a carboxyl group may further contain a structural unit having an ester group. The structural unit having an ester group not only functions as a component that suppresses alkali solubility of the photocurable resin composition, but also functions as a component that improves the solubility in a solvent and further the solvent resolubility.

Examples of the acrylic copolymer having a carboxyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec- Butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) Acrylate, n-decyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, disi Lopentanyl (meth) acrylate, 1-adamantyl (meth) acrylate, allyl (meth) acrylate, 2,2′-oxybis (methylene) bis-2-propenoate, styrene, γ-methylstyrene, glycidyl (meth) acrylate, 2- Selected from hydroxylethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, N-vinyl-2-pyrrolidone, N-methylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, etc. 1 type or more and (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, and dimer of acrylic acid (for example, Toagosei Chemical Co., Ltd. M -5600), itaconic acid, crotonic acid Maleic acid, fumaric acid, vinyl acetate, a copolymer consisting of one or more selected from these anhydrides can be exemplified. In addition, for example, a polymer having an ethylenically unsaturated bond introduced by adding an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group or a hydroxyl group to the above copolymer can be exemplified, but the present invention is not limited thereto. Is not to be done.
Among these, a polymer having an ethylenically unsaturated bond introduced, for example, by adding an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the copolymer is polymerized with a polyfunctional monomer described later at the time of exposure. This is particularly suitable in that the colored layer becomes more stable.

  The copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by mass, preferably 10 to 10% from the viewpoints of alkali developability and substrate adhesion of the formed pattern. 40% by mass.

  The preferred weight average molecular weight of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 500,000, more preferably 3,000 to 200,000. If it is less than 1,000, the binder function after curing is remarkably lowered, and if it exceeds 500,000, pattern formation may be difficult during development with an alkaline developer. In addition, the weight average molecular weight in this invention says what is measured by the gel permeation chromatography (GPC) method (polystyrene conversion).

  In addition, the epoxy (meth) acrylate resin having a carboxyl group is not particularly limited, but an epoxy obtained by reacting a reaction product of an epoxy compound and an unsaturated group-containing monocarboxylic acid with an acid anhydride ( A (meth) acrylate compound is suitable.

  It is preferable to select an alkali-soluble resin having a relatively low glass transition temperature Tg. Among them, the glass transition temperature Tg being lower than the reaction peak temperature T ensures the fluidity of the resin composition after exposure. From the viewpoint of obtaining a colored layer having no voids.

In the case where the photocurable resin composition of the present invention further contains an alkali-soluble resin in addition to the photocurable resin having two or more ethylenically unsaturated bonds in one molecule and the initiator, each blending ratio From the point that it is easy to adjust to the above specific physical properties while sufficient alkali developability is obtained, the following is preferable.
The content of the photocurable resin having two or more ethylenically unsaturated bonds in one molecule is 20 to 80% by mass, and further 30 to 60% by mass with respect to the total solid content of the photocurable resin composition. It is preferable to mix | blend in the ratio.
Moreover, it is preferable to mix | blend content of an initiator in the ratio of 5-30 mass% with respect to the solid content whole quantity of a photocurable resin composition, and also 10-25 mass%.
Moreover, it is preferable to mix | blend content of alkali-soluble resin in the ratio of 20-80 mass% with respect to solid content whole quantity of a photocurable resin composition, and also 40-70 mass%.
In addition, in this invention, solid content is all things other than the solvent mentioned above, and the polyfunctional monomer etc. which are melt | dissolving in the solvent are also included.

When the photocurable resin composition of the present invention further contains a colorant and an alkali-soluble resin in addition to a photocurable resin having two or more ethylenically unsaturated bonds in one molecule and an initiator. In the above, it is preferable that each blending ratio is as follows from the viewpoint that it is easy to adjust to the specific physical properties while sufficient alkali developability and sufficient color density are obtained.
The content of the photocurable resin having two or more ethylenically unsaturated bonds in one molecule is 20 to 80% by mass, and further 30 to 60% by mass with respect to the total solid content of the photocurable resin composition. It is preferable to mix | blend in the ratio.
Moreover, it is preferable to mix | blend content of an initiator in the ratio of 5-30 mass% with respect to the solid content whole quantity of a photocurable resin composition, and also 10-25 mass%.
Moreover, it is preferable to mix | blend content of a coloring material in the ratio of 25-60 mass% with respect to solid content whole quantity of a photocurable resin composition, and also 30-55 mass%.
Moreover, it is preferable to mix | blend content of alkali-soluble resin in the ratio of 20-80 mass% with respect to solid content whole quantity of a photocurable resin composition, and also 40-70 mass%.

(solvent)
The photo-curable resin composition according to the present invention preferably contains a solvent in order to disperse the color material. The solvent used in the photocurable resin composition is not particularly limited as long as it is an organic solvent that does not react with each component in the photocurable resin composition and can dissolve or disperse them. For example, diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl Ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether Le acetate, dipropylene glycol, can be used diethylene glycol monobutyl ether acetate and the like.
What is necessary is just to set content of the said solvent suitably. For example, it is usually preferably in the range of 65 to 95% by mass, and more preferably in the range of 75 to 88% by mass, with respect to the total amount of the resin composition containing the solvent. When the content of the solvent is within the above range, the coating property can be excellent.

(Method for adjusting Q ₃ / E and Q ₂ / T)
Q ₃ / E and Q ₂ / T are adjusted by the type and content of a photocurable resin, an initiator, and other components having two or more ethylenically unsaturated bonds in one molecule to be used. .
Increasing the proportion of the photo-curable resin having two or more ethylenically unsaturated bonds in one molecule, there is a tendency that pre-exposure heat of reaction Q ₁ and post-exposure heat of reaction Q ₂ is increased.
When the content ratio of the photoinitiator that generates radicals or cations by heat is increased, the pre-exposure reaction heat Q ₁ tends to be larger than the post-exposure reaction heat Q ₂ , and the exposure reaction heat Q ₃ tends to increase. It is in.
Further, the reaction peak temperature tends to increase by reducing the content ratio of the monomer and initiator described later or by selecting an initiator that reacts at a higher temperature.
With reference to such a tendency, a photocurable resin composition having (Q ₃ / E) of 0.85 or less and (Q ₂ / T) of 0.5 or less can be appropriately adjusted.

Next, the color filter of the present invention will be described.
[Color filter]
The color filter of the present invention is a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, and at least one of the colored layers cures the photocurable resin composition of the present invention. It is characterized by being a colored layer formed.
Since the color filter of the present invention includes a colored layer formed by curing the photocurable resin composition of the present invention, even when the opening is widened, the generation of a cavity in the opening is prevented, Although it is high brightness, it can be set as the color filter with which the glare of the display apparatus and the panel nonuniformity were suppressed.
Since the colored layer formed by curing the photocurable resin composition of the present invention has fluidity in the post-exposure heating step and can fill the cavity as described above, the shape of the colored layer The colored layer does not have a reverse taper shape (the cross section is trapezoidal, and the width of the surface opposite to the substrate is the largest), but the reverse taper shape melts and tends to be a forward taper shape rather than the light shielding portion.

  Such a color filter of the present invention will be described with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of the color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has a transparent substrate 1, a light shielding part 2, and a colored layer 3.

(Colored layer)
The colored layer used in the color filter of the present invention is not particularly limited as long as it is formed by curing using the above-described photocurable resin composition of the present invention, and is usually on a transparent substrate described later. The light shielding part is usually formed of a coloring pattern of three or more colors.
In addition, the arrangement of the colored layers is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type can be used. Moreover, the width | variety, area, etc. of a colored layer can be set arbitrarily.
Although the thickness of the said colored layer is suitably controlled by adjusting the coating method, solid content concentration, viscosity, etc. of a photocurable resin composition, it is preferable normally that it is the range of 1-5 micrometers.

  In the present invention, at least one chromaticity coordinate of the colored layer may be y = 0.620 to 0.710. The photocurable resin composition of the present invention has a high color purity of y = 0.620 to 0.710 because it can form a colored layer without voids even if it contains a high concentration of green color material. In addition, a high-quality colored layer free from glare can be formed.

(Shading part)
The light shielding part in the color filter of the present invention is formed in a pattern on a transparent substrate described later, and can be the same as that used as a light shielding part in a general color filter.
The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape. Examples of the light-shielding portion include those obtained by dispersing or dissolving a black pigment in a binder resin, and metal thin films such as chromium and chromium oxide. The metal thin film may be a CrO _x film (x is an arbitrary number) and a laminate of two Cr films, and a CrO _x film (x is an arbitrary number) with a reduced reflectance. , CrN _y film (y is an arbitrary number) and three layers of Cr film may be laminated.

The thickness of the light shielding part is set to about 0.2 to 0.4 μm in the case of a metal thin film, and about 0.5 to 2 μm in the case where a black colorant is dispersed or dissolved in a binder resin. Is set.
In the present invention, since the photocurable resin composition of the present invention hardly causes cavities, the line width of the light shielding portion can be 7 μm or less, and preferably 3 to 7 μm. By doing so, a high-luminance color filter having a large opening can be obtained.

(Transparent substrate)
The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used for a general color filter can be used. Specific examples include inflexible transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials having flexibility such as transparent resin films and optical resin plates. It is done.
Although the thickness of the said transparent substrate is not specifically limited, According to the use of the color filter of this invention, the thing of about 100 micrometers-1 mm can be used, for example.
The color filter of the present invention may be one in which, for example, an overcoat layer, a transparent electrode layer, an alignment film, a columnar spacer, or the like is formed in addition to the transparent substrate, the light shielding portion, and the colored layer. .

(Shading part)
In the transparent substrate provided with the light-shielding part, the light-shielding part is formed in a pattern on a transparent substrate described later, and can be the same as that used as a light-shielding part in a general color filter.
When using a printing method or an inkjet method as a method for forming the light shielding part, examples of the binder resin include polymethyl methacrylate resin, polyacrylate resin, polycarbonate resin, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, hydroxyethyl cellulose resin, carboxymethyl cellulose resin, Examples thereof include a polyvinyl chloride resin, a melamine resin, a phenol resin, an alkyd resin, an epoxy resin, a polyurethane resin, a polyester resin, a maleic acid resin, and a polyamide resin.

  In the above case, when a photolithography method is used as a method for forming the light shielding portion, the binder resin may be, for example, an acrylate-based, methacrylate-based, polyvinyl cinnamate-based, or cyclized rubber-based reactive material. A photosensitive resin having a vinyl group is used. In this case, a photopolymerization initiator may be added to the photocurable resin composition for a light shielding part containing a black colorant and a photosensitive resin, and further, a sensitizer and a coating property improver as necessary. , Development improvers, crosslinking agents, polymerization inhibitors, plasticizers, flame retardants, and the like may be added.

  On the other hand, when the light shielding part is a metal thin film, the method for forming the light shielding part is not particularly limited as long as the light shielding part can be patterned, and for example, photolithography, vapor deposition using a mask. Method, printing method and the like.

[Color filter manufacturing method]
If the color filter of this invention has a colored layer formed by hardening | curing the photocurable resin composition of the said this invention, the manufacturing method will not be specifically limited. However, the method for producing a color filter according to the present invention described below is preferable in that the colored layer hardly causes cavities.

That is, the method for producing a color filter of the present invention is a method for producing a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate,
A photocurable resin composition comprising a photocurable resin having two or more ethylenically unsaturated bonds in one molecule and an initiator, wherein the photocurable resin composition is subjected to differential scanning calorimetry. In the DSC curve (A) obtained by the above, the pre-exposure reaction heat Q ₁ [J / g] calculated from the area value of the DSC curve (A) in the temperature range of 100 to 250 ° C., and the photocurability DSC curve (B) obtained by differential scanning calorimetry of the resin composition after exposure obtained by exposing the resin composition with an exposure amount E [mJ / cm ² ] using a high-pressure mercury lamp , The reaction heat at the time of exposure Q ₃ (= Q ₁₎ defined by the difference from the post-exposure reaction heat Q ₂ [J / g] calculated from the area value of the DSC curve (B) in the temperature range of 100 to 250 ° C. -Q ₂₎ of [J / g], the exposure amount E Against values _(Q 3 / E) is not less than 0.85, with respect to the DSC curve (B) heat flow reaction peak temperature T [° C.] defined at a temperature which takes the maximum value in the temperature range of 100 to 250 ° C. of the post-exposure value of the heat of reaction Q ₂ (Q _{2 / T)} is 0.5 or less, a step of preparing a photocurable resin composition,
On the transparent substrate, the step of coating the photocurable resin composition to form a coating film,
Exposure with an exposure dose E [mJ / cm ² ] using a high-pressure mercury lamp;
And a step of firing in a temperature range of 100 to 250 ° C.

FIG. 4 is a schematic view showing an example of a method for producing a color filter of the present invention. The photocurable resin composition according to the present invention is applied onto the transparent substrate 1 to form a coating film 14, and then an exposure dose E [mJ / cm] using a high-pressure mercury lamp through a mask 13 having a predetermined pattern. ² ] is exposed to light 11 and then developed with a developer to form a cured coating film 15. Subsequently, the cured film 15 obtained is baked in a temperature range of 100 to 250 ° C., whereby the sufficiently cured colored layer 16 is formed.
Since the production method of the present invention uses the photocurable resin composition of the present invention as the photocurable resin composition, the resin composition after the exposure at the time of firing can be obtained even when the cavity 17 is generated by development. The fluidity is increased and the cavity can be filled. Therefore, according to the method for manufacturing a color filter according to the present invention, a colored layer without a cavity can be formed, and a high-definition color filter can be obtained.

First, the photocurable resin composition according to the present invention is prepared. The said preparation process has the determination process of a photocurable resin composition as needed other than the preparation process of a photocurable resin composition. That is, the method for producing a photocurable resin composition according to the present invention may include a photocurable resin composition determination step described later and a physical property adjustment step including the determination step. The said determination process and physical property adjustment process may be abbreviate | omitted when preparing the photocurable resin composition of the same composition as the composition once determined with the physical property specified by this invention.
In addition, since each component in the said photocurable resin composition is as having mentioned above, description here is abbreviate | omitted.

What is necessary is just to select the preparation process of a photocurable resin composition suitably from a conventionally well-known method. For example, there may be mentioned a method in which a photocurable resin having two or more ethylenically unsaturated bonds in one molecule, an initiator, and various additive components used as desired are added to a solvent and mixed.
When preparing a photocurable resin composition containing a colorant, after preparing a colorant dispersion by a conventionally known method, the colorant dispersion in a solvent and two or more ethylenes in one molecule And a method of adding and mixing a photocurable resin having a polymerizable unsaturated bond, an initiator, and various additive components used as desired.

The obtained photocurable resin composition is determined by the following determination process.
The photocurable resin composition to be determined is applied onto a substrate and dried to form a dry coating film having a thickness of 3.5 μm. Next, in accordance with the plastic transition temperature measurement method described in JIS K7121, a DSC curve (A) in a temperature range of 100 to 250 ° C. is obtained from a part of the dried coating film by a differential scanning calorimeter. From the obtained DSC curve (A), the reaction heat before exposure Q ₁ [J / g] is determined.
Next, the exposed resin composition is obtained by exposing the dried coating film with an exposure amount E [mJ / cm ² ] using a high-pressure mercury lamp. The obtained resin composition after exposure is measured with a differential scanning calorimeter in the same manner as described above to obtain a DSC curve (B) in a temperature range of 100 to 250 ° C. From the obtained DSC curve (B), post-exposure reaction heat Q ₂ [J / g] and reaction peak temperature T [° C.] are determined.
The Q ₃ / E and the Q ₂ / T are calculated from the obtained results.
If the value of Q ₃ / E thus obtained is 0.85 or less and the value of Q ₂ / T is 0.5 or less, the photocurable resin composition is a colored layer without voids. It is determined that the photocurable resin composition can be formed. What was determined in this way is prepared as a photocurable resin composition that satisfies the specific physical properties described above.
In addition, you may include the physical property adjustment process which adjusts the structure and content of a composition suitably so that the said specific physical property may be satisfied according to the above guidelines, using the said determination process.

Next, the photocurable resin composition is applied onto a transparent substrate to form a coating film. The said coating-film formation process can be suitably selected from conventionally well-known methods.
Usually, the above-mentioned photocurable resin composition of the present invention is applied on a transparent substrate having a light-shielding portion using a coating means such as a spray coating method, a dip coating method, a bar coating method, a coal coating method, or a spin coating method. Then, it is applied on a transparent substrate to be described later to form a wet coating film, and the wet coating film is dried using a hot plate or an oven as necessary.

Next, the obtained coating film is exposed at an exposure amount E [mJ / cm ² ] using a high-pressure mercury lamp through a mask having a predetermined pattern. By the exposure, a photocurable resin having two or more ethylenically unsaturated bonds in at least one molecule is subjected to a photopolymerization reaction to obtain a coated film after exposure of the photocurable resin composition. Although exposure amount E [mJ / cm < ² >] is suitably adjusted with the composition of a photocurable resin composition, the thickness of a coating film, etc., it is not specifically limited, Exposure amount E is 20-300 mJ / in conversion of 365 nm wavelength. is preferably set in the range of cm ^2, further more preferably to 30~200mJ / cm ² to E, among others, it is more preferred to 40 mJ / cm ² to E. By setting E within the above range, the colored layer is less likely to form cavities.
The coating film after the exposure is usually developed using a developing solution, and a coating film having a desired pattern is formed by dissolving and removing unexposed portions. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to the alkaline solution. Further, a general method can be adopted as the developing method. After the development treatment, the developer is usually washed and the cured coating film is dried to form a colored layer.

Next, the obtained coating film after exposure is baked in a temperature range of 100 to 250 ° C. The firing step includes at least a colored layer flow step and a colored layer curing step. The colored layer flow step is a step of providing fluidity to at least a part of the reverse-tapered colored layer obtained after exposure and development, and filling the void even when a void is generated during development. The colored layer curing step is a step of sufficiently increasing the degree of curing of the colored layer.
In the firing step, the colored layer flow step and the colored layer curing step are not completely separable, but when the firing temperature is lower than the reaction temperature peak T [° C.], the colored layer flow step is mainly performed. When the firing temperature is higher than the reaction temperature peak T [° C.], the colored layer curing step mainly proceeds.

  The firing conditions in the firing step are not particularly limited, but after sufficiently heating at a temperature lower than the reaction peak temperature T [° C.], the temperature is gradually increased until the temperature rises above the reaction peak temperature T [° C.]. Even when cavities sometimes occur, it is preferable that the photocurable resin composition flows and the cavities are easily filled. For example, it is preferable to raise the temperature at 5 to 15 ° C./min until the temperature becomes higher than the reaction peak temperature T [° C.].

Next, the liquid crystal display device of the present invention will be described.
[Liquid Crystal Display]
The liquid crystal display device of the present invention includes the color filter of the present invention described above, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic cross-sectional view showing an example of the liquid crystal display device of the present invention. As illustrated in FIG. 2, the liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30.
Note that the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, but can be a configuration generally known as a liquid crystal display device using a color filter.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for a liquid crystal display device can be employed. Examples of such a drive method include a TN method, an IPS method, an OCB method, and an MVA method. In the present invention, any of these methods can be preferably used.
Further, the counter substrate can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention.
Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used according to the driving method of the liquid crystal display device of the present invention.

As a method for forming the liquid crystal layer, a method generally used as a method for manufacturing a liquid crystal cell can be used. Examples thereof include a vacuum injection method and a liquid crystal dropping method.
In the vacuum injection method, for example, a liquid crystal cell is prepared in advance using a color filter and a counter substrate, and the liquid crystal is heated to obtain an isotropic liquid, and the liquid crystal is applied to the liquid crystal cell using the capillary effect. The liquid crystal layer can be formed by injecting in this state and sealing with an adhesive. Thereafter, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.
In the liquid crystal dropping method, for example, a sealant is applied to the periphery of the color filter, the color filter is heated to a temperature at which the liquid crystal becomes isotropic, and the liquid crystal is dropped in an isotropic liquid state using a dispenser or the like. In addition, the liquid crystal layer can be formed by overlapping the color filter and the counter substrate under reduced pressure and bonding them with a sealant. Thereafter, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.

Next, the organic light emitting display device of the present invention will be described.
[Organic light emitting display]
The organic light emitting display device of the present invention includes the above-described color filter of the present invention and an organic light emitter.
Such an organic light emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic cross-sectional view showing an example of the organic light emitting display device of the present invention. As illustrated in FIG. 3, the organic light emitting display device 100 of the present invention includes a color filter 10 and an organic light emitter 80. An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80.

As a method for laminating the organic light emitter 80, for example, the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76 are sequentially formed on the upper surface of the color filter. Examples thereof include a method and a method in which an organic light emitter 80 formed on another substrate is bonded onto the inorganic oxide film 60. As the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other configurations in the organic light emitting body 80, known structures can be appropriately used. The organic light emitting display device 100 manufactured as described above can be applied to, for example, a passive drive type organic EL display or an active drive type organic EL display.
Note that the organic light emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and may be a known configuration as an organic light emitting display device that generally uses a color filter.

  Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.

[Production Example 1: Preparation of green light curable resin composition A]
(1) Preparation of alkali-soluble resin 63 parts by mass of methyl methacrylate (MMA), 12 parts by mass of acrylic acid (AA), 6 parts by mass of 2-hydroxyethyl methacrylate (HEMA), diethylene glycol dimethyl ether in the polymerization tank After 88 parts by mass of (DMDG) was charged and stirred and dissolved, 7 parts by mass of 2,2′-azobis (2-methylbutyronitrile) was added and dissolved uniformly.
Then, it stirred at 85 degreeC under nitrogen stream for 2 hours, and also was made to react at 100 degreeC for 1 hour.
Further, 7 parts by mass of glycidyl methacrylate (GMA), 0.4 parts by mass of triethylamine, and 0.2 parts by mass of hydroquinone were added to the obtained solution, and the mixture was stirred at 100 ° C. for 5 hours, and a curable alkali. A soluble resin solution (solid content 50%) was obtained.

(2) Preparation of photocurable resin composition A Next, the following materials were stirred and mixed at room temperature to obtain a photocurable resin composition A.
<Composition of photocurable resin composition A>
-Alkali-soluble resin solution (solid content 50%) ... 58 parts by mass-Dipentaerythritol pentaacrylate (Sartomer SR399: photocurable resin (monomer)) ... 17 parts by mass-IRGACURE 907 (manufactured by BASF, initiator; Absorption maximum wavelength 315nm)
... 4 parts by mass, diethylene glycol dimethyl ether ... 21 parts by mass

(3) Preparation of green light curable resin composition A The following components were mixed and sufficiently dispersed in a sand mill to obtain green light curable resin composition A.
<Composition of green light curable resin composition A>
・ C. I. Pigment Green 7: 7 parts by mass / C.I. I. Pigment Yellow 150 ... 0.7 parts by mass, polysulfonic acid type polymer dispersant ... 3.3 parts by mass, photocurable resin composition A (solid content 50%) ... 22 parts by mass, 3-methoxybutyl acetate ... 67 parts by mass

[Production Example 2: Preparation of green light curable resin composition B]
(1) Preparation of photocurable resin composition B Photocurable resin was prepared in the same manner as (2) of Production Example 1 except that the ratio of each component in Production Example 1 (2) was changed as follows. Composition B was obtained.
<Composition of photocurable resin composition B>
-Alkali-soluble resin solution of Production Example 1 (1) (solid content 50%) ... 44 parts by mass-Dipentaerythritol pentaacrylate (Sartomer SR399)
... 24 parts by mass-IRGACURE 907 ... 4 parts by mass-diethylene glycol dimethyl ether ... 28 parts by mass

(2) Preparation of green light curable resin composition B Green light curable resin composition B was prepared in the same manner as (3) of Production Example 1 except that the following components were changed to (3) of Production Example 1. Got.
<Composition of green light curable resin composition B>
・ C. I. Pigment Green 7: 7 parts by mass / C.I. I. Pigment Yellow 150 ... 0.7 parts by mass, polysulfonic acid type polymer dispersant ... 3.3 parts by mass, the photocurable resin composition B (solid content 50%) ... 22 parts by mass, 3-methoxybutyl acetate ... 67 parts by mass

[Production Example 3: Preparation of green light curable resin composition C]
(1) Preparation of photocurable resin composition C In (2) of Production Example 1, a photocurable resin was produced in the same manner as in (2) of Production Example 1 except that the ratio of each component was changed as follows. Composition C was obtained.
<Composition of photocurable resin composition C>
-Alkali-soluble resin solution of Production Example 1 (1) (solid content 50%) ... 58 parts by mass-Dipentaerythritol pentaacrylate (Sartomer SR399)
... 17 parts by mass · IRGACURE 907 ... 3.8 parts by mass · Vam-110 (manufactured by Wako Pure Chemical Industries, Ltd.) ... 0.2 parts by mass · diethylene glycol dimethyl ether ... 21 parts by mass

(2) Preparation of green light curable resin composition C Green light curable resin composition C was prepared in the same manner as (3) of Production Example 1 except that the following components were changed to (3) of Production Example 1. Got.
<Composition of green light curable resin composition C>
・ C. I. Pigment Green 7: 7 parts by mass / C.I. I. Pigment Yellow 150 ... 0.7 parts by mass, polysulfonic acid type polymer dispersant ... 3.3 parts by mass, the photocurable resin composition C (solid content 50%) ... 22 parts by mass, 3-methoxybutyl acetate ... 67 parts by mass

[Production Example 4: Preparation of green light curable resin composition D]
(1) Preparation of photocurable resin composition D In (2) of Production Example 1, a photocurable resin was produced in the same manner as (2) of Production Example 1 except that the ratio of each component was changed as follows. Composition D was obtained.
<Composition of photocurable resin composition D>
-Alkali-soluble resin solution of Production Example 1 (1) (solid content 50%) ... 58 parts by mass-Dipentaerythritol pentaacrylate (Sartomer SR399)
... 17 parts by mass · IRGACURE 907 ... 3.8 parts by mass · V-40 (Wako Pure Chemical Industries, Ltd .: initiator) ... 0.2 parts by mass · diethylene glycol dimethyl ether ... 21 parts by mass

(2) Preparation of green light curable resin composition D Green light curable resin composition D was prepared in the same manner as (3) of Production Example 1 except that the following components were changed to (3) of Production Example 1. Got.
<Composition of green light curable resin composition D>
・ C. I. Pigment Green 7: 7 parts by mass / C.I. I. Pigment Yellow 150 ... 0.7 parts by mass, polysulfonic acid type polymer dispersant ... 3.3 parts by mass, photocurable resin composition D (solid content 50%) ... 22 parts by mass, 3-methoxybutyl acetate ... 67 parts by mass

[Production Example 5: Preparation of green light curable resin composition E]
(1) Preparation of photo-curable resin composition E Photo-curable resin was prepared in the same manner as in Production Example 1 (2) except that the ratio of each component in Production Example 1 (2) was changed as follows. Composition E was obtained.
<Composition of photocurable resin composition E>
-Alkali-soluble resin solution of Production Example 1 (1) (solid content 50%) ... 62 parts by mass-Dipentaerythritol pentaacrylate (Sartomer SR399)
... 17 parts by mass IRGACURE 369 (manufactured by BASF, initiator; absorption maximum wavelength 320 nm)
... 2 parts by mass, diethylene glycol dimethyl ether ... 19 parts by mass

(2) Preparation of green light curable resin composition E Green light curable resin composition E in the same manner as (3) of Production Example 1 except that the following components were changed in (3) of Production Example 1. Got.
<Composition of green light curable resin composition E>
・ C. I. Pigment Green 7: 7 parts by mass / C.I. I. Pigment Yellow 150 ... 0.7 parts by mass, polysulfonic acid type polymer dispersant ... 3.3 parts by mass, the photocurable resin composition E (solid content 50%) ... 22 parts by mass, 3-methoxybutyl acetate ... 67 parts by mass

[Production Example 6: Preparation of green light curable resin composition F]
(1) Preparation of photocurable resin composition F In (2) of Production Example 1, a photocurable resin was produced in the same manner as (2) of Production Example 1 except that the ratio of each component was changed as follows. Composition F was obtained.
<Composition of photocurable resin composition F>
-Alkali-soluble resin solution of Production Example 1 (1) (solid content 50%) ... 50 parts by mass-Dipentaerythritol pentaacrylate (Sartomer SR399)
... 17 parts by mass IRGACURE 2959 (manufactured by BASF, initiator) ... 8 parts by mass diethylene glycol dimethyl ether ... 25 parts by mass

(2) Preparation of green light curable resin composition F Green light curable resin composition F was prepared in the same manner as (3) of Production Example 1 except that the following components were changed to (3) of Production Example 1. Got.
<Composition of green light curable resin composition F>
・ C. I. Pigment Green 7: 7 parts by mass / C.I. I. Pigment Yellow 150 ... 0.7 parts by mass, polysulfonic acid type polymer dispersant ... 3.3 parts by mass, photocurable resin composition F (solid content 50%) ... 22 parts by mass, 3-methoxybutyl acetate ... 67 parts by mass

[Production Example 7: Preparation of green light curable resin composition G]
(1) Preparation of photocurable resin composition G Photocurable resin was prepared in the same manner as (2) of Production Example 1 except that the ratio of each component in Production Example 1 (2) was changed as follows. Composition F was obtained.
<Composition of photocurable resin composition G>
-Alkali-soluble resin solution of production example 1 (1) (solid content 50%) ... 64 parts by mass-Dipentaerythritol pentaacrylate (Sartomer SR399)
... 17 parts by mass / N-1919 (manufactured by Adeka, initiator; absorption maximum wavelength 340 nm)
... 1 part by mass ・ Ethylene glycol dimethyl ether ... 18 parts by mass

(2) Preparation of green light curable resin composition G Green light curable resin composition G was prepared in the same manner as (3) of Production Example 1 except that the following components were changed to (3) of Production Example 1. Got.
<Composition of green light curable resin composition G>
・ C. I. Pigment Green 7: 7 parts by mass / C.I. I. Pigment Yellow 150 ... 0.7 parts by mass, polysulfonic acid type polymer dispersant ... 3.3 parts by mass, photocurable resin composition G (solid content 50%) ... 22 parts by mass, 3-methoxybutyl acetate ... 67 parts by mass

[Production Example 8: Preparation of green light curable resin composition H]
(1) Preparation of green light curable resin composition H Photocurability was the same as (2) of Production Example 1 except that the ratio of each component in Production Example 1 (2) was changed as follows. Resin composition H was obtained.
<Composition of photocurable resin composition H>
-Alkali-soluble resin solution of Production Example 1 (1) (solid content 50%) ... 32 parts by mass-Dipentaerythritol pentaacrylate (Sartomer SR399)
... 26 parts by mass IRGACURE 907 ... 3.2 parts by mass IRGACURE 369 ... 3.2 parts by mass biimidazole ... 1.6 parts by mass diethylene glycol dimethyl ether ... 34 parts by mass

(2) Preparation of green light curable resin composition H Green light curable resin composition H was the same as (3) of Production Example 1 except that the following components were changed to (3) of Production Example 1. Got.
<Composition of green light curable resin composition H>
・ C. I. Pigment Green 7: 7 parts by mass / C.I. I. Pigment Yellow 150 ... 0.7 parts by mass, polysulfonic acid type polymer dispersant ... 3.3 parts by mass, the photocurable resin composition H (solid content 50%) ... 22 parts by mass, 3-methoxybutyl acetate ... 67 parts by mass

[Production Example 9: Preparation of green light curable resin composition I]
(1) Preparation of green light curable resin composition I Photocurability was the same as (2) of Production Example 1 except that the ratio of each component in Production Example 1 (2) was changed as follows. Resin composition I was obtained.
<Composition of photocurable resin composition I>
-Alkali-soluble resin solution of Production Example 1 (1) (solid content 50%) ... 32 parts by mass-Dipentaerythritol pentaacrylate (Sartomer SR399)
... 27 parts by mass IRGACURE 907 ... 2.8 parts by mass IRGACURE 369 ... 2.8 parts by mass biimidazole ... 1.4 parts by mass diethylene glycol dimethyl ether ... 34 parts by mass

(2) Preparation of green light curable resin composition I Green light curable resin composition I was prepared in the same manner as (3) of Production Example 1 except that the following components were changed to (3) of Production Example 1. Got.
<Composition of green light curable resin composition I>
・ C. I. Pigment Green 7: 7 parts by mass / C.I. I. Pigment Yellow 150: 0.7 parts by mass, polysulfonic acid type polymer dispersant: 3.3 parts by mass, photocurable resin composition I (solid content: 50%): 22 parts by mass, 3-methoxybutyl acetate: 67 parts by mass

[Production Example 10: Preparation of green light curable resin composition J]
(1) Preparation of green light curable resin composition J Photocurability was the same as (2) of Production Example 1 except that the ratio of each component in Production Example 1 (2) was changed as follows. Resin composition J was obtained.
<Composition of photocurable resin composition J>
-Alkali-soluble resin solution of Production Example 1 (1) (solid content 50%) ... 58 parts by mass-Dipentaerythritol pentaacrylate (Sartomer SR399)
... 17 parts by mass · IRGACURE 907 ... 3.6 parts by mass · 0.4 parts by mass of Vam-110 · 21 parts by mass of diethylene glycol dimethyl ether

(2) Preparation of green light curable resin composition J Green light curable resin composition J was prepared in the same manner as (3) of Production Example 1 except that the following components were changed to (3) of Production Example 1. Got.
<Composition of green light curable resin composition J>
・ C. I. Pigment Green 7: 7 parts by mass / C.I. I. Pigment Yellow 150 ... 0.7 parts by mass, polysulfonic acid type polymer dispersant ... 3.3 parts by mass, photocurable resin composition J (solid content 50%) ... 22 parts by mass, 3-methoxybutyl acetate ... 67 parts by mass

[Production Example 11: Preparation of green light curable resin composition K]
(1) Preparation of green photocurable resin composition K Photocurability was the same as (2) of Production Example 1 except that the ratio of each component in Production Example 1 (2) was changed as follows. A resin composition K was obtained.
<Composition of photocurable resin composition K>
-Alkali-soluble resin solution of Production Example 1 (1) (solid content 50%) ... 58 parts by mass-Dipentaerythritol pentaacrylate (Sartomer SR399)
... 17 parts by mass · IRGACURE 907 ... 3.6 parts by mass · V-40 ... 0.4 parts by mass · diethylene glycol dimethyl ether ... 21 parts by mass

(2) Preparation of green light curable resin composition K Green light curable resin composition K in the same manner as (3) of Production Example 1 except that the following components were changed in (3) of Production Example 1. Got.
<Composition of green light curable resin composition K>
・ C. I. Pigment Green 7: 7 parts by mass / C.I. I. Pigment Yellow 150 ... 0.7 parts by mass, polysulfonic acid type polymer dispersant ... 3.3 parts by mass, the photocurable resin composition K (solid content 50%) ... 22 parts by mass, 3-methoxybutyl acetate ... 67 parts by mass

  Table 1 shows the content of each component in the green light curable resin compositions of Production Examples 1 to 11 described above. In addition, the value in Table 1 is a mass% unit. Moreover, the polymer in Table 1 represents the sum total of alkali-soluble resin and a polymer dispersing agent.

[Evaluation of physical properties of green light curable resin composition]
(Measurement of DSC curve (A))
Each of the green light curable resins obtained in Production Examples 1 to 11 was applied onto a substrate and dried to form a dry coating film having a thickness of 3.5 μm. The obtained dried coating film was scraped off and 5 mg was enclosed in a sample pan. Next, a DSC curve (A) in a temperature range of 100 to 250 ° C. was obtained by a differential scanning calorimeter according to the plastic transition temperature measurement method described in JIS K7121. In the DSC curve (A), the horizontal axis x is temperature [° C.] and the vertical axis y is heat flow [W / g]. From the area value of the region formed by the obtained DSC curve (A) and y = 0, the pre-exposure reaction heat Q ₁ [J / g] was calculated. As the suggested scanning calorimeter, DSC-60 manufactured by Shimadzu Corporation was used, and the temperature raising condition was 10 ° C./min. The results are shown in Table 2.

(Measurement of DSC curve (B))
The green light curable resins obtained in Production Examples 1 to 11 were each coated on a substrate and dried to form a dry coating film having a thickness of 3.5 μm. Subsequently, the resin composition after exposure was obtained by exposing by the exposure amount of 40 [mJ / cm < ² >] using a high pressure mercury lamp. The obtained resin composition after exposure was scraped off and 5 mg was enclosed in a sample pan. Next, a DSC curve (B) in a temperature range of 100 to 250 ° C. was obtained by a differential scanning calorimeter in accordance with the plastic transition temperature measurement method described in JIS K7121. In the DSC curve (B), the horizontal axis x is temperature [° C.] and the vertical axis y is heat flow [W / g]. The post-exposure reaction heat Q ₂ [J / g] was calculated from the area value of the region formed by the obtained DSC curve (B) and y = 0. Further, the temperature at which the heat flow reached the maximum value in the temperature range of 100 to 250 ° C. of the DSC curve (B) was defined as the reaction peak temperature T [° C.]. As the suggested scanning calorimeter, DSC-60 manufactured by Shimadzu Corporation was used, and the temperature raising condition was 10 ° C./min. The results are shown in Table 2.

From the pre-exposure reaction heat Q ₁ , post-exposure reaction heat Q ₂ , and reaction peak temperature T obtained by the above measurement, Q ₃ , Q ₃ / E, and Q ₂ / T were calculated. The results are shown in Table 2.

As a result of the physical property evaluation of the photocurable resin composition, the green photocurable resin compositions of Production Examples 1 to 7 have Q ₃ / E of 0.85 or less and Q ₂ / T of 0.5 or less. It was confirmed that this corresponds to the example. On the other hand, in the green light curable resin compositions of Production Examples 8 and 9, both Q ₃ / E and Q ₂ / T are out of range, and the green light curable resin compositions of Production Examples 10 and 11 are Since Q ₂ / T is out of the range, it was confirmed that it corresponds to a comparative example. Hereinafter, as shown in Table 2, the green light curable resin compositions A to G of Production Examples 1 to 7 are compared with Examples 1 to 7 and the green light curable resin compositions H to K of Production Examples 8 to 11, respectively. Let it be Examples 1-4.

[Production Example 12: Preparation of red photocurable resin composition]
The following amounts of each component were mixed and sufficiently dispersed with a sand mill to obtain a red photocurable resin composition.
<Composition of red photocurable resin composition>
・ C. I. Pigment Red 177 3 parts by mass / C.I. I. Pigment Red 254 4 parts by mass, polysulfonic acid type polymer dispersant 3 parts by mass, photocurable resin composition A of Production Example 1 (2) 22 parts by mass, 3-methoxybutyl acetate 68 parts by mass

[Production Example 13: Preparation of blue light curable resin composition]
The following amounts of each component were mixed and sufficiently dispersed by a sand mill to obtain a blue light curable resin composition.
<Composition of blue light curable resin composition>
・ C. I. Pigment Blue 1 ... 5 parts by mass, polysulfonic acid type polymer dispersant ... 3 parts by mass, photocurable resin composition A of Production Example 1 (2) ... 22 parts by mass, 3-methoxybutyl acetate ... 70 parts by mass

[Production Example 14: Preparation of composition for light shielding part]
First, the following amounts of each component were mixed and sufficiently dispersed with a sand mill to prepare a black pigment dispersion.
<Composition of black pigment dispersion>
Black pigment (Mitsubishi Chemical Corporation # 2600) 20 parts by mass Polymer dispersing agent (Big Chemie Japan, Ltd. Disperbyk 111)
... 16 parts by mass, solvent (diethylene glycol dimethyl ether) ... 64 parts by mass

Next, the following components were sufficiently mixed to obtain a light shielding part composition.
<Composition of composition for light shielding part>
-Black pigment dispersion liquid: 50 parts by mass-Photocurable resin composition A in Production Example 1 (2)-20 parts by mass-Diethylene glycol dimethyl ether-30 parts by mass

[Example 1: Production of color filter]
(1) Formation of light shielding part The composition for light shielding part of Production Example 14 was applied on a transparent substrate by a spin coater and dried at 100 ° C. for 3 minutes to form a light shielding part forming layer.
The light-shielding part forming layer is exposed to a light-shielding pattern with an ultra-high pressure mercury lamp, and then developed with a 0.05 wt% potassium hydroxide aqueous solution. To form a light shielding part.

(2) Formation of red colored layer The red photocurable resin composition of Production Example 12 was applied by spin coating so as to have a predetermined color coordinate, and then dried in an oven at 70 ° C for 3 minutes.
Next, a photomask is placed at a distance of 100 μm from the coating film of the red light curable resin composition, and an ultraviolet ray is applied only to the region corresponding to the colored layer forming region using a 2.0 kW ultrahigh pressure mercury lamp by a proximity aligner. Was irradiated for 10 seconds.
Subsequently, it was immersed in 0.05 wt% potassium hydroxide aqueous solution (liquid temperature 23 degreeC) for 1 minute, and alkali development was carried out, and only the uncured part of the coating film of the red photocurable resin composition was removed.
Thereafter, the substrate is allowed to stand in an atmosphere of 230 ° C. for 15 minutes, so that a heat treatment is performed to form a red color layer (hereinafter referred to as a red colored layer on the entire frame portion forming region serving as a non-display region) , Also called a relief pattern).

(Formation of green colored layer)
Next, in the same process as the formation of the red relief pattern, the green light curable resin composition A of Example 1 is applied so as to have a predetermined color coordinate, and the green colored layer is applied to the green pixels in the display area. A pattern consisting of

(Formation of blue colored layer)
Further, in the same process as the formation of the red relief pattern, the red photocurable resin composition of Production Example 13 is applied on the side on which the green relief pattern is formed so as to have predetermined color coordinates. A pattern composed of a blue colored layer was formed on the blue pixels in the working area, and the color filter of Example 1 was obtained.

[Examples 2 to 7: Production of color filter]
In the production of the color filter of Example 1, the same procedure as in Example 1 was conducted except that the green light curable resin compositions B to G of Examples 2 to 7 were used instead of the green light curable resin composition A, respectively. Thus, color filters of Examples 2 to 7 were obtained.

[Comparative Examples 1-4: Production of Color Filter]
In the production of the color filter of Example 1, the same procedure as in Example 1 was conducted except that the green light curable resin compositions H to K of Comparative Examples 1 to 4 were used instead of the green light curable resin composition A, respectively. Thus, color filters of Comparative Examples 1 to 4 were obtained.

[Cavity evaluation]
The color filters obtained in the above Examples and Comparative Examples were cut, and the cut surfaces of the green pixels were observed for the presence or absence of cavities using an electron microscope (VE-9800, manufactured by Keyence Corporation). The results are shown in Table 3.
(Cavity evaluation criteria)
○: No cavity was observed.
X: A cavity was observed.

[Development adhesion evaluation]
Only in Examples 1 to 7 and Comparative Examples 1 to 4, the green light curable resin composition was applied on a transparent substrate by a spin coating method. Then, it dried for 3 minutes in 70 degreeC oven. Next, a photomask was placed at a distance of 100 μm from the obtained coating film, and ultraviolet rays were irradiated by a proximity aligner using a 2.0 kw ultrahigh pressure mercury lamp so that a colored layer of 50 μm square was formed. It was immersed in a 0.05 wt% potassium hydroxide aqueous solution (liquid temperature: 23 ° C.) for 60 seconds and alkali-developed, and the adhesion of the colored layer formed in a 50 μm square pattern was evaluated.
Further, the adhesiveness was evaluated by the same method as described above with the development time (immersion time) changed to 40 seconds and 80 seconds.
(Adhesion evaluation criteria)
A: The adhesion of the colored layer was confirmed even when the development time was 80 seconds.
A: The adhesion of the colored layer was confirmed when the development time was 40 seconds and 60 seconds.
X: Adhesiveness was insufficient when the development time was 60 seconds.
If the development adhesion is A or B, it is evaluated as being within the practical range. The results are shown in Table 3.

[Summary of results]
A pixel formed using the photocurable resin composition of Examples 1 to 7 having Q ₃ / E of 0.85 or less and Q ₂ / T of 0.5 or less does not generate a cavity, It became clear that the development adhesion was excellent. On the other hand, when the photocurable resin compositions of Comparative Examples 1 to 4 that do not satisfy the above physical properties were used, it became clear that a cavity as shown in FIG. 7 was generated.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Light-shielding part 3 Colored layer 10 Color filter 11 Exposure light 13 Photomask 14 Coating film of photocurable resin composition 15 Cured coating film 16 Colored layer 17 Cavity generated by development 18 Cavity 20 Counter substrate 30 Liquid crystal layer 40 Liquid crystal display device 50 Organic protective layer 60 Inorganic oxide film 71 Transparent anode 72 Hole injection layer 73 Hole transport layer 74 Light emitting layer 75 Electron injection layer 76 Cathode 80 Organic light emitter 100 Organic light emitting display device

Claims (10)

A photocurable resin composition comprising a photocurable resin having two or more ethylenically unsaturated bonds in one molecule, and an initiator,
In the DSC curve (A) obtained by differential scanning calorimetry of the photocurable resin composition, the pre-exposure reaction heat calculated from the area value of the DSC curve (A) in the temperature range of 100 to 250 ° C. Differential scanning was performed on Q ₁ [J / g] and the exposed resin composition obtained by exposing the photocurable resin composition to an exposure amount E [mJ / cm ² ] using a high-pressure mercury lamp. In the DSC curve (B) obtained by calorimetric measurement, the difference from the post-exposure reaction heat Q ₂ [J / g] calculated from the area value of the DSC curve (B) in the temperature range of 100 to 250 ° C. The value (Q ₃ / E) of the reaction heat Q ₃ (= Q ₁ −Q ₂ ) [J / g] defined for the exposure amount E is 0.85 or less,
The value (Q ₂ / T) of the post-exposure reaction heat Q ₂ with respect to the reaction peak temperature T [° C.] defined by the temperature at which the heat flow takes the maximum value in the temperature range of 100 to 250 ° C. of the DSC curve (B). The photocurable resin composition which is 0.5 or less.   The photocurable resin composition according to claim 1, wherein an absorption spectrum of the initiator has a maximum value in a wavelength range of 310 to 400 nm.   Furthermore, the photocurable resin composition of Claim 1 or 2 containing a coloring material.   The photocurable resin composition according to any one of claims 1 to 3, wherein the coloring material contains a green coloring material.   The photocurable resin as described in any one of Claims 1 thru | or 4 whose content rate of the said coloring material is 30 mass parts or more with respect to 100 mass parts of total solid of the said photocurable resin composition. Composition.   A photocurable resin composition according to any one of claims 1 to 5, wherein the color filter includes at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers is the color curable resin composition. A color filter comprising a colored layer formed by curing a product.   The color filter according to claim 6, wherein at least one chromaticity coordinate of the colored layer is y = 0.620 to 0.710. A method for producing a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate,
A photocurable resin composition comprising a photocurable resin having two or more ethylenically unsaturated bonds in one molecule and an initiator, wherein the photocurable resin composition is subjected to differential scanning calorimetry. In the DSC curve (A) obtained by the above, the pre-exposure reaction heat Q ₁ [J / g] calculated from the area value of the DSC curve (A) in the temperature range of 100 to 250 ° C., and the photocurability DSC curve (B) obtained by differential scanning calorimetry of the resin composition after exposure obtained by exposing the resin composition with an exposure amount E [mJ / cm ² ] using a high-pressure mercury lamp , The reaction heat at the time of exposure Q ₃ (= Q ₁₎ defined by the difference from the post-exposure reaction heat Q ₂ [J / g] calculated from the area value of the DSC curve (B) in the temperature range of 100 to 250 ° C. -Q ₂₎ of [J / g], the exposure amount E Against values _(Q 3 / E) is not less than 0.85, with respect to the DSC curve (B) heat flow reaction peak temperature T [° C.] defined at a temperature which takes the maximum value in the temperature range of 100 to 250 ° C. of the post-exposure value of the heat of reaction Q ₂ (Q _{2 / T)} is 0.5 or less, a step of preparing a photocurable resin composition,
On the transparent substrate, the step of coating the photocurable resin composition to form a coating film,
Exposure with an exposure dose E [mJ / cm ² ] using a high-pressure mercury lamp;
And a step of firing in a temperature range of 100 to 250 ° C.   8. A liquid crystal display device comprising: the color filter according to claim 6; a counter substrate; and a liquid crystal layer formed between the color filter and the counter substrate.   8. An organic light emitting display device comprising the color filter according to claim 6 and an organic light emitter.