JP2018087956A - Method for producing colored cured film and method for forming pixel pattern of color filter - Google Patents

Abstract

The present invention provides a method for producing a colored cured film which hardly undergoes color transfer even in low-temperature post-baking and has good solvent resistance and good adhesion to a substrate. A method for producing a colored cured film including steps (1) to (4). Step (1): a step of applying a colored radiation-sensitive composition containing (A) a colorant, (B) a polymerizable compound, and (C) a radiation-sensitive polymerization initiator on a substrate to form a coating film Step (2): irradiating the coating film obtained in Step (1) with radiation (1); Step (3): developing the coating film obtained in Step (2); Step (4) ): A step of irradiating the coating film obtained in step (3) with radiation (2), provided that radiation (1) and radiation (2) may be the same or different. [Selection diagram] None

Description

  The present invention relates to a colored cured film manufacturing method and a color filter pixel pattern forming method.

  As a method for producing a color filter, for example, an ink jet method, an electrodeposition method, a printing method, a photolithography method, and the like are known, but in recent years, a photolithography method has become mainstream. When producing a color filter by a photolithography method, for example, a colored radiation-sensitive composition is applied on a substrate to form a coating film, and then exposed to radiation through a photomask having a predetermined opening pattern, A method of forming a pattern by developing and removing unexposed portions by dissolution is employed (Patent Document 1). And after pattern formation, in order to ensure reliability, such as heat resistance and solvent resistance, adhesion to a substrate, and electrical properties, by post-baking at a temperature of 200 to 250 ° C. for about 30 to 60 minutes, It is usual to accelerate the curing of the coating film.

  In recent years, flexible display devices have attracted attention, and replacement of a conventional glass substrate with a flexible plastic substrate has been studied. However, the plastic substrate generally has low heat resistance, and the plastic substrate tends to stretch or shrink at a post-bake temperature of 200 to 250 ° C. In the case of using such a plastic substrate, it is conceivable that post baking is not performed or post baking is performed at a lower temperature. When the coloring composition is overcoated, problems such as color transfer to the adjacent pattern of other colors, reduction in solvent resistance of the colored pattern, and adhesion to the substrate occur.

  For such a problem, by using a photosensitive coloring composition for a color filter containing a resin in which the content of the structural unit containing an ethylenically unsaturated double bond in the side chain is within a specific range, 150 ° C. It has been reported that even after post-baking at the following temperatures, it is difficult to transfer colors and a colored pattern having good solvent resistance and sensitivity can be formed (Patent Documents 2 and 3).

JP-A-2-144502 JP2015-125402A JP-A-2015-143840

  An object of the present invention is to provide a method for producing a colored cured film and a color filter, which do not cause post-baking or are low-temperature post-baking, are difficult to transfer colors, and have good solvent resistance and adhesion to a substrate. The object is to provide a method of forming a pixel pattern.

  The present inventors have studied to develop a method capable of forming a desired coloring pattern even after low-temperature post-baking using a wide range of colored radiation-sensitive compositions, and as a result, colored radiation-sensitive compositions on a substrate. After coating and forming a coating film, exposing and developing the coating film, by performing post-exposure using radiation having a specific spectral distribution, no post-baking or low-temperature post-baking Even if it exists, it discovered that a color pattern which was hard to transfer colors and had favorable solvent resistance and adhesiveness with a board | substrate could be formed.

  That is, this invention provides the manufacturing method of a colored cured film characterized by including the following process (1)-(4).

  The present invention also provides a method for forming a pixel pattern of a color filter, comprising the following steps (1) to (4).

  The present invention further includes a colored cured film produced by a process including the following steps (1) to (4), a color filter including the colored cured film (pixel), a display element and a light emitting element, and a display element including the color filter. And a light-emitting element.

Step (1): A step of applying a colored radiation-sensitive composition containing (A) a colorant, (B) a polymerizable compound and (C) a radiation-sensitive polymerization initiator on a substrate to form a coating film. Step (2): Step (3) for irradiating the coating film obtained in the step (1) with radiation (1) Step: Step (4) for developing the coating film obtained in the step (2) : A step of irradiating the coating film obtained in the step (3) with radiation (2).
However, the radiation (1) and the radiation (2) may be the same or different.

  According to the present invention, a method for producing a colored cured film and a color filter that are difficult to transfer even when post-baking or low-temperature post-baking and that have good solvent resistance and adhesion to the substrate are provided. A method for forming a pixel pattern can be provided.

It is a figure which shows the spectral distribution of the radiation (A) used in the Example. It is a figure which shows the spectral distribution of the radiation (B) used in the Example. It is a figure which shows the spectral distribution of the radiation (C) used in the Example. It is a figure which shows the spectral distribution of the radiation (D) used in the Example.

Hereinafter, the present invention will be described in detail.
<Method for producing colored cured film>
The method for producing a colored cured film of the present invention includes steps (1) to (4). Colored cured films include color pixels used in display elements and solid-state image sensors, interlayer insulating films, planarization films, banks (partitions) that define areas for forming light emitting layers, black matrices, spacers, protective films, etc. Is mentioned. Examples of the display element include a color liquid crystal display element, an organic EL element, and electronic paper. Examples of the solid-state imaging element include a CCD image sensor and a CMOS image sensor.
Hereinafter, each step will be described in detail.

-Step (1)-
Step (1) forms a coating film by applying a colored radiation-sensitive composition containing (A) a colorant, (B) a polymerizable compound, and (C) a radiation-sensitive polymerization initiator on a substrate. It is a process.
(substrate)
Examples of the substrate include a transparent substrate having a high transmittance with respect to visible light. Specific examples include glass substrates such as borosilicate glass, aluminoborosilicate glass, alkali-free glass, quartz glass, synthetic quartz glass, soda lime glass, white sapphire; polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate. Examples of the resin substrate include:
Further, a substrate on which a light emitting element is mounted may be used as the substrate. As a light emitting element, solid light emitting elements, such as a light emitting diode, a semiconductor laser, and an organic EL element, are mentioned, for example, The surface of a solid light emitting element may be coat | covered with transparent resin, a sheet | seat, etc. As the substrate, the above-mentioned transparent substrate is usually used, and it may be a glass substrate or a resin substrate. The bonding type between the light emitting element and the substrate is not particularly limited, and for example, a conductive paste, a heat conductive sheet, a heat conductive adhesive, a double-sided tape, solder, or the like can be selected as appropriate.
Among these, as the substrate, a resin substrate and a light emitting element mounting substrate are preferable because the effects of the present invention can be easily obtained.

  Further, the substrate may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc. A transparent electrode made of indium oxide, tin oxide, or the like may be formed for liquid crystal driving or organic EL light emission. Further, a light shielding layer (black matrix) may be formed on the substrate so as to partition a portion where pixels are formed. Examples of the light shielding layer include inorganic films such as chromium and titanium nitride, multilayer films of chromium / chromium oxide, and resin films in which a light shielding agent is dispersed. Moreover, a black radiation sensitive composition may be apply | coated on a board | substrate and a desired pattern may be formed by the photolithographic method. The thickness of the light shielding layer is usually 0.1 to 0.2 μm.

(Application)
As a method for applying the colored radiation-sensitive composition, a known method can be employed. For example, a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method and the like can be mentioned. Among these, a spin coating method, A slit die coating method is preferred.
After application, pre-baking can be performed. Pre-baking can be performed by combining vacuum drying and heat drying. The drying under reduced pressure is usually at a temperature of 70 to 110 ° C. for about 1 to 15 minutes, preferably at a temperature of 80 to 100 ° C. for 1 to 10 minutes. Moreover, the thickness of a coating film is 0.6-8 micrometers normally as a film thickness after drying, Preferably it is 1.2-5 micrometers.

  In addition, as another example of forming a coating film of a colored radiation-sensitive composition on a substrate, an ink jet method may be adopted. For example, in JP-A-7-318723 and JP-A-2000-310706 The described method can be mentioned. In this method, a partition having a light shielding function is first formed on a substrate, and then a colored radiation-sensitive composition is discharged into the partition by an ink jet apparatus. Thereafter, pre-baking is performed to evaporate the solvent. The prebaking method and conditions are the same as described above.

  Further, as a further example of forming a coating film of a colored radiation-sensitive composition on a substrate, a dry film method can be employed, for example, a method described in JP-A-9-5991 and the like. It is done. In this method, the colored radiation-sensitive composition layer was formed on the support by coating the colored radiation-sensitive composition on the film-like support, pre-baking, and evaporating the organic solvent. Manufacture dry film. And the support body in which this colored radiation sensitive composition layer was formed is laminated on a board | substrate using a laminator. Thereafter, the colored radiation-sensitive composition layer is peeled from the support, and the colored radiation-sensitive composition layer is transferred to the substrate. The method for applying the colored radiation-sensitive composition on the support and the prebaking method and conditions are the same as described above.

-Step (2)-
Step (2) is a step of irradiating the coating film obtained in step (1) with radiation (1), that is, pre-exposure.
In the step (2), at least a part of the coating film obtained in the step (1) may be usually exposed through a photomask having a predetermined pattern, or scanning exposure may be performed. In addition, the pattern shape on a photomask is not specifically limited, The pattern shape according to the intended use is used.
Examples of the radiation (1) include ultraviolet rays such as g-line, h-line, i-line, and j-line. Among these, from the viewpoints of suppressing color transfer and improving solvent resistance and adhesion to a substrate, radiation including g-line, h-line and i-line is preferable, and includes g-line, h-line, i-line and j-line. Radiation is more preferred. In the spectral distribution, the peak at 436 nm is the g-line, the peak at 405 nm is the h-line, the peak at 365 nm is the i-line, and the peak at 313 nm is the j-line.
As the light source, ultrahigh pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet lasers, and the like can be used.
The exposure amount is usually 1 to 1,000 mJ / cm ² , but in order to enhance the desired effect, it is preferably 5 to 500 mJ / cm ² , more preferably 10 to 100 mJ / cm ² , and still more preferably 30 to 60 mJ. / Cm ² .

-Step (3)-
Step (3) is a step of developing the coating film obtained in step (2).
In the development, a developing solution is used to dissolve and remove the non-cured portion after exposure (non-exposed portion in the case of a negative type).
Any developer can be used as long as it dissolves the non-cured portion and does not dissolve the cured portion. For example, a combination of various organic solvents and an alkaline aqueous solution can be used. Among these, an alkaline aqueous solution is preferable. Examples of the alkaline aqueous solution include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- An aqueous solution of [4.3.0] -5-nonene and the like can be mentioned. For example, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, an antifoaming agent, or a surfactant can be added to the developer.
As the development method, for example, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions can be, for example, 5 to 300 seconds at room temperature.
When an alkaline aqueous solution is used as the developer, it is usually washed with water after development. Moreover, after washing | cleaning, a coating film can also be air-dried with compressed air, compressed nitrogen, etc., for example.

-Step (4)-
Step (4) is a step of irradiating the coating film obtained in step (3) with radiation (2), that is, post-exposure.
The exposure amount of the post-exposure is preferably 200 mJ / cm ² or more, more preferably 500 mJ / cm ² or more, from the viewpoints of curability, solvent resistance and adhesion to the substrate, color transfer suppression, and substrate protection. more preferably 800 mJ / cm ² or more, more preferably 1000 mJ / cm ² or more, more preferably 1500 mJ / cm ² or more, 2000 mJ / cm ² or more and further preferably more. The exposure amount, from the viewpoint of photo-degradation suppression of colorant is preferably 10000 mJ / cm ² or less, more preferably 8000 mJ / cm ² or less, more preferably 6000 mJ / cm ² or less. As the range of the exposure amount is preferably 200~10000mJ / cm ^2, more preferably 500~10000mJ / cm ^2, more preferably 800~8000mJ / cm ^2, more preferably 1000~8000mJ / cm ^2, more preferably 1500~6000mJ / cm ^2, more preferably from 2000~6000mJ / cm ^2. Examples of the light source used for the post-exposure include the same light sources as those used for the pre-exposure.

The radiation (2) may be the same as or different from the radiation (1) used in the pre-exposure. For example, as in the pre-exposure, radiation including g-line, h-line and i-line, or g-line, Radiation including h-line, i-line and j-line can be applied. Specifically, there are the following four modes as the radiation (2).
(I) A mode in which radiation having the same spectral distribution as that of the radiation (1) is irradiated with the same exposure amount as that of the radiation (1).
(II) A mode in which radiation having the same spectral distribution as that of the radiation (1) is irradiated with an exposure amount different from that of the radiation (1).
(III) A mode in which radiation having a spectral distribution different from that of the radiation (1) is irradiated with the same exposure amount as that of the radiation (1).
(IV) A mode in which radiation having a spectral distribution different from that of the radiation (1) is irradiated with an exposure amount different from that of the radiation (1).

The radiation (2) has a spectral distribution different from that of the above-mentioned (III) or (IV), that is, the radiation (1), from the viewpoint of suppression of color transfer, solvent resistance and improvement of adhesion to the substrate. Preferably, for example, the following radiation can be mentioned. Among these, (b) and (c) are preferable in that suppression of color transfer, solvent resistance, and improvement in adhesion to the substrate can be achieved at a higher level. In addition, when (A) the colorant contains a dye, the dye generally absorbs ultraviolet rays or short-wavelength visible light and may undergo photodecomposition, so that radiation (c) with less high-intensity components on the short-wavelength side is present. preferable.
(A) Radiation having a spectral distribution different from that of radiation (1), and the peak intensity at a wavelength of 313 nm (j line) is 1/6 or more and less than 1/3 of the peak intensity at a wavelength of 365 nm (i line) (For example, radiation B in the examples described later).
(B) Radiation having a spectral distribution different from that of radiation (1) and having a peak intensity at a wavelength of 313 nm (j-line) that is 1/3 or more of the peak intensity at a wavelength of 365 nm (i-line) ( For example, radiation C) in the examples described later. The upper limit of the peak intensity at a wavelength of 313 nm is not particularly limited, but is preferably smaller than the peak intensity at a wavelength of 365 nm, and more preferably 3/4 or less.
(C) Radiation having a spectral distribution different from that of radiation (1), including wavelength 405 nm (h line) and wavelength 436 nm (g line), and peak intensities at wavelength 313 nm (j line) and wavelength 365 nm (i line) However, the peak intensity at a wavelength of 405 nm (h line) and the peak intensity at a wavelength of 436 nm (g line) are 1/4 or less, preferably 1/10 or less, more preferably 1/20 with respect to a smaller peak intensity. Certain radiation (for example, radiation D in the examples below). The lower limit of the peak intensity at the wavelength 313 nm (j line) and the wavelength 365 nm (i line) is not particularly limited.
In this case, the radiation (1) is a radiation including a wavelength of 365 nm (i-line), a wavelength of 405 nm (h-line), and a wavelength of 436 nm (g-line), and a peak intensity at a wavelength of 313 nm (j-line) has a wavelength of 365 nm ( Radiation that is less than 1/6 of the peak intensity at i-line) is preferred.

  Radiation exhibiting such spectral characteristics can be obtained, for example, using a light source exhibiting spectral characteristics as described above, or radiation radiated from a high-pressure mercury lamp via an ultraviolet cut filter or a band-pass filter.

In the step (4), the coating film may be heated, that is, post-baked. In this case, the coating film obtained in the step (3) can be subjected to the following i) or ii). That is, when post-baking is performed in step (4), post-baking and post-exposure can be performed in an arbitrary order.
i) Radiation (2) is irradiated after heating.
ii) Heat after irradiation with radiation (2).

Post baking usually heats the patterned coating film at 20 to 150 ° C., but preferably 40 to 40 from the viewpoint of curability, solvent resistance and adhesion to the substrate, color transfer suppression, and substrate protection. It is 140 degreeC, More preferably, it is 70-130 degreeC, More preferably, it is 90-120 degreeC. If the post-baking temperature is within this range, a colored cured film having a sufficiently cured coating film and excellent solvent resistance can be formed, and shrinkage and deformation of the substrate are reduced, which is preferable. Furthermore, since the difference between the shrinkage ratio of the substrate and the shrinkage ratio of the patterned coating film is small, it is also preferable from the viewpoint of reducing the possibility that the patterned coating film peels from the substrate.
The heating time can be appropriately set depending on the heating temperature, but is usually 5 to 120 minutes, preferably 10 to 100 minutes, more preferably 15 to 60 minutes, and further preferably 15 to 40 minutes.
When post-baking is performed in step (4), as described above, post-baking and post-exposure can be performed in any order. From the viewpoint of obtaining a colored cured film having excellent adhesion, post-baking is performed first. Preferably it is done. That is, i) is more preferable.

  Thus, although the colored cured film formed by the manufacturing method of the colored cured film of this invention can be provided, the film thickness of a colored cured film is 0.5-5 micrometers normally, Preferably it is 1-3 micrometers. is there. The obtained colored cured film has good solvent resistance and adhesion to the substrate, and can effectively prevent peeling. Further, even when the colored radiation-sensitive composition is overcoated on the substrate, the color transfer to the adjacent pattern of other colors is suppressed.

(Colored radiation-sensitive composition)
Next, the coloring radiation sensitive composition used for the manufacturing method of this invention is demonstrated.
The colored radiation-sensitive composition is not particularly limited as long as it contains (A) a colorant, (B) a polymerizable compound, and (C) a radiation-sensitive polymerization initiator, and a known one may be used. it can. The colored radiation-sensitive composition is usually used as a liquid composition by blending a solvent. Hereinafter, the components of the colored radiation-sensitive composition will be described.

-(A) Colorant-
(A) It is not specifically limited as a coloring agent, According to a use, it is possible to select a color and material suitably, and any of a pigment and dye can be used. (A) 1 type (s) or 2 or more types can be used for a coloring agent.

  The pigment may be either an organic pigment or an inorganic pigment, and examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyer's and Colorists). Specific examples thereof include compounds described in paragraphs [0014] to [0016] of JP2011-028219A and paragraph [0028] of JP2013-205832.

  Examples of inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, and chromium oxide green. , Cobalt green, amber, titanium black, synthetic iron black, carbon black and the like.

  In addition to these, a brominated diketopyrrolopyrrole pigment represented by the formula (Ic) of JP-T-2011-523433 can also be used as a red pigment. JP-A-2001-081348, JP-A-2010-026334, JP-A-2010-191304, JP-A-2010-237384, JP-A-2010-237569, JP-A-2011-006602, Examples include lake pigments described in JP-A-2011-145346. Also, the lactam pigments described in paragraphs [0019] to [0025] of JP-T-2012-515233, JP-2012-515234, WO2016 / 027798, and Japanese Imaging Society Vol. 45 No. 4, pages 321 to 327 (2006), and the like.

Among these pigments, C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 179, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. Pigment red 264, C.I. I. Pigment Red 279, red pigments such as brominated diketopyrrolopyrrole pigments represented by formula (Ic) of JP-T-2011-523433;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment green 59, C.I. I. Pigment green 62, C.I. I. Green pigments such as CI Pigment Green 63;
C. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 16, C.I. I. Pigment blue 60, C.I. I. Pigment blue 79, C.I. I. Blue pigments such as CI Pigment Blue 80;
C. I. Pigment yellow 83, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 179, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 211, C.I. I. Pigment yellow 215, C.I. I. Yellow pigments such as CI Pigment Yellow 231;
C. I. Pigment orange 38, C.I. I. Pigment orange 43, C.I. I. Pigment orange 64, C.I. I. Orange pigments such as CI Pigment Orange 72;
C. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Purple pigments such as CI Pigment Violet 29;
Perylene Black (CI Pigment Black 31, CI Pigment Black 32, BASF Lumogen Black FK4280, FK4281, Palogen Black S0084, L0086), Cyanine Black, Fast Black HB (C.I.26150) Black pigments such as lactam black (Irgaphor Black S 0100 CF manufactured by BASF) are preferred.

  (A) When a pigment is used as the colorant, it can be purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. Moreover, the pigment surface may be used by modifying the particle surface with a resin if desired. Further, the organic pigment can be used by refining primary particles by so-called salt milling. As a salt milling method, for example, a method disclosed in Japanese Patent Laid-Open No. 8-179111 can be employed. Moreover, at least 1 sort (s) chosen from a well-known dispersing agent and a dispersing aid can further be contained.

  The dye can be appropriately selected from various oil-soluble dyes, direct dyes, acid dyes, metal complex dyes, and the like, and for example, the following color index (CI) names are given. Things can be mentioned.

C. I. Solvent Yellow 4, C.I. I. Solvent Yellow 14, C.I. I. Solvent Yellow 15, C.I. I. Solvent Yellow 24, C.I. I. Solvent Yellow 82, C.I. I. Solvent Yellow 88, C.I. I. Solvent Yellow 94, C.I. I. Solvent Yellow 98, C.I. I. Solvent Yellow 162, C.I. I. Solvent yellow 179;
C. I. Solvent Red 45, C.I. I. Solvent red 49;
C. I. Solvent Orange 2, C.I. I. Solvent Orange 7, C.I. I. Solvent Orange 11, C.I. I. Solvent Orange 15, C.I. I. Solvent Orange 26, C.I. I. Solvent orange 56;
C. I. Solvent Blue 35, C.I. I. Solvent Blue 37, C.I. I. Solvent Blue 59, C.I. I. Solvent blue 67;

C. I. Acid Yellow 17, C.I. I. Acid Yellow 29, C.I. I. Acid Yellow 40, C.I. I. Acid Yellow 76;
C. I. Acid Red 91, C.I. I. Acid Red 92, C.I. I. Acid Red 97, C.I. I. Acid Red 114, C.I. I. Acid Red 138, C.I. I. Acid Red 151;
C. I. Acid Orange 51, C.I. I. Acid Orange 63;
C. I. Acid Blue 80, C.I. I. Acid Blue 83, C.I. I. Acid Blue 90;
C. I. Acid Green 9, C.I. I. Acid Green 16, C.I. I. Acid Green 25, C.I. I. Acid Green 27.

  In addition to these, a cyanine dye represented by the formula (I-1) described in paragraph [0120] of JP2012-214718A can also be used.

  (A) Content of a coloring agent is 5-70 mass% normally in solid content of a coloring radiation sensitive composition, Preferably it is 10-60 mass%. Solid content here is components other than the solvent mentioned later. Moreover, when a coloring agent contains both a pigment and dye, it is preferable that the content rate of a pigment is 25 mass% or more of the whole coloring agent, and it is more preferable that it is 35 mass% or more.

-(B) Polymerizable compound-
In the present specification, the “polymerizable compound” refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. (B) The polymerizable compound is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups. (B) 1 type (s) or 2 or more types can be used for a polymeric compound.

  As the compound having two or more (meth) acryloyl groups, a reaction product of an aliphatic polyhydroxy compound and (meth) acrylic acid [polyfunctional (meth) acrylate], a caprolactone-modified polyfunctional (meth) acrylate, Alkylene oxide-modified polyfunctional (meth) acrylate, reaction product of (meth) acrylate having hydroxyl group and polyfunctional isocyanate [polyfunctional urethane (meth) acrylate], (meth) acrylate having hydroxyl group and acid anhydride A reaction product [polyfunctional (meth) acrylate having a carboxyl group] and the like can be mentioned. Specific examples of the polyfunctional (meth) acrylate include trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and the like. Specific examples of the polyfunctional (meth) acrylate having a carboxyl group include a reaction product of pentaerythritol triacrylate and succinic anhydride, a reaction product of dipentaerythritol pentaacrylate and succinic anhydride, and the like. .

  Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. The melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and is a concept including melamine, benzoguanamine or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′. , N′-tetra (alkoxymethyl) benzoguanamine, N, N, N ′, N′-tetra (alkoxymethyl) glycoluril and the like.

  (B) Content of a polymeric compound is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-700 mass parts.

-(C) Radiation sensitive polymerization initiator-
(C) The radiation-sensitive polymerization initiator is a compound that generates an active species capable of initiating a curing reaction of the polymerizable compound (B) by exposure to radiation. (C) 1 type (s) or 2 or more types can be used for a radiation sensitive polymerization initiator.

(C) Examples of the radiation sensitive polymerization initiator include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, and benzophenone compounds. , Α-diketone compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds, and the like.
In addition, (C) radiation sensitive polymerization initiator can be used together with a well-known sensitizer and a hydrogen donor.

  (C) Content of a radiation sensitive polymerization initiator is 0.01-120 mass parts normally with respect to 100 mass parts of (B) polymeric compounds, Preferably it is 1-100 mass parts.

-(D) Radiation sensitive acid generator-
(D) A radiation-sensitive acid generator is a compound that generates an acid upon exposure to radiation. (D) 1 type (s) or 2 or more types can be used for a radiation sensitive acid generator.

  (D) The radiation-sensitive acid generator is preferably a compound that generates an acid in response to light having a wavelength of 300 nm or more, preferably 300 to 450 nm, but its chemical structure is not limited. In addition, a radiation-sensitive acid generator that does not directly respond to light having a wavelength of 300 nm or more can be used as a sensitizer as long as it is a compound that reacts with light having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.

  (D) Examples of the radiation sensitive acid generator include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, oxime sulfonate compounds, and the like. . Among these, it is preferable to use triazines. (D) A radiation sensitive acid generator can be used 1 type or in combination of 2 or more types. Specific examples of trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane derivatives include paragraphs [0083] to [0088] of JP2011-221494A. The compounds described can be exemplified.

  (D) As for content of a radiation sensitive acid generator, 10-100 mass parts is preferable with respect to 100 mass parts of (C) radiation sensitive polymerization initiators, and 30-80 mass parts is more preferable.

-Binder resin-
The colored radiation-sensitive composition can contain a binder resin. The binder resin is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter also referred to as “carboxyl group-containing polymer”) is preferable, and an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer ( b1) ") and other copolymerizable ethylenically unsaturated monomers (hereinafter also referred to as" unsaturated monomer (b2) ") are more preferred. More preferred is a copolymer of the monomer (b1) and an ethylenically unsaturated monomer having an oxygen-containing saturated heterocyclic group. Examples of the oxygen-containing saturated heterocyclic group include cyclic ether groups having 3 to 7 atoms constituting the ring, and specific examples thereof include oxiranyl group, oxetanyl group, tetrahydrofuranyl group, 3,4- Examples thereof include an epoxycyclohexyl group and a tetrahydropyranyl group.

Examples of the unsaturated monomer (b1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], and ω-carboxypolycaprolactone mono (meth). Examples thereof include acrylate and p-vinylbenzoic acid.
An unsaturated monomer (b1) can be used 1 type or in mixture of 2 or more types.

Moreover, as an unsaturated monomer (b2), for example,
N-substituted maleimides such as N-phenylmaleimide, N-cyclohexylmaleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, polyethylene Glycol (degree of polymerization 2-10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2-10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2-10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl (meth) acrylate, Jishikurope Thenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxybutyl such phenyl (meth) acrylate (meth) acrylic acid ester;
Glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, compounds described in paragraphs [0076] to [0080] of JP2013-203955, 3-[(meth) acryloyloxymethyl] oxetane , (Meth) acrylate cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 having an oxygen-containing saturated heterocyclic group such as 3-[(meth) acryloyloxymethyl] -3-ethyloxetane. ] Vinyl ethers such as decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
An unsaturated monomer (b2) can be used 1 type or in mixture of 2 or more types.

The acid value of the binder resin is preferably 10 to 200 mgKOH / g, more preferably 30 to 270 mgKOH / g, and still more preferably 50 to 250 mgKOH / g. Here, the “acid value” represents the number of mg of KOH required to neutralize 1 g of the solid content of the binder resin.
In this invention, binder resin can be used 1 type or in mixture of 2 or more types.
The binder resin has a weight average molecular weight (Mw) of usually 1,000 to 100,000, preferably 3,000 to 50,000. Furthermore, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin is preferably 1.0 to 5.0, more preferably 1.0 to 3.0. is there. Here, Mw and Mn are polystyrene-reduced weight average molecular weight and number average molecular weight measured by gel permeation chromatography (elution solvent: tetrahydrofuran).

  Content of binder resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts.

-Solvent-
The solvent may be appropriately selected and used as long as each component constituting the colored radiation-sensitive composition is dispersed or dissolved and does not react with these components and has appropriate volatility. it can. 1 type (s) or 2 or more types can be used for a solvent.

Examples of the solvent include (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether acetate and propylene glycol monoethyl ether; lactic acid alkyl esters such as ethyl lactate; (ethanol, propanol, 2-ethylhexanol, cyclohexanol and the like ( Cyclo) alkyl alcohols; keto alcohols such as diacetone alcohol; (poly) alkylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; cyclic ethers such as tetrahydrofuran; ketones such as methyl ethyl ketone; propylene glycol Diacetates such as diacetate; Alkoxycals such as methyl 3-methoxypropionate Phosphate esters; fatty acid alkyl esters such as ethyl acetate, aromatic such as toluene hydrocarbons; N, N-amides such as dimethylformamide; can be exemplified lactam. Among them, (poly) alkylene glycol monoalkyl ether,
(Poly) alkylene glycol monoalkyl ether acetate is preferred.

  The content of the solvent is not particularly limited, but the total concentration of each component excluding the solvent from the colored radiation-sensitive composition is preferably 5 to 50% by mass, and preferably 10 to 40% by mass. A more preferred amount.

-Additives-
The colored radiation-sensitive composition of the present invention can contain various additives as necessary.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorosurfactants and silicone surfactants; vinyl Adhesion promoters such as trimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-t) -Butylphenol), antioxidants such as 2,6-di-t-butylphenol; ultraviolet light such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenones Absorbent; Anti-aggregation agent such as sodium polyacrylate; Malonic acid, adipic acid, amino Residue improvers such as ethanol, aminopropanol, aminopropanediol; developability improvers such as succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. it can.

  The colored radiation-sensitive composition of the present invention can be prepared by an appropriate method. For example, the components (A) to (C) can be prepared by mixing and dispersing together with a solvent and other components optionally added using a bead mill, a roll mill or the like.

<Method for forming pixel pattern of color filter>
The method for forming the pixel pattern of the color filter of the present invention includes steps (1) to (4), as in the method for producing a colored cured film of the present invention. For example, in order to manufacture a color filter in which a pixel array of three primary colors of red, green, and blue is arranged on a substrate, first, it is subjected to steps (1) to (4) using a red radiation-sensitive colored composition. A red pixel pattern is then formed, and then a green pixel pattern is obtained by subjecting the substrate on which the red pixel pattern is formed to steps (1) to (4) using a green radiation-sensitive colored composition. And using the blue radiation-sensitive coloring composition, the green pixel pattern is formed by subjecting the substrate on which the red and green pixel patterns are formed to steps (1) to (4). . Note that the order in which the pixel patterns of the respective colors are formed on the substrate is not limited to the above example, and can be changed as appropriate. Moreover, the specific aspect of process (1)-(4) and the specific aspect of a colored radiation-sensitive coloring composition are as having demonstrated in the manufacturing method of the above-mentioned colored cured film.

 The pixel pattern constituting the color filter is not limited to red, green, and blue, but may be a pixel pattern having three primary colors of yellow, magenta, and cyan. In addition to the coloring patterns corresponding to the pixels of the three primary colors, a fourth coloring pattern and a fifth coloring pattern can also be formed. For example, as disclosed in JP-T-2005-523465, etc., a fourth pixel (yellow pixel) for expanding the color specification range in addition to the coloring patterns corresponding to the three primary color pixels of red, green, and blue And a fifth pixel (cyan pixel) can be arranged.

  The film thickness of the pixel pattern thus formed is usually 0.5 to 5 μm, preferably 1 to 3 μm. The obtained pixel pattern has good solvent resistance and adhesion to the substrate, and has a rectangular or tapered cross-section at the end, so that peeling can be effectively suppressed. Further, even if the colored radiation-sensitive composition is overcoated on the substrate, the color transfer to the adjacent other color pattern can be sufficiently suppressed.

  Further, a protective film may be further provided on the pixel pattern in order to improve display characteristics of the display element. Examples of the protective film include organic films formed from curable compositions, inorganic films such as SiNx films and SiOx films, and organic-inorganic hybrid films. As a method for forming the protective film, for example, JP-A-4-53879, JP-A-6-192389, JP-A-3-188153, JP-A-4-53879, JP-A-6-192389. Examples thereof include methods described in JP-A-8-183819, JP-A 2006-195420, JP-A 2008-208342, and the like.

  The manufacturing method of the present invention is used for manufacturing various color filters including, for example, color filters for color liquid crystal display elements, color filters for color separation of solid-state imaging elements, color filters for organic EL elements, and color filters for electronic paper. Is preferred. For example, a color filter including a colored cured film (pixel) formed by the manufacturing method of the present invention, a display element and a light emitting element including the color filter, and a colored cured film formed by the manufacturing method of the present invention ( For example, a display element or a light-emitting element including an interlayer insulating film, a planarization film, a bank (partition wall) that defines a region for forming a light-emitting layer, a black matrix, a spacer, or a protective film can be provided. The invention can also provide an illumination device including a light emitting element mounting substrate.

  The color liquid crystal display element has, for example, a structure in which a driving substrate on which a thin film transistor (TFT) is disposed and another substrate on which the color filter of this embodiment is provided face each other through a liquid crystal layer. It can be. The color liquid crystal display element includes a substrate in which the color filter of this embodiment is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and an ITO (Indium Tin Oxide) electrode. It is also possible to adopt a structure in which the substrate on which the film is formed faces the liquid crystal layer. The color liquid crystal display element includes a backlight unit. As the backlight unit, for example, a structure in which a fluorescent tube such as a cold cathode fluorescent lamp (CCFL) and a scattering plate are combined can be used. A backlight unit using a white LED as a light source can also be used. The color liquid crystal display element includes a TN (twisted nematic) type, an STN (super twisted nematic) type, an IPS (in-plane switching) type, a VA (vertical alignment) type liquid crystal, an OCB (optically compatible liquid crystal type), and the like. Mode can be applied.

  The organic EL element can take an appropriate structure, and examples thereof include a structure disclosed in JP-A-11-307242. Also, electronic paper can adopt an appropriate structure, and examples thereof include a structure disclosed in Japanese Patent Application Laid-Open No. 2007-41169.

  Hereinafter, embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

<Synthesis of binder resin>
Synthesis example 1
According to the method described in Synthesis Example 6 of JP2013-203955A, a solution containing a resin having the following structural units was obtained. Subsequently, it adjusted so that solid content concentration might be 40 mass% using propylene glycol monomethyl ether acetate, and the binder resin (X-1) solution was obtained.

<Preparation of pigment dispersion>
Preparation of pigment dispersion 1
(A) C.I. I. 9.6 parts by mass of CI Pigment Red 269 I. Pigment Yellow 139 2.4 parts by mass, BYK-LPN21116 (manufactured by BYK) (solid content concentration 40% by mass) as a dispersant, 13.0 parts by mass, binder resin (X-1) (solid) Using a bead mill to mix and disperse red using 10.0 parts by weight of 40% by weight) and 57.0 parts by weight of propylene glycol monomethyl ether acetate and 8.0 parts by weight of propylene glycol monoethyl ether as a solvent. A pigment dispersion (r-1) was prepared.

Pigment dispersion preparation examples 2 to 11
In the pigment dispersion preparation example 1, red pigment dispersions (r-2) to (r-) were prepared in the same manner as in the pigment dispersion preparation example 1, except that the types and amounts of the respective components were changed as shown in Table 1. 4) Green pigment dispersions (g-1) to (g-3), blue pigment dispersions (b-1) and black pigment dispersions (bk-1) to (bk-3) were prepared. .

In Table 1, each component is as follows.
-PGMEA: Propylene glycol monomethyl ether acetate-PGEE: Propylene glycol monoethyl ether-Cyanine dye-1: "Represented by formula (I-1)" described in paragraph [0120] of JP2012-214718A Salt "(cyanine dye)
Lactam pigment: Irgaphor (registered trademark) Black S0100 CF (manufactured by BASF)

<Preparation of coloring composition>
Coloring composition preparation example 1
542.5 parts by mass of the pigment dispersion (r-1), 37.6 parts by mass of the binder resin (X-1) solution (solid content concentration 40% by mass), (B) KAYARAD DPHA (Nipponization) as the polymerizable compound Made by Yakuhin Co., Ltd. 18.4 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate), (C) Irgacure 369 (manufactured by BASF Corp., 2-benzyl-2-dimethyl) as a radiation sensitive polymerization initiator Amino-1- (4-morpholinophenyl) butan-1-one) 0.7 parts by mass and NCI-930 (manufactured by ADEKA Co., Ltd.) 5.5 parts by mass, Megafac F as a fluorosurfactant -554 (manufactured by DIC Corporation) is 0.3 parts by mass, and propylene glycol monomethyl ether acetate as a solvent is 99. 2 parts by mass, 253.5 parts by mass of 3-methoxybutyl acetate and 42.3 parts by mass of DPMA were mixed to prepare a red colored composition (RS-1).

Coloring composition preparation examples 2 to 18
In the colored composition preparation example 1, the red colored compositions (RS-2) to (RS-) were the same as the colored composition preparation example 1 except that the types and amounts of the respective components were changed as shown in Table 2. 8) Green coloring compositions (GS-1) to (GS-6), blue coloring compositions (BS-1), and black coloring compositions (BKS-1) to (BKS-3) were prepared. .

In Table 2, each component is as follows.
-B-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
C-1: Irgacure 369 (manufactured by BASF)
C-2: NCI-930 (manufactured by ADEKA Corporation)
D-1: 2- [2- (4-methoxyphenyl-2-yl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine (manufactured by Wako Pure Chemical Industries, Ltd.)
D-2: 2- (3,4-methylenedioxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine (manufactured by Wako Pure Chemical Industries, Ltd.)
・ X-2: Megafuck F-554 (manufactured by DIC Corporation)
MBA: 3-methoxybutyl acetate DPMA: Dipropylene glycol methyl ether acetate

  The radiation used in this example is as shown in Table 3.

The spectral distribution of radiation (A) is shown in FIG. 1, the spectral distribution of radiation (B) is shown in FIG. 2, the spectral distribution of radiation (C) is shown in FIG. 3, and the spectral distribution of radiation (D) is shown in FIG. Show each one. In FIG. 1, the relative light intensities at wavelengths of 313 nm, 365 nm, 405 nm, and 436 nm are 16.19, 100.00, 78.96, and 91.48, respectively. In FIG. 2, the relative light intensities at wavelengths of 313 nm, 365 nm, 405 nm, and 436 nm are 23.06, 100.00, 78.72, and 90.83, respectively. In FIG. 3, the relative light intensities at wavelengths of 313 nm, 365 nm, 405 nm, and 436 nm are 44.10, 100.00, 71.64, and 81.44, respectively. In FIG. 4, the relative light intensities at wavelengths of 313 nm, 365 nm, 405 nm, and 436 nm are 0.00, 0.01, 69.14, and 79.24, respectively.
Therefore, the peak intensity at a wavelength of 313 nm of the radiation (A) is less than 1/6 of the peak intensity at a wavelength of 365 nm, and the peak intensity at a wavelength of 313 nm of the radiation (B) is 1/6 or more of the peak intensity at a wavelength of 365 nm. The peak intensity at a wavelength of 313 nm of radiation (C) is 1/3 or more of the peak intensity at a wavelength of 365 nm. The radiation (D) includes wavelengths of 405 nm (h line) and 436 nm (g line), and the peak intensity at 313 nm and 365 nm is smaller than the peak intensity of h line and the peak intensity of g line. The radiation is 1/20 or less.

<Production and evaluation of colored cured film>
Example A-1
After applying the coloring composition (RS-1) as a first coloring composition on a substrate, a Teijin Tetron film HB (manufactured by Teijin DuPont Films Ltd., polyethylene terephthalate film, thickness 25 μm) using a slit die coater. The film was pre-baked for 10 minutes on a hot plate at 80 ° C. to form a coating film having a thickness of 2.0 μm. After cooling to room temperature, the coating film was exposed to radiation (A) at an exposure dose of 40 mJ / cm ² through a photomask using a high-pressure mercury lamp. Thereafter, a developer composed of a 0.45 mass% potassium hydroxide aqueous solution at 23 ° C. is discharged at a development pressure of 1 kgf / cm ² (nozzle diameter 1 mm) to perform shower development for 90 seconds, followed by washing with ultrapure water. Air dried. Next, the air-dried coating film was post-baked for 20 minutes in a clean oven at 100 ° C., cooled to room temperature, and then exposed to radiation (B) at an exposure dose of 1,000 mJ / cm ² . As a result, island patterns (total 100 colored cured films) in which colored cured films (length 30 μm × width 30 μm) formed from the first colored composition were formed in length 10 rows × width 10 columns were produced. The same operation was performed to produce three substrates.

Evaluation of Solvent Resistance A colored composition (GS-1) was applied as a second colored composition on the first substrate using a slit die coater so as to have a film thickness of 2.0 μm.
When the board | substrate was observed with the optical microscope and the island pattern formed from the 1st coloring composition did not melt | dissolve, it evaluated as "(circle)" and the case where it melt | dissolved was evaluated as "*". The results are shown in Table 4.

Evaluation of adhesion After applying a colored composition (GS-1) as a second colored composition on a second substrate using a slit die coater, pre-baking was performed on a hot plate at 80 ° C. for 10 minutes. A coating film having a thickness of 2.0 μm was formed. After cooling to room temperature, the coating film was exposed to radiation (A) at an exposure dose of 40 mJ / cm ² through a photomask using a high-pressure mercury lamp. Then, shower development was performed for 90 seconds by discharging a developer composed of a 0.45 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter 1 mm). Thereafter, the substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 100 ° C. for 20 minutes. Thereby, next to the island pattern (100 colored cured films in total), the island pattern of the colored cured film formed from the second colored composition (the shape is the same as the island pattern of the first colored composition). ) Was formed. At this time, the positional relationship between the island pattern formed from the first colored composition and the island pattern formed from the second colored composition is adjacent to each other within 30 μm without overlapping, or the overlapping width is within 3 μm. Within the range.
The substrate was observed with an optical microscope, and the number of island patterns formed from the first coloring composition remaining on the substrate was counted. The case of 95 or more was evaluated as “◯”, the case of 90 to 94 was evaluated as “Δ”, and the case of 89 or less was evaluated as “×”. The results are shown in Table 4. It can be said that the greater the number of island patterns remaining on the substrate, the better the adhesion.

Evaluation of color transfer For the island pattern formed on the third substrate, a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) was used to measure the chromaticity coordinate value ( x, y) and the stimulus value (Y) were measured.
After coating a coloring composition (GS-1) as a second coloring composition on the third substrate using a slit die coater, pre-baking is performed for 10 minutes on a hot plate at 80 ° C. to obtain a film thickness of 2 A coating film of 0.0 μm was formed. After cooling to room temperature, the coating film was exposed to radiation (A) at an exposure dose of 40 mJ / cm ² through a photomask using a high-pressure mercury lamp. Then, shower development was performed for 90 seconds by discharging a developer composed of a 0.45 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter 1 mm). Thereafter, the substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 100 ° C. for 20 minutes. Thereby, the colored cured film formed from the second colored composition was formed next to the island pattern (total of 100 colored cured films). The positional relationship between the pattern shape and the pattern is the same as in the above “evaluation of adhesion”.
About the island pattern formed from the 1st coloring composition on a board | substrate, using the color analyzer (MCPD2000 by Otsuka Electronics Co., Ltd.), the part which the island pattern formed from the 2nd coloring composition does not overlap, C The chromaticity coordinate value (x, y) and the stimulus value (Y) in the CIE color system are measured with a light source and a 2-degree visual field, and before and after forming a colored cured film using the second colored composition. The color change, ie ΔE ^* _ab, was determined. The case where ΔE ^* _ab is less than 1.0 is evaluated as “◯”, the case where 1.0 or more and less than 3.0 is evaluated as “Δ”, and the case where 3.0 or more is evaluated as “×”. Show. It can be said that the smaller the ΔE ^* _ab is, the more the color transfer is suppressed.

Examples A-2 to A-12
In Example A-1, solvent resistance and adhesion were obtained in the same manner as in Example A-1, except that the colored compositions described in Table 4 were used as the first colored composition and the second colored composition. And color transfer was evaluated. However, only in Example A-12, the radiation used for the exposure after post-baking at 100 ° C. for 20 minutes was not radiation of 1,000 mJ / cm ² (B) but radiation of 3000 mJ / cm ² ( A). The results are shown in Table 4.
In addition, about the case where the black coloring composition (BKS-1)-(BKS-3) is used as a 1st coloring composition, the evaluation of color migration was evaluated not with (DELTA ⁾ E ^* _ab but with the variation | change_quantity of optical density. That is, the stimulus value (Y) (%) is converted into optical density = −log ₁₀ (Y / 100), and the amount of change in optical density before and after the colored cured film is formed using the second colored composition. Was evaluated for color transfer. When the amount of change is less than 3.0%, it is evaluated as “O”, when it is 3.0% or more and less than 5.0%, “△”, and when it is 5.0% or more, it is evaluated as “X”. Table 4 shows. In addition, it can be said that color transfer is suppressed, so that the variation | change_quantity of optical density is small. Also in each of the examples and comparative examples described later, the evaluation of the color transfer in the case where the black colored compositions (BKS-1) to (BKS-3) are used as the first colored composition is similarly performed. .

Examples B-1 to B-11
In Example A-1, Example 1 was used except that the colored composition described in Table 5 was used as the first colored composition and the second colored composition, and the radiation (C) was applied instead of the radiation (B). In the same manner as A-1, solvent resistance, adhesion and color transfer were evaluated. The results are shown in Table 5.

Reference examples C-1 to C-11
In Example A-1, the colored compositions described in Table 6 were used as the first colored composition and the second colored composition, and the first colored composition was post-baked in a clean oven at 60 ° C. for 20 hours. The solvent resistance, adhesion and color transfer were evaluated in the same manner as in Example A-1, except that the measurement was performed for a minute. The results are shown in Table 6.

Reference examples D-1 to D-11
In Example A-1, the coloring composition described in Table 7 was used as the first coloring composition and the second coloring composition, and the first coloring composition was post-baked in a clean oven at 160 ° C. for 20 hours. The solvent resistance and adhesion were evaluated in the same manner as in Example A-1, except that the measurement was performed for a minute. In order to prevent the substrate from being excessively deformed during post-baking of the first colored composition and the second colored composition cannot be applied, the post-baking of the first colored composition is performed by forming the substrate into a metal mold. The test was carried out with a frame. The results are shown in Table 7. In all of Reference Examples D-1 to D-11, the evaluation result of adhesion was “x”, and therefore, the evaluation of color migration was not performed.

Comparative Examples E-1 to E-11
In Example A-1, Example 1 was used except that the colored composition described in Table 8 was used as the first colored composition and the second colored composition, and radiation (B) was not exposed. Similarly, solvent resistance was evaluated. The results are shown in Table 8. In addition, since evaluation results of solvent resistance were “x” in all cases except for Comparative Example E-10, evaluation of adhesion and color transfer was not performed.

Example F-1
After applying the colored composition (RS-1) as a first colored composition on a polyethylene terephthalate film (Teijin Tetron Film HB, manufactured by Teijin DuPont Films, Inc., thickness 25 μm) as a substrate using a slit die coater. The film was pre-baked for 10 minutes on a hot plate at 80 ° C. to form a coating film having a thickness of 2.0 μm. After cooling to room temperature, the coating film was exposed to radiation (A) at an exposure dose of 40 mJ / cm ² through a photomask using a high-pressure mercury lamp. Thereafter, a developer composed of a 0.45 mass% potassium hydroxide aqueous solution at 23 ° C. is discharged at a development pressure of 1 kgf / cm ² (nozzle diameter 1 mm) to perform shower development for 90 seconds, followed by washing with ultrapure water. Air dried. Next, the air-dried coating film was exposed to radiation (B) at an exposure amount of 1,000 mJ / cm ² and then post-baked in a clean oven at 100 ° C. for 20 minutes. As a result, island patterns (total 100 colored cured films) in which colored cured films (length 30 μm × width 30 μm) formed from the first colored composition were formed in length 10 rows × width 10 columns were produced. The same operation was performed to produce three substrates.
Next, using the colored composition (GS-1) as the second colored composition, the solvent resistance, adhesion and color transfer were evaluated in the same manner as in Example A-1. The results are shown in Table 9.

Examples F-2 to F-11
In Example F-1, solvent resistance and adhesion were obtained in the same manner as in Example F-1, except that the colored compositions described in Table 9 were used as the first colored composition and the second colored composition. And color transfer was evaluated. The results are shown in Table 9.

Examples G-1 to G-11
In Example A-1, the coloring composition described in Table 10 was used as the first coloring composition and the second coloring composition, and the exposure dose of radiation (B) was changed to 2,000 mJ / cm ^2. Were evaluated for solvent resistance, adhesion and color transfer in the same manner as in Example A-1. The results are shown in Table 10.

Example H
In Example B-1, except that “organic EL element 1 (EL-1)” obtained according to the method described in paragraphs [0301] to [0302] of JP-A-2015-232641 was used as the substrate. In the same manner as B-1, solvent resistance, adhesion and color transfer were evaluated. As a result, all were evaluated as “◯”.

Examples J-1 to J-7
In Example F-1, the colored composition described in Table 11 was used as the first colored composition and the second colored composition, and the radiation (D) was used instead of the radiation (B). In the same manner as in F-1, solvent resistance, adhesion, and color transfer were evaluated. The results are shown in Table 11.

Colored Composition Preparation Examples 19-22
In the colored composition preparation example 1, the blue colored composition (BS-2) and the black coloration were the same as the colored composition preparation example 1 except that the types and amounts of the respective components were changed as shown in Table 12. Compositions (BKS-4) to (BKS-6) were prepared.

Examples J-8 to J-11
In Example F-1, the colored composition described in Table 13 was used as the first colored composition and the second colored composition, and the radiation (D) was used instead of the radiation (B). In the same manner as in F-1, solvent resistance, adhesion, and color transfer were evaluated. The results are shown in Table 13.

Example K
In Example J-4, the solvent resistance, adhesion and color transfer were evaluated in the same manner as in Example J-4 except that the radiation (B) was applied instead of the radiation (D). As a result, the solvent resistance, adhesion and color transfer were all “◯”. However, the spectral distribution measurement revealed that the colored cured film formed from the colored composition (RS-8) faded after irradiation with the radiation (B). From this result, there is a possibility that cyanine dye-1 contained in the colored composition (RS-8) was decomposed by irradiation with radiation (B).

Claims (9)

The manufacturing method of a colored cured film characterized by including the following process (1)-(4).
Step (1): A step of applying a colored radiation-sensitive composition containing (A) a colorant, (B) a polymerizable compound and (C) a radiation-sensitive polymerization initiator on a substrate to form a coating film. Step (2): Step (3) for irradiating the coating film obtained in the step (1) with radiation (1) Step: Step (4) for developing the coating film obtained in the step (2) : A step of irradiating the coating film obtained in the step (3) with radiation (2).
However, the radiation (1) and the radiation (2) may be the same or different.   The radiation (2) includes a wavelength of 405 nm and a wavelength of 436 nm, and the peak intensity at the wavelength of 313 nm and the wavelength of 365 nm is 1/4 or less with respect to the smaller peak intensity of the peak intensity of the wavelength of 405 nm and the peak intensity of the wavelength of 436 nm. The manufacturing method of the colored cured film of Claim 1 which exists.   (A) The manufacturing method of the colored cured film of Claim 1 or 2 with which a coloring agent contains dye.   The colored radiation-sensitive composition further comprises (D) a radiation-sensitive acid generator, and the (D) radiation-sensitive acid generator is a trichloromethyl-s-triazine, sulfonium salt, iodonium salt, quaternary ammonium. The manufacturing method of the colored cured film of any one of Claims 1-3 which is at least 1 sort (s) chosen from the group which consists of salts, a diazomethane compound, an imide sulfonate compound, and an oxime sulfonate compound.   The manufacturing method of the colored cured film of any one of Claims 1-4 whose board | substrate is a resin-made board | substrate.   The manufacturing method of the colored cured film of any one of Claims 1-5 whose board | substrate is a light emitting element mounting board | substrate. A method for forming a pixel pattern of a color filter, comprising the following steps (1) to (4):
Step (1): A step of applying a colored radiation-sensitive composition containing (A) a colorant, (B) a polymerizable compound and (C) a radiation-sensitive polymerization initiator on a substrate to form a coating film. Step (2): Step (3) for irradiating the coating film obtained in the step (1) with radiation (1) Step: Step (4) for developing the coating film obtained in the step (2) : Step of irradiating the coating film obtained in the step (3) with radiation (2) However, the radiation (1) and the radiation (2) may be the same or different.   The radiation (2) includes a wavelength of 405 nm and a wavelength of 436 nm, and the peak intensity at the wavelength of 313 nm and the wavelength of 365 nm is 1/4 or less with respect to the smaller peak intensity of the peak intensity of the wavelength of 405 nm and the peak intensity of the wavelength of 436 nm. The method for forming a color filter pixel pattern according to claim 7.   The method for forming a pixel pattern of a color filter according to claim 7 or 8, wherein the substrate is a resin substrate.