JP4527489B2 - Thermosetting resin composition for color filter, color filter, liquid crystal panel, and method for producing color filter - Google Patents

Description

  The present invention relates to a color filter curable resin composition used for forming a cured layer on a color filter substrate, a color filter using the curable resin composition, and a liquid crystal panel using the color filter. And a method for manufacturing a laminate including an inorganic material thin film.

  In recent years, color liquid crystal display devices are rapidly spreading as flat displays for personal computers and the like. In general, as shown in FIG. 1A, a color liquid crystal display device (101) is provided with a gap portion 3 of about 1 to 10 μm with a color filter 1 and an electrode substrate 2 such as a TFT substrate facing each other. 3 is filled with a liquid crystal compound L, and the periphery thereof is sealed with a sealing material 4. The color filter 1 includes a black matrix layer 6 formed in a predetermined pattern on the transparent substrate 5 to shield the boundary between pixels, and a plurality of colors (usually red (R (R)) to form each pixel. ), Green (G), blue (B) three primary colors) arranged in a predetermined order, a protective film 8 and a transparent electrode film 9 are laminated in this order from the side close to the transparent substrate. Have taken. An alignment film 10 is provided on the inner surface side of the color filter 1 and the electrode substrate 2 facing the color filter 1. Furthermore, a spacer is provided in the gap portion 3 in order to maintain a constant and uniform cell gap between the color filter 1 and the electrode substrate 2. As the spacer, pearls 11 having a fixed particle diameter are dispersed, or columnar spacers 12 having a height corresponding to the cell gap as shown in FIG. It forms in the area | region which overlaps with the position in which the layer 6 is formed. A color image is obtained by controlling the light transmittance of each of the pixels colored in each color or the liquid crystal layer behind the color filter.

  As a conventional method for forming a colored layer of a color filter or the like in a predetermined pattern shape, for example, a staining method can be mentioned. In this dyeing method, first, a water-soluble polymer material, which is a dyeing material, is formed on a glass substrate, patterned into a desired shape by a photolithography process, and then the obtained pattern is immersed in a dyeing bath. To get a colored pattern. By repeating this three times, R, G, and B color filter layers are formed. Another method is a pigment dispersion method. In this method, a photosensitive resin layer in which a pigment is dispersed is first formed on a substrate, and this is patterned to obtain a monochromatic pattern. Further, this process is repeated three times to form R, G, and B color filter layers. Still other methods include an electrodeposition method, a method in which a pigment is dispersed in a thermosetting resin, R, G, and B are printed three times, and then the resin is thermoset.

  However, in any method, in order to color three colors of R, G, and B, it is necessary to repeat the same process three times, which causes a problem of high cost, and the yield decreases because the same process is repeated. There is a problem of doing.

  As a method of manufacturing a color filter that solves these problems, Patent Document 1 discloses that a colored layer (pixel portion) is formed by spraying colored ink containing a thermosetting resin onto a substrate by an inkjet method and heating. It is described to do.

Japanese Patent Laid-Open No. 9-21910 Japanese Patent Laid-Open No. 11-72613

  The curable resin composition is used to form, for example, a colored layer of a color filter, a black matrix, a protective film, a spacer, etc., but after heat treatment in a thermosetting step or other steps, or after becoming a product. Depending on the high temperature environment, there are problems such as deformation of the cured pattern, cracking of the coating film, deterioration of adhesion, or generation of wrinkles and cracks in the inorganic material thin film laminated adjacent to the coating film.

  In particular, when forming a colored layer of a color filter for a display panel such as a liquid crystal display panel, a black matrix or a protective film using a curable resin composition, after forming the colored layer on the substrate, if necessary A protective film is formed thereon, and then a transparent electrode film is formed. At this time, a problem arises that wrinkles are generated on the surface of the transparent electrode film. As a method for forming the transparent electrode film, it is necessary to heat the substrate under a reduced pressure atmosphere such as a vacuum deposition method, a sputtering method, or an ion plating method. For example, when vacuum deposition of a typical ITO film as a transparent electrode film is performed, the underlying colored layer and protective film are exposed to a high temperature of about 120 ° C. or higher and an ultra-low pressure due to vacuum. When a cured film such as a colored layer formed from a curable resin composition is exposed to such a high temperature condition, the cured film thermally expands and contracts to generate wrinkles, which distorts adjacent layers such as a transparent electrode film. It is considered that wrinkles and cracks are generated on the surface. If wrinkles or cracks occur on the surface of the transparent electrode film, the local resistivity is increased at the location where the transparent electrode film is generated, resulting in disconnection, resulting in an afterimage, and in turn causing display defects.

  Patent Document 2 discloses that a color filter having an overcoat film has a Young's modulus of 2 GPa or more at 200 ° C. as a means for providing a color filter in which wrinkles or cracks of the conductive film are unlikely to occur and the spacer is not peeled off. It is disclosed that it has a value of. However, Patent Document 2 only describes the idea that the overcoat film should not be soft at high temperatures.

  The present invention has been achieved in view of the above-mentioned actual situation, and a first object thereof is a curable resin composition for a color filter which is less likely to cause wrinkles and cracks in a cured film and less likely to cause wrinkles and cracks in an adjacent layer. Is to provide.

  The second object of the present invention is to provide a color filter manufactured using a curable resin composition that achieves the above object.

  A third object of the present invention is to provide a liquid crystal panel provided with a color filter that achieves the above object.

  A fourth object of the present invention is to provide a method for producing a laminate of a cured resin film and an inorganic material thin film, in which wrinkles and cracks are unlikely to occur in the inorganic material thin film.

For color filters thermosetting resin composition according to the present invention, at least it comprises the following formula (1) and the structural unit represented by (2), having two or more glycidyl groups per molecule as the curable resin, A binder epoxy compound having a weight average molecular weight of 3000 to 20000 and an intercrosslinking molecular weight Mc represented by the following formula of 300 or less and a polyfunctional having 4 or more epoxy groups in one molecule and a weight average molecular weight of 3000 or less containing epoxy compound, the content of the binder epoxy compound in the total binder component is not less than 30% by weight, Ri Do because only the organic component in the solid content of the composition, 80 ° C., 5 minutes under 150Torr heated and dried under reduced pressure, the elastic deformation ratio in the indentation test by ISO-14577 obtained that the cured product is heated 30 minutes at 260 ° C. 40% On, and the surface roughness (Ra) is equal to or that can be 10nm or less.
M _c = M ₀ / (xF ₀ -2)
(In the formula, M ₀ is the average molecular weight per molecule, x is the reaction rate of 1 or less, and F ₀ is the average number of functional groups per molecule.)

（Ｒ ^１ は水素原子または炭素数１〜３のアルキル基であり、Ｒ ^２ は炭素数１〜１２の炭化水素基であり、Ｒ ^３ は水素原子又は炭素数１〜１０のアルキル基である。）
本発明者は、透明電極膜形成時のしわやクラックの発生について詳細に検討した結果、透明電極膜の下地である着色層や保護膜やブラックマトリックス層等の硬化膜に含まれるバインダー成分を主成分とする有機成分が、しわやクラックを生じにくいと、透明電極膜形成時のしわやクラックが生じにくいことを見出した。更に、着色層や保護膜やブラックマトリックス層等の組成物の固形分中の有機成分のみからなる硬化物の硬さ試験における総変形量のうちの弾性変形割合が大きいほど、しわやクラックが生じにくいことを見出し、本発明を完成させた。
また、本発明に係るカラーフィルター用熱硬化性樹脂組成物は、有機成分のみからなる硬化物の表面粗度（Ｒａ）が１０ｎｍ以下であることにより、隣接する無機材料薄膜にしわやクラックを生じにくい。

(R ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ² is a hydrocarbon group having 1 to 12 carbon atoms, and R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. )
As a result of detailed studies on the generation of wrinkles and cracks during the formation of the transparent electrode film, the present inventor has found that the binder component contained in the cured film such as a colored layer, a protective film or a black matrix layer, which is the base of the transparent electrode film, is mainly used. It has been found that when the organic component as a component is less likely to cause wrinkles and cracks, wrinkles and cracks are less likely to occur during the formation of the transparent electrode film. Furthermore, wrinkles and cracks occur as the elastic deformation ratio of the total deformation amount in the hardness test of the cured product consisting only of organic components in the solid content of the composition such as the colored layer, the protective film and the black matrix layer increases. As a result, the present invention was completed.
Moreover, the thermosetting resin composition for color filters according to the present invention produces wrinkles and cracks in the adjacent inorganic material thin film because the surface roughness (Ra) of the cured product composed only of organic components is 10 nm or less. Hateful.

  In the present invention, the elastic deformation ratio in the indentation test according to ISO-14577 of the cured product consisting only of the organic component in the solid content in which the binder component consisting of one or two or more components is the main component in the composition is 40. The organic component in the solid content is selected so that it can be at least%, and the cured product composed only of the organic component is cured under the curing conditions in which the elastic deformation ratio in the indentation test according to ISO-14577 is 40% or more. By making the cured film of the composition less susceptible to thermal expansion and contraction and less likely to cause wrinkles and cracks, even if an inorganic material thin film such as a transparent electrode film is formed on it at a high temperature and under an ultra-low pressure by vacuum, Wrinkles and cracks are unlikely to occur in the inorganic material thin film.

  When a colored layer, a black matrix, a protective film, or the like of a color filter is formed using the curable resin composition for a color filter according to the present invention, wrinkles and cracks are hardly generated in an inorganic material thin film adjacent to at least one of them.

  In the curable resin composition for a color filter according to the present invention, it is possible that an elastic deformation ratio in an indentation test according to ISO-14577 of a cured product composed only of the organic component can be 60% or less, because the cured film is difficult to be colored. preferable.

The color filter for the thermosetting resin composition according to the present invention, after curing, further before and after heating 60 minutes at 240 ° C., the change amount of the crosslinking component is within the measurement error range, and by ISO-14577 It is preferable that the elastic deformation rate in the indentation test is increased. If further proportion elastic deformation cured film in the conditions is a thermosetting resin composition increases, wrinkles and cracks in the inorganic material thin film is less likely to occur.

  The curable resin composition for a color filter according to the present invention can be suitably used as an inkjet ink.

The color filter according to the present invention may a transparent substrate, comprising a colored layer provided on the transparent substrate, also comprise further the coloring interlayer and / or the resin cured film on the colored layer, the The colored layer and / or the resin cured film is a cured product formed by curing the thermosetting resin composition for a color filter according to the present invention, and an elastic deformation ratio in an indentation test according to ISO-14577 of the cured product. Is 40% or more, and the surface roughness (Ra) is 10 nm or less, and includes an inorganic material thin film adjacent to the colored layer and / or the cured resin film made of the cured product.

  The color filter according to the present invention is formed by curing the curable resin composition for a color filter according to the present invention, wherein the resin cured film such as the colored layer and / or the black matrix, the protective film, and the partition wall is cured. Therefore, the colored layer using the curable resin composition and / or the cured resin film such as a black matrix, a protective film, and a partition for an ink jet system are not easily wrinkled or cracked. An inorganic material thin film adjacent to any of the above is unlikely to be wrinkled or cracked. Therefore, the color filter according to the present invention is free from the problem of conduction due to wrinkles and cracks and the problem of image defects, and has reduced display defects.

  In the color filter according to the present invention, one embodiment of the inorganic material thin film is a transparent electrode film.

  In the color filter according to the present invention, the inorganic material thin film preferably has a surface roughness (Ra) of 10 nm or less.

  The liquid crystal panel according to the present invention is a liquid crystal panel in which a display side substrate and a liquid crystal driving side substrate are opposed to each other, and liquid crystal is sealed therebetween, and the display side substrate is the color filter according to the present invention. It is characterized by being.

In addition, the method for producing a color filter according to the present invention includes the step of isolating the thermosetting resin composition for a color filter according to the present invention on a substrate from an organic component only in an organic component in the solid content of the composition. A step of forming a cured resin film by curing under a condition that the elastic deformation ratio in the indentation test by 14577 is 40% or more and the surface roughness of the cured product is 10 nm or less ; and an inorganic material on the cured resin film Forming a thin film.

Method for producing a color filter according to the present invention, the thermosetting resin composition on a substrate, the elastic deformation ratio in the indentation test by ISO-14577 only cured product obtained from the organic component in the solid content of the composition is The resin cured film thus formed has a process of forming a cured resin film by curing it under the condition that the surface roughness (Ra) of the cured product is 10 nm or less under 40% or more . because the less likely, be further formed inorganic material thin film on the resin cured film, the inorganic material thin film wrinkles and cracks rather difficulty occurs, the color filter is obtained in which the display defect is reduced.

In the method for producing a color filter according to the present invention, the step of forming the inorganic material thin film may be performed by using any one of a physical vapor deposition method, a chemical vapor deposition method, and a sol-gel method. It is preferable from the point.

In the color filter manufacturing method according to the present invention, the step of forming the inorganic material thin film may include a heating step of 180 ° C. or higher.

The method of manufacturing a color filter according to the present invention, the step of forming a resin cured film, even after the progress of the crosslinking reaction of the thermosetting resin composition is stopped, further increase the elastic deformation rate and continue heating It is preferable to include the step of causing the inorganic material thin film to be free from wrinkles and cracks.

The method of manufacturing a color filter according to the present invention, the step of forming the resin cured film, the thermosetting resin composition in a predetermined region on the substrate selectively deposited was by an ink jet method to form an ink layer It is preferable to include a step and a step of curing the ink layer by heating to form a cured resin film having a predetermined pattern. This is because a predetermined fine pattern can be accurately and uniformly formed by ejecting the substrate surface according to the predetermined pattern by the ink jet method.

In the color filter manufacturing method according to the present invention, it is preferable that the inorganic material thin film has a surface roughness (Ra) of 10 nm or less.

  The curable resin composition for a color filter according to the present invention hardly causes wrinkles and cracks in the cured film, and hardly causes wrinkles and cracks in adjacent layers. When a color filter coloring layer, a black matrix, a protective film, an ink jet partition, etc. are formed using the curable resin composition for a color filter according to the present invention, the inorganic material thin film adjacent to at least one of these is wrinkled. And cracks are less likely to occur.

  The curable resin composition for a color filter according to the present invention can provide the above effect by selecting an organic component in a solid content containing a binder component as a main component so as to meet the conditions of the present invention. It is efficient because there is no need for a step of selecting a curable resin composition with few wrinkles and cracks by repeating the actual production of an adjacent layer such as an inorganic material thin film on the cured film of the composition.

  The color filter according to the present invention is free from problems of conduction due to wrinkles and cracks and image defects, and has reduced display defects.

  The liquid crystal panel according to the present invention is a liquid crystal panel with reduced display defects because the color filter according to the present invention with reduced display defects is used.

  In the method for producing a laminate of a cured resin film and an inorganic material thin film according to the present invention, wrinkles and cracks are not easily generated in the inorganic material thin film.

  The present invention is described in detail below. In the present invention, light includes electromagnetic waves having wavelengths in the visible and non-visible regions, and 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, (meth) acrylate means acrylate or methacrylate, and (meth) acryloyl means acryloyl or Means either methacryloyl.

1. Curable resin composition for color filter The curable resin composition for a color filter according to the present invention is a composition containing at least a curable resin, and is a cured product composed only of organic components in the solid content of the composition. The elastic deformation ratio in the indentation test according to ISO-14577 can be 40% or more.

  The organic components in the solid content of the color filter curable resin composition include all binder components, pigment dispersants, ultraviolet absorbers, and the like. Pigments (organic pigments and inorganic pigments), inorganic fillers and the like are not included. Even if it is an organic component, a pigment is not contained in the organic component in the said solid content of this invention. Further, it does not include a silicon polymer as a leveling agent or a silane coupling agent as an adhesion promoter. Therefore, the organic component in the solid content of the curable resin composition for color filters is composed mainly of the binder component and may be composed of only the binder component.

  In the present invention, the elastic deformation ratio in the indentation test according to ISO-14577 of the cured product consisting only of the organic component in the solid content in which the binder component consisting of one or two or more components is the main component in the composition is 40. The organic component in the solid content is selected so that it can be at least%, and the cured product composed only of the organic component is cured under the curing conditions in which the elastic deformation ratio in the indentation test according to ISO-14577 is 40% or more. By making the cured film of the composition less susceptible to thermal expansion and contraction and less likely to cause wrinkles and cracks, even if an inorganic material thin film such as a transparent electrode film is formed on it at a high temperature and under an ultra-low pressure by vacuum, Wrinkles and cracks are unlikely to occur in the inorganic material thin film.

  An organic component in the solid content is selected so that the elastic deformation ratio in the indentation test according to ISO-14577 of the cured product consisting only of the organic component in the solid content can be 40% or more. When the composition is cured under a condition that the elastic deformation ratio in the indentation test according to ISO-14577 is 40% or more, the cured film of the composition is less likely to be wrinkled or cracked. It is presumed that the high deformation rate has the function of relaxing the internal stress generated during the formation of the inorganic material thin film.

  It is preferable that the cured product itself consisting only of the organic component has less wrinkles, and the surface roughness (Ra) is preferably 10 nm or less, more preferably 7 nm or less, and particularly preferably 5 nm or less. Here, the surface roughness (Ra) refers to the arithmetic average roughness obtained by the following formula.

In the formula, N is the number of divisions with respect to the reference length at the time of measurement, and Rn is a deviation from the average height of the divided sections n when the thickness direction with respect to the surface is height. The surface roughness (Ra) can be measured by an AFM (atomic force microscope).

  When a color filter coloring layer, a black matrix, a protective film, an ink jet partition, etc. are formed using the curable resin composition for a color filter according to the present invention, the inorganic material thin film adjacent to at least one of these is wrinkled. And cracks are less likely to occur.

(Elastic deformation ratio)
In the present invention, the elastic deformation ratio is shown in an indentation work consisting of a plastic deformation work (Wplast) and an elastic deformation work (Welast), which is obtained in an instrumented indentation test of hardness and various material parameters according to ISO-14577. This refers to the ratio of the elastic deformation work (Welast) to the total mechanical work (Wtotal) (Welast / Wtotal × 100). FIG. 4 shows a load (F) / indentation depth (h) curve in the indentation test. Here, the total mechanical work (Wtotal) is A-B-D-A, the plastic deformation work (Wplast) is A-B-C-A, and the elastic deformation work (Welast) is C-B-D-C. is there. The instrumentation indentation test of hardness and various material parameters according to ISO-14577 is equivalent to the conventional universal hardness test.

  Further, in the present invention, the cured product composed only of the organic component in the solid content includes at least a curable resin in the solid content of the composition of the present invention. This refers to the entire organic component in the solid content after the curing reaction has progressed under the condition that the bridging elements such as bonds and epoxy groups react. If the elastic deformation ratio in the indentation test according to ISO-14577 is 40% or more The crosslinking element of the curable resin, that is, all of the crosslinkable functional groups may not be reacted.

  The elastic deformation ratio in the indentation test by ISO-14577 of the cured product consisting only of the organic component in the solid content of the composition in the present invention can be measured according to ISO-14577, and can be measured as follows. . A tester that satisfies the conditions of ISO-14577-2 is used. As a testing machine that satisfies the conditions of ISO-14577-2, there is a microhardness measuring device. Specifically, for example, a Fischer scope H100V (manufactured by Helmut Fischer) can be used.

As a measurement sample, for example, a composition composed only of organic components in the solid content of the composition is dissolved in a solvent so as to have a solid content of 30% to prepare a coating liquid, and the coating liquid is applied onto the substrate. In the case of heating and vacuum drying (for example, on a hot plate at 80 ° C., 5 minutes, 150 Torr) and containing a photocurable resin as a curable resin, it is converted into 365 nm using an ultrahigh pressure mercury lamp as a light source. When light is irradiated for 3 to 10 seconds at an illuminance of 30 mW / cm ² and further heated at 200 to 240 ° C. for 30 to 60 minutes, or when only a thermosetting resin is contained as the curable resin Heated at 200 ° C. to 260 ° C. for 30 to 60 minutes to form a coating film so that the final cured film thickness is about 2 μm, a cured product consisting only of organic components in the solid content Can be used as

  The cured product consisting only of the organic component in the solid content obtained as described above is measured using the tester. In the case of a cured film having a film thickness of about 2 μm, for example, using a pyramid diamond indenter having a base as a square indenter (for example, MK320 in Fisherscope H100V) under a temperature of 23 ° C. and a humidity of 45%, for example, a load According to the control method, the load load speed is 30 mN / min, the maximum load is 30 mN, the holding time at the maximum load is 5 seconds, the load F under test and the corresponding indentation depth h and time are recorded, and are indicated during the indentation work. Measure work.

  The measured work amount can be processed as η = Welast / Wtotal × 100 to determine the elastic deformation ratio.

  The composition of the present invention can have an elastic deformation ratio of 40% or more in an indentation test according to ISO-14577 of a cured product composed only of organic components in the solid content of the composition. %, Preferably those that can have an elastic deformation ratio of 42% or more.

  The elastic deformation ratio in the indentation test according to ISO-14577 can be 40% or more, and the cured product composed only of organic components in the solid content has a higher elastic deformation ratio when heated more or irradiated with light. A trend was found. However, when more heating or light irradiation is performed, the cured film may turn yellow. When the cured film used in the display area of the color filter turns yellow, the brightness of the color filter is reduced. Therefore, the elastic deformation ratio in the indentation test according to ISO-14577 of a cured product composed only of organic components is preferably 60% or less, more preferably 55% or less, and particularly preferably 50% or less.

Moreover, from the point of making yellowing of a cured film difficult to occur, as a curing condition for performing an indentation test according to ISO-14577, when a photocurable resin is contained as a curable resin, an ultrahigh pressure mercury lamp is used as a light source. And irradiated with light at an illuminance of 30 mW / cm ^{2 in} terms of 365 nm for 3 to 10 seconds and further heated at 200 to 240 ° C. for 30 to 60 minutes, or contains only a thermosetting resin as a curable resin. When it does, it is preferable that it is the conditions which heat for 30 minutes-90 minutes at 200 to 240 degreeC. Furthermore, when it contains photocurable resin as curable resin, an ultrahigh pressure mercury lamp is used as a light source. It is irradiated with light at an illuminance of 30 mW / cm ^{2 in} terms of 365 nm for 3 to 5 seconds, and further heated at 220 ° C. to 240 ° C. for 30 minutes to 60 minutes, or only a thermosetting resin is used as the curable resin. Contains When it does, it is preferable that it is the conditions which heat at 220 degreeC-240 degreeC for 30 minutes-90 minutes.

Moreover, in this invention, when the hardened | cured material which consists only of the said organic component contains a photocurable resin, it is further irradiated with light for 30 second by the illumination intensity of 30 mW / cm < ² > in conversion of 365 nm using an ultrahigh pressure mercury lamp as a light source. , And before and after heating at 240 ° C. for 60 minutes, or when containing only a thermosetting resin as the curable resin, the amount of change in the cross-linking element is within the measurement error range before and after heating at 240 ° C. for 60 minutes. It is preferable that the elastic deformation ratio in the indentation test according to ISO-14577 is within the range from the viewpoint that wrinkles and cracks hardly occur in the adjacent inorganic material thin film.

Here, the amount of change in the cross-linking element is within the measurement error range, for example, with a heating IR measuring device (for example, FT / IR 610, manufactured by JASCO Corporation), a typical cross-linking of a thermosetting resin. The amount of change with respect to an epoxy group as an element and an ethylenic double bond (C = C) as a typical crosslinking element of a photocurable resin can be measured and used as an index. Specifically, for example, in one measurement, a functional group such as an ester group (for example, around 1720 cm ⁻¹ ) that does not change even when heated or irradiated with light is selected as a reference peak to obtain a peak area, and is derived from an epoxy group The peak area is also obtained for the peak around 986 cm ⁻¹ (890 to 990 cm ⁻¹ ), the area ratio of the epoxy peak to the reference peak is calculated, and the peak area before and after the heating and light irradiation more severely after curing When the ratio is compared, it means that the ratio is substantially zero, specifically 0.002% or less. Here, for example, the peak area can be calculated by connecting two valleys with respect to the peak top with a straight line. Similarly, in the case of the photocurable resin, for example, in one measurement, a functional group such as an ester group (for example, around 1720 cm ⁻¹ ) that does not change even when heated or irradiated with light is selected as a reference peak, and the peak area is determined. determined, determine the peak area even for the peak of the derived ethylenic double bond (C = C) 810cm ^-1 longitudinal (800~830cm ^-1), it is possible to calculate the area ratio of the epoxy peak relative to the reference peak.

(Binder component)
The binder component used in the present invention contains at least a curable resin and can be a main component of a cured product composed only of organic components in the solid content. Therefore, it is preferable that the elastic deformation ratio in the indentation test by ISO-14577 of the hardened | cured material of the binder component used for this invention can be 40% or more.

Next, the binder component used in the present invention will be specifically described.
The binder component used in the present invention includes at least a curable resin, may include one or more curable resins, and imparts film formability and adhesion to a surface to be coated. Therefore, a resin having no curability may be included. The binder component used in the present invention is not particularly limited as long as the elastic deformation ratio in the indentation test according to ISO-14577 of the cured product composed only of the organic component in the solid content can be 40% or more, and only the organic component. The cured product made of is suitably selected or used in combination so that the elastic deformation ratio in the indentation test according to ISO-14577 is 40% or more.

  Examples of the curable resin contained in the binder component include a photocurable resin that can be polymerized and cured by visible light, ultraviolet light, electron beam, and the like, and a thermosetting resin that can be polymerized and cured by heating. As the binder component of the present invention, a photocurable binder system containing a photocurable resin, a thermosetting binder system containing a thermosetting resin that can be polymerized and cured by heating, and a photocurable binder system and Those containing both thermosetting binder systems can be used.

(1) Photo-curable binder system In the binder system containing a photo-curable resin that can be polymerized and cured by light such as ultraviolet rays and electron beams, the purpose is to provide film formability and adhesion to the coated surface. It is preferable to include a polymer having a relatively high molecular weight. Here, the relatively high molecular weight means that the molecular weight is higher than that of so-called monomers and oligomers, and the weight average molecular weight can be 5,000 or more. As a polymer having a relatively high molecular weight, any of a polymer having no polymerization reactivity per se and a polymer having a polymerization reactivity per se may be used, and a combination of two or more types may be used. May be. It is mainly composed of a polymer having a relatively high molecular weight, and if necessary, a polyfunctional monomer or oligomer, a monofunctional monomer or oligomer, a photopolymerization initiator activated by light, and a sensitizer. Thus, a photocurable binder system is constituted.

  When a polymer having no polymerization reactivity is used as a polymer having a relatively high molecular weight, a polyfunctional monomer such as a bifunctional or higher polyfunctional monomer or oligomer is blended in the binder system. In this case, in the binder system, the polyfunctional polymerizable component itself spontaneously polymerizes by light irradiation, or polymerizes by the action of other components such as a photopolymerization initiator activated by light irradiation. A network structure is formed in the coating film, and components such as resins and pigments having no polymerization reactivity are encapsulated in the network structure and cured.

  As such a polymer having no polymerization reactivity, for example, a copolymer comprising two or more of the following monomers can be used: acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate. 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, styrene, polystyrene macromonomer, and polymethyl methacrylate macromonomer.

  More specifically, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, benzyl methacrylate / styrene copolymer, benzyl methacrylate macromonomer / styrene copolymer, benzyl methacrylate / styrene macromonomer A copolymer etc. can be illustrated.

  The polymer itself having polymerization reactivity is an oligomer obtained by introducing a polymerizable functional group into a non-polymerizable binder molecule or a polymer having a higher molecular weight than an oligomer, and is itself exposed to light irradiation. May cause a polymerization reaction, or may induce a polymerization reaction by the action of other components such as a photopolymerization initiator activated by light irradiation.

  Various ethylenic double bond-containing compounds themselves have polymerization reactivity and can be used as photocurable resins. Conventionally, a prepolymer blended in a UV curable resin composition used in various fields such as inks, paints, and adhesives can be used as a polymer having a relatively high molecular weight in the present invention. Conventionally known prepolymers include radical polymerization type prepolymers, cationic polymerization type prepolymers, thiol / ene addition type prepolymers, and any of them may be used.

  Among these, radical polymerization type prepolymers are most easily available on the market, such as ester acrylates, ether acrylates, urethane acrylates, epoxy acrylates, amino resin acrylates, acrylic resin acrylates, unsaturated polyesters. Examples can be given.

  Especially, the following two types of graft polymers are mentioned as a polymer with comparatively high molecular weight which can be used suitably in this invention.

  The first graft polymer has a weight average molecular weight of 5,000 or more, and one of the main chain and the graft portion is composed of a styrene polymer chain containing a styrene monomer unit, and the other is a methacrylate monomer. It is a graft polymer composed of methacrylate polymer chains containing units.

  The first graft polymer may have a structure in which a main chain (trunk part) is constituted by a styrene polymer chain and a graft part is constituted by a methacrylate polymer chain, and conversely, a methacrylate polymer chain. It may have a structure in which the main chain is constituted by and the graft portion is constituted by a styrene polymer chain. Among the above, those having a structure in which a main chain is constituted by a styrene polymer chain and a graft part is constituted by a methacrylate polymer chain are preferred.

  The styrenic polymer chain is a polymer chain mainly composed of a styrenic monomer, and may be a homopolymer of only one kind of styrenic monomer or a copolymer of two or more kinds of styrenic monomers. It may be a copolymer of a styrene monomer and another monomer.

  In addition to styrene, the styrenic monomer includes styrene monomers with substituents such as alkyl-substituted styrene (methyl styrene, ethyl styrene, trimethyl styrene, octyl styrene, etc.), methoxy styrene, and α-methyl styrene.

  Examples of the monomer that can be copolymerized with the styrene monomer include various (meth) acrylate monomers, acrylonitrile, amide monomers, and the like.

  When the curable resin composition according to the present invention contains a pigment, the styrene polymer chain preferably contains a styrene monomer unit in a proportion of 50% by weight or more from the viewpoint of pigment dispersibility. It is particularly preferable to contain it in a proportion of not less than wt%.

  The methacrylate polymer chain is a polymer chain mainly composed of methacrylate and may be a homopolymer of only one type of methacrylate or a copolymer of two or more types of methacrylate, or methacrylate. And a copolymer of other monomers.

Methacrylate monomers include alkyl methacrylate (methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate), benzyl methacrylate, phenoxyethyl methacrylate, tetrahydrophthalimide Examples include ethyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, tetrahydrofurfuryl methacrylate, methoxypolyethylene glycol methacrylate, and butoxyethyl methacrylate. It is preferable to select and use a methacrylate monomer so that a graft polymer having a Tg of 30 ° C. or higher can be obtained. A graft polymer having a Tg of less than 30 ° C. is not preferable because the film hardness after curing decreases.

  Moreover, as a monomer to be copolymerized with methacrylate, alkyl acrylate, hydroxyalkyl acrylate, amide monomer, imide group-containing monomer, alkylene glycol (meth) acrylate, Daicel Chemical's brand name Plexel FM series, or the like can be used.

  The methacrylate polymer has a relatively high Tg and is excellent in hardness and dispersibility because it causes microphase separation from styrene. From this point of view, the methacrylate polymer chain preferably contains a methacrylate monomer unit in a proportion of 50% by weight or more, more preferably 70% by weight or more.

  The first graft polymer may have a polymerizable group such as an ethylenically unsaturated bond or an epoxy group. Reaction curability can be imparted by introducing a polymerizable group into the graft polymer. The graft polymer into which the polymerizable group has been introduced can be suitably used as a photocurable resin having a relatively high molecular weight in the present invention since the crosslinking point is improved and the surface hardness is improved. When the polymerizable group of the graft polymer is an ethylenically unsaturated bond, it can be cured by light or thermal radical polymerization reaction, and when the polymerizable group is an epoxy group, thermal polymerization or photocationic polymerization is performed. Is possible. In particular, when the graft polymer having an ethylenically unsaturated bond is used in combination with an ethylenically unsaturated bond-containing monomer such as a (meth) acrylic monomer and / or an oligomer, a curable resin composition having excellent reaction curability is obtained. can get. The polymerizable group may be introduced into one or both of the styrenic polymer chain or the methacrylate polymer chain of the first graft polymer, or may be introduced into one or both of the main chain and the graft portion.

  The first graft polymer needs to have a polystyrene-equivalent weight average molecular weight measured by GPC in the range of 5,000 or more, particularly when the curable resin composition according to the present invention is used for an ink jet ink. The weight average molecular weight in terms of polystyrene measured by GPC is preferably 20,000 or less, and more preferably in the range of 5,000 to 15,000. If the weight average molecular weight is less than 5,000, the strength and hardness of the resulting film tends to be insufficient. When the weight average molecular weight exceeds 20,000, it becomes difficult to dissolve in the solvent of the inkjet ink, or the viscosity when dissolved in the solvent becomes high, and the fluidity of the ink and the discharge property from the inkjet head deteriorate. .

  Further, the graft part of the graft polymer needs to have a polystyrene-equivalent weight average molecular weight measured by GPC (gel permeation chromatography) in the range of 5,000 to 20,000, and 5,000 to 15,000. It is preferable to be in the range.

  The weight ratio of the graft (branch) portion / main chain (trunk) portion of the graft polymer is preferably 20/80 to 80/20, and more preferably 30/70 to 70/30. If the weight ratio of the graft portion is less than 20%, the solubility, viscosity, fluidity, dischargeability and the like are deteriorated. On the other hand, when the weight ratio of the main chain portion is less than 20%, the pigment dispersibility is deteriorated.

  Furthermore, by changing the acid value and amine value of the first graft polymer, various physical properties such as solubility in the ink solvent, solvent resistance of the film, dispersion stability of the pigment, dyeability, film hardness, film strength, etc. Can be adjusted.

  As the second graft polymer, the graft polymer has an ethylenically unsaturated bond in an ethylenically unsaturated bond equivalent ratio of 1200 g / eq or less, and one of the main chain and the graft portion is a styrene monomer. Examples thereof include a graft polymer composed of a styrenic polymer chain containing units and the other composed of a benzyl methacrylate polymer chain containing monomer units derived from benzyl methacrylate.

  The second graft polymer may have a structure in which a main chain (trunk) is constituted by a styrene polymer chain and a graft part is constituted by a benzyl methacrylate polymer chain, and conversely, a benzyl methacrylate type The main chain may be constituted by a polymer chain, and the graft portion may be constituted by a styrenic polymer chain. Among the above, those having a structure in which a main chain is constituted by a styrene polymer chain and a graft part is constituted by a benzyl methacrylate polymer chain are preferred.

  The styrenic polymer chain of the second graft polymer is a polymer chain mainly composed of a styrenic monomer, like the first polymer chain.

  On the other hand, the benzyl methacrylate polymer chain of the second graft polymer is a polymer chain mainly composed of benzyl methacrylate, and may be a homopolymer of benzyl methacrylate, or a copolymer of benzyl methacrylate and other monomers. It may be a coalescence.

  As a monomer to be copolymerized with benzyl methacrylate, a monomer to be copolymerized with methacrylate in order to form the methacrylate polymer chain of the first main polymer described above can be used. Further, benzyl methacrylate may be copolymerized with other methacrylate monomers to form a benzyl methacrylate polymer chain, and in that case, various kinds of polymers that can form the methacrylate polymer chain of the first graft polymer described above. Methacrylate monomers can be copolymerized with benzyl methacrylate.

  Among methacrylate monomers, benzyl methacrylate is particularly excellent in pigment dispersibility, and therefore the second graft polymer is preferably used in a curable resin composition for a color filter for forming a colored layer or a black matrix layer. . The benzyl methacrylate-based polymer chain preferably contains benzyl methacrylate monomer units in a proportion of 30% by weight or more, particularly preferably 50% by weight or more.

  In the second graft polymer, at least one of the main chain or the graft portion has an ethylenically unsaturated bond, and can be cured by light or thermal radical polymerization reaction.

  The main chain may contain a monomer unit having an ethylenically unsaturated bond, regardless of whether it is composed of a styrene polymer chain or a benzyl methacrylate polymer chain. On the other hand, the graft portion may similarly contain a monomer unit having an ethylenically unsaturated bond, regardless of whether it is composed of a styrene polymer chain or a benzyl methacrylate polymer chain.

  The ethylenically unsaturated bond equivalent of the second graft polymer needs to be 1200 g / eq or less, preferably 700 g / eq or less. Here, the ethylenically unsaturated bond equivalent is a value obtained by dividing the weight of 1 gram molecule of the graft polymer by the number of ethylenically unsaturated bonds contained in one molecule. When the ethylenically unsaturated bond equivalent of the graft polymer exceeds 1200 g / eq, the film hardness after curing, the elastic deformation ratio according to the present invention, and the solvent resistance are insufficient, which is not preferable. On the other hand, since the graft polymer having an ethylenically unsaturated bond equivalent of 1200 g / eq or less has a large amount of ethylenically unsaturated bonds contained in one molecule, the elastic deformation ratio, solvent resistance, hardness and strength according to the present invention. Excellent physical properties such as adhesion. Even when a graft polymer having a relatively low molecular weight is used in order to improve ejection properties, it can be sufficiently cured if the ethylenically unsaturated bond equivalent is 1200 g / eq or less. As a result, an ink composition having excellent ejection properties can be obtained, and a cured film having excellent physical properties including the elastic deformation ratio according to the present invention can be formed.

  Furthermore, by changing the acid value and amine value of the second graft polymer, the solubility of the ink in the solvent, the solvent resistance of the film, the dispersion stability of the pigment, the dyeability, the film, as in the case of the first graft polymer. Various physical properties such as hardness and film strength can be adjusted.

  In the present invention, a graft polymer having both the properties of the first graft polymer and the second main polymer, that is, the weight average molecular weight is 5,000 or more, and the ethylenically unsaturated bond is represented by an ethylenically unsaturated bond equivalent. It has a ratio of 1200 g / eq or less, and one of the main chain and the graft part is composed of a styrene polymer chain containing a styrene monomer unit, and the other contains a benzyl methacrylate unit as a methacrylate monomer unit. It is more preferable to use a graft polymer composed of benzyl methacrylate-based polymer chains to increase the elastic deformation rate according to the present invention.

  Among them, the graft polymer introduced with a polymerizable group, which can be suitably used as a photocurable resin having a relatively high molecular weight in the present invention, has a weight average molecular weight of 5,000 or more and an ethylenically unsaturated bond. In which the main chain is composed of a styrene polymer chain and the graft portion is composed of a benzyl methacrylate polymer chain containing benzyl methacrylate units. A polymer or a weight average molecular weight of 5,000 or more, having an ethylenically unsaturated bond in an ethylenically unsaturated bond equivalent ratio of 1200 g / eq or less, and the main chain being composed of a styrenic polymer chain; , Methyl methacrylate-based poly (methacrylate) units containing methyl methacrylate units It includes formed graft polymer by chromatography chains. These are also preferable from the viewpoint of good resolubility.

  The production method of the graft polymer used as the first or second graft polymer is as follows: (1) A method in which a monomer is polymerized in the presence of a polymer and a peroxide catalyst and then post-grafting is performed by hydrogen abstraction; The method of addition reaction of a polymer with a functional group and a polymer with another functional group and (3) a method of copolymerizing a polymerizable polymer (macromonomer) and a monomer can be used. The macromonomer method is preferable because of its high point.

  The main chain skeleton (trunk part) of the graft polymer obtained by the macromonomer method is formed by polymer chains grown by polymerization of the ethylenically unsaturated bond at the terminal of the polymerizable polymer and the ethylenically unsaturated bond of the monomer, and the graft part. Are formed by polymer chains derived from a polymerizable polymer.

  The polymerizable polymer, which is a raw material for synthesizing the graft polymer, is composed of a polymer chain portion to constitute the graft portion of the graft polymer and a group having an ethylenically unsaturated bond at the terminal.

  The polymer chain of the polymerizable polymer is a styrenic polymer chain or a methacrylate polymer chain, and is formed by polymerizing a styrene monomer or a methacrylate monomer alone, or by copolymerizing with other monomers as required. it can.

  The ethylenically unsaturated bond-containing group at the end of the polymerizable polymer is usually introduced after the polymer chain portion of the polymerizable polymer is synthesized. As the ethylenically unsaturated bond-containing group at the terminal of the polymerizable polymer, a (meth) acryloyl group or a vinyl group is preferable, and a (meth) acryloyl group is particularly preferable. The group having an ethylenically unsaturated bond is preferably contained only at one end of the polymerizable polymer.

  On the other hand, as a monomer that forms a main chain by copolymerizing with the polymerizable polymer, when the polymerizable polymer has a styrene polymer chain, one or two or more methacrylate monomers are used. When it has a methacrylate polymer chain, a styrene monomer is used. As the monomer to be copolymerized with the polymerizable polymer, other monomers may be used in combination with the styrene monomer or methacrylate monomer, and in that case, the same monomer as that for forming the polymer chain of the polymerizable polymer is used. Can be used.

  When it is desired to introduce an ethylenically unsaturated bond into the graft portion or main chain portion of the graft polymer, a monomer having a functional group that can serve as a scaffold for introducing an ethylenically unsaturated bond is introduced into the styrene monomer or methacrylate monomer. An appropriate amount is mixed and copolymerized to synthesize the graft portion and / or main chain portion, and finally condensed to the functional group remaining in the graft portion and / or main chain portion of the graft polymer. Alternatively, a compound having a functional group to be polyadded and an ethylenically unsaturated bond may be reacted.

  That is, when an ethylenically unsaturated bond is to be introduced into the graft portion of the graft polymer, an appropriate amount of a monomer having a functional group that can serve as a scaffold for introducing the ethylenically unsaturated bond is mixed with the styrene monomer or methacrylate monomer. Then, the resulting polymerizable polymer is polymerized with a monomer to form a graft polymer, and then condensed or polyadded to the functional group remaining in the graft portion of the graft polymer. By reacting a compound having a functional group and an ethylenically unsaturated bond, a graft polymer in which an ethylenically unsaturated bond is introduced into the graft portion is obtained.

  In addition, when it is desired to introduce an ethylenically unsaturated bond into the main chain part of the graft polymer, an appropriate amount of a monomer having a functional group that can serve as a scaffold for introducing the ethylenically unsaturated bond is mixed with the monomer that forms the main chain. Then, copolymerization is performed to form a graft polymer, and then a functional group that is condensed or polyadded to the functional group and an ethylenically unsaturated bond are added to the functional group remaining in the main chain portion of the graft polymer. By reacting the compound having the above, a graft polymer having an ethylenically unsaturated bond introduced into the main chain portion can be obtained.

  When a graft polymer is synthesized using a polyfunctional polymerizable polymer having an ethylenically unsaturated bond at a position other than one end or a polyfunctional polymerizable monomer having two or more ethylenically unsaturated bonds, a crosslinking reaction occurs. However, when an ethylenic double bond is introduced after the copolymerization of a monofunctional oligomer and a monofunctional monomer, a photosensitive graft having an ethylenic double bond is produced without causing such a crosslinking reaction. A polymer is obtained.

  Monomers having a functional group that can serve as a scaffold for introducing an ethylenically unsaturated bond include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, other hydroxyl group-containing monomers, or (meth) Unsaturated carboxylic acids such as acrylic acid and other carboxyl group-containing monomers are preferred.

  In the case of using a hydroxyl group-containing monomer, after synthesizing a polymerizable polymer and a polymerizable monomer to synthesize a graft polymer, 2- (meth) acryloyloxy is added to the hydroxyl group remaining in the graft portion and / or the main chain portion. An ethylenically unsaturated bond can be introduced by urethane-bonding an isocyanate group-containing acrylic monomer such as ethyl isocyanate by an addition reaction.

  In addition, when a carboxyl group-containing monomer is used, a polymerizable polymer and a polymerizable monomer are copolymerized to synthesize a graft polymer, and then glycidyl (meta) is added to the carboxyl group remaining in the graft portion and / or main chain portion. ) An ethylenically unsaturated bond can be introduced by bonding an epoxy group-containing (meth) acrylate such as an acrylate by an epoxy reaction.

  According to any of the above methods, the ethylenically unsaturated bond is introduced into the polymer chain in the form of a (meth) acryloyloxy group.

  As a procedure for synthesizing the graft polymer, reference can be made to specific examples of paragraph numbers 0094 to 0105 of JP-A-2002-201387.

  In particular, when the resin composition according to the present invention is used as an ink jet ink, a polymer having a relatively high molecular weight is used so that the viscosity of the composition is not too high to adversely affect the ejection properties from the ejection head. The molecular weight of is preferably 25,000 or less in terms of weight average molecular weight.

  The polymer having a relatively high molecular weight is preferably blended at a ratio of 1 to 50% by weight with respect to the total solid content of the curable resin composition. Here, the solid content of the curable composition for specifying the blending ratio includes all components except the solvent, and liquid polymerizable monomers and the like are also included in the solid content.

  Even in the case of using a binder component that can be polymerized and cured per se, it is preferable to incorporate a polyfunctional polymerizable component such as a polyfunctional monomer or oligomer in order to improve the strength of the coating film and the adhesion to the substrate. Polymer molecules with relatively high molecular weight that are polymerizable not only polymerize with polymers with relatively high molecular weight, but also polymerize with other polymerizable components such as polyfunctional monomers to form a network and cure. To do.

  As the polyfunctional polymerizable component forming the network structure of the coating film, a bifunctional or higher functional monomer or oligomer can be used. In order to impart sufficient film strength and adhesion to the photocurable resin, a tetrafunctional or higher functional monomer or oligomer is usually used.

  However, in particular, when the curable resin composition according to the present invention is used as an ink jet ink, the polymerizable component other than the polymer having a relatively high molecular weight is a bifunctional to trifunctional functional group having a relatively small number of functional groups. It is preferable to use a monomer or oligomer, particularly a monomer as a main component, and it is particularly preferable to use a bi- or trifunctional monomer having a viscosity of 100 cps or less. During ink jet spraying, it is difficult for the viscosity to increase at the tip of the head, clogging of the head does not occur, and ink ejection during operation is stable, so the amount and direction of ink ejection is stable. This is because the ink can be accurately and uniformly deposited on the substrate in a predetermined pattern.

  Examples of the bifunctional to trifunctional monomers include 1,6-hexanediol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, and polyethylene glycol diester. Examples thereof include acrylate, polypropylene glycol diacrylate, trimethylolpropane triacrylate, and 3-butylene glycol dimethacrylate.

  Particularly when the curable resin composition according to the present invention is used as an ink jet ink, the blending ratio of the bifunctional to trifunctional monomer is 20 to 70% by weight with respect to the total solid content of the curable resin composition. It is preferable to mix | blend in a ratio.

  When the blending ratio of the bi- to trifunctional monomer is less than 20% by weight of the total solid content, the curable resin composition is not sufficiently diluted with the monomer, and the viscosity of the ink is high from the beginning, or the solvent content is volatilized. There is a risk that it will become higher later and the nozzles of the inkjet head may become clogged. When the blending ratio of the bi- or trifunctional monomer exceeds 70% by weight of the total solid content, the cross-linking density of the coating film is lowered, the elastic deformation ratio is lowered, and the solvent resistance and adhesion of the coating film are reduced. This is because the hardness is inferior and sufficient characteristics may not be obtained.

  However, when all the polyfunctional monomers blended in the curable resin composition are di- or tri-functional monomers, the viscosity increase due to drying of the ink is unlikely to occur, and thus the ejection performance of the inkjet head is stable. On the other hand, the film strength of the cured layer obtained by curing the ink layer, adhesion to the substrate, solvent resistance, etc. may be insufficient. Therefore, by adding an appropriate amount of a tetrafunctional or higher polyfunctional monomer or oligomer together with the above bifunctional to trifunctional monomers, the crosslinking density can be increased, and sufficient film strength and adhesion can be imparted to the pattern of the cured layer. .

  Examples of tetrafunctional monomers and oligomers include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like.

  The polyfunctional component having 4 or more functional groups is usually preferably blended at a ratio of 1 to 30% by weight with respect to the total solid content of the curable resin composition. Particularly when the curable resin composition according to the present invention is used as an ink-jet ink, the balance between the ejection stability stabilization by the bi- or tri-functional monomer and the strength and adhesion improvement by the tetrafunctional or higher polyfunctional component is balanced. Therefore, the blending ratio of the tetrafunctional or higher polyfunctional component is usually 1 to 50 parts by weight with respect to 100 parts by weight of the 2 to 3 functional monomer, and preferably the lower limit of the blending ratio is 2 parts by weight or more. And / or the upper limit of the blending ratio is preferably 35 parts by weight or less.

  When the blending ratio of the tetrafunctional or higher polyfunctional component is less than 1 part by weight with respect to 100 parts by weight of the bi- to tri-functional monomer, characteristics such as hardness and solvent resistance after the ink is cured May not be sufficiently obtained. Moreover, when the said mixture ratio of the polyfunctional component more than tetrafunctional exceeds 50 weight part, there exists a possibility that the cure rate of an ink may become slow and process speed may become slow.

  Moreover, you may mix | blend a monofunctional monomer and an oligomer with a photocurable binder system as needed.

  Examples of monofunctional monomers and oligomers include vinyl monomers such as styrene and vinyl acetate, and monofunctional acrylic monomers such as n-hexyl acrylate and phenoxyethyl acrylate.

  The photocurable binder system is usually blended with a photopolymerization initiator having activity with respect to the wavelength of the light source to be used. The photopolymerization initiator is appropriately selected in consideration of the difference in the reaction format of the binder and the polyfunctional monomer (for example, radical polymerization and cationic polymerization) and the type of each material. For example, 1-hydroxycyclohexyl-phenyl ketone 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-monforinopropan-1-one, 2-benzyl-2- Dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] 2-hydroxy-2-methyl-1-propan-1-one, 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide, bisacylphospho Fin oxide, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2- (3-dimethylamino-2-hydroxypropoxy) -3,4-dimethyl-9H-thioxanthone -9-one mesochloride, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl), p- Dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, 1,3,5-triacroylhexahydro-s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl]- 4,6-bis (trichloro Methyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, methylbenzoylformate, 2,4,6-trimethylbenzoyldiphenyl A photopolymerization initiator such as phosphine oxide can be used.

(2) Thermosetting binder system As the thermosetting binder system, a combination of a compound having two or more thermosetting functional groups in one molecule and a curing agent is usually used, and further a catalyst capable of promoting a thermosetting reaction. May be added. An epoxy group is preferably used as the thermosetting functional group. In addition, a polymer having no polymerization reactivity as described above may be further used.

  As a compound having two or more thermosetting functional groups in one molecule, an epoxy compound having two or more epoxy groups in one molecule is usually used. An epoxy compound having two or more epoxy groups in one molecule is an epoxy compound having two or more, preferably 2 to 50, more preferably 2 to 20 epoxy groups in one molecule (referred to as an epoxy resin). Is included). The epoxy group should just be a structure which has an oxirane ring structure, for example, can show a glycidyl group, an oxyethylene group, an epoxycyclohexyl group, etc. Examples of the epoxy compound include known polyvalent epoxy compounds that can be cured by carboxylic acid. Examples of such an epoxy compound include “Epoxy resin handbook” edited by Masaki Shinbo, published by Nikkan Kogyo Shimbun (Showa 62). These can be used widely.

  As an epoxy compound, in order to impart solvent resistance and heat resistance to the cured film, to increase the crosslink density of the polymer with a relatively high molecular weight and the cured film, or to improve the inkjet ejection performance by lowering the viscosity In addition, it is preferable to use a compound having a relatively low molecular weight in combination.

  As an epoxy compound that is a polymer having a relatively high molecular weight that is usually used as a binder component (hereinafter sometimes referred to as “binder epoxy compound”), at least the structural unit represented by the following formula (1) and the following formula ( A polymer composed of the structural unit represented by 2) and having two or more glycidyl groups can be used.

（Ｒ¹は水素原子または炭素数１〜３のアルキル基であり、Ｒ²は炭素数１〜１２
の炭化水素基である。）

(R ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ² is an alkyl group having 1 to 12 carbon atoms.
It is a hydrocarbon group. )

（Ｒ³は水素原子又は炭素数１〜１０のアルキル基である。）
式（１）で表される構成単位は、下記式（３）で表されるモノマーから誘導される。

(R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
The structural unit represented by the formula (1) is derived from a monomer represented by the following formula (3).

（Ｒ¹およびＲ²は式（１）と同じである。）

(R ¹ and R ² are the same as in formula (1).)

By using the monomer represented by the formula (3) as a constituent unit of the binder epoxy compound, sufficient hardness and transparency can be imparted to the cured coating film formed from the curable resin composition of the present invention. . In the formula (3), R ² is a hydrocarbon group having 1 to 12 carbon atoms, and may be any of a linear aliphatic, alicyclic, and aromatic hydrocarbon group, and an additional structure, For example, it may contain a double bond, a side chain of a hydrocarbon group, a side chain of a spiro ring, an intra-ring bridged hydrocarbon group, or the like.

  Specific examples of the monomer represented by the formula (3) include methyl (meth) acrylate, ethyl (meth) acrylate, i-propyl (meth) acrylate, n-propyl (meth) acrylate, and i-butyl (meth). Acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, Examples thereof include para-t-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and phenyl (meth) acrylate.

In formula (3), R ¹ is preferably hydrogen or a methyl group, and R ² is preferably an alkyl group having 1 to 12 carbon atoms. Among them, a methyl group and a cyclohexyl group are particularly preferable. Preferable examples of the monomer represented by the above formula (3) include methyl methacrylate (MMA) and cyclohexyl methacrylate (CHMA).

  The structural unit represented by the formula (2) in the polymer is derived from a monomer represented by the following formula (4).

（Ｒ³は式（２）と同じである。）

(R ³ is the same as in formula (2).)

  The monomer represented by the formula (4) is used for introducing an epoxy group (epoxy reaction point) into the polymer. The curable resin composition containing the polymer is excellent in storage stability, and hardly increases in viscosity during storage and discharge operation. One of the reasons is in formula (2) or formula (4). It is presumed that this is because the epoxy group is a glycidyl group. When an alicyclic epoxy acrylate is used instead of the monomer represented by formula (4), the viscosity of the curable resin composition tends to increase.

In the formula (4), R ³ is preferably hydrogen or a methyl group. Specific examples of the monomer represented by the formula (4) include glycidyl (meth) acrylate, and glycidyl methacrylate (GMA) is particularly preferable.

  The polymer may be a random copolymer or a block copolymer. Further, the polymer may contain main chain constituent units other than those of formula (1) or formula (2) as long as performance required for each detail of the color filter, such as hardness and transparency, can be ensured. Good. Specific examples of such a monomer include acrylonitrile and styrene.

  The content of the structural unit of formula (1) and the structural unit of formula (2) in the binder epoxy compound is derived from the monomer that derives the structural unit of formula (1) and the structural unit of formula (2). The weight ratio with the monomer to be charged (monomer that derives formula (1): monomer that derives formula (2)) is in the range of 10:90 to 90:10. preferable.

  When the amount of the structural unit of the formula (1) is more than the above ratio of 10:90, there is a possibility that the reaction point of curing decreases and the crosslinking density is lowered, whereas the structural unit of the formula (2) If the amount is more than the above ratio 90:10, the bulky skeleton may be reduced and curing shrinkage may be increased.

  The weight average molecular weight of the binder epoxy compound is preferably 3,000 or more, particularly 4,000 or more, when expressed in terms of polystyrene-converted weight average molecular weight. This is because if the molecular weight of the binder epoxy compound is less than 3,000, physical properties such as strength and solvent resistance required for the cured resin layer as details of the color filter are likely to be insufficient. On the other hand, in particular, when the curable resin composition according to the present invention is used as an ink jet ink, the binder epoxy compound has a weight average molecular weight of 20,000 or less when expressed in terms of polystyrene equivalent weight average molecular weight. It is preferable that it is 15,000 or less. If the molecular weight is more than 20,000, the viscosity is likely to increase, the stability of the ejection amount when ejected from the ejection head and the straightness in the ejection direction may be degraded, and the stability of long-term storage is degraded. Because there is a fear.

  As the binder epoxy compound, it is particularly preferable to use a glycidyl methacrylate (GMA) / methyl methacrylate (MMA) copolymer having a polystyrene-reduced weight average molecular weight (Mw) in the above range. The GMA / MMA copolymer may contain other monomer components as long as the object of the present invention can be achieved.

  As a synthesis example of the binder epoxy compound, for example, a solvent containing no hydroxyl group is charged into a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, and the temperature is raised to 120 ° C. while stirring. . The reason why a solvent containing no hydroxyl group is used is to avoid the decomposition of the epoxy group during the synthesis reaction. Next, a mixture of the monomer represented by the above formula (3), the monomer represented by the above formula (4), and a composition obtained by combining other monomers as necessary with a polymerization initiator (dropping component) is 2 Drop at a constant rate from the dropping funnel over time. After completion of the dropping, the temperature is lowered to 120 ° C., a catalyst is added, the reaction is performed for 3 hours, and the reaction is terminated when the temperature is raised to 130 ° C. and kept for 2 hours, whereby the binder epoxy compound is obtained.

  The thermosetting binder system according to the present invention is an epoxy compound having two or more epoxy groups in one molecule (hereinafter sometimes referred to as “polyfunctional epoxy compound”), which is more than the above-mentioned binder epoxy compound. However, it is preferable to add one having a low molecular weight. The polystyrene-reduced weight average molecular weight of the polyfunctional epoxy compound is preferably 4,000 or less, particularly preferably 3,000 or less, on the condition that it is smaller than the binder epoxy compound combined therewith.

  In addition, the polystyrene conversion weight average molecular weight of an epoxy compound can be calculated | required by GPC (gel permeation chromatography), As a measurement condition, tetrahydrofuran is used as a developing solution, for example, HLC-8029 (made by Tosoh Corporation) is used. Can be measured.

  Since the epoxy group (glycidyl group) is introduced into the binder epoxy compound by the structural unit represented by the formula (2), there is a limit to the amount of epoxy that can be introduced into the molecule of the copolymer. When a polyfunctional epoxy compound having a relatively small molecular weight is added to the curable resin composition, the epoxy group is replenished in the curable resin composition, the reaction point concentration of the epoxy is increased, and the crosslinking density can be increased.

  Among polyfunctional epoxy compounds, it is preferable to use an epoxy compound having four or more epoxy groups in one molecule in order to increase the crosslink density of the acid-epoxy reaction. In particular, when the curable resin composition of the present invention is used in an ink jet system, the weight average molecular weight of the binder epoxy compound is set to 10,000 or less in order to improve the discharge performance from the ink jet discharge head. In such a case, since the strength and hardness of the cured resin layer are likely to be lowered, it is preferable to sufficiently increase the crosslinking density by blending such a tetrafunctional or higher polyfunctional epoxy compound into the curable resin composition.

  The polyfunctional epoxy compound is not particularly limited as long as it contains two or more epoxy groups in one molecule. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, Bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, phenol novolac type epoxy resin, orthocresol novolak type epoxy resin, trishydroxyphenylmethane type epoxy Resin, trifunctional epoxy resin, tetraphenylolethane type epoxy resin, dicyclopentadienephenol type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A included Polyol type epoxy resins, polypropylene glycol type epoxy resins, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, glyoxal type epoxy resins, alicyclic epoxy resins, and the like heterocyclic epoxy resin.

  More specifically, bisphenol A type epoxy resins such as trade name Epicoat 828 (manufactured by Yuka Shell Epoxy), bisphenol F type epoxy resins such as trade name YDF-175S (manufactured by Tohto Kasei Co., Ltd.), trade name YDB-715 Brominated bisphenol A type epoxy resins (made by Toto Kasei Co., Ltd.), bisphenol S type epoxy resins such as trade name EPICLON EXA1514 (Dainippon Ink Chemical Co., Ltd.), trade name YDC-1312 (made by Toto Kasei Co., Ltd.), etc. Hydroquinone type epoxy resin, Naphthalene type epoxy resin such as trade name EPICLON EXA4032 (manufactured by Dainippon Ink and Chemicals), Biphenyl type epoxy resin such as trade name Epicoat YX4000H (made by Yuka Shell Epoxy), Trade name Epicoat 157S70 (oil) Shell Epoxy Bisphenol A type novolak epoxy resin, product name Epicoat 154 (manufactured by Yuka Shell Epoxy Co., Ltd.), product name YDPN-638 (manufactured by Tohto Kasei Co., Ltd.), phenol novolac type epoxy resin, product name YDCN-701 ( Cresol novolak type epoxy resin such as Toto Kasei Co., Ltd., dicyclopentadiene phenol type epoxy resin such as EPICLON HP-7200 (Dainippon Ink Chemical Co., Ltd.) Such as trishydroxyphenylmethane type epoxy resin, trifunctional epoxy resin such as trade name VG3101M80 (manufactured by Mitsui Chemicals), tetraphenylolethane type epoxy resin such as trade name Epicoat 1031S (manufactured by Yuka Shell Epoxy), Name Denako Tetrafunctional epoxy resin such as Le EX-411 (manufactured by Nagase Kasei Kogyo Co., Ltd.), hydrogenated bisphenol A type epoxy resin such as trade name ST-3000 (manufactured by Toto Kasei Co., Ltd.), trade name Epicoat 190P (Oka Chemical Shell Epoxy Co., Ltd.) Glycidyl ester type epoxy resin such as trade name YH-434 (manufactured by Tohto Kasei Co., Ltd.), glyoxal type epoxy resin such as trade name YDG-414 (manufactured by Tohto Kasei Co., Ltd.) Examples include alicyclic polyfunctional epoxy compounds such as GT-401 (manufactured by Daicel Chemical Industries), and heterocyclic epoxy resins such as triglycidyl isocyanate (TGIC). Further, if necessary, a trade name Neotote E (manufactured by Toto Kasei Co., Ltd.) can be mixed as an epoxy reactive diluent.

  Among these polyfunctional epoxy compounds, bisphenol A type novolac epoxy resins such as trade name Epicoat 157S70 (manufactured by Yuka Shell Epoxy Co., Ltd.) and cresol novolac type epoxies such as trade name YDCN-701 (manufactured by Tohto Kasei Co., Ltd.) Resins are particularly preferred.

  The thermosetting binder system used in the present invention is usually combined with a curing agent. As the curing agent, for example, a polyvalent carboxylic acid anhydride or a polyvalent carboxylic acid is used.

  Specific examples of polyhydric carboxylic acid anhydrides include phthalic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, hexahydrophthalic anhydride, dimethyltetrahydro anhydride Aliphatic or alicyclic dicarboxylic anhydrides such as phthalic acid, hymic anhydride, and nadic anhydride; fats such as 1,2,3,4-butanetetracarboxylic dianhydride and cyclopentanetetracarboxylic dianhydride Aromatic polycarboxylic dianhydrides; aromatic polycarboxylic anhydrides such as pyromellitic anhydride, trimellitic anhydride, and benzophenone tetracarboxylic anhydride; ester groups such as ethylene glycol bistrimellitate and glycerin tristrimitate Containing acid anhydrides, particularly preferably aromatic poly It may be mentioned carboxylic acid anhydrides. Moreover, the epoxy resin hardening | curing agent which consists of a commercially available carboxylic acid anhydride can also be used suitably.

  Specific examples of the polyvalent carboxylic acid used in the present invention include aliphatic polyvalent carboxylic acids such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid, and itaconic acid; hexahydrophthalic acid, Aliphatic polycarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid, and phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, Aromatic polyvalent carboxylic acids such as 1,4,5,8-naphthalenetetracarboxylic acid and benzophenonetetracarboxylic acid can be mentioned, and aromatic polyvalent carboxylic acids can be mentioned preferably.

  These polyvalent carboxylic acid anhydrides and polyvalent carboxylic acids can be used singly or in combination of two or more. The compounding quantity of the hardening | curing agent used for this invention is the range of 1-100 weight part normally per 100 weight part of components (monomer and resin) containing an epoxy group, Preferably it is 5-50 weight part. When the blending amount of the curing agent is less than 1 part by weight, curing becomes insufficient and a tough coating film cannot be formed. Moreover, when the compounding quantity of a hardening | curing agent exceeds 100 weight part, while the adhesiveness with respect to the board | substrate of a coating film is inferior, a uniform and smooth coating film cannot be formed.

In order to improve the hardness and heat resistance of the cured resin layer, a catalyst capable of promoting an acid-epoxy thermosetting reaction may be added to the thermosetting binder system of the present invention. As such a catalyst, a thermal latent catalyst that exhibits activity during heat curing can be used.
The heat-latent catalyst exhibits catalytic activity when heated, accelerates the curing reaction and gives good properties to the cured product, and is added as necessary. The thermal latent catalyst is preferably one that exhibits acid catalytic activity at a temperature of 60 ° C. or higher. As such, a compound obtained by neutralizing a protonic acid with a Lewis base, a compound obtained by neutralizing a Lewis acid with a Lewis base, Lewis Examples thereof include a mixture of an acid and a trialkyl phosphate, sulfonic acid esters, onium compounds and the like, and various compounds described in JP-A-4-218561 can be used. Specifically, (i) compounds obtained by neutralizing halogenocarboxylic acids, sulfonic acids, phosphoric acid mono- and diesters with various amines such as ammonia, monomethylamine, triethylamine, pyridine, ethanolamine, or trialkylphosphine (B) compounds obtained by neutralizing Lewis acids such as BF ₃ , FeCl ₃ , SnCl ₄ , AlCl ₃ , ZnCl ₂ with the aforementioned Lewis base, (c) methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, etc. Examples include primary alcohols, ester compounds with secondary alcohols, (d) primary alcohols, secondary monoalcohol phosphate monoester compounds, and phosphate diester compounds. Examples of the onium compound include an ammonium compound [R ₃ NR ′] ⁺ X ⁻ , a sulfonium compound [R ₃ SR ′] ⁺ X ⁻ , and an oxonium compound [R ₃ OR ′] ⁺ X ⁻ . Here, R and R ′ are alkyl, alkenyl, aryl, alkoxy and the like.

  Of the binder components as described above, the cured product composed only of organic components in the solid content of the composition is cured so that the elastic deformation ratio in the indentation test according to ISO-14577 tends to be 40% or more. Examples of an index for selecting a binder component such that the elastic deformation ratio in the indentation test according to 14577 can be 40% or more include the following.

  It is preferable that the number of cross-linking elements in the entire binder component is large. This is because the higher the degree of cross-linking, the easier the elastic deformation ratio is to be 40% or more. Therefore, for example, when only a photocurable resin is included as the curable resin, the ethylenically unsaturated bond is an ethylenically unsaturated bond equivalent of 1200 g / eq or less, more preferably the ethylenically unsaturated bond is an ethylenically unsaturated bond. It is preferable that the photocurable resin having a saturated bond equivalent at a rate of 800 g / eq or less is 30% by weight or more and further 50% by weight or more in the whole binder component.

Further, when only the thermosetting resin is included as the curable resin, the molecular weight between crosslinks is 300 or less, more preferably, the thermosetting resin having a molecular weight between crosslinks of 250 or less is 30% by weight or more in the whole binder component, Further, it is preferably 50% by weight or more. Here, the molecular weight between crosslinks is a value obtained by dividing the average molecular weight by the average number of functional groups. Berger's formula (molecular weight between crosslinks: M _c = M ₀ / (xF ₀ -2), where M ₀ Is calculated by the average molecular weight per molecule, x is the reaction rate (x ≦ 1), and F ₀ is the average number of functional groups per molecule. Since two functional groups per molecule are used for chain extension, the amount is subtracted for calculation.

  Further, when both a photocurable resin and a thermosetting resin are included as the curable resin, the ethylenically unsaturated bond is an ethylenically unsaturated bond equivalent of 1200 g / eq or less, more preferably ethylenically unsaturated. A total amount of a photocurable resin having a bond at an ethylenically unsaturated bond equivalent ratio of 800 g / eq or less and a thermosetting resin having a molecular weight between crosslinks of 300 or less, more preferably a molecular weight between crosslinks of 250 or less. It is preferable to have 50% by weight or more, and more preferably 60% by weight or more in the whole binder component. The curable resin contained in the binder component preferably includes both a photocurable resin and a thermosetting resin.

  Moreover, it is preferable that the weight average molecular weight of the whole binder component is high, or the binder component whole contains many components with a high average molecular weight. Accordingly, the weight average molecular weight of the entire binder component is preferably 3000 or more, and more preferably 4000 or more. Further, it is preferable that a component having a weight average molecular weight of 8000 or more is contained in the binder component by 30% by weight or more, more preferably 50% by weight or more. In addition, the weight average molecular weight in this invention is calculated | required by polystyrene conversion in GPC measurement.

  Moreover, it is preferable that Tg of the whole binder component is high or a binder component contains many components with high Tg. Therefore, it is preferable that Tg of a binder component is 20 degreeC or more or 30 degreeC or more. Further, it is preferable that a component having a Tg of 30 ° C. or higher is contained in the binder component by 30% by weight or more, and further by 50% by weight or more.

  As described above, in the curable resin composition for a color filter according to the present invention, the binder component including the curable resin as an essential component has been described. However, the curable resin composition for a color filter according to the present invention is usually coated. A solvent is included in order to impart properties. The color filter curable resin composition used for forming a colored layer or a black matrix layer usually further contains a pigment or a pigment dispersant. Further, other components may be included.

(Pigment)
The pigment as the colorant should be selected from the organic colorants and inorganic colorants according to the color required by the color layer (pixel part) R, G, B, etc. and the black matrix layer. Can do. As the organic colorant, for example, dyes, organic pigments, natural pigments, and the like can be used. Moreover, as an inorganic coloring agent, an inorganic pigment, an extender pigment, etc. can be used, for example. Among these, organic pigments are preferably used because they have high color developability and high heat resistance. As organic pigments, for example, compounds classified as Pigments in the Color Index (CI; published by The Society of Dyers and Colorists), specifically, the following Color Index (CI) numbers are attached. Can be mentioned.

  CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI Pigment Yellow 65, CI Pigment Yellow 71, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment .... DOO Yellow 155, C.I Pigment Yellow 156, C.I Pigment Yellow 166, C.I Pigment Yellow 168, C.I Pigment Yellow 175;

  CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73; CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Buy Olet 32, C.I. pigment violet 36, C.I. pigment violet 38;

  CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 8, CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 11, CI Pigment Red 12, CI Pigment Red 14, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 17, CI Pigment Red 18, CI Pigment Red 19, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 30, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 37, CI Pigment Red 38, CI Pigment Red 40, CI Pigment Red 41, CI Pigment Red 42, CI Pigment Red 48: 1, CI Pigment Red 48: 2, CI Pigment Red 48: 3, CI Pigment Red 48: 4, CI Pigment Red 49: 1, CI Pigment Red 49: 2, CI CI Pigment Red 50: 1, CI Pigment Red 52: 1, CI Pigment Red 53: 1, CI Pigment Red 57, CI Pigment Red 57: 1, CI Pigment Red 57: 2, CI Pigment Red 58: 2, CI Pigment Red 58 : 4, CI Pigment Red 60: 1, CI Pigment Red 63: 1, CI Pigment Red 63: 2, CI Pigment Red 64: 1, CI Pigment Red 81: 1, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90: 1, CI pigmentless 97, CI Pigment Red 101, CI Pigment Red 102, CI Pigment Red 104, CI Pigment Red 105, CI Pigment Red 106, CI Pigment Red 108, CI Pigment Red 112, CI Pigment Red 113, CI Pigment Red 114, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 151, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 174, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 77, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 193, CI Pigment Red 194, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 245, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red . 64, C.I Pigment Red 265;

  CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Blue 60; CI Pigment Green 7, CI Pigment Green 36; CI Pigment Brown 23, CI Pigment Brown 25 CI pigment black 1, pigment black 7.

  Specific examples of the inorganic pigment or extender pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red rose (red iron oxide (III)), cadmium red, ultramarine blue, Examples include bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, and carbon black. In this invention, a pigment can be used individually or in mixture of 2 or more types.

  When forming the pattern of the black matrix layer on the substrate of the color filter using the curable resin composition of the present invention, a black pigment having high light shielding properties is blended in the curable resin composition. As the black pigment having a high light shielding property, for example, an inorganic colorant such as carbon black or iron trioxide, or an organic colorant such as cyanine black can be used.

  Ink layers formed of a curable resin composition containing a pigment having a high light-shielding property make it difficult for light to reach the inside, so the pattern of the black matrix layer is formed using the curable resin composition of the present invention. For this, it is preferable to use a thermosetting binder system rather than a photocurable binder system. However, it can be cured by light by adjusting the curing method such as increasing the thickness of the ink layer and the exposure time.

  When forming the colored layer, the pigment is usually blended in a proportion of 1 to 60% by weight, preferably 15 to 40% by weight, based on the total solid content of the curable resin composition. When there are too few pigments, there exists a possibility that the permeation | transmission density | concentration at the time of apply | coating curable resin composition to predetermined | prescribed film thickness (usually 0.1-2.0 micrometers) may not be enough. In addition, if there are too many pigments, the coating properties such as adhesion to the substrate when the curable resin composition is applied and cured on the substrate, surface roughness of the cured film, and coating film hardness are insufficient. There is a risk of becoming.

(Pigment dispersant)
The pigment dispersant is blended as necessary in the curable resin composition in order to disperse the pigment satisfactorily. Examples of the pigment dispersant that can be used include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. Among the surfactants, polymer surfactants (polymer dispersants) as exemplified below are preferable.

  That is, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl phenyl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether Polymeric surfactants such as polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes are preferably used.

  The heat resistance of the pigment dispersant is preferably higher because wrinkles and cracks are less likely to occur. For the heat resistance of the pigment dispersant, for example, the glass transition temperature (Tg) can be used as one index. The glass transition temperature (Tg) of the pigment dispersant used in the present invention is preferably 70 ° C. or higher, more preferably 150 ° C. or higher, and particularly preferably 180 ° C. or higher. When two or more peaks indicating Tg appear in the Tg measurement, the peak area of the chart, that is, the peak area that protrudes from the base line is the representative value of the sudden change point from the viewpoint of heat resistance. The glass transition temperature (Tg) can be measured by DSC method.

  Further, the heat resistance of the pigment dispersant can be determined by a test of whether or not to melt by performing a heat treatment at 70 ° C. for 30 minutes (hereinafter sometimes referred to as “melting test”). The pigment dispersant used in the present invention is preferably one that does not melt when subjected to a heat treatment at 70 ° C. for 30 minutes, and more preferably a solid state in which no tack appears. In this melting test, it is more preferable not to melt under heating conditions of 150 ° C. for 30 minutes, and it is particularly preferable not to melt under heating conditions of 180 ° C. for 30 minutes.

(Other ingredients)
Further, the curable resin composition for a color filter of the present invention may contain one or more other additives as required. The following can be illustrated as such an additive. Among them, in the present invention, a cured product consisting only of organic components in the solid content of the composition is cured under curing conditions such that the elastic deformation ratio in an indentation test according to ISO-14577 is 40% or more to form a cured resin film. Thus, from the viewpoint of preventing wrinkles and cracks, it is preferable to supplement the adhesion, and it is preferable to add an adhesion promoter.

a) Filler: For example, glass, alumina and the like.
b) Adhesion promoter: for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane.
c) Ultraviolet absorber: For example, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like.
d) Anti-aggregation agent: for example, sodium polyacrylate or various surfactants.
e) Leveling agent: For example, commercially available silicon-based, polyoxyalkylene-based, fatty acid ester-based, special acrylic-based polymer, and the like.

(Organic solvent)
In order to prepare the curable resin composition for a color filter of the present invention into a high-concentration ink for storage or an ink that can be applied immediately, an organic solvent that suitably dissolves and disperses the solid content, There is no particular limitation.

  In particular, when the curable resin composition for a color filter of the present invention is applied to an ink jet method, the boiling point is 180 ° C. to 260 ° C., particularly 210 ° C. to 260 ° C., in order to improve the dischargeability from the head. In addition, a solvent component having a vapor pressure of 0.5 mmHg or less, particularly 0.1 mmHg or less at room temperature (particularly in the range of 18 ° C. to 25 ° C.) is used as the main solvent, and such main solvent is used with respect to the total amount of the organic solvent. It is preferable to blend in a proportion of not less than mass%, particularly not less than 85 mass%. The surface tension of the main solvent is preferably 29 dyn / cm or more.

  A solvent component having a boiling point of 180 ° C. to 260 ° C. and a vapor pressure at room temperature of 0.5 mmHg or less has an appropriate drying property and evaporation property. For this reason, when a single solvent or mixed solvent containing such a solvent component at a high blending ratio is used, the ink does not dry rapidly at the nozzle tip of the ejection head in the case of an ink jet ink, so that the viscosity of the ink increases rapidly. Clogging does not occur, and there is no adverse effect on the straightness and stability of discharge. At the same time, since the drying proceeds at an appropriate speed after spraying on the surface to be ejected, the ink becomes familiar with the surface to be coated and the surface of the coating film becomes horizontal and smooth, followed by natural drying or a general heating process. The ink can be dried quickly and completely. Compared to the case of using a wetting agent or a solvent having a very high boiling point, there is less possibility that the solvent remains in the coating film after the drying step.

  Even if it is a case where it applies to an inkjet system, the organic solvent may contain the solvent components other than the main solvent as needed if it is a small amount. However, even in that case, it is preferable to use the main solvent having the above boiling point and vapor pressure at a ratio of 80% by mass or more based on the total amount of the solvent. When the ratio of the main solvent is less than 80% by mass of the total amount of the solvent, there are cases where it is not possible to reliably obtain the drying property and the evaporation property suitable for the ink jet method.

  The main solvent is desirably used at the highest possible blending ratio, specifically, at least 80% by mass or more, preferably 85% by mass or more, and desirably 100% by mass as much as possible.

  By forming a wettability variable layer on the substrate surface and exposing it, an ink-philic region is formed on a portion of the substrate where an ink layer is desired to be formed, and the curable resin composition of the present invention is formed in the ink-philic region by an inkjet method. Is used as a main solvent, the standard solution shown in the wettability test specified in JIS K6768 is used, and the contact angle (θ) after 30 seconds is measured after contacting the droplets, The contact angle with respect to the surface of the test piece having a critical surface tension of 30 mN / m determined from the Zisman plot graph is 25 ° or more, preferably 30 ° or more, and the critical surface tension obtained by the same measurement method is 70 mN / m. You may select and use what shows the contact angle with respect to the surface of the test piece of m of 10 degrees or less.

  When an ink is prepared using a solvent that exhibits the above behavior with respect to wettability, the ink exhibits a large repellent property with respect to the surface of the wettability variable layer before changing the wettability of the wettability variable layer described later. After changing the wettability of the wettability variable layer to increase the hydrophilicity, the wettability variable layer shows a great affinity for the surface of the wettability variable layer. Therefore, the difference between the wettability of the ink with respect to the ink-philic region formed by selectively exposing a part of the surface of the wettability variable layer and the wettability of the ink repellent region with respect to the surrounding region can be increased. As a result, the ink sprayed onto the ink-philic area by the ink jet method spreads evenly to every corner of the ink-philic area. As a result, a fine and precise ink layer pattern can be formed by the inkjet method.

  Here, the test piece having the above characteristics with respect to the critical surface tension may be formed of any material. Examples of test pieces having a critical surface tension of 30 mN / m include, for example, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate having a smooth surface, and the polymer or surface modifier applied on a smooth glass surface. The above test can be actually performed from among those, and the corresponding one can be selected. Moreover, as a test piece which shows critical surface tension 70mN / m, the said test is actually performed from what apply | coated nylon, the glass surface which hydrophilized, etc., and the applicable thing can be selected.

  The main solvent can be selected from the following solvents: ethylene glycol monoethyl ether, glycol ethers such as diethylene glycol diethyl ether; glycol ether esters such as ethylene glycol monomethyl ether acetate; diethylene glycol Glycol oligomer ethers such as monomethyl ether; glycol oligomer ether esters such as diethylene glycol monomethyl ether acetate; aliphatic or aromatic esters such as ethyl acetate, propyl benzoate; dicarboxylic acid diesters such as diethyl carbonate; Alkoxycarboxylates such as methyl 3-methoxypropionate; ketocarboxylates such as ethyl acetoacetate; ethanol Alcohols or phenols such as isopropanol and phenol; aliphatic or aromatic ethers such as diethyl ether and anisole; alkoxy alcohols such as 2-ethoxyethanol and 1-methoxy-2-propanol; diethylene glycol and tripropylene Glycol oligomers such as glycol; alkoxy alcohol esters such as 2-ethoxyethyl acetate; ketones such as acetone and methyl isobutyl ketone.

  In addition, when a pigment is contained in the curable resin composition for a color filter according to the present invention, as a main solvent occupying most of the organic solvent, particularly the solvent, from the viewpoint of dispersibility of the pigment, dispersion stability, It is preferable to use one that does not contain a hydroxyl group.

  Preferred solvents include ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethyl adipate, dibutyl oxalate, dimethyl malonate, diethyl malonate, succinate Examples thereof include dimethyl acid and diethyl succinate. These solvents are preferable not only because they satisfy the requirements of a boiling point of 180 ° C. to 260 ° C. and a vapor pressure at room temperature of 0.5 mmHg or less, but also have no hydroxyl group in the molecule. Furthermore, these solvents are mixed with or without mixing with highly dispersible solvents conventionally used for preparing pigment dispersions such as 3-methoxybutyl acetate and propylene glycol monomethyl ether acetate (PGMEA). It can be used as a solvent to prepare a pigment dispersion.

  The above-mentioned solvent exemplified as a preferable example uses a standard solution shown in the wettability test specified in JIS K6768, measures the contact angle (θ) 30 seconds after contacting a droplet, The contact angle with respect to the surface of the test piece having a critical surface tension of 30 mN / m determined by the above is 25 ° or more, and the contact angle with respect to the surface of the test piece having a critical surface tension of 70 mN / m determined by the same measurement method is 10 Also meets the requirement to show below. Therefore, these solvents are used when a wettable variable layer is provided on the surface of the substrate for exposure, and the curable resin composition is selectively attached using the difference in wettability between the exposed and unexposed areas. Can also be suitably used as the main solvent.

  Further, when water is mixed in the solvent, the hydroxyl group of the water molecule is present in the solvent, so that the same problem as in the case of using the solvent having a hydroxyl group may be caused. Therefore, in order to substantially exclude moisture from the acid-epoxy crosslinking reaction system, it is preferable to prepare the curable resin composition using an organic solvent having low miscibility with water. From this viewpoint, the solubility of the solvent for preparing the curable resin composition in water is preferably 20 parts by weight or less with respect to 100 parts by weight of water having a liquid temperature of 20 ° C.

  Among the main solvents mentioned as specific examples, diethylene glycol monobutyl ether acetate does not have a hydroxyl group, and the solubility in 100 parts by weight of water at a liquid temperature of 20 ° C. is low at 6.5 parts by weight. It is particularly preferable since it exhibits the property.

  The organic solvent is usually used at a ratio of 40 to 95% by mass with respect to the total amount of the curable resin composition containing the solvent to prepare the curable resin composition. When the amount of the solvent is too small, the viscosity of the curable resin composition is high, and in the case of inkjet ink, it becomes difficult to eject from the inkjet head. If there is too much solvent, the ink film deposited on the wettability change site will be broken before the ink deposit amount (ink deposition amount) for the predetermined wettability change site (ink layer formation site) is not sufficient, It protrudes to the surrounding unexposed area and further spreads to the adjacent wettability change site (ink layer forming site). In other words, the amount of ink that can be deposited without protruding from the wettability change site (ink layer forming site) to which the ink is to be deposited becomes insufficient, the film thickness after drying is too thin, The transmission density cannot be obtained.

(Method for producing composition)
The curable resin composition for a color filter of the present invention is produced by mixing a binder component with other compounding components, if necessary, into a single solvent or a solvent that is a mixed solvent, and dissolving or dispersing the solid component. You may do it.

  However, when a pigment is included, if the pigment is directly put into the whole solvent together with other components such as a binder component and stirred and mixed, the pigment cannot often be sufficiently dispersed in the solvent. Therefore, usually, a solvent having good dispersibility and dispersion stability of the pigment is prepared, and the pigment is added thereto together with the dispersant, and sufficiently stirred with a dissolver or the like to prepare a pigment dispersion. Then, the obtained pigment dispersion, together with the components other than the pigment, is put into a solvent consisting essentially of the main solvent or consisting only of the main solvent, and sufficiently stirred and mixed with a dissolver or the like, thereby curing according to the present invention. Resin composition.

  The remaining solvent into which the pigment dispersion is charged has a composition obtained by subtracting the solvent used for the preparation of the pigment dispersion from the total composition of the final solvent, and is diluted to the final concentration and cured. A resin composition may be completed. Further, a high concentration curable resin composition may be prepared by introducing the pigment dispersion into a relatively small amount of the main solvent. The high-concentration curable resin composition can be stored as it is, diluted to the final concentration just before use, and used in the ink jet system.

  In the present invention, in particular, when a blending ratio of a solvent component having a boiling point of 180 ° C. to 260 ° C. and a vapor pressure at room temperature of 0.5 mmHg or less as a main solvent is used by 90% by weight or more of the whole solvent, pigment dispersion In preparing the liquid, there may be a case where a sufficient amount of a conventionally used dispersion solvent such as 3-methoxybutyl acetate or propylene glycol monomethyl ether acetate (PGMEA) cannot be used. In that case, select a solvent with relatively good dispersibility and dispersion stability from among the solvents that can be used as the main solvent, and use a solvent mixed with the conventionally used dispersion solvent as the dispersion solvent. Alternatively, the main solvent is used as a dispersion solvent as it is.

(Physical properties of cured film)
The cured film formed using the curable resin composition according to the present invention has an elastic deformation ratio of 40% or more in an indentation test according to ISO-14577 of a cured product composed only of organic components in the solid content of the composition. By curing the composition under the curing conditions, the cured film of the composition is less likely to be wrinkled or cracked. The surface roughness (Ra) of the cured film obtained by curing the composition under the condition that the elastic deformation ratio in the indentation test according to ISO-14577 is 40% or more is 10 nm or less, and The thickness is preferably 8 nm or less, and particularly preferably 5 nm or less.

Further, when the curable resin composition according to the present invention contains a photocurable resin after curing, it is further irradiated with light at an illuminance of 30 mW / cm ^{2 in} terms of 365 nm using an ultrahigh pressure mercury lamp as a light source. Before and after irradiation and heating at 240 ° C. for 60 minutes, or when containing only a thermosetting resin as the curable resin, the amount of change in the cross-linking element is within the measurement error range before and after heating at 240 ° C. for 60 minutes. And that the elastic deformation ratio in the indentation test according to ISO-14577 is increased because the inorganic material thin film is less likely to be wrinkled or cracked due to thermal expansion and contraction of the cured film during the inorganic material film formation. preferable. The measurement error range here is the same as described above.

  In addition, the cured film formed using the curable resin composition according to the present invention has an elastic deformation ratio of 40% in an indentation test according to ISO-14577 of a cured product composed only of organic components in the solid content of the composition. Even when the composition is cured under the above curing conditions, for example, the elastic deformation ratio in the indentation test according to ISO-14577 is not less than 40% because it is affected by other compounding components such as inorganic pigments. Don't be.

  The curable resin composition for a color filter according to the present invention can produce a cured film by various methods, but the ink jet method is used from the viewpoint of drastically reducing the cost and the discharge amount of waste liquid and waste gas. It is preferably selected and used, and can be suitably used as an ink-jet ink.

2. Color filter The color filter according to the present invention includes a transparent substrate and a colored layer provided on the transparent substrate, and may further include a cured resin film on the colored layer and / or the colored layer. A color filter comprising an inorganic material thin film adjacent to a colored layer and / or the cured resin film, wherein the colored layer and / or the cured resin film cures the curable resin composition for a color filter according to the present invention. It is characterized by being formed.

  Here, examples of the cured resin film provided on the colored layer and / or on the colored layer include a black matrix, a protective film, and an inkjet type partition.

  The color filter according to the present invention is formed by curing the curable resin composition for a color filter according to the present invention, wherein the resin cured film such as the colored layer and / or the black matrix, the protective film, and the partition wall is cured. Therefore, the colored layer using the curable resin composition and / or the cured resin film such as a black matrix, a protective film, and a partition for an ink jet system are not easily wrinkled or cracked. An inorganic material thin film adjacent to any of the above is unlikely to be wrinkled or cracked. Therefore, the color filter according to the present invention is free from the problem of conduction due to wrinkles and cracks and the problem of image defects, and has reduced display defects. Among these, when the colored layer and the protective film are further provided, the protective film is formed by curing the curable resin composition for a color filter according to the present invention. This is effective because the contact area with an adjacent layer such as an inorganic material thin film is large.

  FIG. 2 is a longitudinal sectional view showing an example (color filter 103) of the color filter according to the present invention. In this example, the inorganic material thin film in the present invention is a transparent electrode film, but may be an antireflection film or another functional film instead of the transparent electrode film.

  The color filter 103 covers a black matrix 6 formed in a predetermined pattern on the transparent substrate 5, a colored layer 7 (7R, 7G, 7B) formed in a predetermined pattern on the black matrix, and the colored layer. The protective film 8 formed in this way is provided. A transparent electrode film 9 for driving liquid crystal is formed on the protective film 8. An alignment film 10 is formed on the innermost surface of the color filter 103, in this case on the transparent electrode.

  The columnar spacer 12 is a shape of a convex spacer, and is formed at a plurality of predetermined locations (five locations in FIG. 2) on the transparent electrode 9 in accordance with the region (non-display region) where the black matrix layer 6 is formed. ing. The columnar spacer 12 is formed on the transparent electrode 9, the colored layer 7, or the protective film 8. In the color filter 102, columnar spacers are formed in a sea-island shape on the protective film 8 via the transparent electrode film 9, but the protective film 8 and the columnar spacer 12 are integrally formed and covered thereover. A transparent electrode film 9 may be formed. Further, when the color filter does not include a black matrix layer, columnar spacers can be formed in a region where the colored layer is not formed.

(Transparent substrate)
The transparent substrate 5 is not particularly limited as long as it is conventionally used for a color filter. For example, the transparent substrate 5 is not transparent, such as quartz glass, Pyrex (registered trademark) glass, or synthetic quartz plate. A transparent material having flexibility such as a rigid material, a transparent resin film, an optical resin plate, or the like can be used. Among them, Corning 7059 glass is a material having a small coefficient of thermal expansion, excellent dimensional stability and workability in high-temperature heat treatment, and is an alkali-free glass containing no alkali component in the active matrix. Suitable for color filters for color liquid crystal display devices. In the present invention, a transparent substrate is usually used, but a reflective substrate or a white colored substrate can also be used. Moreover, you may use the board | substrate which surface-treated for the purpose of alkali elution prevention, gas-barrier provision, and other purposes as needed.

(Colored layer)
The colored layer 7 is preferably formed using the curable resin composition according to the present invention from the viewpoint that wrinkles and cracks are not easily generated in adjacent layers. Such a colored layer is usually formed of three colors of red (R), green (G), and blue (B). The colored pattern shape in the colored layer can be a known arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type, and the colored area can be arbitrarily set.

  In the present invention, the method for forming the colored layer is not particularly limited. For example, a pigment dispersion method, a dyeing method, and a printing method using photolithography using the curable resin composition according to the present invention. In the present invention, as described later, the curable resin composition according to the present invention is preferably used to form the ink-jet method. This is because the colored layer can be formed with high definition.

(Black matrix layer)
The black matrix layer 6 is provided so as to surround between the colored layers 7R, 7G, and 7B and the outside of the colored layer forming region in order to improve the contrast of the display image. As a method of forming the black matrix layer 6, there are a method of using either a metal thin film or a light shielding resin and a photosensitive resist, and a method of using a curable resin composition containing light shielding particles. In the present invention, the black matrix layer 6 is preferably formed using the curable resin composition according to the present invention containing light-shielding particles from the viewpoint that wrinkles and cracks hardly occur in adjacent layers.

(Protective film)
The protective film 8 is provided to flatten the surface of the color filter and prevent the components contained in the colored layer 7 from eluting into the liquid crystal layer. The protective film 8 is formed by applying a transparent curable resin composition so as to cover the black matrix layer 6 and the colored layer 7 by a method such as a spin coater, a roll coater, a spray, or a printing, and is cured by light or heat. Can be formed. As the transparent curable resin composition for forming the protective film, it is preferable to use the transparent curable resin composition according to the present invention. When the curable resin composition according to the present invention is used, it is possible to form a protective film that hardly causes wrinkles and cracks in adjacent layers.

(Partition wall)
The partition for the ink jet system will be described in the description of the ink jet system in the manufacturing method described later.

(spacer)
A plurality of convex spacers are provided in a non-display area on the substrate in order to maintain a cell gap when the color filter 103 is bonded to a liquid crystal driving side substrate such as a TFT array substrate. The shape and size of the convex spacer are not particularly limited as long as it can be selectively provided in a non-display region on the substrate and can maintain a predetermined cell gap over the entire substrate. When the columnar spacer 12 as shown in the figure is formed as the convex spacer, it has a certain height in the range of about 2 to 10 μm, and the protruding height (pattern thickness) is required for the liquid crystal layer. It can set suitably from thickness etc. Moreover, the thickness of the columnar spacer 12 can be appropriately set within a range of about 5 to 20 μm. Further, the formation density (density) of the columnar spacers 12 can be appropriately set in consideration of the thickness unevenness of the liquid crystal layer, the aperture ratio, the shape and material of the columnar spacers, for example, red, green and blue Necessary and sufficient spacer function is expressed at a ratio of one for each pixel. The shape of such a columnar spacer may be a columnar shape, and may be, for example, a columnar shape, a prismatic shape, a truncated cone shape, or the like.

  The convex spacer may be formed using the curable resin composition according to the present invention. That is, first, the coating liquid of the curable resin composition according to the present invention is applied directly on a transparent substrate by a method such as a spin coater, roll coater, spray, printing, or through another layer such as a transparent electrode. And drying to form a curable resin layer. The rotational speed of the spin coater may be set within a range of 500 to 1500 revolutions / minute, as in the case of forming the protective film. Usually, a photo-curable resin composition is preferably used as the curable resin composition for forming the spacer. Therefore, the resin layer is then exposed through a photomask for convex spacers, and an alkali solution is used. A predetermined convex pattern is formed by developing with a developing solution, and the convex spacer is formed by subjecting this convex pattern to heat treatment (post-baking) in a clean oven or the like as necessary.

  The convex spacer can be provided directly on the color filter or indirectly through another layer. For example, a transparent electrode such as ITO or a protective film may be formed on the color filter, and a convex spacer may be formed thereon, or a protective film and a transparent electrode may be formed on the color filter in this order, and the transparent electrode A convex spacer may be formed on the top.

(Inorganic material thin film)
In the color filter according to the present invention, the inorganic material thin film is provided adjacent to any of the colored layer, the black matrix, the protective film, the partition walls, and the like. In the present invention, “adjacent” may be adjacent to each other or may be adjacent to each other via other layers.

  In the color filter according to the present invention, one embodiment of the inorganic material thin film is the transparent electrode film 9, but it may be an antireflection film or another functional film.

  The surface roughness (Ra) of the inorganic material thin film in the color filter according to the present invention is preferably 10 nm or less, more preferably 8 nm or less, and particularly preferably 5 nm or less. This is because in the inorganic material thin film, an adjacent colored layer, black matrix, protective film, partition walls, and the like are formed using the curable resin composition according to the present invention, so that wrinkles and cracks are hardly generated.

  The transparent electrode film 9 can be formed using indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO), or an alloy thereof.

  When the inorganic material thin film is an antireflection film, it can be formed using, for example, silica or indium tin oxide (ITO).

  In addition, examples of the functional layer made of other inorganic material thin film include, but are not limited to, a capacitor, an optical element, a sensor, and a translucent electrode.

(Other layers)
Other members usually formed on the color filter may be further included. The alignment film and other members can be formed by a usual method using those usually used for color filters. In the case of a member made of a cured resin film, where wrinkles between adjacent layers become a problem, it is preferably formed using the curable resin composition according to the present invention.

3. Liquid crystal panel A liquid crystal panel according to the present invention is a liquid crystal panel in which a display side substrate and a liquid crystal driving side substrate are opposed to each other, and liquid crystal is sealed therebetween, and the display side substrate is a color according to the present invention. It is a filter.

  When the color filter 103 (display side substrate) obtained as described above and the TFT array substrate (liquid crystal drive side substrate) are opposed to each other and the inner peripheral side peripheral portions of both the substrates are bonded with a sealant, the two substrates are separated by a predetermined distance. Are bonded together with the cell gap maintained. An active matrix color liquid crystal display device belonging to the liquid crystal panel according to the present invention is obtained by filling the liquid crystal in the gap between the substrates and sealing the liquid crystal.

  Since other configurations and manufacturing methods in the liquid crystal panel can use commonly used configurations and methods, description thereof is omitted here.

  As described above, when the colored layer, the black matrix layer, the protective film, the spacer, and the like of the color filter for a display panel such as a liquid crystal panel are formed using the curable resin composition according to the present invention, the subsequent transparent A colored layer formed by using the curable resin composition according to the present invention, a black matrix layer, even when exposed to a high temperature and an ultra-low pressure due to vacuum in a process of forming an inorganic material thin film such as an electrode film or an adjacent layer, Since the protective film and spacer are less likely to cause wrinkles or cracks, it is possible to avoid the problem of distorting the adjacent layer such as the transparent electrode film and generating wrinkles on the surface thereof, and a color filter and display panel with few display defects Is obtained.

4). The manufacturing method of the laminated body of resin cured film and an inorganic material thin film The manufacturing method of the laminated body of resin cured film and an inorganic material thin film which concerns on this invention is a curable resin composition on a board | substrate. A process of forming a cured resin film by curing under a condition that an elastic deformation ratio in an indentation test according to ISO-14577 of a cured product composed only of organic components is 40% or more, and forming an inorganic material thin film on the cured resin film The process of carrying out.

  In the method for producing a laminate of a cured resin film and an inorganic material thin film according to the present invention, a curable resin composition is pressed onto a substrate by injecting a cured product consisting only of organic components in the solid content of the composition with ISO-14577. By having a step of forming a cured resin film by curing under the condition that the elastic deformation ratio in the test is 40% or more, the formed cured resin film is less likely to cause wrinkles and cracks. Even if an inorganic material thin film is further formed, wrinkles and cracks are hardly generated in the inorganic material thin film.

The method for producing a laminate of a cured resin film and an inorganic material thin film according to the present invention can be applied to various materials as long as the inorganic material thin film is preferably free from wrinkles and cracks. For example, a laminate of a cured resin film used for an IC substrate or wear-resistant coating and an inorganic material thin film such as Al ₂ O _{3, a} cured resin film used for a translucent electrode, indium tin oxide (ITO), In -Laminated bodies of inorganic material thin films such as Zn-O, cured resin films used for capacitor elements and sensors, laminated bodies of inorganic material thin films such as TiO _2, resin cured used for surface coating materials, fuel cell partition walls, etc. Examples include a laminate of a film and an inorganic material thin film such as ZrO ₂ . In particular, when used as a method for manufacturing a color filter having a laminate of a resin cured film such as a colored layer, a black matrix layer, a protective film, an inkjet partition wall and an inorganic material thin film such as a transparent electrode film, the inorganic material thin film Wrinkles and cracks are less likely to occur, and this is preferable because a color filter with reduced display defects can be obtained.

Hereinafter, the manufacturing method of the laminated body of the resin cured film and inorganic material thin film which concerns on this invention is demonstrated in detail.
(1) Step of forming a cured resin film In this step, an elastic deformation in an indentation test according to ISO-14577 of a curable resin composition on a substrate and a cured product composed only of an organic component in the solid content of the composition. It has at least a step of curing under the condition that the ratio is 40% or more.

  For the curable resin composition used in the step, it is necessary to select an organic component that can have an elastic deformation ratio of 40% or more in an indentation test according to ISO-14577 of a cured product composed only of the organic component in the solid content of the composition. There is. In such a composition, various organic components including a binder component are selected, a coating film of the organic component is formed, the coating film is cured under various conditions, and ISO-14577 of the obtained cured film is obtained. Obtaining the elastic deformation ratio in the indentation test by selecting a binder component having the elastic deformation ratio of 40% or more from the above, and using the selected binder component, appropriately mixing other components to prepare it can. As such a composition, the curable resin composition according to the present invention can be suitably used.

  In the step of forming a cured resin film in the present invention, a step of applying a curable resin composition on a substrate to form a coating film, and an ISO- of a cured product consisting only of organic components in the solid content of the composition 14577 has a step of curing the coating film under the condition that the elastic deformation ratio in the indentation test is 40% or more.

  The method for forming the coating film of the curable resin composition is not particularly limited, and when patterning is necessary, methods such as a photolithography method, a dyeing method, a printing method, an electrodeposition method, and an ink jet method are exemplified. Moreover, when patterning is unnecessary, methods, such as a spin coater, a roll coater, spray, printing, are mentioned, for example. As illustrated below, various methods can be used according to the coating film to be produced.

  In addition, the curing condition in which the elastic deformation ratio in the indentation test according to ISO-14577 of the cured product composed only of the organic component in the solid content of the composition is 40% or more is determined when the organic component is selected. Conditions under which the elastic deformation ratio in the indentation test according to ISO-14577 of the cured film is 40% or more are appropriately used.

  In particular, when forming a cured resin film having a fine pattern, the step of forming the cured resin film is performed by selectively attaching the curable resin composition to a predetermined region on the substrate by an inkjet method, It is preferable to include a step of forming an ink layer and a step of curing the ink layer by heating and / or light irradiation to form a cured resin film having a predetermined pattern. This is because a predetermined fine pattern can be accurately and uniformly formed by ejecting the substrate surface according to the predetermined pattern by the ink jet method.

  In addition, the step of forming the cured resin film includes a step of further increasing the elastic deformation rate by continuing heating even after the progress of the crosslinking reaction of the curable resin composition is stopped. This is preferable because wrinkles and cracks are less likely to occur.

  Next, the process of forming a cured resin film using an inkjet method will be described in more detail using a color filter manufacturing method as an example.

First, a transparent substrate for a color filter is prepared as shown in FIG.
Next, as shown in FIG. 3B, a black matrix layer 6 is formed in a region serving as a boundary between pixel portions on one surface side of the transparent substrate 5. The black matrix layer 6 can be formed using the process of forming a cured film in the present invention. In this case, the black matrix layer 6 is a layer in which light shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are contained in a resin binder. Although it may be formed by using an ink jet method similarly to the colored layer 7 described later, a generally used method such as a photolithography method or a printing method can be used.

  First, a curable resin composition containing light-shielding particles such as carbon black and metal oxide is applied on the transparent substrate 5 and dried as necessary to form a photosensitive coating film. Is exposed to light and developed through a photomask for black matrix under the condition that the elastic deformation ratio in the indentation test according to ISO-14577 of the cured product consisting only of organic components in the solid content of the composition is 40% or more. The black matrix layer 6 can be formed by performing heat treatment as necessary.

  The thickness of the black matrix layer is about 1000 to 2000 mm in the case of a metal thin film, and about 0.5 to 2.5 μm in the case of a light shielding resin layer.

  In the color filter, the black matrix layer 6 may be formed by forming a metal thin film of chromium or the like having a thickness of about 1000 to 2000 mm by sputtering, vacuum deposition, or the like, and patterning the thin film.

  Next, as shown in FIG. 3C, an ink-repellent partition wall 20 having a width smaller than that of the black matrix layer is formed in the center in the width direction of the pattern of the black matrix layer as necessary. The composition of such an ink repellent partition is not particularly limited as long as it is a resin composition having ink repellent properties. Moreover, it does not need to be transparent in particular and may be colored. For example, a material that is used for the black matrix layer and does not include a black material can be used. Specifically, a composition in which one or more aqueous resins such as polyacrylamide, polyvinyl alcohol, gelatin, casein, and cellulose are mixed, or an O / W emulsion type resin composition, for example, reactive silicone emulsion And the like. For reasons such as easy handling and curing, a photocurable resin is preferably used. Further, since the ink-repellent partition wall is more preferable as the ink repellency is stronger, the surface thereof may be treated with an ink-repellent treatment agent such as a silicone compound or a fluorine-containing compound. Moreover, the curable resin composition according to the present invention can also be suitably used.

  The patterning of the ink repellent partition wall can be performed by printing using a coating liquid of the ink repellent resin composition or photolithography using a photocurable coating liquid. The height of the ink repellent partition is preferably set to a certain degree because it is provided to prevent ink from being mixed when colored by the ink jet method as described above. In consideration of the overall flatness of the film, the thickness is preferably close to the thickness of the colored layer. Specifically, although it varies depending on the amount of ink deposited, it is usually preferably in the range of 0.1 to 2.0 μm.

  Next, a colored layer forming curable resin composition according to the present invention in which an R, G, or B pigment is blended is prepared. Then, as shown in FIG. 3D, a colored layer of a corresponding color is formed on the colored layer forming regions 21R, 21G, and 21B of each color defined by the pattern of the black matrix layer 6 on the surface of the transparent substrate 5. An ink layer is formed by spraying the curable resin composition for ink jet by an inkjet method. The ink layer is formed so that a red pattern, a green pattern, and a blue pattern are arranged in a desired form such as a mosaic type, a stripe type, a triangle type, or a four-pixel arrangement type. In this ink spraying process, the colored layer forming curable resin composition is unlikely to increase in viscosity at the tip of the head 22 and needs to continue to maintain good ejection properties. In this case, the ink of the corresponding color can be adhered accurately and uniformly in a predetermined colored layer forming region, and a pixel portion free from color unevenness and color loss can be formed with an accurate pattern. . In addition, since the curable resin composition for forming a colored layer for each color can be sprayed onto the substrate simultaneously using a plurality of heads, the working efficiency is higher than when forming a pixel portion for each color by a method such as printing. Can be improved.

  Next, as shown in FIG. 3 (E), the ink layers 23R, 23G, and 23B of the respective colors are dried and pre-baked as necessary, and then an ISO of a cured product composed only of organic components in the solid content of the composition. It is cured by exposure and / or heating under curing conditions such that the elastic deformation ratio in the indentation test of −14577 is 40% or more. When the ink layer is exposed and / or heated, the crosslinking element of the curable resin contained in the curable resin composition causes a crosslinking reaction, and the ink layer is cured. The thickness of the colored layer is usually about 0.1 to 2.0 μm in consideration of optical characteristics and the like.

  Next, as shown in FIG. 3F, the protective film 8 is formed on the side of the transparent substrate on which the colored layers 24R, 24G, and 24B are formed. The thickness of the protective film 8 can be set in consideration of the light transmittance of the material used, the surface state of the color filter, and the like, and can be set in the range of 0.1 to 2.0 μm, for example. A protective film can be formed by methods, such as a spin coater, a roll coater, a spray, and printing, using a transparent curable resin composition. For example, the elastic deformation ratio in an indentation test by ISO-14577 of a cured product consisting of only an organic component in the solid content of the composition is 40% or more when coated with a spin coater within a range of 500-1500 rpm. It is preferable to make it harden | cure by exposure and / or heating on the conditions which become.

(2) The process of forming an inorganic material thin film on the said resin cured film In the manufacturing method of the laminated body of the resin cured film and inorganic material thin film which concern on this invention, the process of forming the said inorganic material thin film is a physical vapor deposition method, chemical A method such as a vapor deposition method or a sol-gel method can be used.

  The inorganic material thin film is formed under an ultra-low pressure condition and / or a high temperature condition using a vacuum regardless of any of the above methods. Therefore, when forming a laminate of a cured resin film and an inorganic material thin film, the inorganic material There was a problem that the inorganic material thin film was wrinkled or cracked when the thin film was formed. However, since the cured resin film formed in the above process hardly generates wrinkles or cracks, an inorganic material thin film is further formed on the cured resin film. However, wrinkles and cracks are unlikely to occur in the inorganic material thin film.

  Therefore, in the method for producing a laminate of a cured resin film and an inorganic material thin film according to the present invention, the step of forming the inorganic material thin film may include a heating process at a high temperature of 180 ° C. or higher. It is difficult for wrinkles and cracks to occur in the thin film. When the step of forming the inorganic material thin film includes a heating process at a high temperature of 180 ° C. or higher, there may be an effect that the transmittance of the inorganic material thin film is improved or the resistance value is lowered.

  In the method for producing a laminate of a cured resin film and an inorganic material thin film according to the present invention, the obtained inorganic material thin film has a surface roughness (Ra) of 10 nm or less, further 8 nm or less, particularly 5 nm or less. preferable.

  In the present invention, the inorganic material used for forming the inorganic material thin film is not particularly limited. For example, as described above, when the inorganic material thin film is the transparent electrode film, the antireflection film, the substrate for IC or the wear-resistant coating, the capacitor element or the sensor, the surface coating material In addition, an appropriate inorganic material can be used according to each case such as a fuel cell partition wall material.

The physical vapor deposition method is not particularly limited, and examples thereof include a sputtering method, a vacuum vapor deposition method, and an ion plating method. The chemical vapor deposition method is not particularly limited, and examples thereof include a thermal CVD method, a plasma CVD method, a photo CVD method, an MO (Metal organic) CVD method, and an EA (Electron assisted) CVD method. The sol-gel method generally refers to a method in which a sol composed of a metal alkoxide is converted into a gel that loses fluidity by hydrolysis and polycondensation reaction, and the gel is heated to obtain a metal oxide. For example, the general formula:
Y _n SiX _(4-n)
(Where Y is an alkyl group, fluoroalkyl group, vinyl group, amino group, phenyl group, chloroalkyl group, isocyanate group, or epoxy group, or an organic group containing these, and X is an alkoxyl group, acetyl group, or Represents halogen, n is an integer from 0 to 3)
And a method of forming an inorganic material thin film by hydrolytic polycondensation of an inorganic material containing one or more of the silicon compounds represented by formula (1).

  When the inorganic material thin film formed in the present invention is a transparent electrode film of the color filter, it is formed by a general method such as a sputtering method, a vacuum deposition method, a CVD method, using the material as described above, If necessary, a predetermined pattern is formed by etching using a photoresist or using a jig. The thickness of the transparent electrode can be about 20 to 500 nm, preferably about 100 to 300 nm.

  In addition, when the inorganic material thin film formed in the present invention is an antireflection film for the color filter, it is formed by a general method such as sputtering, vacuum deposition, or CVD using the materials described above. Is done. The thickness of the antireflection film can be about 10 nm to 500 nm, preferably about 50 nm to 200 nm.

(Production Examples 1-2: Synthesis of Binder Epoxy Compounds (1) and (2))
In a four-necked flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel, the solvent diethylene glycol monobutyl ether acetate (also called butyl carbitol acetate, hereinafter referred to as BCA) does not contain a hydroxyl group according to the blending ratio shown in Table 1. 40.7 parts by weight were charged and heated with stirring to 140 ° C. Next, 54.7 parts by weight of a mixture (dropping component) of a monomer having a composition described in Table 1 and a polymerization initiator at 140 ° C. was dropped at a constant rate from a dropping funnel over 2 hours. After completion of the dropwise addition, the temperature was lowered to 110 ° C., 4.6 parts by weight of a mixture of polymerization initiator and solvent-free diethylene glycol monobutyl ether acetate (BCA) (additional catalyst component) was added, and the temperature at 110 ° C. was maintained for 2 hours. By terminating the reaction, a binder epoxy compound (1) having the characteristics shown in Table 1 was obtained. Moreover, according to the mixture ratio shown in Table 1, it synthesize | combined similarly to the binder-type epoxy compound (1), and obtained the binder-type epoxy compound (2) which has the characteristic of Table 1.

* 1) Abbreviations in the table are as follows.
GMA: Glycidyl methacrylate MMA: Methyl methacrylate MEA: Methoxyethyl acrylate Perbutyl O: t-Butylperoxy 2-ethylhexanoate (trade name, manufactured by NOF Corporation)
* 2) Weight average molecular weight: A value in terms of polystyrene by gel permeation chromatography.

(Test Examples 1-4: Indentation test by ISO-14577 of a cured product consisting only of organic components in solid content)
<Test compositions 1-4>
Test compositions 1 to 4 consisting only of organic components in the solid content were prepared by thoroughly mixing the compositions shown in Table 2.

Abbreviations in the table are as follows.
* 3) Ep157: Bisphenol A type (Oilized Shell Epoxy Co., Ltd.) (Epoxy functionality: 4.3)
* 4) Ep828: Bisphenol A type (Oilized Shell Epoxy Co., Ltd.) (Epoxy functionality: 2)
* 5) YDCN704: Cresol novolak type (Toto Kasei Co., Ltd.) (Epoxy functionality: 11)
* 6) NOFUCURE LC-1: (Nippon Yushi Co., Ltd.)
* 7) Disperbyk-161: (Big Chemie Japan Co., Ltd.)
* 8) Addisper PB821: (Ajinomoto Fine Techno Co., Ltd.)
* 9) Solsperse 24000: (AVECIA)

<Production of cured product using test compositions 1 to 4>
Test compositions 1 to 4 are applied on a glass substrate, dried on a hot plate at 80 ° C. for 5 minutes under 150 Torr, and heated under reduced pressure at 260 ° C., and heated at 260 ° C. for 30 minutes to obtain a final cured film thickness. Was formed to be a cured product consisting only of organic components in the solid content.

<Indentation test by ISO-14577>
The cured products using the test compositions 1 to 4 obtained as described above were measured using a microhardness measuring device (Fischer Scope H100V (manufactured by Helmut Fischer)). Using a pyramidal diamond indenter (MK320 in Fischerscope H100V) with a square base as an indenter at a temperature of 23 ° C. and a humidity of 45%, the load loading speed is 30 mN / min, the maximum load is 30 mN, the maximum The load F during the test and the corresponding indentation depth h and time were recorded as a holding time of 5 seconds, and the amount of work indicated during the indentation work was measured.

  The measured work amount was processed as η = Welast / Wtotal × 100, and the elastic deformation ratio was obtained. As a result, the test compositions 1 and 2 had an elastic deformation ratio of 40% or more, and the test compositions 3 and 4 had an elastic deformation ratio of less than 40%. The results are shown in Table 2.

(Examples 1-2, Comparative Examples 1-2: Curable resin composition for color filter)
As a result of the indentation test by ISO-14577 of the cured product consisting only of the organic components in the solid contents of Test Examples 1 to 4, the elastic deformation ratio was 40% or more in Test Composition 1 and Test Composition 2. Thus, the curable resin compositions for color filters of Examples 1 and 2 according to the present invention were prepared using the organic components of Test Compositions 1 and 2, and the organic components of Test Compositions 3 and 4 were used. The curable resin compositions for color filters of Comparative Examples 1 and 2 were prepared.

<Preparation of pigment dispersion>
A pigment, a pigment dispersant, and an organic solvent are mixed in the following ratio, 500 parts by weight of zirconia beads having a diameter of 0.3 mm are added, and dispersed for 4 hours using a paint shaker (manufactured by Asada Steel Corporation). Prepared.

[Composition of pigment dispersion]
Pigment: C.I. I. Pigment Green 36: 3.5 parts by weight / Pigment: C.I. I. Pigment Yellow 150: 3.5 parts by weight • Each pigment dispersant: 4 parts by weight • BCA (diethylene glycol monobutyl ether acetate): 44 parts by weight

  The prepared pigment dispersion and other components were thoroughly mixed to prepare a curable resin composition for a color filter having a composition containing an organic component of the test composition as shown in Table 3. .

<Preparation of hardened | cured material using Examples 1-2 and Comparative Examples 1-2>
Each of the color filter curable resin compositions of Examples 1 and 2 and Comparative Examples 1 and 2 was coated on a glass substrate, dried on a hot plate at 80 ° C. for 5 minutes under 150 Torr, and tested. As with the curing conditions of the composition, the coating was heated at 260 ° C. for 30 minutes to form a coating film so that the final cured film thickness was about 2 μm, and each resin cured film was formed.

<Relationship between change amount of cross-linking element and elastic deformation ratio before and after severe test of cured product of curable resin composition for color filter>
After measuring the amount of change in cross-linking element (the amount of change in epoxy group) by IR measurement of the cured product and the elastic deformation ratio in the indentation test according to ISO-14577, and further heating the cured product at 240 ° C. for 60 minutes, respectively. The change amount of the bridging element (epoxy group change amount) and the elastic deformation ratio in the indentation test according to ISO-14577 were measured, and the relationship between the change amount of the bridging element and the elastic deformation ratio before and after the severe test was observed.

The amount of change of the bridging element (the amount of change of the epoxy group) is an ester group (around 1720 cm ⁻¹ ) whose peak does not change even when heated with a heating IR measuring device (manufactured by JASCO Corporation, FT / IR610). Select the reference peak to obtain the peak area, obtain the peak area for the peak around 986 cm ⁻¹ derived from the epoxy group, calculate the area ratio of the epoxy peak to the reference peak, and before heating more severely after curing The peak area ratio was compared later. When the peak area ratio is within 0.002%, the amount of change of the crosslinking element (the amount of change of the epoxy group) before and after severe heating is in a range that can be said to be substantially zero. The peak area was calculated by connecting two valleys with respect to the peak top with a straight line.

  About the elastic deformation ratio, it measured similarly to the indentation test by ISO-14577 in said test example. Table 4 shows the results of the relationship between the amount of change in the bridging element before and after the severe test and the elastic deformation ratio.

  From the results, before and after the cured products of the compositions of Examples 1 and 2 were further heated at 240 ° C. for 60 minutes, the change amount of the bridging element was within the measurement error range, and the elasticity in the indentation test according to ISO-14577. It became clear that the deformation rate increased.

(Examples 3-4, Comparative Examples 3-4: Production of a laminate of a cured resin film and an inorganic material thin film)
The curable resin compositions for color filters of Examples 1 and 2 and Comparative Examples 1 and 2 were each coated on a glass substrate, dried on a hot plate at 80 ° C. for 5 minutes under 150 Torr, and tested. As with the curing conditions of the composition, the coating was heated at 260 ° C. for 30 minutes to form a coating film so that the final cured film thickness was about 2 μm, and each resin cured film was formed.

Next, using a small sputter film forming apparatus (ULVAC, Inc.) on each cured resin film, a sputter film is formed at a substrate setting temperature of 100 ° C. under a vacuum of 5.7 × 10 ⁻³ Torr. , Heat treatment was performed at 180 ° C. for 60 minutes. As a result, the thickness of ITO (indium tin oxide) was 120 to 140 nm. The following evaluation was performed about the laminated body of the resin cured film and inorganic material thin film which were obtained as mentioned above.

  In addition, each resin cured film of the said hardened | cured material which consists only of the organic component (corresponding to test composition 1-4) in solid content of the curable resin composition for color filters of Examples 1-2 and Comparative Examples 1-2. Similarly to the above, ITO (indium tin oxide) was formed to a thickness of 120 to 140 nm to produce a laminate of a cured resin film and an inorganic material thin film, and the following evaluation was performed. .

<Wrinkle generation on the surface of the inorganic material thin film>
A photograph taken with a microscope for the presence or absence of wrinkles on the surface of the inorganic material thin film after the inorganic material thin film formation of the laminate of the resin cured film and the inorganic material thin film of Examples 3 to 4 and Comparative Examples 3 to 4, 5 (a), 6 (a), 7 (a), and 8 (a), respectively. In addition, the inorganic material thin film about the laminated body of the cured film and inorganic material thin film which consist only of the organic component (corresponding to the test compositions 1-4) in solid content among Examples 1-2 and Comparative Examples 1-2. The presence or absence of wrinkles on the surface of the inorganic material thin film after film formation is shown in FIGS. 5 (b), 6 (b), 7 (b), and 8 (b), respectively.

<Measurement of surface roughness Ra>
In order to evaluate generation | occurrence | production of the wrinkle of the inorganic material thin film surface after inorganic material thin film film-forming, the laminated body of the resin cured film of Examples 3-4 and Comparative Examples 3-4 and an inorganic material thin film, and Examples 1- Surface roughness Ra of the ITO film | membrane formed about the laminated body of the cured film and inorganic material thin film which consist only of the organic component (corresponding to test composition 1-4) in solid content among 2 and Comparative Examples 1-2 Was measured by AFM. The AFM used was NanoScope IIIa manufactured by Biko Japan. Table 5 shows measured values of the surface roughness Ra.

(Examples 5 to 7: curable resin composition for color filter)
Using the organic component of Test Composition 2, curable resin compositions for color filters of Examples 5 to 7 according to the present invention were prepared. As Example 5, the following black matrix pigment dispersion was used, as Example 6, the following blue pigment dispersion was used, and as Example 7, the following red pigment dispersion was used.

<Preparation of pigment dispersion>
A pigment, a pigment dispersant, and an organic solvent are mixed in the following ratio, 500 parts by weight of zirconia beads having a diameter of 0.3 mm are added, and dispersed for 4 hours using a paint shaker (manufactured by Asada Steel Corporation). Prepared.

[Composition of pigment dispersion for black matrix]
Pigment: C.I. I. Pigment Black 7: 7 parts by weight Pigment dispersant (Disperbyk-161): 4 parts by weight BCA (diethylene glycol monobutyl ether acetate): 44 parts by weight

[Composition of blue pigment dispersion]
Pigment: C.I. I. Pigment Blue 15: 6: 7 parts by weight • Pigment dispersant (Disperbyk-161): 4 parts by weight • BCA (diethylene glycol monobutyl ether acetate): 44 parts by weight

[Composition of red pigment dispersion]
Pigment: C.I. I. Pigment Red 254: 3.5 parts by weight / Pigment: C.I. I. Pigment Red 177: 3.5 parts by weight-Pigment dispersant (Disperbyk-161): 4 parts by weight-BCA (diethylene glycol monobutyl ether acetate): 44 parts by weight

  Compositions shown in Table 6 are curable resin compositions for color filters having a composition containing the organic component of the test composition 2 after thoroughly mixing the prepared pigment dispersion and other components. It was prepared with.

(Example 8: Production of color filter)
On a 10 cm × 10 cm glass substrate (manufactured by Asahi Glass Co., Ltd.) having a thickness of 0.7 mm, a line width of 20 μm and a film thickness of 1.2 μm are obtained by photolithography using the curable resin composition for black matrix of Example 5. A black matrix pattern was formed. The curable resin composition of Example 2 was accurately and uniformly attached to the green pixel forming portion partitioned by the black matrix of the substrate by an inkjet method. Next, the blue curable resin composition of Example 6 was adhered to the blue pixel forming portion of the same substrate accurately and uniformly by an inkjet method. Next, the red curable resin composition of Example 7 was adhered to the red pixel forming portion of the same substrate accurately and uniformly by an inkjet method.

  After that, pre-baking is performed for 10 minutes on a hot plate at 80 ° C., and further, post-baking is performed by heating at 260 ° C. for 30 minutes in the same manner as the curing conditions of the test composition. A 1.8 μm RGB three-color pixel pattern was formed.

The substrate on which the RGB pixel pattern was formed was immersed in IPA for 5 minutes, then dried by IPA vapor, washed, and then ITO (indium oxide) at a substrate setting temperature of 200 ° C. under a vacuum of 6 × 10 ⁻³ Torr. A tin) electrode was deposited to a thickness of 120 nm. The substrate on which this ITO film was formed was further immersed in IPA for 5 minutes, steam-washed with IPA, spin-coated with polyimide, and baked at 180 ° C. for 60 minutes to form an alignment film. Got. As a result, no wrinkles or cracks occurred on the ITO (indium tin oxide) electrode.

It is typical sectional drawing about an example of a liquid crystal panel. It is typical sectional drawing about another example of a liquid crystal panel. It is a typical longitudinal section showing an example of a color filter concerning the present invention. It is a figure explaining an example of the method of manufacturing a color filter using the curable resin composition of this invention. The load / indentation depth curve in the instrumentation indentation test of hardness and various material parameters by ISO-14577 of this invention is shown. It is a photograph of the inorganic material thin film surface of the laminated body of the resin cured film and inorganic material thin film using the curable resin composition for color filters of this invention. It is a photograph of the inorganic material thin film surface of the laminated body of the resin cured film and inorganic material thin film using the curable resin composition for color filters of this invention. It is a photograph of the inorganic material thin film surface of the laminated body of the resin cured film and inorganic material thin film using the curable resin composition of a comparative example. It is a photograph of the inorganic material thin film surface of the laminated body of the resin cured film and inorganic material thin film using the curable resin composition of a comparative example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Color filter 2 ... Electrode board 3 ... Gap part 4 ... Sealing material 5 ... Transparent substrate 6 ... Black matrix layer 7 (7R, 7G, 7B) ... Colored layer 8 ... Protective film 9 ... Transparent electrode film 10 ... Orientation film 11 DESCRIPTION OF SYMBOLS ... Pearl 12 ... Columnar spacer 20 ... Ink-repellent partition wall 21 ... Colored layer formation area 22 ... Inkjet head 23 ... Ink layer 24 ... Pixel part 25 ... Photocatalyst containing layer 26 ... Photomask 27 ... Exposure part 28 ... Light beam 101, 102 ... Color liquid crystal display device 103, 104, 105 ... Color filter

Claims (14)

A thermosetting resin composition, comprising at least structural units represented by the following formulas (1) and (2) as a curable resin, having two or more glycidyl groups in one molecule, and having a weight average molecular weight of 3000 to A binder epoxy compound having an intercrosslinking molecular weight Mc of 300 or less and a polyfunctional epoxy compound having 4 or more epoxy groups in one molecule and a weight average molecular weight of 3000 or less. The content of the binder epoxy compound in the entire binder component is 30% by weight or more,
The Ri Do because only the organic component in the solid content of the composition, 80 ° C., for 5 minutes heated vacuum drying under 150 Torr, elasticity in the indentation test by ISO-14577 obtained that the cured product is heated 30 minutes at 260 ° C. deformation ratio of 40% or more, and wherein a surface roughness (Ra) can become a 10nm or less, a thermosetting resin composition for a color filter.

(R ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ² is a hydrocarbon group having 1 to 12 carbon atoms, and R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. )
M _c = M ₀ / (xF ₀ -2)
(In the formula, M ₀ is the average molecular weight per molecule, x is the reaction rate of 1 or less, and F ₀ is the average number of functional groups per molecule.) The elastic deformation ratio in the indentation test by ISO-14577 of the cured product composed of only the organic component is characterized in that which can be 60% or less, the color filter for the thermosetting resin composition of claim 1. After curing, before and after heating at 240 ° C. for 60 minutes, the amount of change in the bridging element is within the measurement error range, and the elastic deformation ratio in the indentation test according to ISO-14577 is increased. claim 1 or the color filter for the thermosetting resin composition according to 2. Characterized in that it is a inkjet ink, color filter thermosetting resin composition according to any one of claims 1 to 3. A transparent substrate and a colored layer provided on the transparent substrate may be provided, and further a resin cured film may be provided on the colored layer and / or the colored layer, and the colored layer and / or the resin cured film is the Ri claims 1 to cured der formed by curing a color filter for a thermosetting resin composition according to any one of 4, the elastic deformation ratio in the indentation test by ISO-14577 of the cured product 40 % or more and a surface roughness (Ra) is not more 10nm or less, a color filter, wherein Rukoto comprises an inorganic material thin film adjacent to the colored layer and / or the resin cured film made of the cured product. The color filter according to claim 5 , wherein the inorganic material thin film is a transparent electrode film. The color filter according to claim 5 or 6 , wherein the inorganic material thin film has a surface roughness (Ra) of 10 nm or less. 8. A liquid crystal panel in which a display side substrate and a liquid crystal driving side substrate are opposed to each other and liquid crystal is sealed therebetween, wherein the display side substrate is the color filter according to any one of claims 5 to 7. A liquid crystal panel characterized by that. The indentation test by ISO-14577 of the hardened | cured material which consists only of the organic component in the solid content of the said composition for the thermosetting resin composition for color filters as described in any one of the said Claims 1 thru | or 4 on a board | substrate. A step of forming a cured resin film by curing under a condition that the elastic deformation ratio in the film is 40% or more and the surface roughness (Ra) of the cured product is 10 nm or less, and an inorganic material thin film on the cured resin film The manufacturing method of a color filter which has the process of forming. The method for producing a color filter according to claim 9 , wherein the step of forming the inorganic material thin film uses a physical vapor deposition method, a chemical vapor deposition method, or a sol-gel method. The method for producing a color filter according to claim 9 or 10 , wherein the step of forming the inorganic material thin film includes a heating step of 180 ° C or higher. Forming the resin cured film, even after the progress of the crosslinking reaction of the thermosetting resin composition is stopped, including the step of further continuing the heating to increase the elastic deformation percentage of claims 9 to 11 The manufacturing method of the color filter in any one. Forming the resin cured film, the thermosetting resin composition in a predetermined region on the substrate selectively deposited was by ink jet method, a step of forming an ink layer by heating the ink layer The manufacturing method of the color filter in any one of Claim 9 thru | or 12 including the process of making it harden | cure and forming the resin cured film of a predetermined pattern. The method for producing a color filter according to claim 9 , wherein the inorganic material thin film has a surface roughness (Ra) of 10 nm or less.

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