JP2011123488A - Resin coating for color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin coating for a color filter using a curable resin composition capable of forming a resin coating having high peeling liquid resistance and a low dielectric constant. <P>SOLUTION: The resin coating for a color filter which is disposed on a color filter layer formed on a substrate is formed using a curable resin composition including a binder, a polymerization initiator, and a polymerizable monomer, wherein the polymerizable monomer includes a triazine-based compound having at least one epoxy group-containing substituent and at least one ethylenic double bond-containing substituent in one of triazine skeletons and the triazine-based compound having the triazine skeleton is a monomer. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a curable resin composition, specifically, it relates to a resin skin layer for a color filter using the curable resin composition which can be suitably used for manufacturing color filters.

Usually, a liquid crystal display device is manufactured by separately manufacturing a color filter substrate and a TFT (Thin-Film-Transistor) substrate and attaching them with a liquid crystal sandwiched therebetween. At this time, the color filter substrate is coated with an alignment film such as polyimide for aligning the liquid crystal on the color filter layer. For this reason, the color filter layer is required to have resistance to a solvent having a strong polarity such as NMP (N-methyl-pyrrolidone) contained in the polyimide resin.
In addition, the color filters are formed in a stripe shape or a mosaic shape for each of the three independent colors. For this reason, unevenness is formed on the surface of the color filter layer, and thus a resin coating (hereinafter sometimes referred to as “overcoat layer”) may be used as a planarizing film on the surface. NMP resistance is required for this resin film as well as the color filter layer.

  Further, in the TFT substrate, when a TFT is produced on the substrate, the surface thereof is uneven. For this reason, a resin film (hereinafter sometimes referred to as an “interlayer insulating film”) is provided thereon, and then flattened, and then ITO (indium tin oxide, a mixture of indium oxide and tin oxide) is sputtered and deposited. A thin film is formed by a vacuum film forming method such as. Usually, ITO is patterned by photolithography using a positive resist to form a pixel electrode. At this time, the underlying interlayer insulating film needs to be resistant to etching liquid (acid resistance) in order to etch ITO. . Here, more importantly, since ITO is an inorganic substance and the resin film is an organic substance, when the resin film swells or expands with a stripping solution, ITO cannot follow it and breaks. Accordingly, the resin film is required not to be peeled off by the stripping solution but also to be less swelled and expanded. As a stripping solution (hereinafter sometimes simply referred to as “stripping solution”) used for stripping the positive resist, a mixture of MEA (monoethanolamine) and DMSO (dimethyl sulfoxide) is used. It is done. Furthermore, since the resin film is sandwiched between the pixel electrode and the TFT, the resin film may be charged and cause a display failure of the liquid crystal. It becomes.

In a COA (Color-filter On Array) type liquid crystal display device, a color filter layer that also serves as the interlayer insulating film is formed on the TFT. For this reason, the required characteristics for the color filter layer are added to the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the stripping solution resistance in addition to the normal required characteristics as described above. In order to satisfy these required characteristics, a resin film is also provided as a protective layer on the color filter layer.
Usually, the NMP resistance used for the evaluation of the color filter is evaluated by the change in chromaticity before and after being immersed at 50 ° C. for 10 minutes, whereas the above-mentioned peeling solution resistance is evaluated by the swelling rate after being immersed at 80 ° C. for 2 minutes. To do. Therefore, generally, the stripping solution resistance is evaluated more severely under these conditions, and it is required to satisfy the stripping solution resistance.

  As described above, in the COA method, since the resin film and the color filter are in direct contact with the pixel semiconductor, it is necessary to have a low dielectric constant, and the interlayer insulating film also has a low dielectric constant. It has been demanded. Particularly in the case of the COA method, since the pixel semiconductor is in direct contact with the resin film and the color filter, the low dielectric constant is important.

  On the other hand, what contains a tris isocyanuric acid compound is proposed as a photosensitive composition for color filters (for example, refer patent document 1). Such a photosensitive composition is excellent in peelability from a cover film and the like, and aims to prevent display unevenness due to line marks. However, such a photosensitive composition also has a problem that the resistance to the stripping solution with respect to the stripping solution is low.

  In addition, as an example of a radical polymerizable compound, a photosensitive resin composition for image formation such as a color filter using a tris (hydroxy) isocyanurate tri (meth) acrylate monomer has been proposed (for example, Patent Document 2). reference.). However, such a photosensitive resin composition also has low resistance to the stripping solution with respect to the stripping solution, and further improvement is desired.

  As described above, no resin film that can form a color filter layer or a resin film that satisfies both high resistance to stripping liquid and a low dielectric constant has not yet been provided, and light capable of forming a resin film having such performance. Development of a curable resin composition and a colorant-containing photocurable resin composition has been desired.

JP-A-10-333330 JP 2003-177534 A

The present invention aims to provide an order to solve the above problems, high peel solution resistance and the resin skin film for color filter using the formable curable resin composition of the resin film having a low dielectric constant To do.

<1> A curable resin for a color filter provided on a color filter layer formed on a substrate, comprising a binder, a polymerization initiator, and a polymerizable monomer having an ethylenic double bond The polymerizable monomer having an ethylenic double bond is at least one epoxy group-containing substituent selected from triazine skeletons represented by the following general formulas (1) to (2). see containing the triazine compound a having one, triazine compound a having a triazine skeleton represented by the general formula (1) is a curable resin composition which is a following monomer M1 or monomer M2 It is the resin film for color filters characterized by being formed using .

[In General Formulas (1) to (2), * represents a linking group. ]

According to the present invention, it is possible to provide a high peel solution resistance and the resin skin film for color filter using the formable curable resin composition of the resin film having a low dielectric constant.

The resin film for a color filter of the present invention is a resin film for a color filter provided on a color filter layer formed on a substrate, and is formed using the following first curable resin composition. Features. The first curable resin composition is a curable resin composition comprising a binder, a polymerization initiator, and a polymerizable monomer having an ethylenic double bond, the polymerization having the ethylenic double bond. sex monomer, at least the following general formula one selected from a triazine skeleton represented by (1) to (2), seen containing a triazine compound a having at least one epoxy group-containing substituent group, the general formula ( The triazine compound A having a triazine skeleton represented by 1) is the following monomer M1 or monomer M2 .

[In General Formulas (1) to (2), * represents a linking group. ]

The second curable resin composition is a curable resin composition comprising a binder, a polymerization initiator, and a polymerizable monomer having an ethylenic double bond, wherein the ethylenic double bond is photopolymerizable monomer having the the one selected from the group consisting of a triazine skeleton represented by at least the following general formula (1) to (2), including a triazine compound B having a substituent represented by the following general formula (3) .

[In General Formulas (1) to (2), * represents a linking group. ]

[In General Formula (3), R ¹ represents an ethylenic double bond-containing substituent. ]

First curable resin composition in the present invention (hereinafter simply referred to as “ curable resin composition in the present invention ”. The curable resin composition in the present invention does not contain a colorant. Both a resin composition and a curable resin composition containing a colorant are included.) Is a triazine skeleton represented by any one of the above general formulas (1) to (2), an epoxy group-containing substituent and ethylene. In particular, since it contains a triazine compound having at least one ionic double bond-containing substituent (hereinafter sometimes referred to as “triazine compound A” ) as a polymerizable monomer having an ethylenic double bond. The resist has excellent resistance to the stripping solution against the stripping solution and has a low dielectric constant. For this reason, the resin film formed using the curable resin composition in the present invention can be suitably used as an interlayer insulating film of a TFT, and further, in a COA color filter, a protective film (overcoat layer) Alternatively, it can be suitably used as a color resist for a color filter (pixel) by containing a colorant.
Examples of the positive resist stripping solution include a mixture of monoethanolamine (MEA) and dimethyl sulfoxide (DMSO); monoethanolamine (MEA) and N-methyl-2-pyrrolidone (NMP). A mixture of MEA, NMP and 2,3-hydroxynaphthalene; and the like. The color filter layer using the curable resin composition in the present invention has high resistance to these stripping solutions (stripping solution resistance).

Hereinafter, the present invention will be described in detail.
<< Curable resin composition >>
The curable resin composition in the present invention contains at least a binder, a polymerization initiator, and a polymerizable monomer having an ethylenic double bond which is the triazine compound A in the present invention, and other components as necessary. It is comprised including. The curable resin composition in the present invention can be subjected to thermosetting, photocuring, light / thermosetting, and electron beam curing depending on the types of the binder, the polymerization initiator, and the polymerizable monomer.
That is, the curable resin composition in the present invention is widely applied as a curable resin composition such as a photocurable, thermosetting, and photo / thermosetting resin composition, and further an electron beam curable resin composition. Is possible.

<Polymerizable monomer having an ethylenic double bond>
In the present invention, the polymerizable monomer having an ethylenic double bond is a polymerizable monomer having light and / or heat polymerizability and having an ethylenic double bond, and includes at least the triazine compound A described above.

(Triazine compound A)
The triazine compound A has at least one of an epoxy group-containing substituent and an ethylenic double bond-containing substituent in one selected from the triazine skeletons represented by the following general formulas (1) to (2). A compound.

[In General Formulas (1) to (2), * represents a linking group. ]

  The triazine-based compound A includes at least one triazine skeleton represented by the general formulas (1) to (2). From the viewpoint of handling properties such as solvent solubility, the triazine skeleton represented by the general formula (1) is used. It is preferable to include. Further, from the viewpoint of developability and resolution, the molecular weight is preferably low, and the number of triazine skeletons in one molecule is preferably one.

  In addition, the triazine compound A includes an epoxy group-containing substituent and an ethylenic double bond-containing substituent in the triazine skeleton, and these substituents are the positions (linkage groups) marked with “*” in each general formula. ). In other words, the triazine skeletons represented by the general formulas (1) to (2) can be bonded to each substituent via a linking group “*” at three positions. When the triazine-based compound A in the present invention is bonded to an epoxy group-containing substituent and an ethylenic double bond-containing substituent at each one of the linking groups represented by “*”, the remaining linking groups ( As long as the effect of the present invention is not inhibited, other substituents may be bonded to the linking site). Examples of such other substituents include an alkyl group. In the triazine compound A, the linking group represented by “*” means a group that links an epoxy group-containing substituent or an ethylenic double bond-containing substituent with a triazine skeleton.

  The epoxy group-containing substituent is a substituent having an epoxy ring at the molecular chain end. Examples of the epoxy group-containing substituent include the following substituents (a-1) to (a-4), and (a-1) is preferable. Moreover, as n in substituent (a-3)-(a-4), 1-2 are preferable. In addition, the following substituents (a-1) to (a-4) are displayed including the linking group represented by the above “*”.

  As the triazine compound A, for example, any one of the substituents (a-1) to (a-4) may be contained as an epoxy group-containing substituent, but the above general formulas (1) to (2) may be used. The above substituents (a-1) to (a-4) may be bonded directly from the * position (linking group) of the triazine skeleton represented by Further, two or more epoxy group-containing substituents may be contained in one substituent bonded to the * position (linking group) of the triazine skeleton. The number of epoxy groups contained in one molecule of the triazine compound A is preferably 1 to 2 and particularly preferably 1 from the viewpoint of reducing the dielectric constant. For the same reason, the number of carbon atoms of the epoxy group-containing substituent is preferably 3-30, and more preferably 3-20.

  The ethylenic double bond-containing substituent is not particularly limited as long as it has an ethylenic double bond, and examples thereof include the following substituents (b-1) to (b-6). In the present invention, the following substituents (b-1) and (b-4) are preferred. The following substituents (b-1) to (b-6) are displayed including the linking group represented by the “*”.

  The triazine-based compound A may contain the substituents (b-1) to (b-6) as the ethylenic double bond-containing substituent, and is represented by the general formulas (1) to (2). The substituents (b-1) to (b-6) may be bonded directly from the * position of the triazine skeleton. 3-30 are preferable and, as for carbon number of the said ethylenic double bond containing substituent, 3-15 are more preferable.

  In addition, the total number of ethylenic double bonds located at the molecular chain ends contained in the triazine-based compound A is preferably 1 to 8 and more preferably 2 from the viewpoint of improving curability. Similarly, the number of ethylenic double bonds located at the end of the molecular chain contained per substituent bonded to the triazine skeleton is preferably 1 to 4, and more preferably 1.

In the curable resin composition in the present invention, the content of the triazine compound A is preferably 10 to 250% by mass, and more preferably 50 to 150% by mass with respect to the binder. When the curable resin composition in the present invention is a photocurable system, from the viewpoint of crosslinking the triazine compound (polymerizable monomer) and the binder without excess or deficiency, the number of epoxy rings contained in the triazine compound A and It is particularly preferable to determine the content of the triazine-based compound A so that the number of acidic groups such as carboxylic acids contained in the alkali-soluble resin described later matches.

That is, when the curable resin composition in the present invention is a photocurable system, the content ratio of the triazine compound A in the composition is equivalent to the carboxyl equivalent of the binder in the curable resin composition in an equivalent ratio. 0.5 to 1.5 equivalents, more preferably 0.8 to 1.2 equivalents. Calculation of the blending amount of the triazine compound A can be obtained by the following formula when the equivalent ratio (1/1) is determined from the acid value of the binder to be crosslinked.
(COOH equivalent) = KOH molecular weight × 1000 / (acid value)

If the ratio of the number of COOH groups in the binder to the number of epoxy groups in the triazine compound A (epoxy equivalent / COOH group equivalent) in the above calculation formula is less than 0.5, the crosslinking density may be low. On the other hand, if it exceeds 1.5, there will be epoxy that does not crosslink, and this may cause a decrease in the voltage holding ratio of the liquid crystal.
The content of the triazine compound A in the composition is based on the amount of carboxyl groups as the functional group of the binder, but other functional groups (such as phenolic OH groups) in the binder may be used as the standard.

  Specific examples of the triazine-based compound A are given below, but the present invention is not limited thereto.

  The triazine compound A in the present invention preferably has a symmetrical structure. The triazine compound A may have a urethane group as represented by the general formula (3) described later.

  In the present invention, as described later, the triazine-based compound A in the present invention and other known polymerizable monomers can be used in combination. As a polymerizable monomer that can be used in combination with the triazine compound A, an acrylate of the following isocyanuric acid ethylene oxide adduct is particularly preferable.

  In this case, the mass ratio of the triazine compound A and the acrylate of the isocyanuric acid ethylene oxide adduct is preferably 20/1 to 1/10 from the viewpoint of achieving both improvement of the stripping solution resistance and reduction of the low dielectric constant. 15/1 to 1/4 are more preferable.

(Triazine compound B)
The triazine compound B is a substituent selected from the triazine skeleton represented by the general formulas (1) to (2) as in the case of the triazine compound A (urethane group) represented by the following general formula (3). ).

[In General Formula (3), R ¹ represents an ethylenic double bond-containing substituent. ]

  The triazine-based compound B includes at least one triazine skeleton represented by the general formulas (1) to (2). From the viewpoint of handling properties such as solvent solubility, the triazine skeleton represented by the general formula (1) is used. It is preferable to include. Moreover, it is preferable that it is low molecular weight from a viewpoint of developability or resolution, and it is preferable that the number of triazine skeletons in one molecule is one.

Further, the triazine compound B includes a substituent represented by the general formula (3) in the triazine skeleton, and these substituents are bonded at a position (linking group) marked with “*” in each general formula. The That is, the triazine skeletons represented by the general formulas (1) to (2) can be bonded to each substituent at each of three positions via a linking group. Incidentally, the bets triazine compound B, a substituent represented by the general formula (3), when attached at each one point at a time in the linking group represented by "*", the rest of the linking group (linking site) May be bonded to a hydrogen atom or other substituents as long as the effects of the present invention are not impaired. Examples of such other substituents include an alkyl group. In the triazine compound B, the linking group represented by “*” means a group linking the substituent represented by the general formula (3) and the triazine skeleton.

In the general formula (3), R ¹ represents an ethylenic double bond-containing substituent. The ethylenic double bond-containing substituent in R ¹ is not particularly limited as long as it has an ethylenic double bond, but is a monohydric alcohol residue having an ethylenic double bond at the end of the molecular chain. The substituent which has is preferable. Examples of the substituent include the following substituents (c-1) to (c-14).

In the triazine compound B, the ethylenic double bond-containing substituent represented by R ¹ is preferably a bifunctional substituent, that is, a substituent having two ethylenic double bonds. As the ethylenic double bond-containing substituent represented by R ¹ , the substituents (c-1) to (c-3) are preferable, and the substituent (c-1) is particularly preferable. Further, since the triazine compound B preferably has a symmetrical structure, the substituents bonded to the triazine skeleton are preferably the same.

  In the triazine skeleton B, the linking group represented by “*” is preferably a linking group “Y” of a diisocyanate compound represented by OCN—Y—NCO. Examples of the linking group represented by * include the following linking groups (d-1) to (d-11).

  As the linking group represented by *, those having an aliphatic chain with low heat discoloration resistance and good light resistance are preferable. Particularly, the linking group (d-1) having n = 6, a linking group having an alicyclic structure ( d-4), (d-6), (d-10), (d-11) and the like are preferable, and among them, the linking groups (d-1) and (d-4) are more preferable.

  The total number of substituent molecular chain terminal ethylenic double bonds contained in the triazine-based compound B is preferably larger from the viewpoint of improving curability. In particular, considering the symmetry of the cured product and the heat shrinkage during curing, the total number of ethylenic double bonds at the substituent molecular chain terminals is preferably 3 to 12, and most preferably 3 to 6. When the total number is in the range of 3 to 12, the film shrinks due to heat shrinkage due to the large number of bonding groups, or the resistance to the peeling solution decreases due to too few bonding groups. There is nothing to do.

In the curable resin composition of the present invention, the content of the triazine compound B is preferably 50 to 100% by mass with respect to the binder.

  Specific examples of the triazine compound B are given below. However, the present invention is not limited to this.

  The triazine compound B may have the above-described epoxy group-containing substituent or ethylenic double bond. The triazine compound A and the triazine compound B may be used in combination.

(Polymerizable monomer having another ethylenic double bond)
In this invention, the polymerizable monomer which has other ethylenic double bonds other than the said triazine type compounds A and B may be contained in the range which does not impair the effect of this invention. Examples of the other polymerizable monomer having an ethylenic double bond include at least one ethylenically unsaturated group capable of addition polymerization in addition to the acrylate of the above isocyanuric acid ethylene oxide adduct, and 100 at normal pressure. A compound having a boiling point of not lower than ° C is preferred.

  Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher under normal pressure include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl. Monofunctional acrylates and methacrylates such as (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) A , Tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, and then (meth) acrylates after addition of ethylene oxide or propylene oxide, or poly (pentaerythritol or dipentaerythritol) (Meth) acrylates, urethane acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, etc., JP-A-48-64183 Polyfunctional acrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, which are described in Japanese Patent Publication Nos. 49-43191, 52-30490, etc. Acrylate and methacrylate It can gel. Furthermore, the Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308, those introduced as photocurable monomers and oligomers can also be used.

  A compound obtained by adding ethylene oxide or propylene oxide to the above polyfunctional alcohol and then (meth) acrylated is described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. These can also be used as polymerizable monomers having an ethylenic double bond.

When these other polymerizable monomers having an ethylenic double bond are used, considering the symmetry of the cured product, the total amount of the polymerizable monomer having an ethylenic double bond contained in the curable resin composition in the present invention. On the other hand, the triazine compound A or B is preferably contained in an amount of 50% by mass or more, and more preferably 75% by mass or more.

(binder)
As the binder used in the present invention, an alkali-soluble resin can be suitably used. The alkali-soluble resin is preferably an acrylic copolymer having an acid value in the range of 30 to 150 mgKOH / g. Moreover, when using for a color filter or CCD, it is preferable that the alkali-soluble resin has no discoloration and has light resistance.
In the curable resin composition of the present invention , as the preferable alkali-soluble resin, an acrylic copolymer having an acid value in the range of 30 to 150, preferably 35 to 120 (mgKOH / g polymer) (hereinafter referred to as “acrylic”). May be referred to as a “binder resin”).

  The acrylic binder resin is not particularly limited as long as it is an acrylic copolymer that satisfies the above acid value, dissolves in a solvent described later, and forms a film to function as a binder resin. Can do.

  As a preferable structural unit of the acrylic binder resin, a copolymer of (meth) acrylic acid and another monomer capable of copolymerization may be mentioned.

  Examples of other monomers copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent. Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth). Examples include acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl acrylate, tolyl acrylate, naphthyl acrylate, and cyclohexyl acrylate.

  Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like. be able to.

Particularly preferred other copolymerizable monomers are phenyl (meth) acrylate, benzyl (meth) acrylate and styrene.
These other copolymerizable monomers can be used singly or in combination of two or more.

  Particularly preferred as the acrylic binder resin is a copolymer of (meth) acrylic acid and at least one monomer selected from phenyl (meth) acrylate, benzyl (meth) acrylate, and styrene.

As described above, the acrylic binder resin preferably has an acid value in the range of 30 to 150 mgKOH / g. If the oxidation of the acrylic binder resin is within the above range, the acrylic binder resin will not be so soluble in alkali that the appropriate development range (development latitude) will not be reduced, and it will dissolve in alkali. And the development does not take too much time.
Moreover, the weight average molecular weight Mw (polystyrene conversion value measured by GPC method) of the acrylic binder resin is used to realize a viscosity range that is easy to use in a process such as applying a color resist, and to secure film strength. Therefore, it is preferably 5,000 to 100,000, more preferably 8,000 to 50,000.

In order to set the acid value of the acrylic binder resin within the range specified above, it can be easily performed by appropriately adjusting the copolymerization ratio of each monomer.
In addition, in order to make the range of the weight average molecular weight of the acrylic binder resin within the above range, it is easily performed by using an appropriate amount of a chain transfer agent according to the polymerization method when copolymerizing the monomers. be able to.
The acrylic binder resin can be produced, for example, by a known radical polymerization method. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an acrylic binder resin by radical polymerization can be easily set by those skilled in the art. You can also know the conditions experimentally.

  Moreover, in order to improve the crosslinking efficiency, the alkali-soluble resin may have a polymerizable group in the side chain, a polymer containing an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain, etc. Is also useful as an alkali-soluble resin in the present invention. Examples of polymers containing these polymerizable groups are shown below, but are not limited to the following as long as they contain alkali-soluble groups of bases such as COOH groups, OH groups, and ammonium groups and carbon-carbon unsaturated bonds. . A copolymer of an OH group such as 2-hydroxyethyl acrylate, a COOH group such as methacrylic acid, and a monomer such as an acrylic or vinyl compound that can be copolymerized therewith has an reactivity with the OH group. A compound obtained by reacting a compound having an epoxy ring and a carbon-carbon unsaturated bond group, for example, a compound such as glycidyl acrylate, can be used. In the reaction with OH, in addition to the epoxy ring, a compound having an acid anhydride, an isocyanate group, and an acryloyl group can also be used. Further, a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring disclosed in JP-A-6-102669 and JP-A-6-1988 is saturated or unsaturated polyunsaturated. A reaction product obtained by reacting a basic acid anhydride can also be used. As a compound having both an alkali solubilizing group and a carbon-carbon unsaturated group such as COOH, for example, Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd., acid value: 25 KOH mg / g, polyacryl (meth) acrylate), Photomer 6173 (COOH-containing Polyurethane acrylic oligomer, manufactured by Diamond Sharmrock Co., Ltd.), Biscote R-264, KS resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Taicel Chemical) Kogyo Co., Ltd.), Ebecry 13800 (Daicel UCP Co., Ltd., acid value: 25 KOH mg / g, acid functional epoxy acrylate) and the like.

Among these various resins, the alkali-soluble resin used in the present invention includes polyhydroxystyrene resin, polysiloxane resin, acrylic resin, acrylamide resin, and acrylic / acrylamide copolymer resin from the viewpoint of heat resistance. Acrylic resins, polyhydroxystyrene resins, and polysiloxane resins are more preferable. From the viewpoint of control of developability, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable.
Examples of the acrylic resin include copolymers consisting of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and cyclomer P series, Plaxel CF200 series ( All are manufactured by Taicel Chemical Industry Co., Ltd.), Ebecry 13800 (manufactured by Daicel UCP Co., Ltd.), Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Biscote R-264, KS resist 106 (all of which are Osaka Organic Chemical) Kogyo Co., Ltd.) is preferable.
In addition, in order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) propane and epichlorohydrin, and the like are also useful.

The content of the binder in the curable resin composition in the present invention is preferably 5 to 90% by mass, and more preferably 10 to 60% by mass, based on the total solid content of the composition. When the content of the binder is within the above range, the film strength is sufficient, and since the acidic content is reduced, the solubility can be easily controlled, and a relatively large amount of pigment can be used. Therefore, a sufficient image density can be obtained.

Moreover, the curable resin composition in this invention can be used only by thermosetting, without photocuring. As its application, an insulating film for a multilayer circuit board of a printed circuit board that requires a low dielectric constant is useful. In this case, the binder is preferably a bifunctional or trifunctional epoxy resin capable of maintaining regularity. Examples of such an epoxy resin include those represented by the following structural formula. In this case, a curing catalyst such as imidazole can be separately used for the epoxy. In the insulating film, generally, the conduction hole can be formed by laser drilling with a carbon dioxide laser when a multilayer circuit is formed by assembling an insulating layer such as drilling or a build-up substrate.

(Polymerization initiator)
As the polymerization initiator, a photopolymerization initiator, a thermal polymerization initiator, or the like can be used. That is, when the curable resin composition in the present invention is formed as a photopolymerization, thermal polymerization, or photo / thermal polymerization composition, a polymerization initiator corresponding to each system is used.

-Photopolymerization initiator-
A conventionally well-known thing can be used as a photoinitiator used in this invention. For example, active halogen compounds such as halomethyloxadiazole compounds described in JP-B-57-6096, halomethyl-s-triazines described in JP-B-59-1281 and JP-A-53-133428, etc. Aromatic carbonyl compounds such as ketals, acetals and benzoin alkyl ethers described in U.S. Pat. No. 4,318,791 and European Patent No. 88050A, and fragrances such as benzophenones described in U.S. Pat. No. 4,199,420. Group ketone compounds, (thio) xanthones, acridine compounds described in French Patent No. 2456741, coumarins, lophine dimer compounds described in JP-A-10-62986, and JP-A-8-15521 And the sulfonium organoboron complexes described The

  Specifically, an acetophenone initiator (for example, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, etc.), ketal initiators (eg, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal, etc.), benzophenone initiators (eg, benzophenone, 4 , 4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, 1-hydroxy-cyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl)- Thanone-1, 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, etc. ), Benzoin-based and benzoyl-based initiators (eg, benzoinpropyl ether, benzoin butyl ether, benzoin methyl ether, methyl-o-benzoylbenzoate, etc.), xanthone-based initiators (diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, etc. ), Triazine initiators (for example, 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine) 2,4-bis (Trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2,4-bis (trichloromethyl) -6-biphenyl-s-triazine, 2,4-bis (Trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl-2,6-di (trichloromethyl) -s-triazine, methoxystyryl-2,6-di (trichloromethyl) -S-triazine, 3,4-dimethoxystyryl-2,6-di (trichloromethyl) -s-triazine, 4-benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o -Bromo-pN, N- (diethoxycarbonylamino) phenyl) -2,6-di (chloromethyl) -s-triazine, 4- (p-N N- (diethoxycarbonylamino) phenyl) -2,6-di (chloromethyl) -s-triazine, etc.), halomethyloxadiazole-based initiators (for example, 2-trichloromethyl-5-styryl-1,3 , 4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (naphth-1-yl) -1,3,4- Oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, etc.), acridine initiators (for example, 9-phenylacridine, 1,7-bis (9- Acridinyl) heptane, etc.), coumarin initiators (eg 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro 5-diethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, etc.) , Lophine dimer initiators (eg, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- ( o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, etc.), 1-phenyl-1,2-propanedione- 2- (o-ethoxycarbonyl) oxime, o-benzoyl-4 ′-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trime Examples include tilphenylcarbonyl-diphenylphosphonyl oxide, hexafluorophospho-trialkylphenylsulfonium salt, 2-mercaptobenzimidazole, 2,2'-benzothiazolyl disulfide and the like.

0.5-60 mass% is preferable with respect to the photopolymerizable monomer in a composition, and, as for content of the photoinitiator in the curable resin composition in this invention , 1-50 mass% is preferable. When the content of the photopolymerization initiator is within the above range, the polymerization reaction is not inhibited and the film strength can be prevented from being lowered.

-Thermal polymerization initiator-
In the light and / or thermosetting resin composition of the present invention, only the thermal polymerization initiator can be used without using the photopolymerization initiator. That is, in this case, it is possible to cure only with heat, and to form a conduction hole for ITO wiring or the like by drilling with a laser after curing. Further, in this case, since alkali development is not required, a binder-insoluble type such as an acrylic resin such as methyl methacrylate having no carboxylic acid or a polyester resin used for coating is used. Things can also be used. As the thermal polymerization initiator, generally known organic peroxide compounds and azo compounds can be used.

In the present invention, two or more organic peroxide compounds and azo compounds can be used in combination as the thermal polymerization initiator. It can also be used in combination with the above-described photopolymerization initiator.
Examples of the organic peroxide compound include peroxyketal compounds such as 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane; diacyl peroxide compounds such as benzoyl peroxide; t-butylperoxybenzoate Peroxy ester compounds such as Examples of the azo compound include 1,1′-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl) azo] formamide (2- (carbamoylazo) isobutyro Nitrile) and the like. These compounds have a relatively high half-life temperature, good storage stability, and good curing characteristics (characteristics such as curing speed and solvent resistance after curing).
Content in the composition of an organic peroxide type | system | group and an azo type compound is 0.5-20 mass% with respect to the quantity of the polymerizable monomer which has an ethylenic double bond in curable resin composition. It is preferably 1 to 15% by mass. When the blending amount of the organic peroxide compound and the azo compound is less than 0.5% by mass relative to the polymerizable monomer having an ethylenic double bond, the effect is not so much. The viscosity may change over time. In addition, among organic peroxide compounds and azo compounds, the viscosity of the composition will deteriorate with time unless one having a relatively high half-life temperature (preferably 50 ° C. or higher, more preferably 80 ° C. or higher) is used. May change.

-Other polymerization initiators-
Further, those containing both a benzophenone skeleton and a peroxide in the structure as shown in the following structural formula shown in JP-A-2003-255531 are suitable as initiators for photopolymerization, thermal polymerization, and photo / thermal polymerization. .

[Wherein, R ¹ and R ² each independently represents an alkyl group having 1 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms. R ³ and R ⁴ are each independently a hydrogen atom, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a halogen atom, cyano Represents a group, a nitro group or a dialkylamino group having 2 to 20 carbon atoms. m is 0, 1 or 2, and n is 1, 2 or 3. ]

  Specific examples of the compound represented by the above structural formula include the following.

(solvent)
In this invention, a solvent can be used when preparing the curable resin composition in this invention . Examples of the solvent include esters, specifically ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, and alkyl esters. , Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, 3-oxy 3-oxypropionic acid alkyl esters such as ethyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2 − Ethyl xylpropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy Methyl-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, pyruvin Propyl acid, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol Monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones such as methyl ethyl ketone, Cyclohexanone, 2-heptanone, 3-heptanone, etc .; aromatic hydrocarbons such as toluene, xyles and the like.

  Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl Carbitol acetate, propylene glycol monomethyl ether acetate (PGMEA) and the like are preferably used.

  These solvents may be used alone or in combination of two or more.

(Coloring agent)
In the present invention, by further containing a colorant, the curable resin composition in the present invention can be used for forming a color filter layer (pixel) and the like.

  As the colorant that can be used in the present invention, various conventionally known pigments, (insulating) carbon black, or dyes can be used singly or in combination.

As the pigment that can be used in the present invention, conventionally known various inorganic pigments or organic pigments can be used. The pigment preferably has a high transmittance, and it is preferable to use a pigment that is as fine as possible. However, in consideration of handling properties, the average particle size is preferably 0.01 μm to 0.1 μm, more preferably 0.01 μm to 0. .05 μm pigment is used.
The inorganic pigment is a metal compound represented by a metal oxide, a metal complex salt, or the like, specifically, a metal oxide such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, etc. And composite oxides of the above metals.

Examples of the organic pigment include CIPigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199, ;
CIPigment Orange 36, 38, 43, 71;
CIPigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177,209, 220, 224,
242, 254, 255, 264, 270; CIPigment Violet 19, 23, 32, 39;
CIPigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
CIPigment Green 7, 36, 37;
CIPigment Brown 25, 28;
CIPigment Black 1, 7;
Etc.

In the present invention, those having a basic N atom in the structural formula of the pigment can be preferably used. These pigments having basic N atoms exhibit good dispersibility in the curable resin composition of the present invention . Although the cause is not fully elucidated, it is presumed that the good affinity between the photosensitive polymerization component and the pigment has an effect.

  Among the various pigments, examples of pigments that can be preferably used in the present invention include, but are not limited to, the following.

CIPigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
CIPigment Orange 36, 71,
CIPigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,
CIPigment Violet 19, 23, 32,
CIPigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
CIPigment Black 1

  These organic pigments are used alone or in various combinations in order to increase color purity. Specific examples of such combinations are shown below. As red pigments, anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments alone or at least one of them, disazo yellow pigments, isoindoline yellow pigments, quinophthalone yellow pigments or perylene red pigments, A mixture of these is used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177 and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224 and diketopyrrolopyrrole pigments include C.I. I. Pigment red 254, and C.I. I. Pigment yellow 83 or C.I. I. Good mixing with Pigment Yellow 139. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. When the mass ratio of the red pigment to the yellow pigment is in the above range, the light transmittance of 400 nm to 500 nm can be suppressed, the color purity can be increased, and the main wavelength does not become shorter than NTSC. The deviation from the target hue is small. The mass ratio of the red pigment to the yellow pigment is particularly preferably 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

  As the green pigment, a halogenated phthalocyanine pigment alone or a mixture with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment is used. I. Pigment green 7, C.I. I. Pigment green 36 or C.I. I. Pigment green 37, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixture with CI Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150. When the mass ratio is within the above range, the light transmittance of 400 nm to 450 nm can be suppressed, and the color purity can be increased. Further, when the mass ratio is within the above range, the dominant wavelength does not become a long wavelength and the deviation from the NTSC target hue is small. A more preferred mass ratio is in the range of 100: 30 to 100: 120.

  As the blue pigment, a phthalocyanine pigment alone or a mixture with a dioxazine purple pigment is used. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 30, more preferably 100: 10 or less.

  Further, a curable resin composition having good dispersibility and dispersion stability by using a powdered processed pigment in which the above pigment is finely dispersed in an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate copolymer and an ethyl cellulose resin. You can get things.

Moreover, the curable resin composition in the present invention can also form a black matrix by using a colorant in which carbon, titanium carbon, iron oxide, titanium oxide or the like is used alone or in combination.

  As the pigment, a pigment coated with a pigment resin film can also be used. As said pigment coating resin, resin, such as an acrylic resin containing a carboxyl group, can be mentioned. Examples of the acrylic resin containing a carboxyl group include a monomer having a carboxyl group such as (meth) acrylic acid, (anhydrous) maleic acid, crotonic acid, itaconic acid, fumaric acid, styrene, α-methylstyrene, (meta ) Methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, vinyl acetate, acrylonitrile, (meth) acrylamide, glycidyl (meth) acrylate, allyl Glycidyl ether, glycidyl ethyl acrylate, glycidyl crotonic acid ether, (meth) acrylic acid chloride, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, N-methylol acrylamide, N, N dimethyl acrylamide, N-meta Leroy Le morpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl acrylamide, polymers of copolymerized copolymerization component such as. Among them, preferred is an acrylic resin containing at least (meth) acrylic acid or (meth) acrylic acid alkyl ether as a constituent monomer, and more preferred is an acrylic resin containing (meth) acrylic acid and styrene.

Moreover, in order to improve the crosslinking efficiency, these resins may have a polymerizable group in the side chain, and an ethylenic double bond can be added to the resin side chain. By imparting a double bond to the resin side chain, the photocurability is increased, so that the resolution and adhesion can be further improved.
Examples of the synthesis means for introducing an ethylenic double bond include the methods described in JP-B-50-34443 and JP-B-50-34444.
Specific examples include a method of reacting a compound having both a glycidyl group, an epoxycyclohexyl group and a (meth) acryloyl group with a carboxyl group or a hydroxyl group, or acrylic acid chloride. For example, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, (3,4-epoxycyclohexyl) methyl (meth) acrylate, (meth) By using a compound such as acrylic acid chloride or (meth) allyl chloride and reacting with a resin having a carboxyl group or a hydroxyl group, a resin having a polymer group in the side chain can be obtained.

  A dispersing agent is usually used for dispersing the organic pigment and carbon. As the dispersant, the pigment coating resin is used as it is, and a dispersant as described later can be used in combination. These dispersants can be used alone or in combination. By the dispersion treatment, the resin is adsorbed on the surface of the pigment, and at the same time, the aggregation of the pigment particles is broken and the particle size is reduced.

  As the dispersant, Anti-Terra-U, Disperbyk-160, 161, 162, 163 manufactured by BYK, Solspers 20000, 24000GR, 26000, 28000 manufactured by ZENECA, DA-703-50, NDC- manufactured by Enomoto Kasei Co., Ltd. 8194 L, NDC-8203L, NDC-8257L, KS-860, Kaogen's homogenal L-18, L-1820, L-95, L-100, Nippon Paint VP5000, Goodrich E5703P, Known dispersion resins such as VAGH manufactured by Union Carbide, UR8200 manufactured by Toyobo, and MR113 manufactured by Nippon Zeon can be used.

  Further, phthalocyanine derivatives (trade name: EFKA-745 (manufactured by Morishita Sangyo)); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, No. 90, No Cationic surfactants such as .95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.) and W001 (manufactured by Yusho); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, poly Nonionic surfactants such as oxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; F-top EF301, EF303, EF352 (manufactured by Shin-Akita Kasei), MegaFuck F171 F172, F173 (Dainippon Ink), Florard FC430, FC431 (Sumitomo 3M), Asahi Guard AG710, Surflon S382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-1068 Fluorosurfactants such as Asahi Glass; anionic surfactants such as W004, W005 and W017 (manufactured by Yusho); EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, Polymer dispersants such as EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (San Nopco); Solsperse 3000, 5000, 9000 1200 , 13240, 13940, 17000, 24000, 26000, 28000, etc., Solsperse dispersants (manufactured by Geneca); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka) and Isonet S-20 (Sanyo Kasei) are also included.

In the present invention, when the colorant is a dye, it is preferable to obtain a curable resin composition by uniformly dissolving in the composition.
The dye that can be used as the colorant constituting the curable resin composition in the present invention is not particularly limited, and conventionally known dyes for color filters can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 The dyes disclosed in JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like can be used.
Chemical structures include pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene , Phthalocyanine, benzopyran, and indigo dyes can be used.

The content rate of the coloring agent in the curable resin composition in this invention is 20-60 mass% with respect to the total solid, Preferably it is 25-65 mass%. The higher the content, the better the light-shielding properties and the high chromaticity color characteristics can be obtained, but the relative dielectric constant may be increased by reducing the resin component.

(Other additives)
In the curable resin composition of the present invention , in addition to the above-described components, various additives, for example, a filler, a polymer compound other than the alkali-soluble resin, a surfactant other than the above, an adhesion promoter, as necessary. Further, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, and the like can be blended.

  Specific examples of these additives include fillers such as glass and alumina; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, hydroxyl group An acid-soluble polymer added to an acid anhydride, an alcohol-soluble nylon, an alkali-soluble resin such as a phenoxy resin formed from bisphenol A and epichlorohydrin; a nonionic, a kachin-based, an anionic surfactant, Specifically, a phthalocyanine derivative (commercially available product EFKA-745 (manufactured by Morishita Sangyo)); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.) and W001 (manufactured by Yusho); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxy Ethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (manufactured by BASF, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1 Nonionic surfactants such as W004, W005, W017 (manufactured by Yusho) and the like; EFKA-46, EFKA-47, EFKA-47EA, EF Polymer dispersion such as A polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (San Nopco) Agents: Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, and other various Solsperse dispersants (manufactured by Geneca); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Asahi Denka) and Isonet S-20 (manufactured by Sanyo Chemical);

  Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltri Methoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyl Adhesion promoters such as methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol) , 2, -Antioxidants such as di-t-butylphenol; ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone; and sodium polyacrylate And the like.

Further, when the alkali solubility in the unirradiated part is promoted to further improve the developability of the curable resin composition in the present invention , an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less is further used. Acid additions can be made. Specifically, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, glutar Aliphatic dicarboxylic acids such as acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as carbaryl acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesin Aromatic polycarboxylic acids such as acid, merophanic acid, pyromellitic acid; phenylacetic acid, Doroatoropa acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

In addition to the above components, the curable resin composition in the present invention preferably further contains a polymerization inhibitor in order to suppress a change in viscosity over time at room temperature or refrigerated storage of the resin composition. Hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-Methyl-6-tert-butylphenol), 2-mercaptobenzimidazole and the like are useful. The storage stability can be improved by adding a thermal polymerization inhibitor to the curable resin composition of the present invention . As a compounding quantity of a polymerization inhibitor, it is 100 ppm-1 mass% normally with respect to a polymerizable monomer, Preferably about 500 ppm is added.

<Method for preparing curable resin composition>
The curable resin composition in the present invention includes a binder, a polymerizable monomer having an ethylenic double bond, and a polymerization initiator, and, if necessary, a colorant and other additives, a solvent, It can be prepared by mixing and mixing and dispersing using various mixers and dispersers.
The mixing and dispersing step preferably comprises kneading and dispersing followed by fine dispersion treatment, but it is also possible to omit the kneading and dispersion and perform only fine dispersion treatment.

The cured product of the curable resin composition according to the present invention (the resin film for a color filter of the present invention ) has excellent transparency, light resistance, heat resistance, stripping solution resistance (including NMP resistance), and development characteristics with an alkaline aqueous solution. Therefore, it can be used for various purposes. Mainly used as solder resist for printed circuit boards, insulating materials for build-up boards, especially for LCDs, for TFT interlayer insulating films, for COA protective films (planarizing films), and for spacers Can do. Further, since the curable resin composition in the present invention into which a colorant is introduced can exhibit the above various resistances as a color filter material, it is disclosed in FIG. 1 of Japanese Patent Application Laid-Open No. 9-31347, for so-called COA. Useful as. In addition, since the curable resin composition according to the present invention containing a colorant is excellent in various resistances, it can be used for a normal color filter without a protective film. Production rationalization can be expected.

  As the TFT substrate, for example, non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film to these, solid-state imaging elements, etc. And a photoelectric conversion element substrate such as a silicon substrate. Furthermore, a plastic substrate is also possible. On these substrates, a black matrix and black stripes that usually isolate each pixel are formed.

A normal TFT type LCD is manufactured by separately manufacturing a TFT substrate and a color filter substrate and bonding them together with a liquid crystal in between. In this case, the color filter is formed by forming a black matrix and each pixel and then forming ITO on the entire surface by a vacuum film formation method such as sputtering or vapor deposition. For this reason, a normal TFT type LCD does not require subsequent patterning, and the underlying color filter is generally used in a situation where the stripper solution resistance, the low dielectric constant, and the contact hole are unnecessary. For this reason, the fabrication of the TFT substrate and the fabrication of the color filter are performed by different companies and have made their own progress. The manufacturing technology of the TFT substrate has been progressed mainly by using the manufacturing technology of the semiconductor, but as the size of the substrate increases, the substrate transport method, the exposure machine and the exposure method, the positive resist coating machine and the coating method In addition, it has problems such as low dielectric constant of interlayer insulating film, resistance to stripping solution and coating method. The resin film for a color filter of the present invention can be suitably used as an interlayer insulating film of this TFT substrate.

  However, in recent years, the use of monitors, TVs, etc. has expanded, and in order to increase production efficiency year by year, newly built mass production factories are using a larger substrate area. The alignment with the pixel is technically difficult. For this reason, if the black matrix is made thick and defects due to misalignment are reduced, the aperture ratio decreases and the screen becomes dark. However, increasing the brightness of the backlight to brighten the screen causes various problems such as a backlight life problem, a heat generation problem, and a power consumption problem.

  For these reasons, a COA method for producing a color filter on the TFT substrate side has been studied. Originally, since the COA forms the color filter directly on the TFT as described above, the black matrix can be made thin because basically no alignment is required. For this reason, the aperture ratio can be increased, and it is not necessary to increase the luminance of the backlight, so that the power consumption of the backlight can be reduced. However, the COA method has been a technology that has been attracting attention for a long time. However, by forming a color filter directly on the TFT, the conventional acid resistance, stripping solution resistance, low dielectric constant, contact hole, etc., which will be described later, are used. Color filter materials have required characteristics that cannot be met, and have not been widely used.

In the above color filter manufacturing method, a TFT film is usually formed on a substrate, each pixel pattern is formed thereon, a color filter layer is provided, and a metal such as a chromium thin film is usually provided on the portion facing the gate electrode. A light-shielding film comprising a film or a coating film in which a black colorant such as carbon black is dispersed is formed. Further, a pixel electrode corresponding to the gate electrode is formed in a pattern on the color filter layer. For the pixel electrode, a positive photoresist is applied to a metal oxide thin film formed by sputtering, vapor deposition or other metal oxide such as ITO, tin oxide, or indium oxide. An electrode pattern is formed. Further, after the pixel electrode is formed, the resist film remaining on the electrode is removed with a stripping solution. The removal of the cured resist film with the stripping solution is usually performed with an organic solvent having a high dissolving power at a high temperature close to 100 ° C., so that the color filter layer may be destroyed. Therefore, a pixel protective film (overcoat layer) may be formed between the color filter layer and the pixel electrode in order to protect the color filter layer from the peeling solution. The curable resin composition in the present invention contains a colorant and is preferably used as a color filter for COA. However, the curable resin composition is used as an overcoat (a resin film for a color filter of the present invention) without a colorant. It can also be suitably used to protect the color filter.

The raw materials for the plastic substrate include (1) amorphous polyolefin, (2) polyethersulfone, (3) polyglutarimide, (4) polycarbonate, (5) from the viewpoint of optical properties, heat resistance, mechanical strength, etc. Examples include polyethylene terephthalate, (6) polyethylene naphthalate, (7) norbornene polymer, (8) polyimide using bisaniline fluorene as a diamine component, and (9) polyester composed of bisphenol fluorene and dibasic acid. Among these, (2) polyethersulfone, (4) polycarbonate, (5) polyethylene terephthalate, and (7) norbornene polymer are preferable. Such raw materials are particularly preferred for LCD applications.
Properties required for plastic substrates include low thermal expansion (preventing deterioration of display accuracy associated with the curing process during color filter fabrication), gas barrier properties (ensuring liquid crystal stability), optical transmittance and optical isotropy, etc. Characteristics, surface smoothness, etc. Regarding thermal expansion, the thermal expansion coefficient is preferably 10 ⁻⁴ or less.
The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.
Moreover, in TFT, performing a high temperature treatment at 400 ° C. or higher in the annealing step is a bottleneck when using a plastic substrate. For this reason, research on lowering the temperature in the annealing process is progressing. On the other hand, in order to avoid the temperature problem, a method of transferring the TFT to a plastic substrate after forming the TFT on a glass substrate or the like has also been studied. Yes.

The pixel is a layer formed by applying a curable resin composition on the TFT substrate. The coating thickness (after drying) of the curable resin composition is generally 0.3 to 5.0 μm, preferably 0.5 to 3.5 μm. The higher the coating thickness, the higher the chromaticity can be achieved. However, the thicker the coating thickness, the lower the resolution of the contact hole.
As the pixel electrode, a conventionally known pixel electrode can be used without any particular limitation.

[Method for Producing COA Using Curable Resin Composition in the Present Invention]
Below, the usage example in the most suitable COA use of the curable resin composition in this invention is described.
A normal color filter is provided on a glass substrate and bonded to a TFT substrate. On the other hand, the COA technique directly forms a color filter on a TFT substrate, and it is necessary to consider the following points (i) to (iii) as compared with a normal color filter material.
(I) Low dielectric constant In the COA, since the pixel electrode is directly provided on the TFT, the voltage is directly applied to the color filter. Therefore, the color filter material is required to be a low dielectric constant material.
(Ii) Contact hole In the COA, the ITO wiring of the pixel electrode needs to be connected to the TFT provided therebelow. For this reason, it is required that the contact hole be reliably formed during development.
(Iii) Resistance to stripping solution In COA, electrode formation is essential for each pixel. The electrodes are formed by sputtering ITO on the pixels, patterning and etching wiring with a positive resist, and then removing the remaining positive resist with a high-temperature stripping solution, usually about 80 ° C. For this reason, in COA, a low swelling rate is required so that the color filter or the like is not attacked by the stripping solution and is swollen by the stripping solution, so that ITO cannot follow and disconnect.

  On the other hand, when a color filter is manufactured on a TFT substrate, the appearance of a defective product in the color filter manufacturing process is a defective product including the TFT substrate, which is very risky. However, as LCDs have recently become larger as typified by liquid crystal TVs, the size of the production substrate has also increased year by year. Furthermore, since the liquid crystal injection time becomes longer, the liquid crystal injection method is changing to the dropping method. As described above, with the increase in the substrate size and the application of the liquid crystal dropping method, when the color filter and the TFT substrate are bonded, the alignment accuracy between the color filter pixel and the TFT becomes severe. Therefore, it is becoming very difficult to correct the positional deviation between the central portion and the peripheral portion of the substrate.

  In this respect, since the COA provides the pixels directly on the TFT, there is no fear of positional displacement, and a substrate on which ITO is sputtered over the entire surface may be prepared as the counter substrate sandwiching the liquid crystal. For this reason, the necessity for alignment becomes about the position of the sealing agent, and the working efficiency is dramatically improved. As described above, since the COA technology does not require alignment accuracy (it is gradual), the line width of the black matrix can be made very narrow, the aperture ratio can be increased, and the power consumption of the backlight can be reduced. There is a merit that can be kept low. In this way, various studies have been made on COA, which may become an indispensable technology for future large LCD substrates. However, as described above, the risk of producing a color filter on a TFT and the color filter material that can meet the above requirements (i) to (iii) are not provided, so that the adoption is advanced. The current situation is not.

The curable resin composition in the present invention solves the problems caused by the above-mentioned materials for COA, and the method of use can be used depending on the purpose.
That is, the most desirable method is a method for producing a color filter using the curable resin composition of the present invention containing a colorant. Further, when the flatness cannot be satisfied by producing a color filter on the TFT, various required characteristics can be obtained by using the curable resin composition according to the present invention which does not contain a colorant as a flattening film. Can be satisfied. Naturally, the planarization layer has good compatibility with the underlying color filter, so that the adhesion is good and the defect rate from the COA material surface can be minimized.

-Manufacturing method and use method of color filter-
As described above, the color filter is formed by applying a curable resin composition of the present invention containing a colorant on the TFT substrate, to form a coating film of the curable resin composition, pattern exposure coating film, an alkali Development and post-bake treatment are performed to form each pixel, a transparent electrode (ITO) film is formed on each pixel by sputtering, then a positive photoresist coating film is formed, and a pattern is formed on the photoresist film. It can be manufactured by performing exposure and development, further etching the necessary ITO to form a pixel electrode pattern, and then removing the photoresist film remaining on the pixel electrode pattern with a stripping solution.

In order to form a coating film by applying the curable resin composition in the present invention, a coating method such as spin coating, slit coating, casting coating, roll coating, or the like, directly or via another layer. Application, drying (pre-baking), etc. Drying (prebaking) of the curable resin composition layer applied on the substrate can be performed at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds using a hot plate, an oven or the like. In recent years, since the substrate has been increased in size, slit coating is also effective as a method for forming a coating film, and such a coating method is becoming common.

The pattern exposure of the coating film is made up of pixels of each color (three colors or four colors) by exposing through a predetermined mask pattern, curing only the coating film portion irradiated with light, and developing with a developer. This can be done by forming a patterned film. As radiation that can be used in exposure, ultraviolet rays such as g-line and i-line are particularly preferably used.
Next, by performing an alkali development treatment, the light-irradiated portion is eluted in the alkaline aqueous solution by the exposure, and only the photocured portion remains. As the developer, an organic alkali developer that does not damage the underlying circuit or the like is desirable. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.
Examples of the alkali include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene. An alkaline aqueous solution obtained by diluting an organic alkaline compound such as the above with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass is used. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.
Next, excess developer is washed away and dried, followed by heat treatment (post-bake). Thus, the said process can be repeated sequentially for every color, and a cured film can be manufactured. Thereby, a color filter is obtained.

The post-baking is a heat treatment after development for complete curing, and usually a heat curing treatment at 200 ° C. to 240 ° C. is performed.
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater or the like so that the coating film after development is in the above-mentioned condition. be able to.

Then, a transparent electrode (ITO) film is formed on the formed pixel by sputtering, a positive photoresist film is further formed thereon, pattern exposure and development are performed, and unnecessary with chemicals such as hydrofluoric acid. ITO is etched to form pixel electrodes. As the photoresist used at this time, a positive photoresist having etching resistance is required. In addition, pattern exposure, development, and etching can be performed using any known method without limitation.
Next, the positive resist remaining on the formed pixel electrode is quickly stripped and removed with a stripping solution. There is no restriction | limiting in particular as this stripping solution, A conventionally well-known stripping solution can be used. For example, various publications disclosed in JP-A-51-72503, JP-A-57-84456, JP-A-6-222573, etc., and U.S. Pat. No. 4,165,294 and European Patent No. 0119337. These organic solvents can be used. A typical stripping solution includes a mixed solvent of monoethanolamine (MEA) and dimethyl sulfoxide (DMSO). Further, by using an organic solvent heated to 60 ° C. or higher as the stripping solution, the stripping process can be shortened, and further, there can be no problem of development residue. Since the curable resin composition in the present invention is particularly excellent in stripping solution resistance, the coating film of the color filter does not peel off even when an organic solvent heated to 60 ° C. or higher is used. Can be removed.

Color filters, typically used for various display devices such as TFT liquid crystal display device in the structure as disclosed in the drawings of JP-A-9-311347 JP.
Since the color filter is a COA type, alignment is easy and the aperture ratio can be increased. In addition, since the pixel is formed using the curable resin composition in the present invention , the resistance to the stripping solution is high, so that the yield rate is high and the production efficiency is also high. In addition, heat discoloration, low dielectric constant, film thickness uniformity, resolution, voltage holding ratio, light resistance and the like normally required for color filters are also good.

The structure of the color filter is that the pixel is composed of only one layer in the embodiment (1) of the present invention, whereas in the present embodiment, the color filter is formed from the coating film of the curable resin composition for pixels. The pixel film and the pixel protective film made of the curable resin composition for the pixel protective film formed on the pixel film are provided between the substrate and the pixel electrode.
The film thickness of the pixel film is preferably 0.3 to 5.0 μm, and more preferably 0.5 to 3.5 μm. The higher the coating thickness, the higher the chromaticity can be achieved. However, the thicker the coating thickness, the lower the resolution of the contact hole. The film thickness of the pixel protective film is preferably 0.2 to 5.0 μm, more preferably 0.2 to 3.0 μm. Further, it is desirable that the unevenness of the underlying pixel is flattened so that the surface is smooth.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[Measurement of relative permittivity]
a) On a chromium-coated glass substrate (one side 75 mm, chromium film thickness 0.3 μm), the rotation speed is adjusted so that the film thickness after curing (after post-baking) is 2.5 μm, and a spin coater is used. The curable resin compositions described in Tables 1 to 4 below were applied.
b) Next, the chromium-coated glass substrate on which the coating film was formed was pre-baked on a hot plate at 100 ° C. for 120 seconds, and the solvent was dried.
c) After pre-baking, the coating film was irradiated with an exposure amount of 200 mJ / cm ² using a 2.5 kw ultra-high pressure mercury lamp.
d) Next, the chromium-coated glass substrate on which the coating film was formed was heated and cured (post-baked) at 220 ° C. for 60 minutes with a hot air circulation dryer to prepare a test piece.
e) After post-baking, the coating film at one corner of the test piece was scraped to expose the chromium surface.
f) Next, a silver paste was spin-coated on the back surface of the test piece and air-dried. Then, the chromium exposed surface on the front surface and the silver paste coated surface on the back surface were electrically connected (connected) with the silver paste.

g) After drying, using a vacuum deposition apparatus (trade name: Ion Sputter E1030, manufactured by Hitachi, Ltd.) on the surface coating surface of the test piece, as shown in FIG. A main electrode 2 (inner circle) and a guard electrode 3 (outer circle) having a deposition thickness of about 50 nm were prepared. On the substrate 1, the chromium surface 4 shaved in e) is exposed.

h) After the electrode was prepared, the thickness of the coating film on the part without the electrode was measured with a stylus type surface shape measuring instrument (trade name: DEKTAK3, manufactured by ULVAC, Inc.).
i) Next, a dielectric test fixture 16451B and an electrode were attached to a capacitance measuring instrument (precision impedance analyzer 4294A, manufactured by Agilent Technologies, Inc.), and the substrate in h) above was attached, and 1 kHz, 0.5 V The relative dielectric constant ε ′ and dielectric loss tangent δ when an AC voltage was applied were measured. The results are shown in Tables 1-4.

(Development characteristics)
a) The number of rotations was adjusted so that the film thickness after curing (after post-baking) was 2.5 μm on a glass substrate for LCD (trade names: 1737, 1.1t, manufactured by Corning), and displayed on a spin coater. The curable resin composition described in 1-4 was applied.
b) Next, the glass substrate on which the coating film was formed was prebaked on a hot plate under conditions of 100 ° C. and 120 seconds, and the solvent was dried.
c) After pre-baking, the glass substrate on which the coating film was formed was irradiated with light at an exposure amount of 200 mJ / cm ² through a mask imitating contact holes of various sizes using a 2.5 kw ultra high pressure mercury lamp.
d) Next, development and washing by immersing in an organic alkali developer (trade name: CD-2000, manufactured by Fuji Film Arch Co., Ltd., 26 ° C., organic alkali developer, diluted with 12.5% pure water) for 50 seconds. , Dried.
e) After drying, the sample was heat-cured (post-baked) at 220 ° C. for 60 minutes in a hot-air circulating dryer to prepare a test piece.
f) After post-baking, the pattern shape of the contact hole is observed with an optical microscope, and to what size the contact hole is missing (through which the contact hole is formed) according to the following criteria evaluated. The results are shown in Tables 1 to 4 below.

[Evaluation]
A: A contact hole of 10 μm □ or more was missing.
○: A contact hole of 20 μm □ or more was missing.
X: A contact hole of 20 μm □ or more was not removed.

[Release solution resistance]
For the stripping solution resistance, the film thickness of the test piece was measured by the following procedure, and the swelling ratio was calculated. However, those with poor stripping solution resistance cannot be measured for film thickness because the coating film dissolves in the stripping solution or peels off from the substrate when immersed in the stripping solution. Such a thing was evaluated as "x".

a) For each Example and Comparative Example, the film thickness (FT ₀ ) of the test piece in f) of the above [Development Characteristics] was measured.
b) After measurement, a mixture of monoethanolamine (MEA) and dimethyl sulfoxide (DMSO) (MEA / DMSO = 7/3 mass ratio) was used as the stripping solution, and the above test piece was used as the stripping solution at 80 ° C. -Soaked for 120 seconds.
c) Fill the bat with a solution of MEA / DMSO = 7/3, immerse the test piece after immersion in b) above, and then stylus type surface shape measuring instrument (trade name: DEKTAK3, ULVAC, Inc.) The test piece with the surface covered with the stripping solution was placed on the test strip support, and the coating thickness (FT ₁ ) was measured (measurement of the film thickness in the swollen state with the stripping solution).
d) Fill another bat with pure water, immerse the test piece swollen in c) above, leave it overnight, and replace the stripping solution and water contained in the coating film. The coating thickness (FT ₂ ) was measured again.
e) Using the FT ₀ , FT ₁ , and FT ₂ measured as described above, the swelling rate and film reduction rate of the test piece were calculated, and the stripping solution resistance was evaluated based on the following criteria.
Since (FT ₁ -FT ₀ ) measures the apparent swelling due to the stripping solution, it is corrected by the film loss (FT ₂ -FT ₀ ) eroded by the stripping solution, and the true swelling rate is calculated. Calculated.
True swelling rate (%) = 100 × (FT ₁ −FT ₂ ) / F ₀ , film reduction rate (%) = 100 × (FT ₂ −FT ₀ ) / F ₀

[Evaluation]
A: True swelling rate ≦ 40%, film reduction rate ≦ 5%, and good stripping solution resistance.
◯: True swelling rate ≦ 40%, film reduction rate> 5%, and resistance to stripping solution was within an allowable range.
X: The coating film was dissolved or peeled off, and the stripping solution resistance was poor.

* The following alkali-soluble resin (1):
Propylene glycol monomethyl ether solution of benzyl methacrylate / methacrylic acid copolymer (copolymerization ratio (mole) 70:30, Mw 30,000, solid content 40%)
* Photopolymerizable monomer / Monomer M1 below
(Triazine compound A: diallyl monoglycidyl isocyanuric acid monomer, trade name: DA-MGIC, manufactured by Shikoku Kasei Co., Ltd.)
・ Monomer M2 below
(Triazine compound A: monoallyl diglycidyl isocyanuric acid monomer, trade name: MA-DGIC, manufactured by Shikoku Kasei Co., Ltd.)
・ Monomer M3 below
(Triazine compound B, trade name: U-6HA, manufactured by Shin-Nakamura Chemical Co., Ltd.)
・ The following monomer M4
(Triallyl isocyanurate monomer, trade name: TAIC, manufactured by Nippon Kasei Co., Ltd.)
・ The following monomer M5
(Triallyl cyanurate, trade name: TAC, manufactured by Degussa Japan Co., Ltd.)
・ M-315 below
(Isocyanuric acid ethylene oxide adduct, manufactured by Toagosei Co., Ltd.)
・ DPHA
Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.)
* Fluorosurfactant (trade name: MegaFac F-781-F, 0.2% propylene glycol monomethyl ether acetate solution, manufactured by Dainippon Ink & Chemicals, Inc.)
* Photopolymerization initiator 2-Methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone * Solvent Propylene glycol monomethyl ether acetate * For monomer A / monomer B, the monomers listed in the upper part of the table Was monomer A, and the lower one was monomer B.

* Alkali-soluble resin (1):
Propylene glycol monomethyl ether solution of benzyl methacrylate / methacrylic acid copolymer (copolymerization ratio (mole) 70:30, Mw 30,000, solid content 40%)
* Photopolymerizable monomer / Monomer M1
(Triazine compound A: diallyl monoglycidyl isocyanuric acid monomer, trade name: DA-MGIC, manufactured by Shikoku Kasei Co., Ltd.)
・ M-315 above
(Isocyanuric acid ethylene oxide adduct, manufactured by Toagosei Co., Ltd.)
・ DPHA
Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.)
* Fluorosurfactant (trade name: MegaFac F-781-F, 0.2% propylene glycol monomethyl ether acetate solution, manufactured by Dainippon Ink & Chemicals, Inc.)
* Photopolymerization initiator 1
2- (4′-methyl-4-biphenyl-4,6-bis (trichloromethyl) -s-triazine * photopolymerization initiator 2
7-[[-4-Chloro-6- (diethylamino) -s-triazinyl] -amino] -3-phenylcoumarin * photopolymerization initiator 3
2,4-trichloromethyl (piperonyl) -6-triazine * photopolymerization initiator 4
2-Benzyl-2-dimethylamino-4′-morpholinobutyrophene * photopolymerization initiator 5
2,4-diethylthioxanthone * red pigment dispersion Pigment Red 254, pigment concentration 19% (the alkali-soluble resin (1) + dispersant (solid conversion) 6%)
* Yellow pigment dispersion 1
Pigment Yellow 139, pigment concentration 19% (the alkali-soluble resin (1) + dispersant (solid conversion) 6%)
* Green pigment dispersion Pigment Green 36, pigment concentration 19% (the alkali-soluble resin (1) + dispersant (solid conversion) 6%)
* Yellow pigment dispersion 2
Pigment Yellow 138, pigment concentration 19% (alkali-soluble resin (1) + dispersant (solid conversion) 6%)
* Blue pigment dispersion Pigment Blue 15: 6, pigment concentration 15% (alkali-soluble resin (1) + dispersant (solid conversion) 10%)
* Solvent Propylene glycol monomethyl ether acetate

From the above Tables 1 to 4, it was found that Examples using the resin film of the present invention had a low relative dielectric constant and excellent development characteristics and stripping solution resistance. On the other hand, in the comparative example, it was not possible to achieve both the relative dielectric constant and the stripping solution characteristics.

It is the schematic of the main electrode and guard electrode which were produced in the measurement of a dielectric constant.

1 Substrate 2 Main electrode 3 Guard electrode 4 Chrome surface

Claims (1)

A color filter resin film provided on a color filter layer formed on a substrate, comprising a binder, a polymerization initiator, and a polymerizable monomer having an ethylenic double bond, and a curable resin composition The polymerizable monomer having an ethylenic double bond has at least one epoxy group-containing substituent in at least one selected from the triazine skeletons represented by the following general formulas (1) to (2). characterized in that seen containing a triazine compound a, the general formula (1) triazine compound a having a triazine skeleton represented by is formed by using the curable resin composition is a following monomer M1 or monomer M2 Resin film for color filters.

[In General Formulas (1) to (2), * represents a linking group. ]