JP2010282211A - Photosetting resin composition and method of manufacturing the same, cyano-color filter and method of manufacturing the same, and solid-state imaging element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosetting composition that has a high spectral characteristic, high light resistance, and high heat resistance, a cyano-color filter, and a solid-state imaging element of high color reproducibility. <P>SOLUTION: The photosetting composition contains at least one selected from PG7 and PG36, at least one selected from PB15:3 and PB15:6, an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator. The cyano-color filter and the solid-state imaging element use the photosetting composition. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a photocurable resin composition, a cyan color filter used for a solid-state imaging device and a liquid crystal display device, a method for producing a photocurable resin composition, and a method for producing a cyan color filter. Relates to a photocurable resin composition, a complementary color filter and a solid-state imaging device using the same, a method for producing a photocurable resin composition, and a method for producing a cyan color filter.

Conventionally, a complementary color filter has been used in many dyeing methods, in which cyan, magenta, and yellow dyes are dyed into a layer to be dyed such as gelatin, but there are problems in light resistance, heat resistance, and the like.
On the other hand, as a method instead of the staining method, a colorant and C.I. I. Pigment blue 16, C.I. I. Pigment Blue 15: 6 or C.I. I. A method using a complementary color filter using a blue pigment such as CI Pigment Blue 15: 4 (for example, see Patent Documents 1 and 2), and a cyan color filter using a fine pigment such as aluminum phthalocyanine and titanium phthalocyanine. There is a method to use (see, for example, Patent Document 3), and a complementary color filter having excellent heat resistance and light resistance has been obtained.

JP 7-270611 A Japanese Patent Laid-Open No. 10-144896 JP 2002-107531 A

However, the cyan color filter obtained by the above method has poor spectral characteristics of the cyan color filter formed as compared with the conventional dyeing method. Also, some colorants used in color filters have been difficult to miniaturize. Moreover, the color reproducibility of the solid-state imaging device using the obtained complementary color filter including the cyan color filter was inferior to the conventional staining method.
An object of the present invention is to provide a cyan color filter having good spectral characteristics and excellent light resistance and heat resistance, and a photocurable resin composition capable of forming the color filter. Moreover, it is providing the manufacturing method of the photocurable resin composition, and the manufacturing method of a color filter. Furthermore, it is providing the solid-state image sensor with favorable color reproducibility.

<1> A photocurable composition containing at least a pigment, wherein the photocurable composition is C.I. I. Pigment green 7 and C.I. I. C.I. at least one selected from Pigment Green 36; I. Pigment blue 15: 3 and C.I. I. A photocurable composition comprising at least one selected from CI Pigment Blue 15: 6, and further comprising an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator.

<2> The photocurable composition according to <1>, wherein the photopolymerization initiator is an oxime compound.

<3> The photocurable composition according to <1> or <2>, wherein the polymerizable monomer has at least one addition-polymerizable ethylene group.

<4> The photocurable composition according to <3>, wherein the polymerizable monomer having at least one addition-polymerizable ethylene group is a monomer having a melting point of 100 ° C. or higher under normal pressure. .

<5> C.I. I. Pigment Green 7 and C.I. I. Pigment Blue 15: 3 is contained in a content ratio of 4: 1 to 1: 2 (mass ratio; CI Pigment Green 7: CI Pigment Blue 15: 3) <1 The photocurable composition according to any one of> to <4>.
<6> C.I. I. Pigment Green 7 and C.I. I. Pigment Blue 15: 6 and a content ratio of 4: 1 to 1: 2 (mass ratio; CI Pigment Green 7: CI Pigment Blue 15: 6) <1 The photocurable composition according to any one of> to <4>.
<7> C.I. I. Pigment green 36, C.I. I. Pigment Blue 15: 3 is contained in a content ratio of 3: 1 to 1: 3 (mass ratio; CI Pigment Green 36: CI Pigment Blue 15: 3) <1 The photocurable composition according to any one of> to <4>.
<8> C.I. I. Pigment green 36, C.I. I. And CI Pigment Blue 15: 6 in a content ratio of 6: 1 to 1: 2 (mass ratio; CI Pigment Green 36: CI Pigment Blue 15: 6) <1 The photocurable composition according to any one of> to <4>.
<9> C.I. I. Pigment green 7 and C.I. I. C.I. at least one selected from Pigment Green 36; I. Pigment blue 15: 3 and C.I. I. Pigment Blue 15: 6 pigment containing at least one selected from a flushing treatment with an alkali-soluble resin solution, or a kneading treatment with an alkali-soluble resin to obtain a finely divided dispersion of the pigment;
Adding an alkali-soluble resin and a solvent to the dispersion and dispersing the dispersion to obtain a dispersion;
Adding a polymerizable monomer, a photopolymerization initiator, and a solvent to the dispersion, and mixing to prepare a photocurable composition;
Applying the photocurable composition onto a substrate to form a coating film;
A step of exposing a specific pattern on the coating film and developing the exposed coating film;
A method for producing a cyan color filter, comprising:
<10> A cyan color filter manufactured by the manufacturing method according to <9>.
<11> C.I. I. Pigment green 7 and C.I. I. C.I. at least one selected from Pigment Green 36; I. Pigment blue 15: 3 and C.I. I. A step of obtaining a finely divided dispersion by flushing a pigment containing at least one selected from CI Pigment Blue 15: 6 with an alkali-soluble resin, or mixing with an alkali-soluble resin;
Adding an alkali-soluble resin and a solvent to the dispersion and dispersing the dispersion to obtain a dispersion;
Adding a polymerizable monomer, a photopolymerization initiator, and a solvent to the dispersion, and mixing to prepare a photocurable composition;
The manufacturing method of the photocurable composition characterized by having.
<12> A photocurable composition produced by the production method according to <11>.
<13> A solid-state imaging device having a light-receiving element and a color filter formed of three colors of cyan, magenta, and yellow, or four colors of green formed thereon, the color filter being <10> In the described cyan color filter, the magenta pigment is C.I. I. This is a magenta color filter including CI Pigment Red 122, and the yellow pigment is C.I. I. A solid-state image sensor, which is a yellow color filter including CI Pigment Yellow 185.

  According to the present invention, there are provided a cyan color filter having good spectral characteristics and excellent light resistance and heat resistance, a photocurable composition capable of forming the color filter, and a method for producing the same. can do. Furthermore, according to the present invention, it is possible to provide a solid-state imaging device having good color reproducibility by using the color filter.

It is a figure which shows the spectral transmittance curve of the cyan color filter produced in Example 2 and Comparative Examples 2 and 6 to this invention. It is a figure which shows the spectral transmittance curve of the cyan color filter produced by the reference example 3 and the comparative examples 1 and 7 to this invention. It is a figure which shows the spectral transmittance curve of the complementary color type color filter used for the CMOS solid-state image sensor of Example 6 of this invention. Cyan used the cyan color filter of Example 2.

The cyan color filter of the present invention is a color filter containing at least a pigment, and the pigment is C.I. I. Pigment Green 7 (hereinafter also referred to as “PG7”) and C.I. I. At least one selected from CI Pigment Green 36 (hereinafter also referred to as “PG36”); I. Pigment Blue 15: 3 (hereinafter also referred to as “PB15: 3”) and C.I. I. And at least one selected from CI Pigment Blue 15: 6 (hereinafter also referred to as “PB15: 6”) (first aspect).
Furthermore, the cyan color filter of the reference aspect of the present invention is a color filter containing at least a pigment, and the pigment includes aluminum phthalocyanine (AlPC), I. Pigment blue 15: 3 (PB15: 3) and C.I. I. And at least one selected from CI Pigment Blue 15: 6 (PB15: 6) (second aspect).
When the cyan color filter contains the specific pigment, it is possible to provide a cyan color filter having excellent spectral characteristics and excellent heat resistance and light resistance.

<Cyan color filter>
[Pigment]
The pigment used as the first embodiment of the cyan color filter of the present invention contains at least one green pigment selected from PG7 and PG36 and at least one blue pigment selected from PB15: 3 and PB15: 6. To do.
Further, as a reference embodiment of the cyan color filter of the present invention, a green pigment of aluminum phthalocyanine (AlPC), C.I. I. Pigment blue 15: 3 (PB15: 3) and C.I. I. At least one blue pigment selected from CI Pigment Blue 15: 6 (PB15: 6).
By containing these pigments, it is possible to produce a cyan color filter having good spectral transmittance and excellent heat resistance and light resistance.

  The aluminum phthalocyanine (AlPC) in the present invention is preferably a compound represented by the following structural formula (I). Moreover, the dimer which 2 molecules of this compound couple | bonded may be sufficient.

In the structural formula (I), X represents OH, Cl, or Br. R ¹ , R ² , R ³ , and R ⁴ each independently represent a halogen atom or an alkyl group having 1 to 4 carbon atoms, and may be the same or different from each other. Y represents an integer of 0 to 4.

  Among the aluminum phthalocyanine pigments represented by the structural formula (I), a compound represented by the following structural formula (II) is particularly preferable. A dimer in which two molecules of this compound are bonded through an oxygen atom of an OH group is also suitable.

In any of the above embodiments, other conventionally known inorganic or organic pigments other than the pigment described in the embodiment can be used in combination.
Further, considering that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a fine one as much as possible, and considering the handling properties, the average particle diameter of the pigment is 0.01 μm to 0.1 μm is preferable, and 0.01 μm to 0.05 μm is more preferable.

Examples of the organic pigment include aluminum phthalocyanine, titanium phthalocyanine, cobalt phthalocyanine, zinc phthalocyanine, tin phthalocyanine, vanadium phthalocyanine, and the following pigments.
Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc And metal oxides such as antimony, and composite oxides of the above metals.

Examples of the organic pigment further include:
C. I. Pigment yellow 11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199;
C. I. Pigment orange 36, 38, 43, 71;
C. I. Pigment red 81,105,122,149,150,155,171,175,176,177,209,220,224,242,254,255,264,270;
C. I. Pigment violet 19, 23, 32, 39;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 66;
C. I. Pigment green 7, 36, 37;
C. I. Pigment brown 25, 28;
C. I. Pigment black 1,7;
Examples thereof include carbon black.
These organic pigments can be used alone or in various combinations.

The combination of the green pigment and the blue pigment in the first aspect may be any combination, two types of green pigment and two types of blue pigment, two types of green pigment and one type of blue pigment, and one type of green pigment and two types of blue pigment. Any combination of one green pigment and one blue pigment can be taken,
One green pigment and one blue pigment (for example, PG7 and PB15: 3, PG7 and PB15: 6, PG36 and PB15: 3, and PG36 and PB15: 6) are preferable.
The content ratio (mass) of the green pigment and the blue pigment is not particularly limited, but generally the green pigment and the blue pigment are in the range of 9: 1 to 1: 9, and the spectral characteristics are From the viewpoint, specifically, in PG7 and PB15: 3, 9: 1 to 1: 3 is preferable, and 4: 1 to 1: 2 is more preferable. In PG7 and PB15: 6, 7: 4 to 1: 3 is preferable, and 4: 1 to 1: 2 is more preferable. In PG36 and PB15: 3, 5: 1 to 1: 7 is preferable, and 3: 1 to 1: 3 is more preferable. In PG36 and PB15: 6, 9: 1 to 1: 4 is preferable, and 6: 1 to 1: 2 is more preferable.

The combination of the green pigment and the blue pigment in the second aspect may be any, and any combination of one green pigment and two blue pigments, one green pigment and one blue pigment,
A combination of one green pigment and one blue pigment (for example, aluminum phthalocyanine and PB15: 3, aluminum phthalocyanine and PB15: 6) is preferable.
The content ratio (mass) of the green pigment and the blue pigment is not particularly limited,
Generally, the green pigment and the blue pigment are in the range of 9: 1 to 1: 9. From the viewpoint of spectral characteristics, specifically, in the case of aluminum phthalocyanine and PB15: 3, 4: 1 to 1: 4 is 10: 3 to 1: 3 are more preferable.
In aluminum phthalocyanine and PB15: 6, 4: 1 to 1: 3 are preferable, and 3: 1 to 1: 2 are more preferable.

  The pigment in the present invention has good dispersibility and dispersion stability when used as a powdery processed pigment finely dispersed in acrylic resin, maleic acid resin, vinyl chloride-vinyl acetate copolymer, ethyl cellulose resin, etc. It can be.

Next, a method for treating a pigment will be described.
In the present invention, it is preferable to treat the pigment with various resins in advance. In other words, the pigment is generally dried by various methods after synthesis, and is usually dried from an aqueous medium and supplied as a powder, but requires a large latent heat of vaporization to dry the water, resulting in a dry powder. Gives a lot of heat energy. Therefore, pigments usually form aggregates (secondary particles) in which primary particles are aggregated, and it is not easy to disperse pigments forming such aggregates into fine particles. It is desirable to process with. Examples of the resin include an alkali-soluble resin described later.

As a processing method, there are a flushing process, a kneading method using a kneader, an extruder, a ball mill, a two or three roll mill and the like. Among these, a flushing process or a kneading method using two or three roll mills is suitable for fine particle formation.
The flushing treatment is usually a method in which an aqueous dispersion of pigment and a resin solution dissolved in a solvent immiscible with water are mixed, the pigment is extracted from an aqueous medium into an organic medium, and the pigment is treated with a resin. According to this method, since the pigment is not dried, the aggregation of the pigment can be prevented and the dispersion becomes easy. In the above kneading by the two or three roll mill, the pigment and the resin or the resin solution are mixed, and then the pigment and the resin are kneaded while applying a high shear (shearing force) to thereby obtain the resin on the pigment surface. This is a method of treating a pigment by coating. The pigment particles aggregated in this process are dispersed from the lower order aggregates to the primary particles.

  Moreover, it can also be used as a processed pigment previously treated with an acrylic resin, vinyl chloride-vinyl acetate resin, maleic acid resin, ethyl cellulose resin, nitrocellulose resin or the like. The form of the processed pigment is preferably a powder, paste, pellet, or paste in which the resin and the pigment are uniformly dispersed. Further, a non-uniform lump in which the resin is gelled is not preferable.

Conventionally known pigment dispersants and surfactants can be used in combination for the purpose of improving the dispersibility of the pigment.
Examples of the pigment dispersant and the surfactant include various compounds. For example, phthalocyanine derivatives (EFKA-745 manufactured by Efka), Solsperse 5000 (manufactured by Geneca); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) ), (Meth) acrylic acid-based (co) polymer polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; 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; anionic surfactants such as W004, W005, W017 (manufactured by Yusho); EFKA-46, EFKA -47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), Disperse Aid 6, Disper Polymer dispersants such as Aid 8, Disperse Aid 15, Disperse Aid 9100 (manufactured by Sannopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000 , 28000, etc. (manufactured by Zeneca); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, the same P94, the same L101, the same P103, the same F108, the same L121, the same P-123 (manufactured by Asahi Denka Co., Ltd.), and the ISONET S-20 (manufactured by Sanyo Kasei Co., Ltd.).

  The total content (mass) of the pigment in the cyan color filter of the present invention is 20 to 90 mass% with respect to the total solid content (mass). 80% by mass is preferable, and 30 to 70% by mass is more preferable.

[resin]
The cyan color filter of the present invention preferably contains a resin, but the resin is not particularly limited as long as it can form a color filter, depending on the method for producing the color filter. Are preferably selected.

  As a method for producing the cyan color filter, any conventionally known color filter forming method such as a negative photolithography method, a positive photolithography method, a printing method, and an ink jet method can be used. In particular, as a color filter for a solid-state imaging device, it is preferable to use a pigment-dispersed negative photolithography method from the viewpoint that a fine color filter having a good shape can be obtained.

(Photo curable resin)
Hereinafter, the cyan color filter according to the present invention will be described with reference to a pigment dispersion negative photolithography method, but the present invention is not limited to this.
The cyan color filter of the present invention has at least the resin and the pigment, and when the cyan color filter is produced by the pigment dispersion positive photolithography method, an alkali-soluble resin, a polymerizable monomer, and photopolymerization It is preferable to contain resin formed using the photocurable composition which has a photoinitiator. In general, the photocurable composition can be further constituted by using a solvent, and further can be constituted by using other components such as additives as required.

-Alkali-soluble resin-
The alkali-soluble resin preferably has an acidic functional group such as a carboxyl group having phenol developability and a phenolic hydroxyl group, and the alkali-soluble resin has an acid value in the range of 100 to 250 mgKOH / g.
As a specific example, a linear organic polymer that is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution is preferable. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful. In addition, a polymer having a hydroxyl group with an acid anhydride added, a polyhydroxystyrene resin, a polysiloxane resin, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl Alcohol and the like are also useful.

The alkali-soluble resin may be copolymerized with a hydrophilic monomer such as hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary and tertiary. Alkylacrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear Examples include propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like.
As other hydrophilic monomers, tetrahydrofurfuryl group, phosphoric acid, phosphate ester, quaternary ammonium salt, ethyleneoxy chain, propyleneoxy chain, sulfonic acid and its salts, monomers containing morpholinoethyl group, etc. are also useful. is there.

  In the present invention, those containing a high molecular polymer having a polymerizable double bond (ethylenically unsaturated group) in the molecule are particularly suitable. The polymer having a double bond in the molecule can be used as long as it is alkali-soluble and has a double bond such as an ethylenically unsaturated bond. For example, a polymer having an ethylenically unsaturated bond, etc. Can be mentioned.

  In this case, the ratio of the “polymer having a polymerizable double bond in the molecule” in the total amount of the alkali-soluble resin is preferably 10% by mass or more, more preferably 20% by mass or more, and 30% by mass. The above is particularly preferable. If the ratio is less than 10% by mass, the pixel pattern profile may deviate from the rectangle. In addition, the amount of double bonds in the alkali-soluble resin is preferably 1 to 5 mmol / g, more preferably 1 to 4.5 mmol / g, even more preferably when expressed in terms of millimolar amount in 1 gram of resin. 1.5 to 4.0 mmol / g.

Next, the example of the polymer which has an ethylenically unsaturated group is shown. However, it is not limited to the following as long as a carbon-carbon unsaturated bond is included.
Examples of the polymer containing an ethylenically unsaturated group include 2-hydroxyethyl acrylate having an OH group, methacrylic acid containing a COOH group, and a monomer such as an acrylic or vinyl compound copolymerizable therewith. And a compound obtained by reacting an OH group-reactive epoxy ring and a compound having a carbon-carbon unsaturated bond group (for example, a compound such as glycidyl acrylate) and the like. As the compound having reactivity with the OH group, in addition to the epoxy ring, a compound having an acid anhydride, an isocyanate group, and an acryloyl group can also be used. In addition, a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring described in JP-A-6-102669 and JP-A-6-1938 is saturated or unsaturated polyunsaturated. A reaction product obtained by reacting a basic acid anhydride can also be used. Examples of the compound having both an alkali solubilizing group such as COOH and a carbon-carbon unsaturated group include, for example, Diamond NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing Polyethane acryloligomer, Diamond Shamrock Co. Ltd.). , Manufactured by), Biscote R-264, KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (Daicel User) CB Co., Ltd.). Among these, a polymer having at least one selected from a crotonyl group, an acryl group, a methacryl group, an allyl group, a propyl ester group, a vinyl ester group, and an allyloxyalkyl group in the side chain is useful. A polymer having at least one selected from a group, a methacryl group and an allyl group in the side chain is useful.

  The weight average molecular weight of the alkali-soluble resin in the present invention is preferably 3,000 to 300,000, more preferably 5,000 to 100,000, and particularly preferably 10,000 to 80,000.

  0.5-15 mass% is preferable and, as for content in the photocurable composition which concerns on this invention of the said alkali-soluble resin, 1.0-12 mass% is more preferable. If the content is less than 0.5% by mass, the progress of development may be slowed, resulting in an increase in production cost. If the content exceeds 15% by mass, a good pattern profile may not be obtained.

-Polymerizable monomer-
The photocurable composition contains at least one polymerizable monomer. As the polymerizable monomer, a compound having an ethylenically unsaturated group having at least one addition-polymerizable ethylene group and having a boiling point of 100 ° C. or higher under normal pressure is preferable. Examples thereof include polyethylene glycol mono (meth). Monofunctional acrylates and methacrylates such as acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, etc .; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Ethylene oxide or propylene oxide is added to polyfunctional alcohols such as glycerol, trimethylol ethane, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate (Meth) acrylates, urethane acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183 Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid described in JP-B Nos. 49-43191 and 52-30490 , And It can be mixtures thereof. Furthermore, the Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 are introduced as photocurable monomers and oligomers.

  The content of the polymerizable monomer in the photocurable composition according to the present invention is preferably 0.1 to 90 mass%, more preferably 1.0 to 80 mass%, based on the solid content of the composition. 0.0 to 70% by mass is particularly preferable.

-Photopolymerization initiator-
The photocurable composition contains at least one photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it can polymerize the above-mentioned polymerizable monomer and alkali-soluble resin in the case of having a polymerizable double bond in the molecule, polymerization characteristics, initiation efficiency, absorption wavelength, It is desirable to select from the viewpoint of availability, cost, and the like.

  For example, it can be suitably configured using at least one compound selected from the group consisting of halomethyltriazine compounds, oxime compounds, and α-aminoketone compounds.

Examples of the halomethyl-s-triazine compound include a vinyl-halomethyl-s-triazine compound described in JP-B-59-1281 and 2- (naphth-1-yl) described in JP-A-53-133428. Examples include -4,6-bis-halomethyl-s-triazine compound and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compound.
Other commercially available products include TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123, etc.) manufactured by Midori Chemical. Can be mentioned.

  The oxime compound is not particularly limited, and examples thereof include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (4-methylsulfanyl-phenyl). -Butane-1,2-butane 2-oxime-O-acetate, 1- (4-methylsulfanyl-phenyl) -butan-1-one oxime-O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl) -acetic acid Examples include ethyl ester-O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl) -acetic acid ethyl ester-O-benzoate, and the like.

  Examples of the α-aminoketone compounds include Irgacure series (for example, Irgacure 907 and Irgacure 369) manufactured by Ciba Geigy, 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1- [4- (Hexyl) phenyl] -2-morpholinopropan-1-one, 2-ethyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and the like.

These photopolymerization initiators can be used in combination with a sensitizer and a light stabilizer.
Specific examples thereof include benzoin, benzoin methyl ether, benzoin, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl. -9-anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methyl Xanthone, 2-methoxyxanthone, 2-methoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyryl ketone, p- (Dimethylamino) phenyl-p-methyl Tinuvin 1130 and 400 Etc.

In addition to the above photopolymerization initiator, other known photopolymerization initiators shown below can also be used. Specifically, the vicinal polykettle aldonyl compound described in US Pat. No. 2,367,660, the α described in US Pat. Nos. 2,367,661 and 2,367,670 Carbonyl compounds, acyloin ethers described in US Pat. No. 2,448,828, aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, US Polynuclear quinone compounds described in Japanese Patent Nos. 3,046,127 and 2,951,758, triallylimidazole dimer / p-aminophenyl ketone described in US Pat. No. 3,549,367. Examples thereof include benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-B 51-48516.
Furthermore, at least one active halogen compound selected from active halogen compounds such as halomethyloxadiazole, halomethyl-s-triazine compounds, 3-aryl-substituted coumarin compounds, lophine dimers, benzophenone compounds, acetophenone compounds, and the like Derivatives, cyclopentadiene-benzene-iron complexes and salts thereof, oxime compounds, and the like.

  Examples of the active halogen compounds such as halomethyloxadiazole include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds described in JP-B-57-6096, 2-trichloro Methyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p- Methoxystyryl) -1,3,4-oxadiazole and the like.

  Moreover, T series (for example, T-OMS, T-BMP, TR, TB, etc.) manufactured by PANCHIM, Irgacure series (for example, Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000, etc.) manufactured by Ciba Geigy. , Irgacure 149, Irgacure 819, Irgacure 261, etc.), Darocur series (eg Darocur 1173, etc.), etc. are also effective. In addition, 4,4′-bis (diethylamino) -benzophenone, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2-benzyl-2-dimethylamino- 4-morpholinobutyrophenone, 2,2-dimethoxy-2-phenylacetophenone, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl Dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole Le dimer, 2-(p-methyl) -4,5-diphenyl imidazolyl dimer, benzoin isopropyl ether are used also useful.

In the present invention, a photopolymerization initiator having maximum absorption in the ultraviolet wavelength region can be used in combination.
In this case, in particular, irradiation during post-curing can be suitably performed using light in the ultraviolet region. When using light in the ultraviolet region, post-cure can be completed in a short time. Thus, a rectangular pixel having a good cross-sectional pattern profile can be obtained.

  As a specific example, at least one photopolymerization initiator having a maximum absorption wavelength in the ultraviolet region of 300 nm or less and at least one photopolymerization initiator having a maximum absorption wavelength in a wavelength region exceeding 300 nm (for example, 310 to 420 nm). Can be suitably configured using two or more kinds of photopolymerization initiators. In this case, it does not simply include two or more kinds of photopolymerization initiators, but contains a photopolymerization initiator having a maximum absorption wavelength of 300 nm or less together with a photopolymerization initiator having a maximum absorption wavelength of more than 300 nm, and pattern exposure. Can be post-cured with short-wavelength light of 300 nm or less using light having a wavelength exceeding 300 nm (particularly 310 to 420 nm).

  When configured as described above, a photopolymerization initiator having a maximum absorption wavelength in a wavelength region exceeding 300 nm (for example, 310 to 420 nm) can be selected from the photopolymerization initiators described above. Examples of the photopolymerization initiator having a maximum absorption wavelength in the ultraviolet region of 300 nm or less include carbonyl compounds such as Epacure TZT (manufactured by Fratelli Lambert), Kayacure BTC, Kayacure ITX (manufactured by Nippon Kayaku Co., Ltd.), and Vice 55 Dicarbonyl compounds such as Stauffer AKZO, Esacure KIP100F, Esacure KT37 (made by Siebel Hegner), acetophenone compounds such as FIRST DEAP (made by FIRST CHEMICAL), and Benzoin B, Benzoin PS-8 made by Sumitomo PS-8A ) And other aminocarbonyl compounds such as Kayacure EPA, Kayacure DMBI (manufactured by Nippon Kayaku Co., Ltd.), Tri zine A, Triazine PP, etc. halides such Triazine B (Panchim Ltd.) can be exemplified.

  Content of the photoinitiator in the said photocurable composition is 0.01-50 with respect to the total solid of alkali-soluble resin in the case of having a polymerizable double bond in the said polymerizable monomer and molecule | numerator. % By mass is preferable, 1 to 30% by mass is more preferable, and 1 to 20% by mass is particularly preferable. When the content is less than 0.01% by mass, the polymerization reaction may not proceed easily. When the content exceeds 50% by mass, the polymerization rate increases but the molecular weight decreases, and the film strength may decrease.

  In addition to the above, it is preferable to add a thermal polymerization inhibitor to the photocurable composition. For example, 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, etc. are useful.

-Solvent-
In general, the photocurable composition can be constituted using a solvent as required. The solvent is not limited as long as it satisfies the solubility of the various components described above and the applicability of the composition, but in particular, considering the solubility, applicability, and safety of the alkali-soluble resin. Preferably it is selected.

  Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .;

3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, etc .; and 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, such as methyl 2-methoxypropionate, 2- Ethyl methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2- Methoxy-2-methyl Methyl acid, 2-ethoxy-2-methylpropionic acid ethyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, 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 methyl ether, propylene glycol methyl Ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; or aromatic hydrocarbons such as toluene and xylene.

  Among the above solvents, 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 methyl ether, propylene glycol methyl ether acetate and the like are more preferable.

-Other ingredients-
Various additives such as fillers, polymer compounds other than the above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, etc. are added to the photocurable composition as necessary. I can do it.

  Specific examples of these additives include fillers such as glass and alumina; polymer compounds other than binder resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; nonionic, cationic And anionic surfactants: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimetoki Adhesion promoters such as silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl- 6-t-butylphenol), 2,6-di-t-butylphenol and other antioxidants: 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, etc. And an anti-aggregation agent such as sodium polyacrylate.

  Further, when the alkali solubility of the uncured part is promoted to further improve the developability of the photocurable composition, the photocurable composition is further reduced to an organic carboxylic acid, preferably a molecular weight of 1000 or less. Molecular weight organic carboxylic acids can be added. Specific examples include 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 acids, 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, hemelic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesin Aromatic polycarboxylic acids such as acids, merophanic acid, pyromellitic acid; Other carboxylic acids such as acetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropaic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, and umberic acid It is done.

《Other resins》
As the resin preferably contained in the cyan color filter of the present invention, in addition to the photocurable resin formed by the pigment dispersion type negative photolithographic method, when the cyan color filter is produced by another method, Of course, a resin suitable for the method is shown.

  As resin content (mass) in the cyan color filter of this invention, 20-90 mass% is mentioned with respect to the total solid content mass, However, 30-80 mass% is preferable among these, 30-70 mass is preferable. % Is more preferable.

  The thickness of the cyan color filter of the present invention is not particularly limited, but is preferably 0.3 to 3.0 μm, and more preferably 0.3 to 1.5 μm.

As the spectral characteristics of the cyan color filter of the present invention, the 400 nm spectral transmittance is 45% or more, the maximum transmittance is 450 to 550 nm, the spectral transmittance is 90% or more, and 600 to 650 nm. It is preferable that the spectral transmittance is 20% or less and the 550 nm spectral transmittance is 50% or more.
More preferably, the spectral transmittance of 400 nm is 60% or more, the maximum transmittance is 450 to 550 nm, the spectral transmittance is 92% or more, and the spectral transmittance of 600 to 650 nm is 20% or less. In addition, the spectral transmittance at 550 nm is preferably 60% or more.
The spectral characteristic (spectral transmittance) was a value measured using MCPD-2000 manufactured by Otsuka Electronics Co., Ltd.

The light fastness of the cyan color filter of the present invention was performed by irradiating with an illuminance of 100,000 lux for 50 hours with SX75F manufactured by Suga Test Instruments Co., Ltd. using a xenon lamp as a light source. Using MCPD-2000 manufactured by Otsuka Electronics Co., Ltd., the color difference (ΔE ^* ab) before and after the irradiation was measured and used as an evaluation index.

The cyan color filter of the present invention was heated on a hot plate at 220 ° C. for 1 hour. The color difference when the color difference (ΔE ^* ab) before and after heating was measured by MCPD-2000 manufactured by Otsuka Electronics Co., Ltd. was used as the evaluation index.

[Cyan color filter manufacturing method]
The method for producing a cyan color filter of the present invention will be described below with reference to a method using a pigment dispersion type negative photolithographic method, but is not limited thereto.
The photocurable composition containing the cyan pigment is applied directly on the substrate or through another layer, and then dried (prebaked) to form a coating film.
Next, a specific pattern is exposed on the formed coating film, and the exposed coating film is developed with an alkali developer.
A cyan color filter can be formed by subjecting the developed coating film to post-baking.

  More specifically, the coating film formation is performed by applying the photocurable composition containing the cyan pigment on a substrate by using a coating method such as spin coating, casting coating, roll coating, slit coating, and the like. Further drying is performed to form a radiation-sensitive composition film (coating film). The application can be performed directly on the substrate or through another layer.

Examples of the substrate include a photoelectric conversion element substrate used for an imaging element, such as a silicon substrate, a CCD (charge coupled device), a complementary metal oxide semiconductor (CMOS), and a soda used for a liquid crystal display element. Examples thereof include glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film thereto. In some cases, a black matrix for isolating each pixel is formed on these substrates.
If necessary, an undercoat layer may be provided on these substrates in order to improve adhesion with the upper layer, prevent diffusion of substances, or planarize the substrate surface.

  In the exposure step, a specific pattern is exposed to the formed coating film through a mask, for example. As radiation used for exposure, ultraviolet rays such as g-line, h-line and i-line are particularly preferably used.

  The developing step is a step of developing the exposed coating film with an alkaline developer. Any alkali developer may be used as long as it dissolves the photocurable composition according to the present invention and does not dissolve the exposed portion (radiation irradiated portion). Specifically, various organic solvents and combinations thereof, or alkaline aqueous solutions can be used.

  Examples of the organic solvent include those described below that can be used when preparing the photocurable composition according to the present invention. Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium. An aqueous solution containing hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene, and the like can be given.

  The alkaline developer used in the present invention is preferably an alkaline aqueous solution adjusted so that the alkali concentration is preferably pH 11 to 13, more preferably pH 11.5 to 12.5. If the alkali concentration exceeds pH 13, pattern roughness, peeling, and remaining film ratio may occur, and if the pH is less than 11, development speed may be reduced or residue may be generated. In this step, development processing can be suitably performed using a developer composed of such an alkaline aqueous solution. Examples of the development method include a dipping method, a spray method, a paddle method, and the like, and the development temperature is preferably 15 to 40 ° C. Further, after development, washing is generally performed with running water.

  Further, the post-baking is performed using, for example, a hot plate. 150-300 degreeC is preferable and the processing temperature in that case has more preferable 180-250 degreeC. The heating time is usually 2 to 10 minutes.

  The cyan color filter of the present invention can be used as a color filter for LCD, but is particularly suitable for use in a high-resolution CCD element, CMOS element, or the like.

<Solid-state imaging device>
The solid-state imaging device of the present invention is a solid-state imaging device having a light-receiving element and a color filter formed thereon with three hues of cyan, magenta, and yellow, or further four hues of green. Is a cyan color filter according to claim 1 or 2, wherein the magenta pigment is C.I. I. This is a magenta color filter including CI Pigment Red 122, and the yellow pigment is C.I. I. It is a yellow color filter including Pigment Yellow 185.
Further, the solid-state imaging device of the present invention is a solid-state imaging device having a light-receiving element and a color filter formed thereon with three hues of cyan, magenta and yellow, or further four hues of green, The cyan pigment is aluminum phthalocyanine and C.I. I. Pigment Blue 15: 3, and a magenta pigment is C.I. I. Pigment Red 122, and a yellow color filter pigment is C.I. I. Pigment Yellow 185 is included.
Furthermore, the solid-state imaging device of the present invention is a solid-state imaging device having a light-receiving element and a color filter formed thereon with three hues of cyan, magenta and yellow, or further four hues of green. The cyan pigment is aluminum phthalocyanine and C.I. I. Pigment Blue 15: 6, and the magenta pigment is C.I. I. Pigment Red 122, and the yellow pigment is C.I. I. Pigment Yellow 185 is included.
The solid-state imaging device of the present invention can achieve good color reproducibility, which is an effect of the present invention, by using an element using a color filter containing the specific pigment.

[Color filter]
The solid-state imaging device of the present invention includes a color filter having hues of three colors (cyan, magenta, and yellow) or four colors (cyan, magenta, yellow, and green) in its configuration.
For a color filter having a hue of magenta, yellow, and green other than the cyan color filter, a method for producing the cyan color filter can be used. For example, the cyan color filter By using pigments corresponding to other colors in place of the cyan pigment of the photocurable composition for use, color filters composed of corresponding three colors or four colors can be obtained.

  Constituent components such as a cyan color filter and a pigment contained in the solid-state imaging device are included in the cyan color filter described in the above-mentioned cyan color filter, and the filter. This is the same as the constituent components and preferred ranges of pigments and the like.

  Hereinafter, other than the cyan color used in the color filter in the solid-state imaging device of the present invention and a color filter having three colors (cyan, magenta, yellow) including cyan or four colors including green. The pigment will be described.

-Yellow color filter-
The yellow color filter used in the solid-state imaging device of the present invention has at least C.I. I. Contains CI Pigment Yellow 185.
Furthermore, it can be appropriately selected from conventionally known inorganic or organic yellow pigments as long as the object of the present invention is not impaired. For example, disazo yellow pigments, quinophthalone yellow pigments, azomethine yellow pigments, isoindoline pigments A yellow pigment etc. are mentioned. Specifically, C.I. I. Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 199 and the like are preferable.
These yellow pigments may be used alone or in combination of two or more.
The content (% by mass) of the pigment for the yellow color filter is preferably 10% by mass to 80% by mass in the yellow color filter, more preferably 20% by mass to 70% by mass, and particularly preferably 30% by mass. % To 60% by mass is preferable.
The average particle diameter of the yellow pigment is preferably 0.01 μm to 0.2 μm, more preferably 0.01 μm to 0.1 μm, and more preferably 0.01 μm to 0.1 μm from the viewpoint of the transmittance of the color filter. A thickness of 0.05 μm is particularly preferable.

  The film thickness of the yellow color filter is not particularly limited, but is preferably 0.3 to 3.0 μm, more preferably 0.3 to 1.5 μm, particularly 0.3. -1.0 micrometer is preferable.

The spectral characteristics (transmittance) of the yellow color filter is preferably 20% or less in the wavelength range of 400 to 470 nm and 80% or more in the range of 510 to 700 nm.
The light resistance of the yellow color filter is preferably such that ΔEab is 3 or less after 50 hours of irradiation with a xenon lamp of 100,000 lux.
The heat resistance of the yellow color filter is preferably such that ΔEab after standing for 1 hour at 220 ° C. on a hot plate is 3 or less.

-Magenta color filter-
The magenta color filter used in the solid-state imaging device of the present invention has at least C.I. as a magenta pigment. I. Pigment Red 122 is contained.
Furthermore, it can be appropriately selected from conventionally known inorganic or organic magenta pigments as long as the object of the present invention is not impaired. I. Pigment Red 81, 144, 169, 177 and the like are preferable.
These magenta pigments may be used alone or in combination of two or more.

The content (% by mass) of the pigment for the magenta color filter is preferably 10% by mass to 80% by mass in the magenta color filter, more preferably 20% by mass to 70% by mass, and particularly preferably 30% by mass. % To 60% by mass is preferable.
The average particle diameter of the magenta pigment is preferably 0.01 μm to 0.2 μm, more preferably 0.01 μm to 0.1 μm, and more preferably 0.01 μm to 0.1 μm from the viewpoint of the transmittance of the color filter. A thickness of 0.05 μm is particularly preferable.

  The film thickness of the magenta color filter is not particularly limited, but is preferably 0.3 to 3.0 μm, more preferably 0.3 to 1.5 μm, particularly 0.3. -1.0 micrometer is preferable.

The spectral characteristics (transmittance) of the magenta color filter is preferably 60% or more when the wavelength is in the range of 400 to 460 nm, 60% or more when 600 to 700 nm, and 20% or less when 540 to 560 nm.
The light resistance of the magenta color filter is preferably such that ΔEab is 3 or less after 50 hours of irradiation with a xenon lamp of 100,000 lux.
The heat resistance of the magenta color filter used in the solid-state imaging device of the present invention is preferably such that ΔEab after standing at 220 ° C. for 1 hour on a hot plate is 3 or less.

−Green color filter−
The green color filter used in the solid-state imaging device of the present invention can be appropriately selected from conventionally known inorganic or organic green pigments as a green pigment, as long as the object of the present invention is not impaired. For example, C.I. I. Pigment Green 7, 36, 37, pigments such as zinc phthalocyanine, aluminum phthalocyanine, cobalt phthalocyanine, titanium phthalocyanine; I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185, and the like.
Preferably, C.I. I. Pigment Green 7, 36 and C.I. I. And a combination of Pigment Yellow 139, 150, and 185. Particularly preferably, the green for a solid-state image sensor is C.I. I. Pigment Green 7, 36 as well as two types, C.I. I. Pigment Yellow 139 and 185, as well as combinations of two.

The content (% by mass) of the pigment for the green color filter is preferably 10% by mass to 80% by mass in the green color filter, more preferably 20% by mass to 70% by mass, and particularly preferably 30% by mass. % To 60% by mass is preferable.
The average particle size of the green pigment is preferably 0.01 μm to 0.2 μm, more preferably 0.01 μm to 0.1 μm, and more preferably 0.01 μm to 0.1 μm from the viewpoint of the transmittance of the color filter. A thickness of 0.05 μm is particularly preferable.

  The film thickness of the green color filter is not particularly limited, but is preferably 0.3 to 3.0 μm, more preferably 0.3 to 1.5 μm, particularly 0.3. -1.0 micrometer is preferable.

The spectral characteristic (transmittance) of the green color filter has a maximum peak in the range of 520 to 560 nm, the peak value is 80% or more, and is 30% or less in the range of 400 to 450 nm. In 650 nm, it is preferable that it is 30% or less.
The light resistance of the green color filter is preferably such that ΔEab is 3 or less after 50 hours of irradiation with a xenon lamp of 100,000 lux.
The heat resistance of the green color filter is preferably such that ΔEab after standing at 220 ° C. for 1 hour on a hot plate is 3 or less.

  The color filter used in the solid-state imaging device of the present invention is a photocurable composition containing a magenta pigment, a yellow pigment, or further a green pigment instead of the cyan pigment in the cyan color filter manufacturing method. And can be manufactured by the same operation as the manufacturing method of the cyan color filter.

[Method for Manufacturing Solid-State Imaging Device]
The manufacturing method of the solid-state imaging device of the present invention is not particularly limited, and a known manufacturing method of a solid-state imaging device can be used. Hereinafter, the manufacturing method thereof will be described in detail by taking one mode of the solid-state imaging device of the present invention as an example, but the present invention is not limited to this.

A cyan color filter having cyan pixels on the light receiving element is obtained by operating the cyan color filter manufacturing method on a light receiving element (for example, CCD: charge coupled device) arranged on a two-dimensional plane. Form.
Next, except for using a photocurable composition in which the pigment in the photocurable composition used for forming the cyan pixel is replaced with a magenta color pigment, the same procedure as in the cyan color filter forming operation is performed. A magenta pixel (M pixel) is formed in the non-formation region.
Subsequently, except for using a photocurable composition in which the pigment in the photocurable composition used for forming the cyan pixel was replaced with a yellow pigment, the same procedure as in the cyan color filter forming operation was performed. A yellow pixel (M pixel) is formed in a non-formation region other than the pixel to produce a CCD solid-state imaging device.
Further, similarly, the pigment in the photocurable composition used for forming the cyan pixel was replaced with a green pigment, and the cyan color filter formation operation was performed in the same manner as in the cyan color filter formation operation. A (CCD) solid-state imaging device can be manufactured by forming green pixels (G pixels) in non-formation regions other than magenta pixels and yellow pixels.
Further, by using a CMOS (complementary metal oxide semiconductor) light receiving element instead of the CCD light receiving element, a CMOS solid-state imaging device can be manufactured by the same method.
The light receiving element of the present invention is not particularly limited, and a known light receiving element can be used.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass. The total amount of pigment used was the same.

Example 1
<Cyan color filter formation>
1) Preparation of photocurable composition C Each component of the following composition A was kneaded with a kneader for 30 minutes, and further subjected to a high viscosity dispersion treatment with two rolls.
[Composition A]
Pigment (CI Pigment Green 7 and CI Pigment Blue 15: 3 1: 1) 30 parts Dispersant (Disper 163, BYK) 3 parts Resin (benzyl (meth) acrylate (BzMA) / meta 20 parts of propylene glycol monomethyl ether acetate solution of acrylic acid (MAA) (solid content 50%)

Each component of the following composition B was added to the dispersion obtained as described above, stirred for 3 hours using a homogenizer, and further added with a 0.3 mm zirconia bead disperser (trade name: Dispermat, manufactured by GETZMZNN). A fine dispersion treatment was performed.
[Composition B]
・ Propylene glycol monomethyl ether acetate solution of resin (copolymer of benzyl (meth) acrylate (BzMA) / methacrylic acid (MAA)) (solid content 50%)
20 parts ・ Propylene glycol monomethyl ether acetate 200 parts

Each component of the following composition C was added to the dispersion liquid obtained by the above, and it stirred and mixed, and the photocurable composition C in this invention was prepared.
[Composition C]
Propylene glycol monomethyl ether acetate 65 parts Polymerizable monomer (dipentaerythritol hexaacrylate) 20 parts (o-acyloxime photopolymerization initiator; manufactured by Ciba Geigy Co., Ltd.)
・ UV polymerization initiator (Irgacure OXE01, Ciba Special Chemicals) 3 parts

2) Production of quartz wafer substrate with undercoat layer A 6-inch quartz wafer transparent substrate was heated in an oven at 200 ° C. for 30 minutes or more. Next, an undercoat resin CT2000L (manufactured by FUJIFILM Arch Co., Ltd.) is applied onto the substrate so as to have a dry film thickness of 2 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to provide a quartz wafer substrate with an undercoat layer. Got.

3) Exposure / development of coating film The photocurable composition C prepared in 1) above is transmitted at a maximum wavelength of 600 nm to 650 nm on the undercoat layer of the quartz wafer substrate with the undercoat layer obtained in 2) above. The coating was applied so that the rate was 20% or less to form a photocurable coating film. And it heat-processed for 120 second (prebaking) using the 100 degreeC hotplate.

Subsequently, the formed coating film is irradiated with an exposure amount of 300 mJ / cm ² through a cyan color Island pattern mask at a wavelength of 365 nm using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.). did. Thereafter, the quartz wafer substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type; manufactured by Chemitronics), and CD-2000 (FUJIFILM Corporation). A paddle development is carried out at 23 ° C. for 60 seconds using a developer diluted with water to a concentration of 60% by mass, and then rotated at a rotational speed of 50 rpm, above the center of rotation. More pure water was ejected from a nozzle and supplied in the form of a shower for rinsing, followed by spray drying to form a cyan pattern on the quartz wafer substrate.

4) Post-baking The quartz wafer substrate after drying was post-baked by further heating for 5 minutes on the hot plate adjusted to 220 ° C. In this way, a cyan color filter having cyan pixels (C pixels) was formed.

(Example 2)
In Example 1, C.I. I. Pigment Green 7 and C.I. I. Instead of using Pigment Blue 15: 3 in a 1: 1 weight ratio, C.I. I. Pigment Green 7 and C.I. I. A cyan color filter was obtained in the same manner as in Example 1 except that Pigment Blue 15: 6 was used at a weight ratio of 1: 1.

(Example 3)
In Example 1, C.I. I. Pigment Green 7 and C.I. I. Instead of using Pigment Blue 15: 3 at 1: 1, C.I. I. Pigment Green 36 and C.I. I. A cyan color filter was obtained in the same manner as in Example 1 except that Pigment Blue 15: 3 was used at 1: 1.

Example 4
In Example 1, C.I. I. Pigment Green 7 and C.I. I. Instead of using Pigment Blue 15: 3 in a 1: 1 weight ratio, C.I. I. Pigment Green 36 and C.I. I. A cyan color filter was obtained in the same manner as in Example 1 except that Pigment Blue 15: 6 was used at a weight ratio of 1: 1.

(Comparative Example 1)
In Example 1, instead of the pigment dispersion method of Example 1, a conventional dyeing method in which a dye is dyed into low molecular gelatin is used, and Procion Turquoise HA (made by CIC) is used instead of the pigment of Example 1. A cyan color filter was obtained in the same manner as in Example 1 except for the above.

(Comparative Example 2)
In Example 1, C.I. I. Pigment Green 7 and C.I. I. Instead of using Pigment Blue 15: 3 at 1: 1, C.I. I. A cyan color filter was obtained in the same manner as in Example 1 except that Pigment Green 7 was used alone.

(Comparative Example 3)
In Example 1, C.I. I. Pigment Green 7 and C.I. I. Instead of using Pigment Blue 15: 3 at 1: 1, C.I. I. A cyan color filter was obtained in the same manner as in Example 1 except that Pigment Green 36 was used alone.

(Reference Example 1)
In Example 1, C.I. I. Pigment Green 7 and C.I. I. Instead of using Pigment Blue 15: 3 at 1: 1, aluminum phthalocyanine and C.I. I. A cyan color filter was obtained in the same manner as in Example 1 except that Pigment Blue 15: 3 was used at 1: 3.

(Reference Example 2)
In Reference Example 1, aluminum phthalocyanine and C.I. I. Instead of using Pigment Blue 15: 3 and 1: 3, aluminum phthalocyanine and C.I. I. A cyan color filter was obtained in the same manner as in Reference Example 1 except that Pigment Blue 15: 3 was used at 1: 1.

(Reference Example 3)
In Reference Example 1, aluminum phthalocyanine and C.I. I. Instead of using Pigment Blue 15: 3 and 1: 3, aluminum phthalocyanine and C.I. I. A cyan color filter was obtained in the same manner as in Reference Example 1 except that Pigment Blue 15: 3 was used at 10: 3.

(Reference Example 4)
In Reference Example 1, aluminum phthalocyanine and C.I. I. Instead of using Pigment Blue 15: 3 and 1: 3, aluminum phthalocyanine and C.I. I. A cyan color filter was obtained in the same manner as in Reference Example 1 except that Pigment Blue 15: 6 was used at 1: 2.

(Reference Example 5)
In Reference Example 1, aluminum phthalocyanine and C.I. I. Instead of using Pigment Blue 15: 6 at 1: 3, aluminum phthalocyanine and C.I. I. A cyan color filter was obtained in the same manner as in Reference Example 1 except that Pigment Blue 15: 6 was used at 1: 1.

(Reference Example 6)
In Reference Example 1, aluminum phthalocyanine and C.I. I. Instead of using Pigment Blue 15: 3 and 1: 3, aluminum phthalocyanine and C.I. I. A cyan color filter was obtained in the same manner as in Reference Example 1 except that Pigment Blue 15: 6 was used at 10: 3.

(Comparative Example 4)
In Reference Example 1, aluminum phthalocyanine and C.I. I. Instead of using Pigment Blue 15: 3 at 1: 3, a cyan color filter was obtained in the same manner as in Reference Example 1 except that aluminum phthalocyanine was used alone.

(Comparative Example 5)
In Reference Example 1, aluminum phthalocyanine and C.I. I. Instead of using Pigment Blue 15: 3 and 1: 3, C.I. I. A cyan color filter was obtained in the same manner as in Reference Example 1 except that Pigment Blue 15: 3 was used alone.

(Comparative Example 6)
In Reference Example 1, aluminum phthalocyanine and C.I. I. Instead of using Pigment Blue 15: 3 and 1: 3, C.I. I. A cyan color filter was obtained in the same manner as in Reference Example 1 except that Pigment Blue 15: 6 was used alone.

(Comparative Example 7)
In Reference Example 1, aluminum phthalocyanine and C.I. I. Instead of using Pigment Blue 15: 3 and 1: 3, C.I. I. A cyan color filter was obtained in the same manner as in Reference Example 1 except that Pigment Blue 16 was used alone.

<Evaluation>
The color filter formed as described above was subjected to the following measurements and evaluations. The results of measurement and evaluation are shown in Table 1 below.

-Spectral transmittance measurement-
Spectral transmittances at the maximum peaks of 400 nm, 450-550 nm, 550 nm, and 600-650 nm were measured using MCPD-2000 manufactured by Otsuka Electronics Co., Ltd.
The evaluation standard is that the 400 nm transmittance is 45% or more and the maximum transmittance is between 450 nm and 550 nm, the transmittance is 90% or more, the 550 nm transmittance is 50% or more, and the transmittance is 600 nm to 650 nm. Of 20% or less was considered good, and other than that was considered bad.
Moreover, about Example 2, the comparative example 2, and the comparative example 6, the spectral transmittance curve in the wavelength range of 400 nm-700 nm was obtained. Similarly, Reference Example 3, Comparative Example 1 and Comparative Example 7 were similarly performed to obtain spectral transmittance curves. Each is shown in FIG.1 and FIG.2.

-Light resistance-
Using a SX75F manufactured by Suga Test Instruments Co., Ltd. using a xenon lamp as a light source, a light resistance test was performed by irradiating with an illuminance of 100,000 lux for 50 hours. The color difference (ΔE ^* ab) before and after the irradiation was measured by MCPD-2000 manufactured by Otsuka Electronics Co., Ltd.

-Heat resistance-
Heated on a hot plate at 220 ° C. for 1 hour. The color difference (ΔE ^* ab) before and after heating was measured by MCPD-2000 manufactured by Otsuka Electronics Co., Ltd., and the color difference was determined to be 3 or less, and the others were determined to be poor.

As is clear from Table 1, Comparative Example 1 had good spectral characteristics but poor light resistance and heat resistance. Further, the spectral characteristics of the cyan color filter using the cyan pigments of Comparative Examples 2 to 7 alone were poor. Furthermore, Comparative Example 4 was not good in heat resistance.
On the other hand, the color filters of Examples 1 to 4 and Reference Examples 1 to 6 all showed good spectral characteristics (spectral transmittance) as complementary color cyan color filters, and also had excellent light resistance and heat resistance. showed that.

(Example 5)
<< Production of CCD solid-state imaging device >>
A cyan color filter having cyan pixels on the element was formed in the same manner as in Example 1 except that a CCD light receiving element arranged on a two-dimensional plane was used instead of the quartz wafer transparent substrate of Example 1. Formed.
Next, the pigment in the <composition> of the photocurable composition C used for the formation of the cyan pixel was changed to C.I. A magenta pixel (M pixel) was formed in a non-formation region other than the C pixel on the element by performing the same operation as in Example 1 except that the photocurable composition M was prepared by changing to IPigment Red122. . A magenta Island pattern mask having a 2 μm square pattern was used for i-line irradiation.
Subsequently, the pigment in <composition> of the photocurable composition C used for the formation of the cyan pixel was changed to C.I. I. A yellow pixel (Y pixel) is formed in the non-formation region of the C pixel and the M pixel by performing the same operation as in Example 1 except that the photo-curable composition Y is prepared by changing to Pigment Yellow 185. Then, a CCD solid-state imaging device was produced. For i-line irradiation, a yellow Island pattern mask having a pattern of 2 μm square was used.
Furthermore, the pigment in the <composition> of the photocurable composition C used for forming the cyan pixel is C.I. I. Pigment Green 7 and C.I. I. Except that the photocurable composition G was prepared by changing to Pigment Yellow 139, the same operation as in Example 1 was performed, and green pixels (G pixels) were formed in the non-formation regions other than the C pixel, the M pixel, and the Y pixel. ) To form a CCD solid-state imaging device. Note that an Island pattern mask for green having a 2 μm square pattern was used for i-ray irradiation.

(Example 6)
<< Production of CMOS solid-state image sensor >>
A cyan color filter having cyan pixels on the element was formed in the same manner as in Example 2 except that CMOS light receiving elements arranged on a two-dimensional plane were used instead of the quartz wafer transparent substrate of Example 2. Formed.
Subsequently, the pigment in <composition> of the photocurable composition C used for forming the cyan pixel was changed to C.I. I. A magenta pixel (M pixel) was formed in the non-formation region of the C pixel on the element by performing the same operation as in Example 2 except that the photocurable composition M was prepared by changing to Pigment Red122. A magenta Island pattern mask having a 2 μm square pattern was used for i-line irradiation.
Furthermore, the pigment in the <composition> of the photocurable composition C used for forming the cyan pixel is C.I. I. A yellow pixel (Y pixel) is formed in a non-formation region other than the C pixel and the M pixel by performing the same operation as in Example 2 except that the photo-curable composition Y is prepared by changing to Pigment Yellow 185. Thus, a CMOS solid-state imaging device was produced. For i-line irradiation, a yellow Island pattern mask having a pattern of 2 μm square was used.

(Example 7, Reference Examples 7, 9, 11 and Comparative Examples 9, 11, 13)
In Example 5, instead of using the cyan pigment of Example 5, the cyan pigment of Example 3, Reference Example 1, Reference Example 3, Reference Example 5, Comparative Example 2, Comparative Example 4 or Comparative Example 6 was used. A CCD solid-state imaging device was manufactured in the same manner as in Example 5 except that the above was performed. A visual test using the color palette was performed on the obtained CMOS solid-state imaging device. The results are shown in Table 2 below.

(Example 8, Reference Examples 8, 10, 12, Comparative Examples 8, 10, 12, 14)
In Example 6, instead of using the cyan pigment of Example 6, the cyan pigment of Example 4, Reference Example 2, Reference Example 4, Reference Example 6, Comparative Example 1, Comparative Example 4 or Comparative Example 6 was used. A CMOS solid-state imaging device was manufactured in the same manner as in Example 6 except that. The obtained CCD solid-state imaging device was subjected to a visual test using a color palette. The results are shown in Table 2 below.

  In the solid-state imaging device of Comparative Example 8, measurement was impossible because magenta was mixed on the cyan filter pattern when the magenta filter was formed after the cyan filter was formed. All of the solid-state imaging devices of Comparative Examples 9 to 14 had poor color reproducibility. On the other hand, all of the solid-state imaging devices of Examples 5 to 8 and Reference Examples 7 to 12 showed good color reproducibility.

Claims (13)

  A photocurable composition containing at least a pigment, wherein the photocurable composition comprises C.I. I. Pigment green 7 and C.I. I. C.I. at least one selected from Pigment Green 36; I. Pigment blue 15: 3 and C.I. I. A photocurable composition comprising at least one selected from CI Pigment Blue 15: 6, and further comprising an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator.   The photocurable composition according to claim 1, wherein the photopolymerization initiator is an oxime compound.   The photocurable composition according to claim 1 or 2, wherein the polymerizable monomer has at least one addition-polymerizable ethylene group.   The photocurable composition according to claim 3, wherein the polymerizable monomer having at least one addition-polymerizable ethylene group is a monomer having a melting point of 100 ° C or higher under normal pressure.   C. I. Pigment Green 7 and C.I. I. Pigment Blue 15: 3 is contained in a content ratio (mass ratio; CI Pigment Green 7: CI Pigment Blue 15: 3) of 4: 1 to 1: 2. The photocurable composition according to any one of claims 1 to 4.   C. I. Pigment Green 7 and C.I. I. Pigment Blue 15: 6 is contained in a content ratio of 4: 1 to 1: 2 (mass ratio; CI Pigment Green 7: CI Pigment Blue 15: 6). The photocurable composition according to any one of claims 1 to 4.   C. I. Pigment green 36, C.I. I. Pigment Blue 15: 3 is contained in a content ratio (mass ratio; CI Pigment Green 36: CI Pigment Blue 15: 3) of 3: 1 to 1: 3. The photocurable composition according to any one of claims 1 to 4.   C. I. Pigment green 36, C.I. I. Pigment Blue 15: 6 is contained in a content ratio (mass ratio; CI Pigment Green 36: CI Pigment Blue 15: 6) of 6: 1 to 1: 2. The photocurable composition according to any one of claims 1 to 4. C. I. Pigment green 7 and C.I. I. C.I. at least one selected from Pigment Green 36; I. Pigment blue 15: 3 and C.I. I. Pigment Blue 15: 6 pigment containing at least one selected from a flushing treatment with an alkali-soluble resin solution, or a kneading treatment with an alkali-soluble resin to obtain a finely divided dispersion of the pigment;
Adding an alkali-soluble resin and a solvent to the dispersion and dispersing the dispersion to obtain a dispersion;
Adding a polymerizable monomer, a photopolymerization initiator, and a solvent to the dispersion, and mixing to prepare a photocurable composition;
Applying the photocurable composition onto a substrate to form a coating film;
A step of exposing a specific pattern on the coating film and developing the exposed coating film;
A method for producing a cyan color filter, comprising:   A cyan color filter manufactured by the manufacturing method according to claim 9. C. I. Pigment green 7 and C.I. I. C.I. at least one selected from Pigment Green 36; I. Pigment blue 15: 3 and C.I. I. A step of obtaining a finely divided dispersion by flushing a pigment containing at least one selected from CI Pigment Blue 15: 6 with an alkali-soluble resin, or mixing with an alkali-soluble resin;
Adding an alkali-soluble resin and a solvent to the dispersion and dispersing the dispersion to obtain a dispersion;
Adding a polymerizable monomer, a photopolymerization initiator, and a solvent to the dispersion, and mixing to prepare a photocurable composition;
The manufacturing method of the photocurable composition characterized by having.   The photocurable composition manufactured by the manufacturing method of Claim 11.   11. A solid-state imaging device having a light-receiving element and a color filter formed thereon with three hues of cyan, magenta, and yellow, or further four hues of green, wherein the color filter is cyan according to claim 10. Color color filter, magenta pigment is C.I. I. This is a magenta color filter including CI Pigment Red 122, and the yellow pigment is C.I. I. A solid-state image sensor, which is a yellow color filter including CI Pigment Yellow 185.