KR20070082026A - Photocurable compositions, anti-reflective film using the same, and solid state image pickup device - Google Patents

Abstract

A photocurable composition having excellent curing characteristics and adhesion to an underlying substrate is provided to obtain an anti-reflective film having excellent adhesion and little color defects and useful for producing a solid imaging device. A photocurable composition comprises: a colorant; a photopolymerizable compound; a photopolymerization initiator; and an alkali-soluble resin, wherein the photopolymerizable compound includes at least one compound selected from the group consisting of bisphenol compounds and isocyanurate ring-containing compounds. The colorant has an average primary particle diameter of 10-30nm and includes an organic pigment having multiple colors.

Description

PHOTOCURABLE COMPOSITIONS, ANTI-REFLECTIVE FILM USING THE SAME, AND SOLID STATE IMAGE PICKUP DEVICE}

1 is a configuration diagram showing an example of a solid state image pickup device of the present invention.

2 is a cross-sectional view showing an example of a solid state image pickup device in the case where the antireflection film of the present invention is formed between RGB pixels of a color filter.

FIG. 3 is a schematic diagram when the image pattern of the antireflection film obtained in Example 1 is observed with a scanning electron microscope (SEM). FIG.

Fig. 4 is a schematic diagram when the image pattern of the antireflection film obtained in Example 2 is observed with a scanning electron microscope (SEM).

Fig. 5 is a schematic diagram when the image pattern of the antireflection film obtained in Example 3 is observed with a scanning electron microscope (SEM).

FIG. 6 is a schematic diagram when the image pattern of the antireflection film obtained in Comparative Example 1 is observed with a scanning electron microscope (SEM). FIG.

(Explanation of the sign)

1: silicon substrate

2: light receiving sensor (PD)

3: vertical transfer register (CCD)

4: horizontal transfer register (CCD)

5: transmission electrode

6: shading film

7: leveling film (on silicon substrate)

8: Anti-reflective coating

9: color filter (R, G, B)

10: Flattening film on color filter

11: Microlens

12: Charge transfer unit

13: insulation film

A: Peripheral circuit part such as driving circuit

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable composition used for a solid state image pickup device such as a CCD and a CMOS, an antireflection film using the same, and a solid state image pickup device.

In the solid state image pickup device, when the color filter or the microlens is formed in the photolithography step, there is a problem that the pattern shape is deteriorated by the light reflected from the aluminum light shielding film or the wiring formed in the lower layer. In addition, in terms of the performance of the solid state image pickup device, the reflected light from the aluminum light shielding film and the wiring reflects again at the interface of the color filter and the flattening film, and enters the photodiode as stray light, thereby generating a false signal. It is becoming.

In order to suppress such a phenomenon, forming the black pattern which absorbs light on an aluminum light shielding film and wiring is performed.

Conventionally, Japanese Patent Laid-Open No. 3-276678 discloses a dyeing method of forming a pattern and then dyeing it with a black dye to form an antireflection film. However, in this method, it is difficult to reduce the thickness, thereby lowering the aperture ratio of the pixel. Moreover, heat resistance and light resistance are inferior by using dye.

Further, a method of forming a nitride film having a low reflectance on an aluminum light shielding film is disclosed in Japanese Patent Laid-Open No. Hei 6-0342896. However, since the wavelength at which the nitride film is absorbed is limited, absorption from visible light to the infrared light region is impossible, and light of some wavelength bands does not have antireflection performance. Therefore, it can be used to prevent a halation when forming a color filter or a microlens to be formed later and to make the pattern shape rectangular, but not to prevent the generation of false signals by stray light. In addition, the process of forming and patterning a nitride film is very complicated, especially in the case where the nitride film is formed without interlayer film, it becomes a local battery between aluminum and nitride film at the time of etching, and thus the aluminum has an edge shape. Deterioration or cracking caused a defect.

On the other hand, the method for improving the peelability of the film transfer method color filter using the photosensitive composition containing a trisisocyanuric acid compound is disclosed by Unexamined-Japanese-Patent No. 10-333330. However, there is only a disclosure example of a color filter for a liquid crystal display, there is no disclosure of the reflection film for a solid state image pickup device, and only a peelability from a cover film in the production of a color filter by a film transfer method is a problem. Doing.

In addition, Japanese Patent Application Laid-Open No. 8-062841 discloses a method for improving the storage stability and curing properties of a color filter using a deep photosensitive resin composition containing isocyanuric acid ethylene oxide modified tri (meth) acrylate as a photopolymerizable compound. Is disclosed. However, this is an invention regarding the color filter by the dyeing method, and is an invention which improves the storage stability of the photosensitive resin composition.

Moreover, it is described in Unexamined-Japanese-Patent No. 10-239859 which can use a bisphenol type compound for the photosensitive coloring image forming material used for manufacture of a color filter. However, the main subject is the invention of the developing solution and only discloses an example of the monomer used for the coloring image preparation material.

Since the carbon black used as the coloring agent of the present invention has light absorption characteristics with respect to the wavelength from the ultraviolet light to the infrared light region, when used as a colorant of the photosensitive composition for forming an antireflection film, the carbon black with respect to the wavelength from the ultraviolet light to the infrared light region, It may have an antireflection effect. However, in accordance with the trend of miniaturization and high resolution of solid state imaging devices, if the line width forming the antireflection film is less than 1.5 µm, regular deformation occurs due to the flow of the developer and the rinse solution in the developing and rinsing process. It can be seen that the phenomenon occurs.

As mentioned above, an object of this invention is to solve the said conventional problem.

In other words, the present invention provides a photocurable composition having good curing performance and excellent adhesion to the lower extremity, and is formed using the photocurable composition, and has excellent adhesion with the lower extremity and generation of false signals due to stray light. It is an object of the present invention to provide an antireflection film that is reduced and has few color defects.

Another object of the present invention is to provide a solid state image pickup device having the above antireflection film that is excellent in adhesion to the base and is less likely to generate color signals due to stray light.

In view of the above circumstances, the present inventors conducted intensive studies, and found that the photocurable composition containing a bisphenol compound or an isocyanurate ring-containing compound having a specific chemical structure as a photopolymerizable compound was added to the photocurable composition of the black colorant dispersion. By using it, what was able to solve the said subject was found and this invention was completed.

That is, the curing performance is good and the adhesion to the base is excellent, the monomer having a (meth) acryloyl group with a bisphenol as a skeleton, and / or the monomer having a (meth) acryloyl group with an isocyanur ring as a skeleton. By using it as a hardening component, the thing which can suppress generation | occurrence | production of a deformation | transformation was found, and the photocurable composition which does not produce a deformation | transformation was completed.

At this time, as a coloring agent, carbon black is preferable. Since carbon black is a stable substance, it does not decompose like a dye after pattern formation, and is excellent in heat resistance and light resistance, and since carbon has a filler effect, it is excellent in workability because it is not deformed by heat.

The present invention is accomplished by the following means.

<1> Photocurable composition containing a coloring agent, a photopolymerizable compound, a photoinitiator, and alkali-soluble resin WHEREIN: The photocurable compound contains at least any one of a bisphenol type compound and an isocyanuric ring containing compound. .

<2> The photocurable composition as described in said <1> containing carbon black whose average primary particle diameter of the said coloring agent is 10 nm or more and 30 nm or less.

<3> The photocurable composition as described in said <1> or <2> in which the said coloring agent contains a plurality of organic pigments.

The photocurable composition in any one of said <1>-<3> in which a <4> above-mentioned photopolymerizable compound contains at least any 1 type of following General formula (I) and (II).

(In general formula (I), R <^1> , R <^2> represents a hydrogen atom and a C1-C8 hydrocarbon group each independently, R <^3> , R <^4> represents a ethylene group or a propylene group each independently, m and n are Each independently represents an integer of 1 or more, m + n represents an integer of 3 to 40 (m + n preferably represents an integer of 4 to 30), and A ¹ and A ² each independently represent an acryloyl group or an allyl group. )

(In General Formula (II), R <^1> , R <^2> , R <^3> represents an ethylene group or a propylene group each independently, and a, b, and c respectively independently represent the integer of 0-6. M, n, l are Each is an integer, and m + n + l represents an integer of 0 to ¹⁸ , and A ¹ , A ² , and A ³ each independently represent an acryloyl group or an allyl group.)

<5> The antireflection film whose width | variety produced on the board | substrate using the photocurable composition in any one of said <1>-<4> is 1.5 micrometers or less.

<6> An antireflection film whose thickness produced on the board | substrate using the photocurable composition in any one of said <1>-<4> is 1.0 micrometer or less.

<7> The solid-state image sensor which has an antireflection film as described in said <5> or <6>.

The photocurable composition of this invention contains a coloring agent, a photopolymerizable compound, a photoinitiator, and alkali-soluble resin, and the said photopolymerizable compound contains at least any one of a bisphenol type compound and an isocyanuric ring containing compound.

When the said photocurable composition contains any one of a bisphenol type compound and an isocyanuric ring containing compound as said photopolymerizable compound, it can be set as the composition with favorable hardening performance and excellent adhesiveness with a base.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

`` Photocurable composition ''

The photocurable composition of this invention is a composition containing a coloring agent, a photopolymerizable compound, a photoinitiator, and alkali-soluble resin, and containing at least any one of a bisphenol type compound and an isocyanur ring containing compound as said photopolymerizable compound. Moreover, generally, a solvent is used and other component can be added as needed.

Photopolymerizable Compound

As described above, the photopolymerizable compound used in the composition of the present invention contains any one of a bisphenol compound and an isocyanurate ring-containing compound.

(Bisphenol-based compound)

As a bisphenol type compound, if it is photopolymerizable, it will not specifically limit, A conventionally well-known compound can be used.

Among the above, it is preferable that it is a compound represented with the following general formula (I).

In general formula (I), R <^1> , R <^2> represents a hydrogen atom and a C1-C8 hydrocarbon group each independently, R <^3> , R <^4> represents a ethylene group or a propylene group each independently, m and n are each independently It is an integer of 1 or more, m + n represents the integer of 3-40, Preferably m + n is an integer of 4-30. A ¹ and A ² each independently represent an acryloyl group or an allyl group.

As a C1-C8 hydrocarbon group represented by said R <^1> , R <^2> , Aliphatic hydrocarbon groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group; Aromatic hydrocarbon groups such as phenyl group; Alicyclic hydrocarbon groups, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and 1-cyclohexenyl group, etc. are mentioned.

The hydrocarbon group may be substituted or unsubstituted.

The said R <^3> , R <^4> represents an ethylene group or a propylene group each independently, and may be same or different, respectively.

The ethylene group and the propylene group may be substituted or unsubstituted. As said substituent, the substituent of the hydrocarbon group shown by said R <^1> , R <^2> is mentioned.

As said bisphenol type compound, NK ester ABE-300, copper A-BPE-4, copper A-BPE-6, copper A-BPE-10, copper A-BPE-13 by Shin-Nakamura Kagaku Kogyo Co., Ltd., Copper A-BPE-20; New Frontier BPE-10, BPE-20, BPP-4, BPEM-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; Aronix M-208, M-210, M-211B manufactured by Toagosei Co., Ltd .; Light ester BP-4EM, copper BP-6EM, copper BP-4PA, copper BP-10EA etc. by Kyoe Co., Ltd. are mentioned.

(Isocyanur ring-containing compound)

The isocyanurate ring-containing compound is not particularly limited as long as it is photopolymerizable, and conventionally known compounds can be used.

Among these, it is preferable that it is a compound represented with the following general formula (II).

In general formula (II), R <^1> , R <^2> , R <^3> represents an ethylene group or a propylene group each independently, and a, b, c respectively independently represents the integer of 0-6. m, n, and l are integers, respectively, and m + n + l represents the integer of 0-18, A <^1> , A <^2> , A <^3> respectively independently represents acryloyl group or an allyl group.

The ethylene group or propylene group represented by said R <^1> , R <^2> , R <^3> may have a substituent and may be unsubstituted.

As said substituent, the substituent of the hydrocarbon group represented by R <^1> , R <^2> in the said general formula (I) is mentioned.

A ¹ , A ² , and A ³ each independently represent an acryloyl group or an allyl group, and the acryloyl group or allyl group may be substituted or unsubstituted. As said substituent, the substituent of the hydrocarbon group represented by R <^1> , R <^2> of the said general formula (I) is mentioned.

As said isocyanur ring-containing compound, tri- (acryloyloxyethyl) -isocyanurate (brand name: Aronix M315 by Toagosei Co., Ltd., NK ester A by Shin-Nakamura Kagaku Kogyo Co., Ltd. make) -9300, FA-731A made by Hitachi Kasei Co., Ltd., New Frontier TEICA made by Seiyaku Co., Ltd., triallyl isocyanurate (brand name: TAIC, Degussa (product made by Nihon Kasei Co., Ltd.) Ltd. TAIC etc.) can be mentioned. Furthermore, (acryloyloxyethoxyethyl) -di- (acryloyloxyethyl) -isocyanurate and di- (acrylic) having a structure in which chains are extended with ethylene oxide or propylene oxide between the side chain and the isocyanurate ring. Loyloxyethoxyethyl)-(acryloyloxyethyl) -isocyanurate, tri- (acryloyloxyethoxyethyl) -isocyanurate, or a compound thereof, such as ethylene oxide and propylene jade It is also possible to further increase the number of additional seeds (21 is the total of carbon atoms including abc in the general formula (II)). Compounds in which triallyl isocyanurate is extended with ethylene oxide or the like can also be used.

Moreover, as a photopolymerizable compound in this invention, a general polymerizable monomer can be used together in the range which does not impair the effect of this invention.

As said polymerizable monomer, it has at least 1 addition-polymerizable ethylene group. The compound which has an ethylenically unsaturated group which has a boiling point of 100 degreeC or more under normal pressure is preferable, Especially, the tetrafunctional or more acrylate compound is more preferable.

As a compound which has the said at least 1 addition-polymerizable ethylenically unsaturated group, and whose boiling point is 100 degreeC or more at normal pressure, a polyethyleneglycol mono (meth) acrylate, a polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate Monofunctional acrylates and methacrylates such as these; Polyethylene glycol di (meth) acrylate, trimethol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Erythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimetholpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin or trimetholethane, etc. (Meth) acrylated after addition of ethylene oxide or propylene oxide to the polyfunctional alcohol of; poly (meth) acrylated of pentaerythritol or dipentaerythritol, Japanese Patent Publication No. 48-41708, Urethane acrylates described in Japanese Patent Application Laid-Open No. 50-6034 and Japanese Patent Publication No. 51-37193, and Japanese Patent Publication No. 48-64183 Polyfunctionals such as the polyester acrylates described in Japanese Patent Application Laid-Open No. 49-43191 and Japanese Patent Laid-Open No. 52-30490, and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid. Acrylate and methacrylate. Moreover, the thing introduce | transduced as a photocurable monomer and oligomer can also be used by Japanese adhesive association Vol.20, No. 7, pages 300-308.

In addition, a compound obtained by adding ethylene oxide or propylene oxide to the above-mentioned polyfunctional alcohol and then (meth) acrylated is formulated in Japanese Patent Application Laid-Open No. 10-62986 as general formulas (1) and (2) together with the specific examples thereof. It is described and these can also be used as a photosensitive polymerization component.

Especially, the structure where dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and these acryloyl groups via ethylene glycol and a propylene glycol residue are preferable. These oligomer types are also used. These photosensitive polymerization components can be used individually by 1 type or in combination of 2 or more types.

Content of the photosensitive polymerization component in a photocurable composition becomes like this. Preferably it is 0.1-80 mass%, More preferably, it is 1-60 mass%, Especially preferably, it is 5-50 mass% with respect to the total solid of the said composition. Even if the usage-amount of the photosensitive polymerization component is too least and too large than the said range, since hardening becomes inadequate, it is unpreferable.

<Colorant>

It does not specifically limit as a coloring agent which can be used for this invention, A conventionally well-known various dye and pigment can be used 1 type or in mixture of 2 or more types.

From a viewpoint of using the photocurable composition of this invention for the antireflection film mentioned later which requires a small optical density | concentration, a coloring agent is black. Hereinafter, a black coloring agent is demonstrated.

As the black colorant which can be used in the present invention, various known black pigments and black dyes can be used. In particular, carbon black, titanium black, titanium oxide, iron oxide, Manganese oxide, graphite, etc. are preferable, Especially, it is preferable to contain at least 1 sort (s) among carbon black and titanium black, and carbon black is especially preferable.

The said black coloring agent may be used individually by 1 type, or may mix and use 2 or more types.

As a coloring agent in this invention, it is preferable to contain a multiple color organic pigment from a viewpoint of manufacturing the antireflection film mentioned later.

When using as a photocurable composition for antireflection films mentioned later, it is preferable to use together with the said black coloring agent. By using a plurality of organic pigments in combination, the optical density of the photocurable composition can be further increased, and it is preferable from the viewpoint of making it more black.

It does not specifically limit as said multiple color organic pigment, What mixes various well-known pigments of R, G, B type | system | group, C, M, Y type | system | group, etc. can be used for it.

It is preferable that the average particle diameter (average primary particle diameter) of the said coloring agent is small in terms of the prevention of protrusion of the surface of the formed image pattern and the improvement of manufacturing efficiency. For example, it is preferable that projections do not occur in the antireflection film pattern, and that in the manufacture of a solid state image pickup device, the average primary particle diameter is small in view of the influence on the yield.

In order to reduce the effects of the present invention, the occurrence of projections on the surface of the formed image pattern, in particular, the generation of false signals due to stray light, and to improve the rectangular shape of the image pattern of the antireflection film, and the edge portion of the rectangle In order not to generate | occur | produce a protrusion, as small as possible is preferable, It is preferable that the average primary particle diameter of the said coloring agent is 30 nm or less, and 10 nm or more and 30 nm or less are more preferable. Especially, it is more preferable that average primary particle diameter (particle size) is 5-25 nm, It is especially preferable that it is 5-20 nm, It is most preferable that it is 5-15 nm or less.

Although the content rate of the said coloring agent in the total solid of the photocurable composition of this invention is not specifically limited, In order to obtain a high optical density as a thin film, the higher one is preferable, 1-90 mass% is preferable, and 3-70 Mass% is more preferable, and 5-50 mass% is especially preferable.

When the amount of the colorant is too small, it is necessary to increase the film thickness in order to obtain a high optical density. When the amount of the colorant is too large, the photocuring does not sufficiently proceed, so that the strength as a film decreases or the developing latitude becomes narrow during alkali development.

As a mass ratio when using a plurality of coloring agents together and using carbon black as a main component, the mass ratio with the coloring agent used together with carbon black has the preferable range of 95: 5-60: 40, and 95: 5-70: 30 is more preferable. And 90:10 to 80:20 are more preferable. The mass of the coloring agent used together becomes these total mass. By setting the mass ratio of the colorant used in combination with the carbon black to be in the range of 95: 5 to 60:40, there is a tendency to produce a stable coating film without aggregation of the dispersion and without variation.

As said carbon black in this invention, the carbon black # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900 made by Mitsubishi Kagaku Corporation # 850, MCF88, # 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45 , # 44, # 40, # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, Diamond Black LI, Diamond Black II, Diamond Black N339, Diamond Black SH, Diamond Black SHA, Diamond Black LH, Diamond Black H, Diamond Black HA, Diamond Black SF, Diamond Black N550M, Diamond Black E, diamond black G, diamond black R, diamond black N760M, diamond black LP. Carbon black surmax N990, N991, N907, N908 made by Cancurb. Asahi carbon black carbon black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 66HN, Asahi # 60H, Asahi # 60U, Asahi # 60, Asahi # 55, Asahi # 50H , Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal, Carbon Black ColorBlack Fw200, ColorBlack Fw2, ColorBlack Fw2V, ColorBlack Fw1, ColorBlack Fw18, ColorBlack S170, ColorBlack S160 , SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, PrintexU, PrintexV, Printex140U, Printex140V, and the like.

Although it does not necessarily need to be insulating as carbon black in this invention, what has insulating property can also be used. Insulating carbon black is carbon black showing insulation when the volume resistance as a powder is measured by the following method. For example, organic matter is adsorbed, coated or chemically bonded (grafted) on the surface of carbon black particles. Refers to having an organic compound on the surface of carbon black particles.

The insulation of carbon black can be measured as follows.

Carbon black was dispersed in propylene glycol monomethyl ether acetate so that benzyl methacrylate and methacrylic acid were in a molar ratio of 70:30 copolymer (mass average molecular weight 30,000) and 20:80 mass ratio, and the coating solution was prepared to have a thickness of 1.1. After coating on a chromium substrate of 10 mm × 10 cm, producing a coating film having a dry film thickness of 3 μm, and further heating the coating film at 220 ° C. for about 5 minutes in a hot plate, Mitsubishi Kagaku (according to JISK6911) was used. It is applied by the high resistivity meter and the Hirester UP (MCP-HT450) made from the above), and the volume resistivity is measured in an environment of 23 ° C and 65% relative humidity. And as this volume resistance value, carbon black which shows 10 <^5> ohm * cm or more, More preferably, it is 10 <^6> ohm * cm or more, More preferably, it is 10 <^7> ohm * cm or more is preferable.

As carbon black, for example, Japanese Patent Laid-Open No. 11-60988, Japanese Patent Laid-Open No. 11-60989, Japanese Patent Laid-Open No. 10-330643, Japanese Patent Laid-Open No. 11-80583 and Japanese Patent Laid-Open The resin-coated carbon black disclosed in Japanese Patent Application Laid-Open No. 11-80584, Japanese Patent Application Laid-Open No. 9-124969 and Japanese Patent Application Laid-Open No. 9-95625 can be used.

In particular, the compound represented by the general formula (I) or (II) in the present invention has an advantage that the relative dielectric constant is small and the influence on the electrical signal can be reduced. In particular, the compound represented by the general formula (II) is effective in combination with insulating carbon black because the dielectric constant is small.

Moreover, the photocurable composition of this invention can be used as a photocurable composition for color filters. When using the photocurable composition of this invention as a photocurable composition for color filters, by containing a several color organic pigment, the optical film equivalent to a black coloring agent, ie, the coating film with low reflectance can be formed.

Alkali-soluble resin

Alkali-soluble resin used for this invention will not be specifically limited if it is alkali-soluble.

In the present invention, conventionally known alkali-soluble resins can be used, but (i) maleic anhydride (MAA), methacrylic acid (MA), isobutyl methacrylic acid (IBMA), acrylic acid (AA), and fumaric acid ( At least one acid component monomer selected from FA), and (ii) acrylic ester monomers such as (ii) alkyl polyoxyethylene (meth) acrylate, benzyl (meth) acrylate, and alkyl (meth) acrylate, and ( iii) It is preferable to contain the acryl-type copolymer of at least 1 sort (s) or more of monomers which can superpose | polymerize, such as styrene from a viewpoint of titration to alkali image development.

The molar content rate of the acid component monomer in the said alkali-soluble resin is 5-50 mol%, Preferably it is 10-40 mol%.

Moreover, 1-60 mass% is preferable, as for content of alkali-soluble resin in the composition of this invention, 3-50 mass% is more preferable, 5-40 mass% is especially preferable. When content of the said alkali-soluble resin is less than 1 mass%, progress of image development may be delayed and an increase in manufacturing cost may be caused. Moreover, when it exceeds 60 mass%, a favorable pattern profile may not be obtained.

In the composition of this invention, you may use together other alkali-soluble resin other than the said acryl-type copolymer as alkali-soluble resin. As alkali-soluble resin, what is a linear organic polymer, is soluble in an organic solvent, and can develop with a weak alkali aqueous solution is preferable.

As such linear organic polymer, a polymer having a carboxylic acid in the side chain, for example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, and Japanese Patent Publication Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers described in Japanese Patent Application Laid-Open No. 54-25957, Japanese Patent Laid-Open No. 59-53836, and Japanese Patent Laid-Open No. 59-71048 Copolymers, partially esterified maleic acid copolymers, and the like, and an acidic cellulose derivative having a carboxylic acid in the side chain. In addition, addition of an acid anhydride to a polymer having a hydroxyl group is also useful.

Among these, a multicomponent copolymer with benzyl (meth) acrylate / (meth) acrylic acid / and other monomers is particularly preferable. In addition, 2-hydroxyethyl methacrylate, polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. are also useful as a water-soluble polymer. Moreover, in order to raise the intensity | strength of a cured film, you may contain alcohol soluble nylon, the polyether of 2, 2-bis- (4-hydroxyphenyl) -propane, epichlorohydrin, etc.

As an acryl-type copolymer, for example, the polyhydroxy copolymer with benzyl (meth) acrylate / (meth) acrylic acid / and other monomers, 2-hydroxypropyl (meth) acryl as described in Unexamined-Japanese-Patent No. 7-140654 Latex / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropylacrylate / polymethylmethacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2 -Hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer. By using together these acrylic copolymers and 2 or more types, the image development characteristic of the composition of this invention can be further improved.

Photoinitiator

As a photoinitiator in this invention, if the said photopolymerizable compound can be polymerized, it will not specifically limit. A conventionally well-known photoinitiator can be used.

As a photoinitiator, active halogen compounds, such as halomethyloxadiazole and halomethyl-s-triazine, a 3-aryl substituted coumarin compound, at least 1 type of lophine dimer, etc. are mentioned.

Among the active halogen compounds such as halomethyloxadiazole and halomethyl-s-triazine, as the halomethyloxadiazole compound, 2-halomethyl represented by the following general formula IV described in Japanese Patent Publication No. 57-6096 -5-vinyl-1,3,4-oxadiazole compound is mentioned.

Formula IV

In General Formula IV, W represents a substituted or unsubstituted aryl group, X represents a hydrogen atom, an alkyl group, or an aryl group. Y represents a fluorine atom, a chlorine atom or a bromine atom. n represents the integer of 1-3.

Specific compounds of the general formula (IV) include 2-trichloromethyl-5-styryl-1,3,4-oxadiazole and 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4 -Oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole, etc. are mentioned.

As the halomethyl-s-triazine-based compound, a vinyl-halomethyl-s-triazine compound represented by the following general formula V described in JP-A-59-1281, JP-A-53-133428 2- (naphtho-1-yl) -4,6-bis-halomethyl-s-triazine compound represented by the following general formula VI and 4- (p-aminophenyl) -2 represented by the following general formula VII And a 6-di-halomethyl-s-triazine compound.

Formula V

In Formula (V), Q represents Br or Cl. P represents -CQ ₃ (Q is synonymous with the above), -NH ₂ , -NHR, -N (R) ₂ , or -OR, where R represents a phenyl or alkyl group. n represents the integer of 0-3. W represents the aromatic group which may be substituted, the heterocyclic group which may be substituted, or the monovalent group represented by the following general formula VA.

General formula VA

In General Formula (VA), Z is -O- or -S- and R is synonymous with the above.

Formula VI

In Formula VI, X represents Br or Cl. m and n are integers of 0-3. R 'represents a group represented by the following general formula VIA.

General formula VIA

In the above general formula VIA, R ₁ represents a hydrogen atom or ORc (Rc represents an alkyl, cycloalkyl, alkenyl, aryl group), and R ₂ represents Cl, Br, alkyl, alkenyl, aryl, or an alkoxy group.

Formula VII

In formula (VII), R ₁ and R ₂ are the same or different and represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, and a group represented by the following general formula VIIA or VIIB. R ₃ and R ₄ are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. X, Y are the same or different and represent Cl or Br. m, n are the same or different and represent 0, 1 or 2.

Formula VIA

Formula VIIB

R <_5> , R <_6> , R <_7> represents an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group in general formula VIA and VIIB. Examples of the substituent in the substituted alkyl group and substituted aryl group include aryl groups such as phenyl groups, halogen atoms, alkoxy groups, carboalkoxy groups, carboaryloxy groups, acyl groups, nitro groups, dialkylamino groups, sulfonyl derivatives, and the like. Can be.

In the formula VII, R ₁ and R ₂ are may be bonded to form a ring having verses non-metallic atoms together with the nitrogen atom linking them, those represented in this case, as to this section ring.

Specific examples of the general formula V include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine and 2,4-bis (trichloromethyl) -6- (1-p- Dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, and the like.

Specific examples of the general formula VI include 2- (naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine and 2- (4-methoxy-naphtho-1-yl) -4 , 6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4- Butoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -naphtho-1-yl] -4,6 -Bis-trichloromethyl-s-triazine, 2- [4- (2-ethoxyethyl) -naphtho-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-Butoxyethyl) -naphtho-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphtho-1-yl)- 4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphtho-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphtho-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphtho-1-yl) -4,6 -Bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naph -1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy-naphtho-2-yl) -4,6-bis-trichloromethyl-s-tri Azine, 2- (4,5-dimethoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, and the like.

As a specific example of general formula VII, 4- [pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN , N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (chloroethyl) aminophenyl] -2,6 -Di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4 -(pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylcarbonylaminophenyl)- 2,6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxyphenyl) carbonylaminophenyl] 2,6-di (trichloromethyl) -s-triazine, 4 [MN, N-di (ethoxycarbonylmethyl) aminophenyl ] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloro Methyl) -s-triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [ m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (Ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl-2 , 6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl)- s-triazine, 4- [o-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN , N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4 -[O-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di ( Chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloro) Rhomethyl) -s-triazine, 4- [m-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m -Bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2 , 6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylamino Phenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o- Luoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2,6- Di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro -pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl ) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloroethyl Aminophenyl) -2,6-di (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6- [3-bromo-4- [N, N-bis (ethoxy Carbonylmethyl) amino] phenyl] -1,3,5-triazine and the like.

The following sensitizers can be used together in these initiators. Specific examples thereof include benzoin, benzoin methyl ether, 9-fluolinone, 2-chloro-9-fluolenonone, 2-methyl-9-fluolenonone, 9-anthrone, 2-bromo-9 -Antron, 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-methylxanthone, 2-methoxyxanthone, thioxanthone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyrylketone, p- (dimethylamino) phenyl -p-methylstyrylketone, benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, 7- {L-4-chloro-6 -(Diethylamino) -S-triazinyl (2), 1-amino} -3-phenylcoumarin, etc., and the benzothiazole type compound of Unexamined-Japanese-Patent No. 51-48516.

Moreover, the said 3-aryl substituted coumarin compound is a compound represented, for example by following General formula VIII.

Formula VIII

R ₈ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms (preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group), and R ₉ is a hydrogen atom, having 1 to 8 carbon atoms. An alkyl group, an aryl group having 6 to 10 carbon atoms, a group represented by the following general formula VIIIA (preferably methyl group, ethyl group, propyl group, butyl group, group represented by general formula VIIIA, particularly preferably represented by general formula VIIIA) Group).

R ₁₀ and R ₁₁ each represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group), and a haloalkyl group having 1 to 8 carbon atoms (for example, a chloromethyl group and a fluoro group). Methyl group, trifluoromethyl group, etc.), alkoxy group having 1 to 8 carbon atoms (for example, methoxy group, ethoxy group, butoxy group), aryl group having 6 to 10 carbon atoms (for example, phenyl group), amino group, N (R ₁₆ ) (R ₁₇ ) and halogen atoms (eg Cl, Br, F). Preferably a hydrogen atom, a methyl group, an ethyl group, a methoxy group, a phenyl _{group, -N (R 16) (R} 17), Cl.

R <_12> represents the C6-C16 aryl group (for example, a phenyl group, a naphthyl group, a tolyl group, cumyl group) which may be substituted. Examples of the substituent group, -N (R ₁₆₎ (R _17), alkyl group having 1 to 8 carbon atoms (e.g. methyl, ethyl, propyl, butyl, octyl), a haloalkyl group (e.g. having 1 to 8 carbon atoms; Chloromethyl group, fluoromethyl group, trifluoromethyl group, etc.), alkoxy group having 1 to 8 carbon atoms (e.g., methoxy group, ethoxy group, butoxy group), hydroxy group, cyano group, halogen atom (e.g. Cl, Br, F) is mentioned.

R <_13> , R <_14> , R <_16> , R <_17> is the same or different, and represents a hydrogen atom and a C1-C8 alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group), respectively. R ₁₃ and R ₁₄ and R ₁₆ and R ₁₇ are bonded to each other to form a heterocyclic ring with a nitrogen atom (for example, piperidine ring, piperazine ring, morpholine ring, pyrazole ring, diazole ring, triazole ring, benzotriazole ring, etc.). ) May be formed.

R ₁₅ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, octyl group), an alkoxy group having 1 to 8 carbon atoms (eg methoxy group, ethoxy group, butoxy group) , An aryl group having 6 to 10 carbon atoms (eg, a phenyl group), an amino group, N (R ₁₆ ) (R ₁₇ ), and a halogen atom (eg Cl, Br, F) may be substituted. Zb represents = O, = S or = C (R ₁₈ ) (R ₁₉ ). Preferably it is = O, = S, = C (CN) ₂ , Especially preferably, it is = O. R ₁₈ and R ₁₉ are the same or different and represent a cyano group, -COOR ₂₀ , -COR ₂₁ . R ₂₀ and R ₂₁ each represent an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group), a haloalkyl group having 1 to 8 carbon atoms (for example, a chloromethyl group, a fluoromethyl group, and a tree). Fluoromethyl group etc.) and the C6-C10 aryl group (for example, phenyl group) which may be substituted.

Particularly preferred 3-aryl substituted coumarin compounds are {(s-triazin-2-yl) amino} -3-arylcoumarin compounds represented by the general formula IX.

Formula VIIIA

Formula IX

Ropin dimer means the 2,4,5-triphenyl imidazolyl dimer which consists of two lophine residues, The basic structure is shown below.

Specific examples thereof include 2- (o-chlorphenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, and 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-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4, 5-diphenyl imidazolyl dimer etc. are mentioned.

Although it does not specifically limit as a photoinitiator of an oxime type compound, 2- (O-benzoyl oxime) -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-methyl Sulfanyl-phenyl) -acetic acid ethyl ester-O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl) -acetic acid ethyl ester-O-benzoate, 1- [4- (phenylthio) phenyl] -2 -(O-benzoyl oxime) -1,2-octanedione etc. are mentioned.

In the present invention, other known ones can be used in addition to the above initiators.

For example, bisinal polyketolaldonyl compounds disclosed in US Pat. No. 2,367,660, α-carbonyl compounds disclosed in US Pat. Nos. 2,367,661 and 2,367,670, US Pat. No. 2,448,828 Acyloinethers, aromatic acyloin compounds substituted with α-hydrocarbons as disclosed in US Pat. No. 2,722,512, multinuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, US Pat. No. 3,549,367 Combinations of triallylimidazole dimers / p-aminophenyl ketones disclosed in the specification and benzothiazole compounds / trihalomethyl-s-triazine compounds disclosed in Japanese Patent Publication No. 51-48516 Can be mentioned.

Asahi Denka Co., Ltd. Adeka Optomer SP-150, 151, 170, 171, N-1717, N1414, etc. can also be used as a polymerization initiator.

In this invention, the usage-amount of a photoinitiator is 0.1-10.0 mass% of the total solid of the composition of this invention, Preferably it is 0.5-5.0 mass%. When the amount of the initiator is less than 0.1% by mass, the polymerization is less likely to proceed, and when it exceeds 10.0% by mass, the film strength is weakened.

-solvent-

As a solvent used as needed in the composition of this invention, it is suitably selected according to the solubility, coating property, and safety of a composition.

As a solvent used when preparing the composition of this invention, ester, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, formic acid amyl, 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 butyl acetate, methyl ethoxyacetate, ethoxy 3-oxypropionic acid alkyl esters such as ethyl acetate, methyl 3-oxypropionate and ethyl 3-oxypropionate; Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2-methoxy Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionic acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate , Methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetic acetate, ethyl acetate, 2-oxo moiety Methyl carbonate, ethyl 2-oxobutanoate, and the like; 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 and the like; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; Aromatic hydrocarbons, for example, toluene, xylene, and the like can be given.

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 and the like are preferably used.

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

Other Ingredients

In the composition of the present invention, for the purpose of improving the dispersibility of the colorant, or as necessary, various conventionally known additives, for example, fillers, polymer compounds other than the alkali-soluble resins, surfactants, pigment dispersants, adhesion promoters, and oxidation An inhibitor, a ultraviolet absorber, an aggregation inhibitor, etc. can be mix | 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, addition of acid anhydride to a polymer having a hydroxyl group, formed of alcohol soluble nylon, bisphenol A and epichlorhydrin Alkali-soluble resins such as phenoxy resins; Surfactants such as nonionics, cationics and anionics, specifically phthalocyanine derivatives (commercially available EFKA-745 (Morishita Sangyo)); Organosiloxane polymer KP341 (made by Shin-Etsu Kagaku Kogyo Co., Ltd.), (meth) acrylic acid type (co) polymer polyflow No.75, No.90, No.95 (Kyoesha Yushi Kagaku Kogyo Co., Ltd.), W001 (made by Yutaka Sho) Cationic surfactants such as; Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid Esters (nonionic surfactants such as Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1 manufactured by BASF; W004, W005, W017 Anionic surfactants such as EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 (above Morishita), Disperse Ade 6, and Disperse Ade. Polymer dispersants such as 8, Disperse Aid 15, Disperse Aid 9100 (manufactured by Sanofucco), and various Solsper dispersants such as Solsper's 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, and 28000 (Geneca). Kabushiki Kaisha); Ade Kafluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denkaze) and Isonet S -20 (made by Sanyo Kasei);

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-epoxy Adhesion of cyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane accelerant;

Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol;

Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone;

And aggregation inhibitors such as sodium polyacrylate.

In addition, in order to promote alkali solubility of the non-irradiated portion and to further improve the developability of the composition of the present invention, the composition of the present invention may contain an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less. Addition can be performed. Specifically, For example, aliphatic monocarboxylic acids, such as formic acid, acetic acid, propionic acid, butyric acid, gil acetic acid, pivalic acid, capronic acid, diethyl acetic acid, enanthic acid, and caprylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, sublinic acid, azeline acid, sebacic acid, brasyl acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, Aliphatic dicarboxylic acids such as citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid and caporonic acid; Aromatic mono carboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemeric acid, and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melanoic acid and pyromellitic acid; Other carboxylic acids such as phenylacetic acid, hydroatroic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropaic acid, cinnamic acid, methyl cinnamic acid, cinnamic acid benzyl, cinnamilidene acetic acid, cumalic acid, unbelic acid Can be mentioned.

In addition to the above, it is preferable to further add a thermal polymerization inhibitor to the composition of the present invention. For example, hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, and fatigue Garol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol ), 2-mercaptobenzoimidazole and the like are useful.

-Production method of photocurable composition-

The photocurable composition of this invention is prepared by mixing and disperse | distributing the said coloring agent, alkali-soluble resin, a photopolymerizable compound, and a photoinitiator, and the said other components used as needed with the said solvent, using various mixers and dispersers. can do.

In addition, the mixing and dispersing step preferably comprises kneading dispersion and undispersed treatment performed subsequently, but it is also possible to omit the kneading dispersion.

In the kneading and dispersing step, the surface of the colorant of the raw material is promoted to be wetted with the constituent mainly composed of the resin component of the vehicle, and from the solid / gas interface of the colorant particles and air to the solid / solution interface of the colorant particles and the vehicle solution. Convert.

In the microdispersion step, the colorant particles are dispersed to a minute state close to the primary particles by mixing and stirring together with the medium for dispersing fine particles of glass or ceramic.

Therefore, in the kneading and dispersing step, the interface formed by the colorant particle surface needs to be converted from the air into the solution. Therefore, a strong shear force and a compressive force are required, and the kneader and the kneaded material suitable for it are preferably of high viscosity.

On the other hand, in the non-dispersion step, it is necessary to distribute the particles uniformly and stably to a minute state, and it is preferable that the disperser for imparting impact force and shear force to the aggregated colorant particles and the to-be-dispersed product have a relatively low viscosity.

The uniformly and stably dispersed means to uniformly disperse the antireflection effect so as not to cause irregularities in the antireflection film pattern for the solid-state imaging element formed on the substrate. It is preferable to make the average primary particle diameter (particle size) of a black coloring agent into the range mentioned above.

The average primary particle diameter can be measured using an electron microscope method.

The kneading and dispersing step in the production of the photocurable composition of the present invention is first kneaded with, for example, a black colorant, a dispersant or a surface treatment agent, an alkali-soluble resin, and a solvent. Machines used for kneading are two rolls, three rolls, ball mills, tron mills, dispersers, kneaders, kneaders, homogenizers, blenders, single screw and twin screw extruders, and are dispersed with strong shearing forces.

Subsequently, a solvent and an alkali-soluble resin (residue used in the kneading step) were added, and a glass, zirconia, or the like having a particle diameter of 0.1 to 1 mm was used mainly using a vertical or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic disperser, or the like. Undispersed with beads.

It is also possible to omit this kneading step. In that case, bead dispersion is performed with a pigment, a dispersing agent or a surface treating agent, an alkali-soluble resin and a solvent. In this case, it is preferable that the remaining alkali-soluble resin in the kneading step is added during the dispersion.

In addition, the details of kneading and dispersion | distribution are detailed in T.C. Patton, "Paint Flow and Pigment Dispersion" (published by John Wiley and Sons, 1964).

≪Anti-reflective coating≫

The antireflection film of the present invention is one having a width of 1.5 μm or less formed on a substrate using the photocurable composition, or an antireflection film having a thickness of 1.0 μm or less formed on a substrate using the photocurable composition.

The anti-reflection film of the present invention can be said to have excellent adhesion to the base, to reduce the occurrence of false signals due to stray light, and to have less color defects by having the above structure.

More specifically, formed on the substrate, directly or through another layer, on the light shielding film formed on the electrode and / or the charge transfer circuit of the solid state image pickup device having the electrode and the charge transfer circuit, for example a color filter. It is preferable that it is an antireflection film between RGB pixels. These are not specifically limited.

The antireflection film of the present invention is formed using the photocurable composition.

In detail, it can obtain through the process of pattern exposure and alkali image development, after drying (prebaking) the antireflective film which apply | coated the said photocurable composition on the board | substrate, and formed it.

More specifically, for example, the light shielding film formed on the electrode and / or the charge transfer circuit of the solid state image pickup device having the electrode and the charge transfer circuit, on the substrate, directly or via another layer of the antireflective film forming composition. Immediately above, the photocurable coating film formed by application by a coating method such as rotary coating, slit coating, flexible coating, roll coating, or the like is dried (prebaked), and then pattern-exposured through a predetermined photomask and irradiated with light. By hardening only a coating film part and developing with a developing solution, a film can be formed in a pattern form on a light shielding film, and an antireflection film can be manufactured.

Although it does not specifically limit as a radiation used for the said light irradiation, Although it can use, the wavelength is suitably selected based on the photoinitiator to be used. Although the said light shielding film is not specifically limited, It is preferable that it is an aluminum light shielding film.

In addition, as said insulating film, although it does not specifically limit, For example, a SiN thin film etc. can be used.

As the radiation, radiation having a bright line spectrum can be used in g-ray (436 nm), h-ray (405 nm), i-ray (365 nm), j-ray (310 nm) and the like.

As a formation position in the solid-state image sensor of the anti-reflection film of this invention, it is (1) planarization film image on a silicon substrate, (2) between RGB pixels of a color filter, (3) light shielding film image, (4) light shielding film and a color filter pixel. Although it is a position which interrupts a planarization film in a liver, (5) a position which covers a light shielding film, etc., you may form other than that in the range which does not impair the effect of this invention. Among these, it is preferable to form between RGB pixels of a color filter on the light shielding film via the planarization film on a silicon substrate.

The formation position of the anti-reflection film in the solid state image pickup device of the present invention will be described in the section on the solid state image pickup device described later.

The above development is preferably an alkali development treatment, and only the portion where the unilluminated portion is eluted in the aqueous alkaline solution and photocured by the exposure remains. As a developing solution, the photocurable film layer of a non-irradiated part is melt | dissolved. Any developer can be used as long as it does not dissolve the light irradiation part.

After the excess developer is washed off and dried, heat treatment (post bake) can be performed at a temperature of 50 ° C to 240 ° C. Thus, a photocurable film can be manufactured. As a result, a light shielding film is obtained.

Since the photocurable composition contains a black colorant exhibiting a filler effect, the antireflection film of the present invention is excellent in workability without being deformed by heat treatment after film formation, and particularly remarkably when carbon black is used. do.

As the substrate, for example, a photoelectric conversion element substrate used for a solid state image pickup device or the like, for example, a silicon substrate, an organic semiconductor substrate, etc. may be mentioned. The color filter which forms each pixel, such as a circuit, may be formed.

Drying (prebaking) of the composition layer of this invention apply | coated on the board | substrate can be performed in a hotplate, oven, etc. at 50-140 degreeC by 10-300 second, and 60-180 second is preferable at the temperature of 70-130 degreeC. And 90-120 second is more preferable at the temperature of 90-120 degreeC.

Although the coating thickness (anti-reflective film after drying) of the composition of this invention is generally 2.0 micrometers or less, the lower surface of an on-chip microlens from the upper surface (substrate surface) of the photoelectric conversion element formed on the board | substrate, such as a silicon wafer, according to micronization of a pixel. Although 1.0 micrometer or less is needed from the viewpoint of thinning of the effective optical function layer to up to, 0.6 micrometer or less is more preferable, and 0.5 micrometer or less is the most preferable.

The reflectance of the anti-reflection film of the present invention is 0.5 µm in thickness and irradiated with irradiation light in a wavelength range of 350 to 800 nm at an irradiation angle of 5 °, 35% or less, preferably 25% or less, most preferably 20% It is as follows.

As the developing solution, any one can be used as long as the antireflection film for solid-state imaging device of the present invention is dissolved and the radiation irradiating portion is not dissolved. Specifically, combinations of various organic solvents and alkaline aqueous solutions can be used, and among them, it is preferable to use alkaline developing solutions.

As an organic solvent, the above-mentioned solvent used when preparing the composition of this invention is mentioned. As image development temperature, it is 20 degreeC-50 degreeC normally, and as image development time, it is 20 to 90 second.

As said alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide The concentration of the alkaline compounds such as roxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene is 0.001 to 10% by mass, preferably 0.01 to 1 The alkaline aqueous solution dissolved so that it may become mass% is used preferably. Moreover, when using the developing solution which consists of such alkaline aqueous solution, generally, after image development, it wash | cleans (rinses) with water.

The said post-baking is post-development heating in order to make hardening complete, and can heat (hard bake) about 200 degreeC-220 degreeC normally.

This post-baking process can be performed continuously or batchwise using heating means, such as a hotplate, a convection oven (hot air circulation type dryer), and a high frequency heater, so that the coating film after image development may be in said condition.

In addition to the post-baking treatment, the coating film may be cured by irradiating ultraviolet rays with a high-pressure mercury lamp while heating (postcure treatment).

The width (line width) of the antireflection film of the present invention needs to be 1.5 µm or less from the viewpoint of miniaturization of a solid state imaging device or the like, but is preferably as small as possible.

An overcoat layer (flattening layer) can be formed on the color filter layer in the solid-state imaging device described later in the present invention. As resin (made by OC) which forms an overcoat layer, an acrylic resin composition, an epoxy resin composition, a polyimide resin composition, etc. are mentioned. Among them, an acrylic resin composition from the viewpoint of excellent adhesiveness when the resin component of the photocurable composition for color filters and the resin component of the photocurable composition contain acrylic resin as a main component are excellent in transparency in the visible light region. This is preferred. In particular, if it is a photocurable (meth) acrylic-type resin for photoresists used by a color filter, matching with the manufacturing process of a color filter will be favorable and it is preferable.

≪Solid Image Imaging Device (Image Sensor) ≫

The solid state image pickup device of the present invention includes the antireflection film of the present invention. The other structure is not specifically limited, A conventionally well-known structure can be employ | adopted.

Hereinafter, although the solid-state image sensor of this invention is demonstrated using FIGS. 1-2, it is not limited to this.

1 is a configuration diagram showing an example of a solid state image pickup device of the present invention. Fig. 2 is a cross-sectional view of a preferred embodiment of the solid state image pickup device of the present invention when the antireflection film of the present invention is formed at a position just above the transfer electrode on the planarization film on a silicon substrate. Note that the same reference numerals are given to those having substantially the same functions.

In the solid state image pickup device of the present invention, as shown in Fig. 1, a plurality of light receiving sensor portions (photoelectric conversion portion PD) 2 for photoelectric conversion are formed in the surface layer portion of the substrate made of the silicon substrate 1. (See Figure 2.).

In addition, adjacent to the light receiving sensor unit 2, a vertical transfer register 3 of a CCD structure for transferring charges formed in the light receiving sensor unit 2 is provided, and at one end of the vertical transfer register 3, The horizontal transfer register 4 is provided.

A signal detector and an output amplifier are formed at the end of the horizontal transfer register 4, and a peripheral circuit portion A such as a driving circuit is formed at the peripheral portion. On the vertical transfer register 3 and the horizontal transfer register 4 of the CCD structure, a light shielding film for a peripheral circuit (not shown, see 6 in FIG. 2) through an interlayer film (not shown, see the insulating film 13 in FIG. 2). ) Is formed of a sputtering device.

Fig. 2 is a cross-sectional view of one embodiment of the solid state image pickup device of the present invention, and a photoelectric conversion element (light receiving sensor portion) 2 for converting and storing light into charge is provided in the surface layer portion of the silicon substrate 1. In addition, in order to transfer charge adjacent to the light receiving sensor portion (photoelectric conversion element portion) 2, a transfer electrode 5 of a CCD structure is formed. In addition, a light shielding film 6 is formed on the upper layer so as to cover the transfer electrode 5. The transfer electrode 5 is covered with an insulating film 13 or the like.

In addition, the planarization film 7 is formed in the whole silicon substrate in which the said light shielding film 6 was formed as needed. The insulating film 13 is normally formed between the planarization film 7 and the silicon substrate 1.

The antireflection film 8 is preferably formed directly on the light shielding film 6 via the planarization film 7 or directly without the planarization film 7 interposed therebetween.

In addition, on the silicon substrate on which the antireflection film 8 and the planarization film 7 are formed, a color filter 9 consisting of three colors of R, G, and B forming color pixels is provided. The center of each of the RGB pixels is positioned directly above the center of the light receiving sensor unit 2, and a part of each of two sides of each color filter pattern is disposed on the antireflection film 8 on the antireflection film 8. It is preferable to overlap so that an aperture ratio may be improved.

The maximum sides of the rectangular unit pixels for each color of the color filter 9 are generally 1.5 to 20 µm or less. Among them, effective use of a substrate such as a silicon wafer, miniaturization of a device using a solid state imaging device, and a solid state imaging device From the standpoint of high speed operation, 5 m or less is preferable, 4 m or less is more preferable, and 3 m or less is particularly preferable.

The planarization film 10 is formed on the color filter 9. In addition, it is preferable that the on-chip microlens 11 for condensing is formed.

The solid state image pickup device of the present invention is characterized by having the above-described antireflection film, and the form thereof is not particularly limited and many forms are possible.

Next, although the manufacturing method of the solid-state image sensor of this invention is demonstrated using FIG. 2, it does not specifically limit but all the well-known manufacturing methods can be used. Other forms other than the form shown in FIG. 2 can be manufactured by the same method.

(Formation of circuit part)

A substrate having a peripheral circuit portion such as a light receiving sensor portion 2, a charge transfer portion 12 (transfer electrode 5, etc.), a signal detection portion, an output amplifier, a driving circuit, and the like is fabricated. The substrate can be produced by a conventionally known method.

A light shielding film 6 is formed on the entire surface of the substrate directly or through an interlayer film (insulating film) 13. Subsequently, after applying a positive resist to the whole surface, it exposes and develops through a mask, and removes in the subsequent etching process, and the light shielding film 6 located in the upper part of the light receiving sensor part 2 is exposed. In addition, after etching by dry-etcher, the remaining resist is peeled off to expose the light shielding film 6 in the portion covering the transfer electrode.

(Formation of Flattening Film)

After uniformly applying the composition for a flattening film on the substrate, the flattening film 7 is formed by heating the substrate on a hot plate.

(Production of Anti-reflective Film)

The photocurable composition is uniformly applied onto the silicon substrate on which the light shielding film 6 is formed.

For example, when a spin coat is used, the film thickness can be adjusted by adjusting the coating rotation speed so that the film thickness from the front of the light shielding film 6 after the heat treatment on the hot plate for 120 seconds at a surface temperature of 90 ° C. after coating is 0.5 μm. have. Moreover, before apply | coating the said photocurable composition, in order to improve adhesiveness, it is also possible to perform the process which forms the oxide film, such as anodizing process and a boehmite process, in the light shielding film 6.

Next, the substrate to which the photocurable composition is applied is heated (for example, hot plated at 90 ° C. for 120 seconds) to form a dry coating film.

Next, radiation (for example, i-line stepper, Canon Co., Ltd. FPA-3000i5 +) is exposed through a mask for forming a pattern of the anti-reflection film 8 on the light shielding film 6, and developed (for example, 23 ° C., Tetramethylammonium hydrooxide (TMAH) 0.3% aqueous solution for 60 seconds), followed by rinsing with pure water (for example, 20 seconds spin shower), washing with water, and drying, followed by image pattern of the antireflection film 8 (For example, line width 0.5 micrometer) is obtained.

A blue color resist (COLOR MOSAIC-EXIS SB-4000L manufactured by Fujifilm Electronics Co., Ltd.) is uniformly applied to the substrate on which the antireflection film 8 is formed.

After coating, for example, heat treatment is performed at a surface temperature of 100 ° C. for 120 seconds on a hot plate.

Radiation exposure (for example, i-line stepper, Canon Co., Ltd. FPA-3000i5 +) was carried out through the mask which has a pattern in which the square pixel of 2 micrometers of one side was arranged, and 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH) The paddle phenomenon is performed at 23 DEG C for 60 seconds, then rinsed with spin water for 20 seconds using pure water, followed by washing with pure water again.

Thereafter, the attached droplets are blown off to remove air, and the substrate is naturally dried to obtain a blue color filter pattern 9B. At this time, it is preferable that a part of two sides of the pixel pattern of the adjacent color filter overlaps the antireflection film 8 so as to overlap the antireflection film 8.

The same process is repeated for green (using COLOR MOSAIC-EXIS SG-4000L manufactured by Fujifilm Electronics) and Red (using COLOR MOSAIC-EXIS SR-4000L manufactured by Fujifilm Electronics). The color filters 9G and 9R are obtained on the light receiving sensor portion 2 on the substrate.

On the silicon substrate on which the color filter 9 was formed, the flattening film composition (COLOR MOSAIC CT-3100L manufactured by Fujifilm Electronics Co., Ltd.) was uniformly applied, and the substrate was then heated on a hot plate at 220 ° C. for 4 minutes. It heats and the planarization film 10 is formed. The microlens 11 is formed thereon again. Dicing packaging of the obtained silicon substrate is carried out to obtain a solid-state imaging device.

Example

Hereinafter, although an Example demonstrates this invention concretely, the content of this invention is not limited to these. In addition, in an Example, a part and% mean a mass part and mass% unless there is particular notice.

(Example 1)

<Solid image pickup device (when a monomer having a (meth) acryloyl group using bisphenol as a skeleton) is used>

[Production of circuit part]

As shown in Figs. 1 and 2, the solid state image pickup device forms a plurality of light receiving sensor portions 2 for photoelectric conversion in the surface layer portion of the substrate made of the silicon substrate 1, and is adjacent to the light receiving sensor 2, A vertical transfer register having a CCD structure for transferring charges formed in the light receiving sensor unit 2, and a horizontal transfer register 4 for transferring in the horizontal direction at one end of the column of the vertical transfer register 3, and horizontally A signal detector (not shown) and an output amplifier (not shown) are formed at the end of the transfer register, and a peripheral circuit portion A such as a drive circuit is formed at the peripheral portion.

The aluminum light shielding film 6 was formed in the sputter | spatter apparatus through the interlayer film (insulating layer 13) in the whole board | substrate surface in which the peripheral circuit etc. were formed.

In addition, after the positive resist was applied to the entire surface, exposure and development were performed through a mask, and the aluminum light shielding film 6 removed in the subsequent etching step was exposed. In addition, after etching by dry-etcher, the remaining resist was peeled off and the aluminum light shielding film 6 was exposed.

[Formation of Flattening Film]

A flattening film (COLOR MOSAIC CT-3100L manufactured by Fujifilm Electronics Co., Ltd.) was uniformly coated on the silicon substrate on which the circuit portion was formed, and then the substrate was heated on a hot plate at 220 ° C. for 4 minutes. The planarization film 7 with a film thickness of 1 micrometer was formed.

[Preparation of Photosensitive Composition for Antireflection Film Formation]

(Preparation of Carbon Black Dispersion)

The carbon black dispersion liquid used for the photosensitive composition for antireflection film formation performed the high viscosity dispersion process of the composition 1 of the following carbon black dispersion liquid with two rolls, and obtained the dispersion. The viscosity of the dispersion at this time was 70000 mPa · s.

The composition 2 of the following carbon black dispersion liquid was added to the said dispersion, and it stirred for 3 hours using the homogenizer on 3000 rpm conditions. The obtained mixed solution was microdispersed for 4 hours using a disperser (brand name: Dispermat GETZMANN Co., Ltd.) which used 0.3 mm zirconia beads, and the carbon black dispersion liquid was prepared. At this time, the viscosity of the mixed solution was 37 mPa · s.

(Composition 1 of Carbon Black Dispersion)

Average primary particle diameter of 15 nm carbon black (PigmentBlack 7); Part 23

Propylene glycol monomethyl ether acetate solution of benzyl methacrylate / methacrylic acid copolymer (BzMA / MAA = 70/30 molar ratio, weight average molecular weight Mw: 30000, solid content: 45%). Part 22

Solsper Sphere 5000 (Geneca Co., Dispersant). Part 1.2

(Composition 2 of Carbon Black Dispersion)

Propylene glycol monomethyl ether acetate solution of benzyl methacrylate / methacrylic acid copolymer (BzMA / MAA = 70/30 molar ratio, weight average molecular weight Mw: 30000, solid content: 45%). Part 22

Propylene glycol monomethyl ether acetate... 200 copies

(Preparation of the photosensitive composition for antireflection film formation)

The following component was mixed with the stirrer and the photosensitive composition for antireflection film formation was prepared.

(Composition of Photosensitive Composition for Antireflection Film Formation)

Cyclomer P (alkali-soluble resin: 50% solution of acrylic copolymer propylene glycol monomethyl ether acetate, Daicel Kagaku Kogyo Co., Ltd. product, weight average molecular weight: 20,000, acid value: 30). Part 1.8

Dipentaerythritol hexaacrylate... 1.5

· NK-ester ABPE-10 (bisphenol A compound, the Shin-Nakamura Kagaku Corporation make, photopolymerizable compound)…. 1.5

The average primary particle diameter of 15 nm carbon black dispersion liquid; Part 12.5

Propylene glycol monomethyl ether acetate... Part 18

Ethyl-3-ethoxypropionate... Part 11.5

1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime)... 0.6 part

[Production of Anti-reflective Film]

The anti-reflection film-forming photosensitive composition was adjusted so that the spin speed of the spin coat was adjusted so that the film thickness after the heat treatment on a hot plate at a surface temperature of 90 ° C. for 120 seconds was 0.5 μm, so that the flattening film was formed on the substrate. Applied.

Next, the board | substrate with which the photosensitive composition for antireflection film formation was apply | coated was 120 degreeC, and it heat-processed in the hotplate for 120 second, and formed the dry coating film.

Next, an i-line stepper and Canon PAK's FPA-3000i + were exposed through a mask for forming a lattice pattern having a line width of 0.5 µm on the aluminum light shielding film 6, and 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH). The paddle phenomenon was performed for 60 seconds at 23 degrees, then rinsed with 20 seconds spin shower using pure water, and washed with pure water again. Thereafter, the attached droplets were jetted with high air to remove the substrate, and the substrate was naturally dried to obtain an image pattern of the antireflection film 8.

The pattern shape obtained at this time is shown in FIG.

[Production of color filter]

On the substrate on which the antireflection film 8 is formed, the surface of the coating after the spin coating is coated using a blue color resist (COLOR MOSAIC-EXIS SB-4000L manufactured by Fujifilm Electronics Co., Ltd.). The film thickness from the planarization film 8 after heat processing on the hotplate for 120 second at the temperature of 100 degreeC was adjusted to 1.1 micrometers, and it apply | coated uniformly on the board | substrate with which the said antireflection film 8 was formed.

Through a pattern of masks in which square pixels of 2 µm on one side are arranged, an i-line stepper and FPA-3000i + manufactured by Canon Corporation are exposed and developed with a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH) to develop a blue color filter. The pattern 9B was obtained. At this time, the pattern was formed so as to embed the pattern within the range of the anti-reflection film 8.

The same process is repeated for green (using COLOR MOSAIC-EXIS SG-4000L manufactured by Fujifilm Electronics) and red (using COLOR MOSAIC-EXIS SR-4000L manufactured by Fujifilm Electronics). Color filters 9R and 9G were obtained on the light receiving sensor portion 2 on the substrate.

[Formation of Flattening Film on Color Filter, Fabrication of Solid State Imaging Device]

After apply | coating a flattening film agent (COLOR MOSAIC CT-3100L by Fujifilm Electronics Co., Ltd.) uniformly on the board | substrate on the silicon substrate in which the said color filter 9 was formed, the board | substrate is applied at 220 degreeC in a hotplate, and 4 It heated for minutes, and the planarization film 10 was formed. The microlens 11 was formed thereon again.

The obtained silicon substrate was diced and packaged, and the solid-state image sensor was obtained.

(Example 2)

<Solid-state imaging device (when a monomer having a (meth) acryloyl group is used with an isocyanur ring as a skeleton)>

In "Preparation of the photosensitive composition for anti-reflective film formation" of Example 1, "NK-ester ABPE-10 (made by Shin-Nakamura Kagaku Co., Ltd.) which is a photopolymerizable compound is" M315 (isocyanuric acid triacrylate, A solid-state imaging device was fabricated in the same manner as in Example 1, except that the product was changed to "Toagosei Co., Ltd." Here, the image pattern shape of the antireflection film formed using the photosensitive composition for antireflection film formation obtained in the intermediate process. 4 is shown.

Example 3

In "Preparation of the photosensitive composition for antireflection film formation" of Example 1, "NK-ester ABPE-10" which is a photopolymerizable compound was changed to "tri- (acryloyloxyethoxyethyl) -isocyanurate" A solid-state imaging device was fabricated in the same manner as in Example 1 except for the above. Here, the image pattern shape of the antireflective film formed using the photosensitive composition for antireflective film formation obtained by the intermediate process is shown in FIG.

(Comparative Example 1)

<Solid-state imaging device (when not using monomers listed in the present invention)>

In "Preparation of the photosensitive composition for antireflection film formation" of Example 1, it is "NK-ester ABPE-10 ... which is a photopolymerizable compound. 1.5 parts "to" dipentaerythritol hexaacrylate... 3.0 part ", and carrying out similarly to Example 1, the solid-state image sensor was produced. Here, the image pattern shape of the anti-reflective film formed using the photosensitive composition for anti-reflective film formation obtained at the intermediate process is shown in FIG.

3-6, the grating part is an image pattern of an anti-reflective film. In Comparative Example 6, the lattice was skewed. This indicates that the antireflection film was lifted off from the substrate during development because of poor adhesion between the antireflection film and the substrate. On the other hand, in FIGS. 3-5 of the Example, the distortion of the grating was not seen.

For this reason, the lattice pattern which improved the deformation | transformation was able to be covered by the black antireflection film, without protruding on a transfer electrode. By separating the color filter elements, light rays passing through the color filter of adjacent pixels are prevented from entering the photodiode which should not be allowed to enter (for example, the light passing through the green color filter is prevented from entering the inside of the device). By preventing scattering and entering a photodiode to detect red or blue), the output of a color signal not seen in the original captured image can be reduced. In particular, the effect was remarkably seen around the image.

In contrast, in the comparative example, it was difficult to produce a color solid state image pickup device by protruding or exposing the transfer electrode from above the transfer electrode.

Further, a device was formed as a monochrome solid-state image pickup device without producing a color filter using the antireflection film of Comparative Example. When imaging was performed using this, there was a deviation in the signal output from the pixel, and the deviation between the pixels was seen in the captured image.

That is, according to this invention, the photocurable composition which is excellent in hardening performance and excellent in adhesiveness with a base can be provided.

In addition, according to the present invention, it is possible to provide an antireflection film which is formed using the photocurable composition, is excellent in adhesion to the underlayer, the occurrence of false signals due to stray light is reduced, and the color defect is low.

In addition, an object of the present invention is to provide a solid state image pickup device having the above-described antireflection film which is excellent in adhesion to the base and is less likely to generate false signals due to stray light.

Claims (7)

In the photocurable composition containing a coloring agent, a photopolymerizable compound, a photoinitiator, and alkali-soluble resin, the said photopolymerizable compound contains at least any one of a bisphenol-type compound and an isocyanuric ring containing compound. Composition. The photocurable composition according to claim 1, wherein the colorant contains carbon black having an average primary particle diameter of 10 nm or more and 30 nm or less. The photocurable composition according to claim 1, wherein the colorant contains a plurality of organic pigments. The photocurable composition according to claim 1, wherein the photopolymerizable compound contains at least one of the following general formulas (I) and (II).

(In general formula (I), R <^1> , R <^2> represents a hydrogen atom and a C1-C8 hydrocarbon group each independently, R <^3> , R <^4> represents a ethylene group or a propylene group each independently, m and n are Each independently represents an integer of 1 or more, m + n represents an integer of 3 to 30, and A ¹ and A ² each independently represent an acryloyl group or an allyl group.)

(In General Formula (II), R <^1> , R <^2> , R <^3> represents an ethylene group or a propylene group each independently, and a, b, and c respectively independently represent the integer of 0-6. M, n, l are Each is an integer, and m + n + l represents an integer of 0 to ¹⁸ , and A ¹ , A ² , and A ³ each independently represent an acryloyl group or an allyl group.) An antireflection film having a width of 1.5 m or less formed on a substrate using the photocurable composition according to claim 1. An antireflection film having a thickness of 1.0 µm or less formed on a substrate using the photocurable composition according to claim 1. A solid state image pickup device comprising the antireflection film according to claim 5.

Images