TW201326328A - Infrared ray shielding composition, infrared ray shielding film, pattern forming method and solid-state imaging device - Google Patents

Abstract

The invention is directed to an infrared ray shielding composition containing a fine particle of tungsten oxide containing an alkali metal, a triazine polymerization initiator and a polymerizable compound, a photosensitive layer formed from the infrared ray shielding composition, an infrared ray shielding film formed from the infrared ray shielding composition, a solid-state imaging device including a substrate having an imaging device unit formed on one surface of the substrate and the infrared ray shielding film provided on other surface side of the substrate, and a pattern forming method including, in the following order: forming the photosensitive layer; pattern-exposing the photosensitive layer to cure an exposed area; and removing an unexposed area by alkali development to form a pattern.

Description

Infrared light blocking composition, infrared light shielding film, pattern forming side Method and solid-state image element

The present invention relates to an infrared light-shielding composition, an infrared light-shielding film, a pattern forming method, and a solid-state image element. In particular, it relates to an infrared light-shielding composition suitable for forming a solder resist, an infrared light-shielding film, a pattern forming method, and a solid-state image element.

With regard to a conventional method of forming a permanent pattern (for example, solder resist), for example, a method is as follows: a photosensitive layer is formed on a germanium wafer to be formed into a permanent pattern, wherein a germanium wafer is formed thereon. Having a wire or having a substrate (eg, a copper clad laminate); and exposing the photosensitive layer of the stack, developing after the photosensitive layer is exposed to form a pattern, and then It is subjected to a curing treatment or the like, thereby forming a permanent pattern.

The formation of a permanent pattern is also applied to a package that is interposed between a semiconductor wafer and a printed board. Regarding the package substrate, in recent years, since the substrate needs to be packaged at a high density, the wiring pitch is lowered, the strength is increased, the insulating property is improved, and the film thickness is reduced. Again, from falling From the viewpoint of via diameter, increased exposure sensitivity, and mounting, a rectangular pattern profile formed by development is required.

On the other hand, a solid-state image sensor (imaging sensor) used in a mobile phone, a digital camera, a digital video recorder, a monitor, or the like is an integrated circuit formed using a semiconductor component production technology ( Integrated circuit, IC) Photoelectric conversion device. In recent years, as mobile phones and digital cameras have decreased in size and weight, solid-state image components have to be further miniaturized.

In order to miniaturize a solid-state image element, JP-A-2009194396 (the term "JP-A" as used herein means "Japanese Unexamined Patent Application") has been published to apply a through electrode and a reduced tantalum wafer. Thickness technique. Miniaturization can be achieved by polishing the germanium wafer to reduce its thickness. Although the light shielding property of light having a wavelength of less than or equal to 800 nm can be maintained, the wavelength is greater than or equal to 800 nm due to the decrease in the thickness of the wafer. The light is still easy to penetrate. Since the photodiode used in the solid-state image element also reacts to light having a wavelength of 800 nm to 1,200 nm, image quality is deteriorated when light having a wavelength of 800 nm or more is penetrated. New problems arise.

The solid-state image element has the following structure: a color filter and a lens are provided on a side adjacent to the photodiode; and an infrared filter is disposed in the vicinity of the color filter or the lens to block a wavelength of 800 nm to 1,200 The light of the nano; and the presence of metal wires, solder resists, and the like on opposite sides of the color filter. In many cases, the gap between the metal wires is filled with the solder resist, but there is a problem in that the solder resist cannot block infrared light (for example, leak light) entering the inside of a mobile phone, a digital camera, or the like. In order to solve this problem, an infrared light shielding layer is further provided on the outer side of the solder resist which is poor in light shielding property against infrared light to ensure the infrared light shielding property thereof. technology. However, since a height difference due to a wire or the like is generally present on the solder resist, it is difficult to coat a uniform thickness of the infrared light shielding layer material on the surface of the substrate having the height difference, and when there is a thin portion This can cause problems with light penetrating the thinner part.

In order to provide an infrared light-shielding layer only in a desired portion, the composition preferably exhibits photosensitivity and has photolithography performance that can be patterned by exposure. A light-shielding photosensitive composition having photolithographic performance includes a black black-containing black resist for forming a color filter of a liquid crystal display (LCD). Carbon black has high light-shielding property in the visible light region, but exhibits low light-shielding property in the infrared light region, and when attempting to use black photoresist as a solder resist, if the amount of carbon black added is large enough to ensure the desired shading in the infrared light region Sexuality, which causes the problem that the light-shielding property becomes extremely high in the visible light region, and the light having a shorter wavelength than the visible light region (usually used when the image is formed, exposed by a high-pressure mercury lamp, KrF, ArF or the like) is blocked. Therefore, the obtained photocurability is insufficient, and an excellent pattern cannot be obtained by a development step using an alkali developer.

Further, at present, since the infrared light shielding layer is separately provided after the formation of the solder resist by the coating method, in the formation of the solder resist and the formation of the infrared light shielding layer, it is necessary to perform a plurality of processes such as coating, exposure, development, and subsequent The step of heating results in a cumbersome process and an increase in cost, so there is an urgent need for improvement.

Therefore, attempts have been made to impart a light-shielding property to the solder resist itself, and a black solder resist composition containing, for example, a black coloring agent, a coloring agent other than black, and a polyfunctional epoxy compound has been disclosed (see, for example, JP-A). -2008-257045). However, this composition is characterized by the content of black colorant It is not sufficient from the viewpoint of using a combination of a coloring agent other than black to keep it low, and satisfying the light blocking property in the infrared region.

In order to achieve the purpose of detecting the position of the semiconductor substrate by a visible sensor in the process of manufacturing a solid-state image element, the surface of the metal substrate and the solder resist side of the semiconductor substrate of the solid-state image element (ie, color) The predetermined position on the opposite surface of the filter or lens provides a convex alignment mark.

For example, in the structure of JP-A-2008-257045, a black colorant is contained in the solder resist composition to impart light shielding property to the solder resist itself, and when the alignment mark is covered by the solder resist layer, the thickness of the solder resist layer may be It is easy to cause problems caused by the problem that the visible light sensor cannot detect the alignment mark.

At present, in these cases, it is required to have high light-shielding property in the infrared light region; high transparency and high exposure sensitivity in the visible light region; and infrared light shading capable of forming a high rectangularity pattern by development. Sexual composition.

Further, in the application of the through electrode to miniaturize the above-described solid-state image element, a technique of providing through holes in a semiconductor substrate (for example, a through-wafer (TSV)) has been Know. When the metal is wired on the substrate having the via hole and the metal is covered with the solder resist layer, the problem of cracking or peeling of the solder resist from the recess of the metal wire (caused by the via hole) occurs.

JP-A-2009205029 discloses a technique of using a near-infrared light absorbing layer containing an inorganic near-infrared light absorber layer as an image display device, and discloses, for example, a near-infrared light absorbing layer in an example thereof. Contains polymerizable compounds, polymerization initiators The initiator and the coating solution of the near-infrared light absorbing agent are not described as an infrared light-shielding composition which can form a solder resist layer which suppresses crack generation and exhibits high adhesion property to the substrate, so that peeling hardly occurs. Therefore, such an infrared light-shielding composition is currently required.

The present invention has been made under these circumstances, and it is an object of the present invention to solve these various conventional problems and achieve the following objects.

Specifically, an object of the present invention is to provide an infrared light-shielding composition which has high light-shielding property in an infrared light region and high light transmittance in a visible light region, and can be formed to be suppressed An infrared light-shielding film which produces cracks, exhibits high adhesion properties to a substrate, and high exposure sensitivity, and an object of the present invention is to provide an infrared light-shielding film using the composition, a method of pattern formation, and a solid-state image element using the composition.

The means to solve the above problems are specifically as follows:

(1) An infrared light-shielding composition comprising an alkali metal-containing tungsten oxide fine particle, a triazine polymerization initiator, and a polymerizable compound.

(2) The infrared light-shielding composition according to (1) above, wherein the triazine polymerization initiator is represented by the following formula (T):

In the formula (T), X ¹ and X ² each independently represent a halogen group-substituted hydrocarbon group, a hydrogen atom, a halogen atom, a dialkylamino group, an alkyl group, an alkoxy group. Or a cyano group; when l is 0, there is no Y ¹ , and when l is 1, Y ¹ represents an ethylene group or an -NH- group; and B ¹ and B ² each independently represent An aromatic ring group having a substituent; and l and m each independently represent an integer selected from 0, 1, and 2.

(3) The infrared light-shielding composition according to (2), wherein each of X ¹ and X ^{2 is} independently represented by a halogen-substituted hydrocarbon group.

(4) (2) or (3) the shielding infrared light-sensitive composition, wherein, in formula (T), constituting the aromatic ^{ring. 1} B B group ² of the aromatic ring is a benzene ring (benzene ring).

(5) The infrared light-shielding composition according to any one of (1) to (4), further comprising an alkali-soluble binder.

(6) The infrared light-shielding composition according to (5), wherein the alkali-soluble binder has an acid group.

(7) The infrared light-shielding composition according to (5) or (6), wherein the alkali-soluble binder has a crosslinking group.

(8) The infrared light-shielding composition according to any one of (1) to (7), wherein the alkali metal-containing tungsten oxide fine particles are represented by the following formula (I): M _x W _y O _z (I)

Wherein M represents an alkali metal; W represents tungsten; O represents oxygen; x/y 1.1; and 2.2 z/y 3.0.

(9) The infrared light-shielding composition according to any one of (1) to (8) wherein the polymerizable compound is a polyfunctional polymerizable compound, and the polyfunctional polymerizable compound has a plurality of molecules on one molecule Polymeric group.

(10) The infrared light-shielding composition according to any one of (1) to (9), which is used as a solder resist or an infrared light-shielding film on the back side of the substrate in the solid-state image sensor.

(11) A photosensitive layer formed of the infrared light-shielding composition according to any one of (1) to (10).

(12) An infrared light-shielding film formed of the infrared light-shielding composition according to any one of (1) to (10).

(13) A solid-state image element comprising a solid-state image element substrate, wherein an image element unit is formed on one surface of the solid-state image element substrate, and (12) is provided on the other surface side of the solid-state image element substrate The infrared light shielding film described.

(14) A pattern forming method comprising: a step of forming a photosensitive layer as described in (11), a step of patterning exposure of the photosensitive layer to cure an exposed region; and forming an unexposed region by alkali development to form The steps of the pattern.

According to the present invention, there is provided an infrared light-shielding composition, an infrared light-shielding film using the composition, a method of pattern formation, and a solid-state image element, wherein the infrared light-shielding composition has high light-shielding property in an infrared light region And it has high light transmittance in the visible light region, and can be formed as an infrared light-shielding film which can suppress crack generation, exhibits high adhesion property to a substrate, and high exposure sensitivity.

10‧‧‧矽 substrate

12‧‧‧Image components

13‧‧‧Interlayer insulating film

14‧‧‧ grassroots

15B‧‧‧Blue filter

15G‧‧‧Green Filter

15R‧‧‧Red Filter

16‧‧‧Overcoat

17‧‧‧Microlens

18, 414‧‧‧ shading film

20, 41, 43, 45‧‧‧ adhesives

22‧‧‧Insulation film

23‧‧‧Metal electrodes

24‧‧‧Anti-flux layer

26‧‧‧Internal electrodes

27‧‧‧ Component surface electrode

30‧‧‧ glass substrate

40‧‧‧Image lens

42‧‧‧Infrared cut-off filter

44‧‧‧Shading and electromagnetic shielding

50‧‧‧ lens holder

60‧‧‧ solder balls

70‧‧‧ circuit board

100‧‧‧Fixed image element substrate

200‧‧‧ camera module

410‧‧‧Substrate

412‧‧‧ lens

Hν‧‧‧ incident light

1 is a cross-sectional view showing the structure of a camera module equipped with a solid-state image element according to an embodiment of the invention.

2 is a schematic cross-sectional view of a solid state image element in accordance with an embodiment of the present invention.

3 is a plan view of an example of a wafer level lens array.

Figure 4 is a cross-sectional view taken along line A-A of Figure 3 .

Regarding the group (atomic group) in the specification of the present invention, when it is not explicitly illustrated as a substituted or unsubstituted group, the group includes two groups having no substituent or a group having a substituent. For example, "alkyl" includes not only an alkyl group having no substituent (that is, an unsubstituted alkyl group) but also an alkyl group having a substituent (that is, a substituted alkyl group).

In the specification, the term "(meth)acrylate" means acrylate and methacrylate, and the term "(meth)acryl" means Acryl and methacryl, and the term "(meth)acryloyl" means acryloyl and methacryloyl. Further, in the specification, the term "monomeric compound" has the same meaning as the term "monomer". The monomeric compound in the present invention means a compound having a weight average molecular weight of 2,000 or less, which is different from an oligomer and a polymer. In the specification, a polymerizable compound means a compound having a polymerizable group and may be a monomer compound or a polymer. A polymerizable group means a group that participates in a polymerization reaction.

The infrared light-shielding composition according to the present invention comprises an alkali metal-containing tungsten oxide fine particle, a triazine polymerization initiator, and a polymerizable compound, and if necessary, may include a binder (preferably an alkali-soluble binder), in addition to An infrared ray blocking agent other than the above tungsten oxide fine particles, a dispersing agent, an ultraviolet absorbing agent, a sensitizer, and a crosslinking agent An agent), a curing accelerator, a filler, an elastomer, a surfactant, and other components.

In the infrared light-shielding composition, incorporated into the alkali metal oxide tungsten fine The granules can obtain an infrared light-shielding composition having high light-shielding property in the infrared light region and high light-transmitting property in the visible light region, and the inventors have found that the triazine polymerization initiator is further incorporated into the infrared light-shielding property. In the composition, an infrared light-shielding film which suppresses crack generation, exhibits high adhesion property to a substrate, and high exposure sensitivity can be formed, and the detailed reason thereof is still unclear. The present invention has been completed based on this finding.

The infrared light-shielding composition according to the present invention is a polymerizable composition (e.g., a negative polymerizable composition) and is generally a negatively polymerizable composition. The structure of this composition is described below.

The constituent elements are described below based on some cases of representative embodiments of the present invention, but the present invention is not construed as being limited thereto. In the specification, the numerical range is expressed by using "(numerical) to (numerical)", which means that the values before and after "to" are included as the lower limit and the upper limit, respectively.

[1] Triazine polymerization initiator

The triazine polymerization initiator for use in the infrared light-shielding composition according to the present invention is not particularly limited, whether by irradiation, heating or both, as long as it has a function of polymerization of the starting polymerizable composition. It may be selected and may be appropriately selected depending on the purpose, but is preferably a photopolymerization initiator. In the case of initial polymerization by irradiation, a compound having photosensitivity to light in the visible light region to the ultraviolet light region is preferred.

In the case of initial polymerization by heating, an initiator which can be decomposed at 150 ° C to 250 ° C is preferred.

The triazine polymerization initiator is preferably an s-triazine derivative having at least one substituent (for example, a halogen atom or a halogen-substituted hydrocarbon group) in the s-triazine ring. The triazine polymerization initiator is preferably represented by the following formula (T).

In the formula (T), X ¹ and X ² are each independently represented by a halogen-substituted hydrocarbon group, a hydrogen atom, a halogen atom, a dialkylamino group, an alkyl group, an alkoxy group or a cyano group.

The halogen atom for X ¹ and X ² or the halogen atom in the halogen-substituted hydrocarbon group includes, for example, a chlorine atom, a fluorine atom, and a bromine atom, and is preferably a chlorine atom.

The halogen-substituted hydrocarbon group includes, for example, a halogen-substituted alkyl group or a halogen-substituted cycloalkyl group. The halogen-substituted alkyl group is preferably a halogen-substituted alkyl group having 1 to 5 carbon atoms. The halogen-substituted cycloalkyl group is preferably a halogen-substituted cycloalkyl group having 3 to 10 carbon atoms.

The alkyl group for the alkyl group of X ¹ and X ² , the alkyl moiety of the dialkylamino group and the alkoxy group is preferably an alkyl group having 1 to 5 carbon atoms, and includes, for example, methyl group, B. Base, propyl and butyl.

Each of X ¹ and X ^{2 is more} preferably a halogen-substituted hydrocarbon group, and still more preferably a halogen-substituted alkyl group. The halogen-substituted alkyl group is preferably a monohalomethyl group, a dihalomethyl group or a trihalomethyl group, and more preferably a trihalomethyl group.

When l is 0, Y ¹ is absent, and when l is 1, Y ¹ represents an ethyl group or an -NH- group, and preferably an ethyl group.

B ¹ and B ² are each independently represented as an aromatic ring group which may have a substituent, and is preferably an aromatic ring group having 5 to 15 carbon atoms. The aromatic ring group can be a heterocyclic group. Examples of the substituent include a halogen atom, a cyano group, an alkyl group, an alkoxy group, a hydroxyl group, an alkyl ester group, an alkylamido group, and an aryl group (preferably having 6 to 10 carbons). Aromatic aryl group).

The aromatic ring constituting the aromatic ring group includes, for example, a benzene ring, a coumalin ring, and a benzodixole ring, and is preferably a benzene ring.

B ^{1 is} preferably a 1,4-phenylene group, and B ^{2 is} preferably a phenyl group.

l and m each independently represent any integer selected from 0, 1, and 2.

Specific examples of the triazine polymerization initiator include 2-diphenyl-4,6-bis(trichloromethyl)-s-triazine (2-biphenyl-4,6-bis(trichloromethyl)-s-triazine) ,2-(3,4-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine (2-(3,4-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine), 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s -triazine (2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine), 2-(1,3-benzodoxy-5-yl)-4,6-bis(trichloromethane) -s-triazine (2-(1,3-benzodioxol-5-yl)-4,6-bis(trichloromethyl)-s-triazine), 3-chloro-5-diethylamino-((s-triazine-2- Amino)-3-phenylpipenone ring (3-chloro-5-diethylamino-((s-triazin-2-yl)amino)-3-phenylcoumalin), 2,4,6-tris(monochloromethyl)-s-triazine (2,4,6-tris(monochloromethyl)-s-triazine), 2,4,6-tris(dichloromethyl)-s-triazine (2,4,6-tris(dichloromethyl)-s-triazine ), 2,4,6-tris(trichloromethyl)-s-triazine (2,4,6-tris(trichloromethyl)-s-triazine), 2-methyl-4,6-bis(trichloro) Methyl)-s-triazine (2-methyl-4,6-bis(trichloromethyl)-s-triazine), 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine (2-n-propyl-4,6-bis(trichloromethyl)-s-triazine), 2-(α,α,β- Trichloroethyl))-4,6-bis(trichloromethyl)-s-triazine (2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine), 2-phenyl-4,6-bis(trichloromethyl)-s-triazine (2-phenyl-4,6-bis(trichloromethyl)-s-triazine), 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine (2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine), 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s -triazine (2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine), 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine (2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine), 2-[1-(p-methoxyphenyl)-2,4-butadienyl]-4,6 -bis(trichloromethyl)-s-triazine (2-[1-(p-methoxyphenyl)-2,4-butadienyl]-4,6-bis(trichloromethyl)-s-triazine), 2-styryl-4,6-bis(trichloromethyl) -s-triazine (2-styryl-4,6-bis(trichloromethyl)-s-triazine), 2-(p-isopropoxystyryl)-4,6-bis(trichloromethyl)-s-triazine (2-(p-isopropyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine), 2-(p-tolyl-4,6-bis(trichloromethyl)-s-triazine (2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine), 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-three Oxazine (2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine), 2-thiophenyl-4,6-bis(trichloromethyl)-s-triazine (2-phenylthio-4,6-bis(trichloromethyl)-s-triazine), 2-benzylthio--4,6-bis(trichloromethyl)-s-triazine (2-benzylthio-4,6-bis(trichloromethyl)-s-triazine), 2,4,6-tris (dibromo-methyl) -s-triazine (2,4,6-tris(dibromomethyl)-s-triazine), 2,4,6-tris(tribromomethyl)-s-triazine (2,4,6-tris) (tribromomethyl)-s-triazine), 2-methyl-4,6-bis(tribromomethyl)-s-triazine (2-methyl-4,6-bis(tribromomethyl)-s-triazine) and 2 -Methoxy-4,6-bis(tribromomethyl)-s-triazine (2-methoxy-4,6-bis(tribromomethyl)-s-triazine). Among the compounds, 2-diphenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3,4-dimethoxystyryl)-4,6- is preferred. Bis(trichloromethyl)-s-triazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(1,3-benzene And bisoxy-5-yl)-4,6-bis(trichloromethyl)-s-triazine or 3-chloro-5-diethylamino-((s-triazin-2-yl) Amine)-3-phenylpipenone ring. More preferably 2-diphenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3,4-dimethoxystyryl)-4,6-bis(trichloromethane) Base)-s-triazine or 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine. More preferably, it is 2-diphenyl-4,6-bis(trichloromethyl)-s-triazine or 2-(3,4-dimethoxystyryl)-4,6-bis(trichloro) Methyl)-s-triazine, particularly preferably 2-diphenyl-4,6-bis(trichloromethyl)-s-triazine.

Specific examples of the triazine polymerization initiator used for the infrared light-shielding composition according to the present invention are as follows, but the invention is not construed as being limited thereto.

The triazine polymerization initiators may be used singly or in combination of two or more.

The content of the triazine polymerization initiator is preferably from 0.01% by mass to 30% by mass, more preferably from 0.1% by mass to 20% by mass, based on the total solid content of the infrared light-shielding composition according to the present invention, particularly preferably 0.1% by mass to 15% by mass.

(combined polymerization initiator)

The infrared light-shielding composition according to the present invention may include a polymerization initiator other than the above-described triazine polymerization initiator (hereinafter, also referred to as "combination polymerization initiator").

The combined polymerization initiator according to the present invention may use a compound as a polymerization initiator as described below.

The combined polymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the above polymerizable compound, and may be appropriately selected from a conventional polymerization initiator. For example, these (polymerization initiators) having radiation sensitivity to light in the visible light region to the ultraviolet light region are preferred. The initiator may also be an activator capable of acting with a photoexcited sensitizer to generate an active radical, or capable of initiating cationic polymerization depending on the type of monomer (cationic) The starting agent for polymerization).

Further, the combined polymerization initiator preferably comprises at least one molecular extinction coefficient of at least about 50 in the range of from about 300 nm to about 800 nm (more preferably from 330 nm to 500 nm). compound of.

Examples of the combined polymerization initiator include a halogenated hydrocarbon derivative (for example, a compound having an oxadiazole skeleton, an acylphosphine compound (for example, acylphosphine oxide), and six Hexabibiimidazole, oxime compounds (eg, anthracene derivatives), organic peroxides, thio compounds, ketone compounds, aromatics An aromatic oxium salt, a ketoxime ether, an aminoacetophenone compound, and a hydroxyacetophenone.

Compounds having a oxadiazole backbone include, for example, the compounds described in U.S. Patent 4,212,976. Specific examples thereof include 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-chlorophenyl)-1,3,4-oxo Diazole, 2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(2-naphthyl)-1,3,4 -oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5-(2-naphthyl)-1,3,4-oxa Diazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-chlorostyryl)-1,3,4- Oxadiazole, 2-trichloromethyl-5-(4-methoxystyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)- 1,3,4-oxadiazole, 2-trichloromethyl-5-(4-n-butoxystyryl)-1,3,4-oxadiazole, 2-tribromomethyl-5- Styryl-1,3,4-oxadiazole.

In addition to the aforementioned combination polymerization initiators, examples of the combination polymerization initiator include acridine derivatives (for example, 9-phenyl acridine, 1,7-bis(9,9'-acridinyl)g. Alkyl), N-phenylglycine, polyhalogen compounds (eg, carbon tetrabromide, phenyl tribromomethyl sulfone or phenyltrichloromethyl ketone) , coumarin (such as 3-(2-benzofuroyl)-7-diethylaminocoumarin), 3-(2- Benzo-yl)-7-(1-pyrrolidinyl)coumarin, 3-benzylidenyl-7-diethylaminocoumarin, 3-(2-methoxybenzimidyl -7-diethylamino coumarin, 3-(4-dimethylaminobenzimidyl)-7-diethylamino coumarin, 3,3'-carbonyl bis (5, 7-di-n-propoxy coumarin), 3,3'-carbonyl bis(7-diethylaminocoumarin), 3-benzylidene-7-methoxycoumarin, 3- (2-indolyl)-7-diethylamino coumarin, 3-(4-diethylamino cinnamate)-7-diethylamino coumarin, 7-methoxy -3-(3-pyridylcarbonyl)coumarin , 3-benzylidene-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, such as JP-A-5-19475, JP-A-7- 271028, JP-A-2002-363206, JP-A-2002-363207, JP-A-2002-363208, and coumarin compounds described in JP-A-2002-363209), mercaptophosphine oxides (for example Bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentyl Phenylphosphine oxide or Lucirin TPO), metallocene (eg bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-) (1H-pyrrol-1-yl)-phenyl)titanium (bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl Titanium) or η5-cyclopentadienyl-η6-cumyl-iron (1+)-hexafluorophosphate (1-) (η5-cyclopentadienyl-η6-cumenyl-iron(1+)-hexafluorophosphate(1) -))) and the compounds described in JP-A-53-133428, JP-B-57-1819, JP-B-57-6096 and U.S. Patent 3,615,455.

Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenone tetracarboxylic acid or Its tetramethyl ester, 4,4'-bis(dialkylamino)benzophenone (such as 4,4'-bis(dimethylamino)benzophenone, 4,4'-double (two Cyclohexylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dihydroxyethylamino)benzophenone, 4-methyl Oxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminobenzene Ethyl ketone, benzyl, anthraquinone, 2-tert-butyl fluorene, 2-methyl hydrazine, phenanthraquinone, xanthone, thioxanthone, 2 -Chloro-thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1-(4-morpholinylphenyl)-1- Butanone, 2-methyl-1-[4-(methylthio)phenyl]-2- Morpholinyl-1-propanone, 2-hydroxy-2-methyl-[4-(1-methylvinyl)phenyl]propanol oligomer, benzoin, benzoin ether (eg benzoin methyl ether, Benzoin ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloroacridone, N-methyl acridone, N-butyl Acridone and N-butyl-chloroacridone.

A hydroxyacetophenone compound, an aminoacetophenone compound, and a mercaptophosphine compound are also suitable as a combined polymerization initiator. More specifically, for example, an aminoacetophenone starter as described in JP-A-10-291969 and a mercaptophosphine oxide starter as described in Japanese Patent No. 4,258,89 can be used.

IRGACURE-184, DAROCUR-1173, Yanjiagu-500, Yanjiagu-2959, and Yanjiagu-127 (manufactured by BASF) can be used as hydroxybenzene. Ethylketone initiator. Commercially available products, Yanjiao-907, Yanjiagu-369, and Yanjiagu-379 (manufactured by BASF, Japan) can be used as the aminoacetophenone initiator. For example, a compound having an absorption wavelength matched with a light source having a wavelength of 365 nm or 405 nm as described in JP-A-2009-191179 can also be used as the aminoacetophenone initiator. A commercially available product, Yanjiao-819 and DAROCUR-TPO (manufactured by BASF, Japan) can also be used as the mercaptophosphine initiator.

The hydrazine starter is also suitable for use as a combined polymerization initiator. Specific examples of the hydrazine initiator which can be used include a compound as described in JP-A-2001-233842, a compound as described in JP-A-2000-80068, and as described in JP-A-2006-342166. compound of.

Examples of the hydrazine compound, for example, an anthracene derivative suitable for use as a combined polymerization initiator in the present invention, includes 3-benzylideneoxyimidobutan-2-one, 3-ethyloxy group Iminobutan-2-one, 3-propenyloxyimidobutan-2-one, 2-ethyloxyiminopentan-3-one, 2-ethyloxyimino-1- -Phenylpropan-1-one, 2-benzylideneoxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)imidobutan-2-one And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

Examples of oxime ester compounds include Chemical Society: JC Perkin II, pp. 1653-1660 (1979), Chemical Society: Parkin Journal II, pp. 156-162 ( 1979), Journal of Photopolymer Science and Technology, pp. 202-232 (1995), Journal of Applicated Polymer Science, pp. 725-731 (2012) and A compound described in JP-A-2000-66385, and a compound described in JP-A-2000-80068, JP-T-2004-534797, and JP-A-2006-342166.

As a commercially available product, Yanjia Tsing-OXE01 (made by BASF Corporation of Japan), Yanjiagu-OXE02 (made by BASF Corporation of Japan) and TR-PBG-304 (Changzhou Tronly New Electric Co., Ltd.) Materials Co., Ltd.) can also be suitably used.

An oxime ester compound other than the above oxime ester compounds may also be used, for example, a compound of N-position bonded to carbazole of ruthenium as described in JP-T-2009-519904, which will be described in U.S. Patent No. 7,626,957. A compound in which a hetero substituent is introduced into a benzophenone moiety, a compound in which a nitro group is introduced into a dye moiety, as described in JP-A-2010-15025, and US Patent Application Publication No. 2009-292039, International Publication No. 2009/131189 The ketone oxime compound, the compound having a triazine skeleton and an anthracene skeleton in the same molecule as described in U.S. Patent No. 7,556,910, and the absorption maximum at 405 nm as described in JP-A-2009-221114 For g Line light sources exhibit good sensitivity to compounds.

Further, the cyclic guanidine compound described in JP-A-2007-231000 and JP-A-2007-322744 can also be suitably used. Among the cyclic oxime compounds, the cyclic ruthenium compound fused with the carbazole dye described in JP-A-2010-32985 and JP-A-2010-185072 is preferred from the viewpoint of high light absorbability and high sensitivity.

Further, a compound having an unsaturated bond at a specific site of a ruthenium compound described in JP-A-2009-242469 achieves high sensitivity by regenerating an active group from a polymerizable inactive group, and thus can be suitably used.

Further, an anthracene compound having a specific substituent described in JP-A-2007-269779 and an anthracene compound having a sulfuryl group described in JP-A-2009-191061 can be exemplified.

Specific examples (PIox-1) to (PIox-13) of the oxime compounds described below may be suitably employed, but the invention is not construed as being limited thereto.

Combination polymerization of infrared light-blocking compositions according to the present invention can be used The initiator is preferably selected from the group consisting of a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, a phosphonium phosphine compound, a phosphinoxide, a metallocene compound, and a ruthenium compound. a compound, a triarylimidazole dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound or a derivative thereof, a cyclopentadiene-benzene-iron A compound of the group consisting of a cyclopentadiene-benzene-iron complex or a salt thereof, a halomethyloxadiazole compound, and a 3-aryl-substituted coumarin compound.

More preferably, it is selected from the group consisting of an α-amino ketone compound, a phosphonium phosphine compound, a phosphine oxide compound, a hydrazine compound, a triaryl imidazole dimer, a hydrazine compound, a benzophenone compound, and an acetophenone compound. A compound of a group consisting of a free α-aminoketone compound, an anthraquinone compound, a triaryl imidazole dimer, and a benzophenone compound.

The content of the combined polymerization initiator contained in the infrared light-shielding composition according to the present invention, based on the total solid content of the infrared light-shielding composition (when two or more types (combination polymerization initiator) are used The total content) is preferably from 0.001% by mass to 10% by mass, more preferably from 0.01% by mass to 5% by mass.

[2] Polymerizable compounds

The infrared light-shielding composition according to the present invention contains a polymerizable compound. Any compound can be used as the polymerizable compound as long as it has a functional group capable of reacting with at least one of an acid, a radical, and heat in the molecule (in the present specification, this functional group is sometimes referred to as a "polymerizable group" And) is preferably a polyfunctional polymerizable compound having a plurality of polymerizable groups in one molecule.

Having a polymerizable capable of reacting with at least one of an acid, a free radical, and heat Examples of the functional group-containing polymerizable compound include an ethylenically unsaturated group-containing compound having an ethylenically unsaturated group (for example, an unsaturated ester functional group, an unsaturated decylamino group, a vinyl ether group or an allyl group), and a hydroxyl group. a methylol compound, a bismaleimide compound, a benzocyclobutene compound, a bisallylndiimide compound, and a benzoxazine compound. .

The polymerizable compound which can be preferably used in the present invention includes a general radical polymerizable compound and a compound having an ethylenically unsaturated double bond which is widely known in the art can be used without particular limitation.

For example, these compounds have chemical forms such as monomers, prepolymers (specifically, dimers, trimers or oligomers) or mixtures or copolymers thereof.

Examples of the monomer and its copolymer include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid or maleic acid (maleic) Acid)) esters, guanamines and copolymers. It is preferred to use an unsaturated carboxylic acid ester, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound.

In particular, an ester of an unsaturated carboxylic acid and an aliphatic polyol compound can exhibit high hydrophobicity in an exposed region, and can be easily formed by alkali to form a pattern having a desired profile and also has high durability. Sexual pattern (especially when the solder resist requires high durability (for example, in the case of a high density of a wire coated with a solder resist), the above effect is remarkable)

In addition, an unsaturated carboxylic acid ester or guanamine having a nucleophilic substituent (for example, a hydroxyl group, an amine group or a mercapto group) and a single official The addition reaction product of an isocyanate or epoxide can be used as well as the dehydration condensation reaction product of an unsaturated carboxylic acid ester or guanamine with a monofunctional or polyfunctional carboxylic acid.

An addition reaction product of an unsaturated carboxylic acid ester having an electrophilic substituent (for example, an isocyanate group or an epoxy group) or a guanamine with a monofunctional or polyfunctional alcohol, an amine or a thiol, and having a releasable substituent (releasable) The substituted carboxylic acid esters of the substituents (for example, a halogen group and a tosyloxy group) or a substituted reaction product of a monofunctional or polyfunctional alcohol, an amine or a thiol are also suitable for use. As another example, a compound in which the above unsaturated carboxylic acid is replaced with, for example, unsaturated phosphoric acid, styrene or vinyl ether may also be used.

The unsaturated carboxylic acid ester is preferably a methacrylate, and examples thereof include tetramethylene glycol dimethacrylate, triethylene golycol dimethacrylate, and dimethacrylate Neopentyl glycol dimethacrylate, trimethylol propane trimethacrylate, trimethylol ethane trimethacrylate, ethylene dimethacrylate Glycol dimethacrylate), 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, Pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate ), sorbitol trimethyl acrylate Trimethacrylate), sorbitol tetramethacrylate, bis[p-(3-methylpropenyloxy-2-hydroxypropoxy)phenyl]dimethylmethane (bis[p-(3- Methacryloxy-2-hydroxypropoxy)phenyl]dimethyl methane), bis[p-(methacryloxyethoxy)phenyl]dimethyl methane) The product of EO modification and the product modified by PO.

The unsaturated carboxylic acid ester is also preferably an isonic acid ester, and examples thereof include ethylene di-iconate, propylene di-conconate, di-i-butane-1,3-butane diester, and diacon Acid-1,4-butane diester, di-butyl iconate, pentaerythritol diconic acid, and sorbitol tetraconate. Examples of the crotonate include ethylene glycol dibromide, butylene dicrotonate, pentaerythritol dicrotonate, and sorbate tetracrotonate. Examples of the isocrotonate include ethylene diisocrotonate, pentaerythritol diisocrotonate, and sorbitan tetraisocrotonate. Examples of the maleic acid ester include ethylene dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

Specific examples of the ester monomer of the aliphatic polyol compound and the unsaturated carboxylic acid include, for example, (meth) acrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3-butyl diacrylate. Butylene diacrylate, propylene diacrylate, neopentyl diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris(propylene methoxypropyl) ether, trimethylolethane Triacrylate, hexanedicarboxylate, 1,4-cyclohexanedicarboxylate, tetraethylenediacrylate diacrylate, tricyclodecane dimethacrylate, tricyclodecane dimethacrylate, two Pentaerythritol acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentoxide, six Sorbyl acrylate, tris(propyleneoxyethoxy) isocyanurate, and polyester acrylate oligomers or EO modified products of these compounds or PO modified products.

Other esters may also be suitably used, for example, JP-B-51-47334 (the term "JP-B" as used herein refers to Japanese Examined Patent Application Publication) and the aliphatic group described in JP-A-57-196231 An alcohol ester; an ester having an aromatic skeleton as described in JP-A-59-5240, JP-A-59-5241, and JP-A-2-226149; and as described in JP-A-1-165613 These (esters) having an amine group. Mixtures of ester monomers can also be used.

Specific examples of the aliphatic polyvalent amine compound and the decylamine monomer of the unsaturated carboxylic acid include methylenebis propylene amide, methylene bis methacrylamide, 1,6-hexamethylene Bis-acrylamide, 1,6-hexamethylene bismethyl acrylamide, di-ethyltriamine propylene amide, xylylene bisacrylamide, and dimethyl bismethyl Acrylamide. Other preferred examples of the guanamine monomer include those having a cyclohexylene structure as described in JP-B-54-21726.

A urethane-based addition polymerizable compound obtained by an addition reaction of an isocyanate with a hydroxyl group is also suitable, and specific examples thereof include an amino group having two or more polymerizable vinyl groups per molecule. a vinyl formate compound obtained by adding a hydroxyl group-containing ethylene monomer represented by the following formula (E) to a polyisocyanate compound having two or more isocyanate groups per molecule as described in JP-B-48-41708 Come to get.

CH ₂ =C(R ⁴ )COOCH ₂ CH(R ⁵ )OH (E) (wherein R ⁴ and R ⁵ each independently represent H or CH ₃ .)

Further, urethane acrylates as described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765; and JP-B-58-49860, JP-B Rings as described in -56-17654, JP-B-62-39417 and JP-B-62-39418 A urethane compound of an ethylene oxide skeleton is also suitable. Further, when an addition polymerizable compound having an amine structure or a sulfide structure in a molecule as described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 is used, An infrared light-shielding composition having an extremely excellent photosensitive speed can be obtained.

Other examples include polyfunctional acrylates or methacrylates, such as the polyester acrylates described in JP-A-48-64183, JP-B-49-43191, and JP-B-52-30490, and by epoxy An epoxy acrylate obtained by reacting a resin with (meth)acrylic acid. Other examples include the specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, and JP-B-1-40336, and the vinyl groups described in JP-A-2-25493. Phosphoric acid compound. In some cases, a perfluoroalkyl group-containing structure described in JP-A-61-22048 is suitably used. Further, photocurable monomers and oligomers described in Journal of Adhesion Society of Japan, Vol. 20, No. 7, pp. 300-308 (1984) can also be used.

In the present invention, when a radical polymerizable compound is to be added, from the viewpoint of curing sensitivity, it is preferred to use a polyfunctional polymerizable compound containing two or more ethylenically unsaturated bonds, and it is more preferably contained. A polyfunctional polymerizable compound having greater than or equal to three ethylenically unsaturated bonds. Among them, a compound having a structure of two (meth) acrylates or more is preferable, and a compound having a structure of three (meth) acrylates or more is more preferable, and preferably contains four or more. A compound of the (meth) acrylate structure.

Further, from the viewpoints of curing sensitivity and developability of the unexposed regions, it is preferred to use a compound containing an EO-modified product, and it is preferably used in view of the curing sensitivity and strength of the exposed region. A urethane bond compound. Further, from the viewpoint of developability of pattern formation, it is preferred to use an acid group. Compound.

From the above viewpoints, preferred examples of the polymerizable compound used in the present invention include bisphenol A diacrylate, EO-modified bisphenol A diacrylate, trimethylolpropane triacrylate, trimethylolpropane Tris(propylene methoxypropyl)ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, four Dipentaerythritol diacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitan pentoxide, sorbitol hexaacrylate, isocyanuric acid tris(propylene oxy ethoxylate B) An ester, an EO-modified pentaerythritol tetraacrylate, an EO-modified dipentaerythritol hexaacrylate, and a tricyclodecane dimethyl diacrylate. Further, preferred are commercially available products, urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Corp.); DPHA-40H (by Nippon Chemical Co., Ltd.) (Manufactured by Nippon Kayaku Co., Ltd.); UA-306H, UA-306T, UA-306I, AH-600, T-600 and AI-600 (by Kyoeisha Chemical Co., Ltd.) .) Manufacturing) and A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.).

Among them, more preferred is EO modified bisphenol A diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tris(propylene methoxyethyl) isocyanate Uric acid ester, EO-modified pentaerythritol tetraacrylate, and EO-modified dipentaerythritol hexaacrylate, and a more commercially available product is DPHA-40H (by Nippon Kayaku Co., Ltd.) .) Manufacturing); UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.) and A-DCP (limited by Shin-Nakamura Chemical Industry Co., Ltd.) Made by the company).

The ethylenically unsaturated compound having an acid group is also suitable, and examples of the commercially available product thereof include TO-756 which is a trifunctional acrylate having a carboxyl group, and TO-1382 (which is a Toagosei Co., Ltd.) A pentyl functional acrylate having a carboxyl group produced by Co., Ltd.).

Further, examples of the highly heat-resistant polymerizable compound include benzocyclobutene (BCB), bis(allyl)nadimide (BANI), benzoxazine, and melamine ( Melamine) and its analogues.

Also, greater than or equal to two polymerizable compounds can be used.

The content of the polymerizable compound is preferably from 3% by mass to 80% by mass, more preferably from 5% by mass to 50% by mass, based on the total solid mass of the infrared light-shielding composition according to the present invention.

The polymerizable compound may be the same as or different from the binder (preferably an alkali-soluble binder).

More specifically, when the polymerizable compound is a polymer, the polymerizable compound may be the same as the alkali-soluble binder described in detail below (that is, the polymerizable compound and the alkali-soluble binder may be the same component). In this embodiment, the content of the polymerizable compound is preferably from 3% by mass to 80% by mass, more preferably from 5% by mass to 60% by mass, based on the total solid content of the infrared light-shielding composition according to the present invention.

[3] Oxide tungsten fine particles containing alkali metals

The infrared light-shielding composition according to the present invention contains tungsten oxide fine particles containing an alkali metal.

The alkali metal-containing tungsten oxide fine particles have high absorption for infrared light (light having a wavelength of about 800 nm to 1200 nm) (that is, light blocking property against light (light blocking property) High) and low light absorption of infrared light blockers. Therefore, the infrared light-shielding composition according to the present invention can form an infrared light-shielding film having high light-shielding property in the infrared light region and high light-transmitting property in the visible light region by containing tungsten oxide fine particles containing an alkali metal.

Further, the alkali metal-containing tungsten oxide fine particles exhibit less absorption of light having a shorter wavelength in the visible light region (for image formation, exposure with a high pressure mercury lamp, KrF, ArF or the like). Therefore, according to the present invention, an excellent pattern is obtained by further incorporating an alkali-soluble binder into an infrared light-shielding composition containing tungsten oxide fine particles containing an alkali metal.

The tungsten oxide fine particles containing an alkali metal are preferably represented by the following formula (composition formula) (I): M _x W _y O _z (I)

In formula (I), M represents a metal; W represents tungsten; O represents oxygen; x/y 1.1; and 2.2 z/y 3.0.

The alkali metal represented by M may be an alkali metal or greater than or equal to two alkali metals.

The alkali metal represented by M is preferably rubidium (Rb) or cesium (Cesium, Cs), and more preferably ruthenium.

When x/y is 0.001 or more, infrared light can be sufficiently blocked, and when it is less than or equal to 1.1, it is possible to more reliably prevent an impurity phase from being generated in the alkali metal-containing tungsten oxide fine particles.

When z/y is greater than or equal to 2.2, the chemical stability as a material can be further improved, and when it is less than or equal to 3.0, infrared light can be sufficiently blocked.

Specific examples of the alkali metal-containing tungsten oxide fine particles represented by the formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ and K _0.33 WO ₃ . The alkali metal-containing tungsten oxide fine particles are preferably Cs _0.33 WO ₃ or Rb _0.33 WO ₃ , more preferably CS _0.33 WO ₃ .

The average particle diameter of the alkali metal-containing tungsten oxide fine particles is preferably less than or equal to 800 nm, more preferably less than or equal to 400 nm, still more preferably less than or equal to 200 nm. When the average particle diameter is within the above range, the alkali metal-containing tungsten oxide fine particles are hardly blocked from visible light due to light scattering, so that light transmittance in the visible light region can be ensured. The average particle diameter is preferably small in view of avoiding light scattering, but the average particle diameter of the alkali metal-containing tungsten oxide fine particles is preferably 1 nm or more for the purpose of easy handling during production and the like.

The content of the alkali metal-containing tungsten oxide fine particles is preferably from 3% by mass to 20% by mass, more preferably from 5% by mass to 10% by mass, based on the total solid content of the infrared light-shielding composition according to the present invention.

Further, two or more kinds of tungsten oxide fine particles containing an alkali metal can be used.

The alkali metal-containing tungsten oxide fine particles may be a commercially available product, and can be obtained by heat-treating an alkali metal-containing tungsten compound in an inert gas atmosphere or a reducing gas atmosphere (see Japanese Patent No. 4,096,205).

Further, the dispersion of the alkali metal-containing tungsten oxide fine particles is, for example, YMF-02 manufactured by Sumitomo Metal Industries, Ltd.

[4] Binder

The infrared light-shielding composition according to the present invention may contain a binder.

The binder may be appropriately selected depending on the purpose, and examples thereof include (meth)acrylic resin, urethane resin, polyvinyl alcohol, polyvinyl butyral, polyethylene formaldehyde, polyamine, and polyester, and preferably. It is a (meth)acrylic resin and a urethane resin. For example, examples of non-alkali-soluble binders include (meth) propylene. An acid resin, a urethane resin, a polyvinyl alcohol, a polyvinyl butyral, a polyethylene formaldehyde, a polyamidamine, and a polyester each having a non-alkali solubility because it does not have an acid group, and includes no acid groups as described below. A polymer obtained by polymerization of a polymerizable compound.

The binder is preferably an alkali-soluble binder (alkali-soluble resin). By forming an ink by exposing the infrared light-shielding film obtained by the infrared light-shielding composition to form a pattern by containing an alkali-soluble binder, the unexposed area can be removed by the alkaline developer to form excellent by alkaline development. picture of.

The alkali-soluble binder is not particularly limited as long as it has alkali solubility, and can be appropriately selected depending on the purpose. Examples thereof include (meth)acrylic resin, urethane resin, polyvinyl alcohol, polyvinyl butyral, polyethylene formaldehyde, polyamine, and polyester, and preferably include (meth)acrylic resin and amine. Carbamate resin.

The alkali-soluble binder preferably has an acid group.

The acid group includes, for example, a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group, and a sulfonamide group. From the viewpoint of the availability of the raw material, a carboxylic acid group is preferred.

The alkali-soluble binder having an acid group is not particularly limited, and is preferably a polymer obtained by using a polymerizable compound containing an acid group as a monomer component, and it is more preferable to use a viewpoint of adjusting an acid value. A copolymer obtained by copolymerization of an acid group-containing polymerizable compound and an acid group-free polymerizable compound.

The acid-based polymerizable compound is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, and p-carboxystyrene. . Among them, acrylic acid, methacrylic acid or p-carboxystyrene is preferred. A polymerizable compound having an acid group can be used alone Or a combination of two or more acid-based polymerizable compounds.

The polymerizable compound having no acid group is not particularly limited, and suitable examples thereof include a (meth) acryloester (for example, an alkyl ester, an aryl ester or an aralkyl ester).

The alkyl group of the alkyl ester moiety in the (meth) acrylate may be linear or branched, and is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. alkyl.

The aryl group of the aryl ester moiety of the (meth) acrylate is preferably an aryl group having 6 to 14 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms.

The aralkyl group of the aralkyl ester moiety of the (meth) acrylate is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 12 carbon atoms.

The molar ratio between the monomer corresponding to the acid group-containing polymerizable compound and the monomer corresponding to the polymerizable compound having no acid group is usually from 1:99 to 99:1, preferably from 30:70 to 99: 1, and more preferably 50:50 to 99:1.

The acid group content in the alkali-soluble binder is not particularly limited, and is preferably from 0.5 meq/g to 4.0 meq/g, and more preferably from 0.5 meq/gram to 3.0 meq/g. When the content of the acid group is 0.5 meq/g or more, sufficient alkali developability is obtained and an excellent pattern can be obtained more reliably. When the content of the acid group is less than or equal to 4.0 meq/g, the risk of impairing the intensity of the infrared light-shielding film when forming a pattern can be surely avoided.

The alkali-soluble binder preferably has a crosslinking group, and by introducing a crosslinking group, the curability of the exposed region and the alkali developability of the unexposed region can be particularly improved. The introduction of a crosslinking group also results in a pattern with high durability (especially when the solder resist needs to have high durability (for example, a wire of a metal wire covered by a solder resist) In the case of a higher density, the above effects are remarkable) and preferred. The crosslinking group is a group which crosslinks the binder polymer during the polymerization reaction carried out in the photosensitive layer when the photosensitive layer is obtained by exposing or heating the infrared light-shielding composition (polymerizable composition). The crosslinking group is not particularly limited as long as it is a group having such a function, and examples thereof include a functional group capable of undergoing addition polymerization, an ethylenically unsaturated bond group, an amine group, and an epoxy group. The crosslinking group may also be a functional group capable of forming a radical upon irradiation with light, and examples thereof include a thiol group and a halogen group. Among them, an ethylenically unsaturated bond group is preferred. The ethylenically unsaturated bond group is preferably a styryl group, a (meth) acrylonitrile group or an allyl group, and the viewpoint of the stability of the crosslinking group before exposure and the intensity of the infrared light-shielding film at the time of pattern formation is satisfied. More preferably, it is a (meth) acrylonitrile group.

In an alkali-soluble binder, for example, a radical (a polymerization starting radical or a radical which grows during polymerization of a polymerizable compound) is added to a crosslinking functional group of an alkali-soluble binder to be between the polymers The addition polymerization is produced directly or via a polymeric chain of a polymerizable compound, thus forming a crosslink between the polymer molecules to effect curing. Alternatively, an atom in the polymer (eg, a hydrogen atom on a carbon atom adjacent to the functional crosslinkable group) is pulled away by the radical to produce a polymer radical, and the polymer radicals are combined with one another to form a polymer molecule. Cross-linking between them to achieve curing.

The content of the crosslinkable group in the alkali-soluble binder is not particularly limited, and is preferably from 0.5 meq/gram to 3.0 meq/g, more preferably from 1.0 meq/gram to 3.0 meq/g, and particularly preferably It is from 1.5 meq/g to 2.8 meq/g. When the content of the crosslinking group is greater than or equal to 0.5 meq/g, the curing reaction amount is sufficient to obtain high sensitivity, and when the content is less than or equal to 3.0 meq/g, the infrared light-shielding composition has high preservation. stability.

The above content (millieq/g) can be, for example, by iodine value Titration) is determined to measure.

The alkali-soluble binder having a crosslinking group is described in detail in JP-A-2003-262958, and the compounds described in this publication can also be used in the present invention.

The alkali-soluble binder having a crosslinking group is preferably an alkali-soluble binder having an acid group and a crosslinking group, and a representative example thereof is described below:

(1) An acrylic resin containing a polymerizable double bond modified with a urethane, which is obtained by reacting a compound with a carboxyl group-containing acrylic resin, which has a pre-reaction reaction between an isocyanate group and a hydroxyl group. The next unreacted isocyanate group and which has at least one (meth) acrylonitrile group.

(2) An unsaturated group-containing acrylic resin obtained by reacting a carboxyl group-containing acrylic resin with a compound having an epoxy group and a polymerizable double bond in the molecule.

(3) An acrylic resin containing a polymerizable double bond, which is obtained by reacting a hydroxyl group-containing acrylic resin with a dibasic acid anhydride having a polymerizable double bond.

Among the above resins, preferred are the resins of (1) and (2).

Further, examples of the alkali-soluble binder having an acid group and a crosslinking group include a polymer compound having an acid group and an ethylenically unsaturated bond in a side chain and a bisphenol A type skeleton and a bisphenol F type skeleton, and having an acid A novolac resin with a olefinic unsaturated bond and a resol resin. These resins can be obtained by the methods described in paragraphs [0008] to [0027] of JP-A-11-240930.

As described above, the alkali-soluble binder is preferably a (meth)acrylic resin or a urethane-based resin. The "(meth)acrylic resin" is preferably a copolymer having the following polymeric components: (meth)acrylic acid derivatives such as (meth)acrylic acid, (meth)acrylic acid esters (for example, alkyl esters, aryl esters) , aralkyl ester), (meth) acrylamide and (methyl) Acrylamine derivatives. The "urethane resin" is preferably a polymer produced by condensation reaction of a compound having two isocyanate groups or a plurality of isocyanate groups with a compound having two hydroxyl groups or a plurality of hydroxyl groups.

Suitable examples of the (meth)acrylic resin include a copolymer containing a repeating unit having an acid group. Suitable examples of the acid group include the above acid groups. The repeating unit having an acid group is preferably a repeating unit derived from (meth)acrylic acid or a repeating unit represented by the following formula (I).

In the formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² represents a single bond or an (n+1)-valent linking group; A represents an oxygen atom or -NR ³ -; R ³ represents a hydrogen atom or has 1 a monovalent hydrocarbon group to 10 carbon atoms; and n represents an integer from 1 to 5. )

In the formula (I), the linking group represented by R ² is preferably composed of one or more atoms selected from the group consisting of a free hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom, and constitutes The number of atoms of the linking group represented by R ² is preferably from 1 to 80. Specific examples of the linking group include an alkylene group and an extended aryl group, and the linking group may have a plurality of these divalent groups via any one of a guanamine bond, an ether bond, a urethane bond, a urea bond, and an ester bond. The structure of the connection. R ^{2 is} preferably a structure in which a single bond, an alkylene group or a plurality of alkylene groups are bonded via at least one of a guanamine bond, an ether bond, a urethane bond, a urea bond, and an ester bond.

The carbon number of the alkylene group is preferably from 1 to 5, more preferably from 1 to 3.

The carbon number of the aryl group is preferably from 6 to 14, more preferably from 6 to 10.

The alkylene group and the extended aryl group may have a more substituent, and the substituent includes a monovalent non-metal atomic group other than a hydrogen atom. Examples thereof include a halogen atom (-F, -Br, -Cl or -I), a hydroxyl group, a cyano group, an alkoxy group, an aryloxy group, a mercapto group, an alkylthio group, an arylthio group ( An arylthio group), an alkylcarbonyl group, an arylcarbonyl group, a carboxyl group and a conjugated base thereof, an alkoxycarbonyl group, an aryloxycarbonyl group, an carbamoyl group, an aryl group, an alkenyl group, and an alkynyl group.

The hydrocarbon group represented by R ³ preferably has a carbon number of from 1 to 10, more preferably from 1 to 5, and still more preferably from 1 to 3.

R ^{3 is} most preferably a hydrogen atom or a methyl group.

n is preferably from 1 to 3, more preferably 1 or 2, and most preferably 1.

From the viewpoint of developability, the ratio (mol%) of the repeating unit containing an acid group in all the repeating unit components of the (meth)acrylic resin is preferably from 10% to 90%. Further, it is more preferably from 50% to 85%, particularly preferably from 60% to 80%, from the viewpoint of satisfying the developability and strength of the infrared light-shielding film at the time of pattern formation.

As described above, the (meth)acrylic resin preferably has a more crosslinking group, and specific examples and contents of the crosslinking group are the same as described above.

The (meth)acrylic polymer used in the present invention may contain an alkyl (meth)acrylate or an aralkyl (meth)acrylate in addition to the polymer group containing an acid group and the polymerization unit containing a crosslinking group. a polymerization unit composed of an ester, a polymerization unit composed of (meth) acrylamide or a derivative thereof, a polymerization unit composed of α-hydroxymethyl acrylate or a polymerization composed of a styrene derivative. unit. The alkyl group of the alkyl (meth)acrylate is preferably an alkyl group having 1 to 5 carbon atoms, or an alkyl group having the above substituent and having 2 to 8 carbon atoms, and more preferably a methyl group. . Examples of the aralkyl (meth)acrylate include benzyl (meth)acrylate. (methyl) propyl Examples of the decylamine derivative include N-isopropylacrylamide, N-phenylmethacrylamide, N-(4-methoxycarbonylphenyl)methacrylamide, N,N-di Methyl acrylamide and (N-morpholinyl) morpholinoacrylamide. Examples of the α-hydroxymethyl acrylate include α-hydroxyethyl methacrylate and α-hydroxymethyl methacrylate. Examples of the styrene derivative include styrene and 4-tert-butylstyrene.

The "urethane-based resin" is preferably a structural unit represented by a reaction product between at least one diisocyanate compound represented by the following formula (1) and at least one diol compound represented by the following formula (2). A basic skeleton urethane resin.

OCN-X-NCO (1)

HO-L ¹ -OH (2)

In the formulae (1) and (2), X and L ¹ are each independently represented as a divalent organic residue.

The at least one diol compound represented by the formula (2) preferably has an acid group. Therefore, an acid-soluble alkali-soluble urethane-based resin can be suitably produced by a reaction of a diisocyanate compound and a diol compound. According to the method, the alkali-soluble urethane-based resin can be easily produced as compared with the case where the acid group is substituted or introduced into the desired side chain after the reaction and the production of the urethane-based resin.

It is preferred that at least one of the diisocyanate compound represented by the formula (1) or the diol compound represented by the formula (2) has a crosslinking group. Examples of the crosslinking group include these above-mentioned crosslinking groups. Therefore, the alkali-soluble urethane-based resin having a crosslinking group can be suitably produced by a reaction of a diisocyanate compound and a diol compound. According to the method, it is easier to produce a cross-linking as compared with the case where the cross-linking group is substituted or introduced on the desired side chain after the reaction and the production of the urethane-based resin. A urethane resin.

(1) Diisocyanate compound

In the formula (1), X is preferably a divalent aliphatic hydrocarbon group, a divalent aromatic group or a group formed by combining the above groups, and the number of carbon atoms included. It is preferably from 1 to 20, more preferably from 1 to 15. The divalent aliphatic hydrocarbon group or the divalent aromatic hydrocarbon group may further have a substituent which cannot react with the isocyanate group.

Specific examples of the diisocyanate compound represented by the formula (1) include aromatic diisocyanate compounds (for example, 2,4-tolylene diisocyanate, diisocyanate). 2,4-tolylene diisocyanate dimer, 2,6-tolylene diisocyanate, diisocyanate Methyl (p-xylylene diisocyanate), m-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, diisocyanate 1,5-naphthlene diisocyanate or 4,4'-diisocyanato-3,3'-dimethylbiphenyl ester (3,3'-dimethylbiphenyl-4,4'- Diisocyanate)), an aliphatic diisocyanate compound (eg, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, and Dimer acid diisocyanate, alicyclic diisocyanate compound (eg isophorone diisocyanate (isophorone dii) Socyanate), 4,4'-methylenebis(cyclohexylisocyanate), methylcyclohexane-2,4 (or 2,6)-diisocyanate (methylcyclohexane-) 2,4(or 2,6)-diisocyanate) or 1,3-(isocyanatemethyl)cyclohexane (1,3-(isocyanatomethyl)cyclohexane)) and a diisocyanate compound which is a reaction product of a diol and a diisocyanate (for example, an addition product of 1 mol of 1,3-butanediol and 2 mol of phenylene diisocyanate) ).

In the case where the diisocyanate compound represented by the formula (1) has a crosslinking group, examples of the diisocyanate compound include a monofunctional group having a triisocyanate compound and 1 equivalent of a crosslinking group (for example, an ethylenically unsaturated bond group) A product obtained by an addition reaction of an alcohol compound or a monofunctional amine compound. Specific examples of the triisocyanate compound and the monofunctional alcohol compound or the monofunctional amine compound having a crosslinking group include those described in paragraphs [0034], [0035], and [0037] to [0040] of the Japanese Patent No. 4,401,262. These (compounds), but the invention is not construed as being limited thereto.

Specific examples of the diisocyanate compound having a crosslinking group include those (compounds) described in paragraphs [0042] to [0049] of Japanese Patent No. 4,401,262, but the present invention is not construed as being limited thereto.

(2) diol compound

There are many examples of the diol compound represented by the formula (2), including a polyether diol compound, a polyester diol compound, and a polycarbonate diol compound. The polyether diol compound includes a compound represented by the following formula (3), formula (4), formula (5), formula (6), and formula (7), and ethylene oxide and propylene oxide having a hydroxyl group at the terminal. Random copolymer.

HO-(CH ₂ CH ₂ CH ₂ CH ₂ O) _c -H (5)

In the formulae (3) to (7), R ¹⁴ represents a hydrogen atom or a methyl group, and X ¹ represents a group shown below. a, b, c, d, e, f, and g are each represented as an integer greater than or equal to 2 and preferably an integer from 2 to 100. The two ds can be the same or different. Also, the two X ^{1 's} may be the same or different.

-CH ₂ CH ₂ -

Specific examples of the polyether diol compound represented by the formula (3) and the formula (4) include diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, and heptaethylene glycol. , octaethylene glycol, di-1,2-propanediol, tri-1,2-propanediol, tetra-1,2-propanediol, hexa-1,2-propanediol, di-1,3-propanediol, tri-1, 3-propanediol, tetra-1,3-propanediol, di-1,3-butanediol, tri-1,3-butanediol, hexa-1,3-butanediol, weight average a polyethylene glycol having a molecular weight of 1,000, a polyethylene glycol having a weight average molecular weight of 1,500, a polyethylene glycol having a weight average molecular weight of 2,000, a polyethylene glycol having a weight average molecular weight of 3,000, and a weight average molecular weight of 7,500. Ethylene glycol, polypropylene glycol having a weight average molecular weight of 400, polypropylene glycol having a weight average molecular weight of 700, polypropylene glycol having a weight average molecular weight of 1,000, polypropylene glycol having a weight average molecular weight of 2,000, polypropylene glycol having a weight average molecular weight of 3,000, and weight. A polypropylene glycol having an average molecular weight of 4,000.

Specific examples of the polyether diol compound represented by the formula (5) include PTMG650, PTMG1000, PTMG2000, and PTMG3000 (manufactured by Sanyo Chemical Industries, Ltd.).

Specific examples of the polyether diol compound represented by the formula (6) include Newper (NEWPOL) PE-61, Newpel PE-62, Newpel PE-64, Newpel PE-68, Newpel PE-71, Neuper PE-74, Neuper PE-75, Neuper PE-78, Neuper PE-108, Neuper PE-128 and Neuper PE-61 (by Sanyo Chemical Industry) Manufacturing company).

Specific examples of the polyether diol compound represented by the formula (7) include Newpel BPE-20, Newpel BPE-20F, Newpel BPE-20NK, Newpel BPE-20T, Newpel BPE-20G , Newper BPE-40, Newpel BPE-60, Newpel BPE-100, Newpel BPE-180, Newpel BPE-2P, Newpel BPE-23P, Newpel BPE-3P and Newpel BPE-5P (manufactured by Sanyo Chemical Industry Co., Ltd.).

Specific examples of random copolymers of ethylene oxide and propylene oxide having a hydroxyl group at the terminal include Newpel 50HB-100, Newpel 50HB-260, Newpel 50HB-400, Newpel 50HB-660, Newpel 50HB-2000 and Newpel 50HB-5100 (manufactured by Sanyo Chemical Industry Co., Ltd.).

The polyester diol compound includes a compound represented by the formula (8) and the formula (9):

In the formulae (8) and (9), L ² , L ³ and L ⁴ each represent a divalent aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group, and L ⁵ represents a divalent aliphatic hydrocarbon group. L ² , L ³ and L ⁵ may be the same or different. Each of L ² to L ⁴ preferably represents an alkylene group, an alkenyl group, an alkynylene group or an extended aryl group, and L ⁵ preferably represents an alkylene group. In L ² to L ⁵ , there may be another bond or a functional group which is incapable of reacting with an isocyanate group, such as an ether bond, a carbonyl bond, an ester bond, a cyano group, an olefin bond, a urethane bond, Amidino group, ureido group or halogen atom. N1 and n2 are each represented as an integer greater than or equal to 2, and are preferably an integer of 2 to 100.

The polycarbonate diol compound includes a compound represented by the following formula (10).

In the formula (10), L ⁶ may be the same or different and each represents a divalent aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group. L ⁶ preferably represents an alkylene group, an alkenyl group, an alkynylene group or an extended aryl group. In L ⁶ , there may be another bond or functional group which cannot react with the isocyanate group, such as an ether bond, a carbonyl group, an ester bond, a cyano group, an olefin bond, a urethane bond, a guanamine bond, a urea group or a halogen. atom. N3 represents an integer greater than or equal to 2, and preferably represents an integer from 2 to 100.

Specific examples of the diol compound represented by the formula (8), the formula (9) or the formula (10) include the compounds No. 1 to No. 18 described below. In a particular example, n represents an integer greater than or equal to two.

In the case of synthesizing the urethane-based resin, in addition to the above diol compound, a diol compound having a substituent which cannot react with an isocyanate group may be used in combination. The diol compound includes a compound represented by the following formula (11) and formula (12): HO-L ⁷ -O-CO-L ⁸ -CO-OL ⁷ -OH (11)

HO-L ⁸ -CO-OL ⁷ -OH (12)

In the formula (11) and the formula (12), L ⁷ and L ⁸ may be the same or different and each represents a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group or a divalent heterocyclic group. In L ⁷ and L ⁸ , if necessary, another bond or a functional group which cannot react with an isocyanate group, such as a carbonyl bond, an ester bond, a urethane bond, a guanamine group, and a urea group may be present. Further, L ⁷ and L ⁸ may be combined with each other to form a ring.

The divalent aliphatic hydrocarbon group, the aromatic hydrocarbon group, and the heterocyclic group may have a substituent, and examples of the substituent include an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, and a halogen atom, for example, -F, - Cl, -Br or -I.

The diol compound which is at least one of the above diol compounds having a substituent which cannot react with an isocyanate group is preferably a diol compound having an acid group. Specific examples of the acid group include the above acid groups, and the acid group is preferably a carboxylic acid group. The diol compound having a carboxylic acid group includes, for example, a compound represented by the following formula (13) to formula (15).

In the formulae (13) to (15), R ¹⁵ represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group or an aryloxy group, preferably a hydrogen atom, having 1 to 8 carbon atoms. An alkyl group, or an aryl group having 6 to 15 carbon atoms.

The alkyl group, the aralkyl group, the aryl group, the alkoxy group, and the aryloxy group may have a substituent, and examples of the substituent include a cyano group, a nitro group, and a halogen atom (for example, -F, -Cl, -Br, or -I). , -CONH ₂ , -COOR ¹⁶ , -OR ¹⁶ , -NHCONHR ¹⁶ , -NHCOOR ¹⁶ , -NHCOR ¹⁶ , -OCONHR ¹⁶ (wherein R ¹⁶ represents an alkyl group having 1 to 10 carbon atoms or has 7 to 15 carbons Aromatic arylalkyl).

L ⁹ , L ¹⁰ and L ¹¹ may be the same or different and each represents a single bond or a divalent aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group, preferably an alkylene group having 1 to 20 carbon atoms or having 6 to An extended aryl group of 15 carbon atoms, and more preferably an alkylene group having 1 to 8 carbon atoms.

The divalent aliphatic hydrocarbon group or the divalent aromatic hydrocarbon group may have a substituent, and examples of the substituent include an alkyl group, an aralkyl group, an aryl group, an alkoxy group, and a halogen atom.

When necessary, L ⁹ to L ¹¹ may have another functional group which cannot react with an isocyanate group (for example, a group containing a carbonyl group, an ester group, a urethane group, a guanyl group, a ureido group or an ether group). Two or three of R ¹⁵ , L ⁷ , L ⁸ and L ⁹ may be combined with each other to form a ring.

Ar represents a trivalent aromatic hydrocarbon group which may have a substituent, and preferably represents an aromatic group having 6 to 15 carbon atoms.

Specific examples of the diol compound having a carboxyl group represented by the formula (13) to the formula (15) include 3,5-dihydroxybenzoic acid, 2,2-bis(hydroxymethyl)propyl group. 2,2-bis(hydroxymethyl)propionic acid, 2,2-bis(2-hydroxyethyl)propionic acid, 2,2-bis(3-hydroxyl) Propyl (2,2-bis(3-hydroxypropyl)propionic acid), bis(hydroxymethyl)acetic acid, bis(4-hydroxyphenyl)acetic acid (bis(4-) Hydroxyphenyl)acetic acid), 2,2-bis(hydroxymethyl)butyric acid (2,2-bis(hydroxymethyl)butyric acid), 4,4-bis(4-hydroxyphenyl)pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine and N,N-bis(2-hydroxyethyl)-3-carboxy-propylamine (N,N-bis(2-hydroxyethyl)-3-carboxypropionamide ).

It is preferred that the carboxyl group be present because it can impart a property such as hydrogen bonding property and alkali solubility to the polyurethane resin.

A preferred embodiment of the polyurethane resin has a carboxyl group-containing resin having a carboxyl group content of from 0.5 meq/gram to 4.0 meq/g, preferably from 1.0 meq/g to 3.0. A urethane-based resin having a molar equivalent/gram amount of a carboxyl group.

In the case where the diol compound represented by the formula (2) has a crosslinking group, a method of producing a polyurethane resin using a diol compound having an unsaturated group as a raw material is also suitable. The diol compound may be a commercially available product such as trimethylolpropane monoallyl ether, or may be a halogenated diol compound, a triol compound or an amino diol compound and an unsaturated group-containing carboxylic acid, A compound produced by the reaction of an acid chloride, an isocyanate, an alcohol, an amine, a thiol or an alkyl halide. Specific examples of the diol compound having a crosslinking group include the compounds described in paragraphs [0057] to [0066] of Japanese Patent No. 4,401,262, but the present invention is not construed as being limited thereto.

The compound No. 13 to No. 17 described above corresponds to the diol compound represented by the formula (8), the formula (9) or the formula (10), and is also a diol compound having a crosslinking group.

One of the preferred embodiments of the polyurethane resin is a polyurethane resin having a crosslinking group of 0.5 meq/g or more, more preferably A polyurethane resin having a crosslinking group in an amount of from 1.0 meq/g to 3.0 meq/g.

In the case of synthesizing a urethane-based resin, a tetracarboxylic dianhydride represented by any one of the following formulas (16) to (18) may be used in combination with a diol compound in addition to the above diol. Acid dianhydride) A compound obtained by ring opening.

In the formulae (16) to (18), L ¹² represents a single bond, may have a substituent (preferably, for example, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, a halogeno group, an ester) a divalent aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group, -CO-, -SO-, -SO ₂ -, -O- or -S-, or preferably a single bond, having 1 a divalent aliphatic hydrocarbon group of up to 15 carbon atoms, -CO-, -SO ₂ -, -O- or -S-.

The divalent aliphatic hydrocarbon group or the divalent aromatic hydrocarbon group may have a substituent, and examples of the substituent include an alkyl group, an aralkyl group, an aryl group, an alkoxy group, a halogen atom, and an ester-containing bond. a group (for example, an alkylcarbonyloxy group, an alkoxycarbonyl group, an arylcarbonyloxy group or an aryloxycarbonyl group) and a decylamino group.

R ¹⁷ and R ¹⁸ may be the same or different and each represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group or a halogenated group, preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms. An aryl group having 6 to 15 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or a halogen group.

Two of L ¹² , R ¹⁷ and R ¹⁸ may be combined with each other to form a ring.

R ¹⁹ and R ²⁰ may be the same or different and each represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or a halogenated group, preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or 6 An aryl group to 15 carbon atoms.

Two of L ¹² , R ¹⁹ and R ²⁰ may be combined with each other to form a ring.

L ¹³ and L ¹⁴ may be the same or different and each represents a single bond, a double bond or a divalent aliphatic hydrocarbon group, and preferably represents a single bond, a double bond or a methylene group. A represents a mononuclear aromatic ring or a multinuclear aromatic ring, preferably an aromatic ring having 6 to 18 carbon atoms.

Specific examples of the compound represented by the formula (16), the formula (17), and the formula (18) include aromatic tetracarboxylic dianhydrides (for example, pyromellitic dianhydride, 3, 3', 4, 4). '-3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride (3,3',4, 4'-diphenyltetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride (1,4 ,5,8-naphthalenetetracarboxylic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, 2,2-bis(3,4-dicarboxylate) 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride , 4,4'-[3,3'-(Alkylphosphonium diphenyl)-bis(iminocarbonyl)]diphthalic dianhydride (4,4'-[3,3'- (alkylphosphoryldiphenylene)-bis(iminocarbonyl)]diphthalic dianhydride), an addition product of hydroquinone diacetate and trimellitic anhydride or an addition product of diacetyldiamine and trimellitic anhydride) An alicyclic tetracarboxylic dianhydride (for example, 5-(2,5-di-oxytetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (5-(2, 5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride) (EPICLON B-4400, manufactured by Dainippon Ink and Chemicals Co., Ltd.), 1, 2, 3, 4 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride or tetrahydrofuran Formic acid dianhydride (tetrahydrofurantetracarboxylic dianhydrid e)) and aliphatic tetracarboxylic dianhydrides (for example, 1,2,3,4-cyclopentanetetracarboxylic dianhydride or 1,2,4,5-pentane 1,2,4,5-pentanetetracarboxylic dianhydride).

Examples of a method of introducing a compound obtained by ring-opening the tetracarboxylic dianhydride with a diol compound into a polyurethane resin include: a) making a diisocyanate compound and a diol compound a method of reacting a compound of a terminal alcohol obtained by ring-opening of a tetracarboxylic dianhydride, and b) an amine group of a terminal alcohol obtained by reacting a tetracarboxylic dianhydride with an excess of a diol compound under an excess of a diol compound A method of reacting a formate compound.

Specific examples of the diol compound used for the ring opening reaction include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butanediol, 1,6-hexanediol, 2-butene-1,4-diol, 2,2,4-trimethyl-1,3-pentanediol, 1,4- Bis-β-hydroxyethoxycyclohexane, cyclohexanedimethanol, tricyclodecane dimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, ethylene oxide addition product of bisphenol A, bisphenol A The propylene oxide addition product, the ethylene oxide addition product of bisphenol F, the propylene oxide addition product of bisphenol F, the ethylene oxide addition product of hydrogenated bisphenol A, and the ring of hydrogenated bisphenol A Oxypropane addition product, hydroquinone dihydroxyethyl ether, p-xylylene glycol, dihydroxyethylsulfone, diamino 2-(2-hydroxyethyl) ) 2,4-methylethyl-2,4-tolylene dicarbamate, 2,4-tolyl-bis(2-hydroxyethylformamide) (2,4-) Tolylene-bis(2-hydroxyethylcarbamide), bis(2-hydroxyethyl)-m-xylylene dicarboxylate (bis(2-hyd) Roxyethyl)-m-xylylene dicarbamate), and bis(2-hydroxyethyl)isophthalate.

According to the reactivity of the respective compounds, the above-mentioned urethanes are synthesized by adding a diisocyanate and a diol compound in an aprotic solvent, adding a conventional catalyst having activity and heating the solution. Resin. The molar ratio (M _a : M _b ) between the diisocyanate for synthesis and the diol compound is preferably from 1:1 to 1.2:1. Preferably, the product having the desired physical properties (e.g., molecular weight or viscosity) is ultimately synthesized into an isocyanate-free form which can be accomplished by treatment with an alcohol, amine or the like.

It is also suitable to use a polymer terminal or a crosslinker in the polymer backbone (for example Unsaturated) urethane resin. The crosslinking reaction between the polymerizable compound and the urethane resin or between the urethane resin and the urethane resin is promoted by having a crosslinking group at the polymer terminal or the polymer main chain. And increase the intensity of the infrared light-shielding film in which the pattern is formed. An unsaturated gene having a carbon-carbon double bond is particularly preferred because it is susceptible to a crosslinking reaction.

The method of introducing a crosslinking group into the terminal of the polymer includes the following methods. Specifically, in the process of treating the above-mentioned synthetic polyurethane resin, the step of treating the residual isocyanate group on the polymer terminal with an alcohol, an amine or the like can be carried out by using an alcohol having a crosslinking group, An amine or an analog thereof is used to introduce a crosslinking group into the polymer end. Specific examples of the compound include the above compounds, such as a monofunctional alcohol compound or a monofunctional amine compound having a crosslinking group.

From the standpoint of easy control of the amount of introduction of the crosslinking group, the crosslinking group is preferably introduced into the side chain of the polymer rather than being introduced into the terminal of the polymer, thus increasing the amount of the crosslinking group introduced and promoting the crosslinking reaction. effectiveness.

The method of introducing a crosslinking group into the main chain includes a method of synthesizing a polyurethane resin using a diol compound having an unsaturated group in the main chain direction. Specific examples of the diol compound having an unsaturated group in the main chain direction include cis-2-butene-1,4-diol, trans-2-butene-1,4-diol, and polybutadiene II. alcohol.

An alkali-soluble binder other than a (meth)acrylic resin and a urethane-based resin, for example, the acetal having an acid group as described in European Patent Nos. 993,966 and 1,204,000 and JP-A-2001-318463 The modified polyvinyl alcohol binder polymer is suitable because of an excellent balance between film strength and developability. Further, polyvinylpyrrolidone, polyethylene oxide or the like is useful as a water-soluble linear organic polymer. In addition, in order to increase the strength of the cured film, alcohol solubility Polyether-soluble nylon, polyether of 2,2-bis(4-hydroxyphenyl)propane, and epichlorohydrin Polyethers and the like are also useful.

In particular, [(meth)acrylic acid methacrylate/(meth)acrylic acid/other addition polymerizable vinylic monomer if necessary] copolymer and [(meth)acrylic acid allyl ester/(methyl)) The acrylic acid/other addition polymerizable vinyl monomer] copolymer is suitable because of excellent balance between film strength, sensitivity, and developability.

The weight average molecular weight of the binder polymer which can be used in the infrared light-shielding composition according to the present invention is preferably 3,000 or more, more preferably 5,000 to 300,000, and most preferably 10,000 to 30,000, and the weight thereof The average molecular weight is preferably greater than or equal to 1,000, and more preferably in the range of 2,000 to 250,000. The polydispersity (weight average molecular weight/number weight average molecular weight) is preferably greater than or equal to 1, more preferably from 1.1 to 10.

The alkali-soluble binder may be any of a random polymer, a block polymer, a graft polymer, or the like.

A binder (preferably an alkali-soluble binder) can be synthesized by a conventional method. Examples of the solvent used in the synthesis include tetrahydrofuran, ethylene dichloride, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and butyl acetate. The solvent may be used singly or in combination of two or more.

The binder may be used singly or in combination of two or more.

The content of the binder is preferably from 5% by mass to 80% by mass, more preferably from 30% by mass to 60% by mass, based on the total solid content of the infrared light-shielding composition according to the present invention. When the content is in the above range, the exposure sensitivity is excellent, the processing performed is as short as possible, and excellent thermal cycle test resistance is obtained (thermal cycle) Test resistance, TCT resistance).

[5] Infrared light blockers other than tungsten oxide fine particles containing alkali metals

The infrared light-shielding composition according to the present invention may contain an infrared light blocking agent other than the alkali metal-containing tungsten oxide fine particles (hereinafter sometimes referred to as "other infrared rays" within a range not impairing the effects of the present invention. Photoinhibitors. Other infrared light blockers are preferably compounds which absorb in the wavelength range from 800 nm to 1,200 nm and which exhibit good light transmission to the light used for exposure. From this point of view, other infrared light The blocker is preferably selected from the group consisting of an infrared-absorbing dye and an infrared-absorbing inorganic pigment.

Examples of the infrared light absorbing dye include a cyanine dye, a phthalocyanine dye, a naphthalocyanine dye, an imimium dye, an aminium dye, and a quinine. A quinolium dye, a pyrylium dye, and a metal complex dye (eg, a nickel complex dye).

The dye which can be used as the infrared light blocker can also be a commercially available product, and suitable examples thereof include the following commercially available dyes: S0345, S0389, S0450, S0253, S0322, S0585, S0402 manufactured by FEW Chemicals. , S0337, S0391, S0094, S0325, S0260, S0229, S0447, S0378, S0306, and S0484; ADS795WS, ADS805WS, ADS819WS, ADS820WS, ADS823WS, ADS830WS, ADS850WS, manufactured by American Dye Source, Inc. ADS845MC, ADS870MC, ADS880MC, ADS890MC, ADS920MC, ADS990MC, ADS805PI, ADSW805PP, ADS810CO, ADS813MT, ADS815EI, ADS816EI, ADS818HT, ADS819MT, ADS819MT, ADS821NH, ADS822MT, ADS838MT, ADS840MT, ADS905AM, ADS956BP, ADS1040P, ADS1040T, ADS1045P, ADS1040P, ADS1050P, ADS1065A, ADS1065P, ADS1100T and ADS1120F; by Yamamoto Chemical Industry Co., Ltd. Manufactured YKR-4010, YKR-3030, YKR-3070, MIR-327, MIR-371, SIR-159, PA-1005, MIR-369, MIR-379, SIR-128, PA-1006, YKR-2080, MIR-370, YKR-3040, YKR-3081, SIR-130, MIR-362, YKR-3080, SIR-132, and PA-1001; and NK manufactured by Hayashibara Biochemical Labs. Inc. -123, NK-124, NK-1144, NK-2204, NK-2268, NK-3027, NKX-113, NKX-1199, NK-2674, NK-3508, NKX-114, NK-2545, NK-3555 , NK-3509 and NK-3519.

Among these dyes, phthalocyanine dyes and metal complex dyes are preferred from the viewpoint of heat resistance.

These dyes may be used singly or in combination for the purpose of exhibiting good light-shielding properties in the wavelength range of 800 nm to 1,200 nm.

Examples of infrared light absorbing inorganic pigments that can be used as other infrared light blocking agents include zinc flower, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, and precipitated sulfuric acid. Sedmentating barium sulfate, barite powder, red lead, red iron oxide, lead yellow, zinc yellow (type 1 zinc yellow, type 2 zinc yellow), ultramarine blue, Prussian Prussian blue (ferricyanide/potassium ferrocyanide), zircon grey, praseodymium yellow, chrome-titanium yellow, chrome green (chrome green), peacock, Victoria green, iron blue (not related to Prussian blue), vanadium-zirconium blue, chrome-tin pink, manganese red (manganese pink) and orange pink. Further, examples of the black pigment that can be used include a metal oxide or a metal containing one or two or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. Nitride or a mixture thereof.

The black pigment is preferably titanium black, which is a black pigment containing titanium nitride because it has good barrier properties in the infrared light region at a wavelength of from 800 nm to 1,200 nm.

Titanium black can be obtained by a conventional method. Further, as a commercially available product, for example, Ishihara Sangyo Kaisha. Ltd., Ako Kasei Co., Ltd., and JEMCO Inc. may be used. Titanium black manufactured by Mitsubishi Materials Corp. or Mitsubishi Materials Electronic Chemicals Co., Ltd.

Titanium black refers to black particles containing titanium atoms. Preferred is low-order titanium oxide, titanium oxynitride or the like. If necessary, surface-modified particles may be used as the titanium black particles for the purpose of, for example, improving dispersibility or preventing aggregation.

The surface modification method includes a method of covering a surface with one or more selected from the group consisting of cerium oxide, titanium oxide, cerium oxide, aluminum oxide, magnesium oxide, and zirconium oxide. Further, the surface may be treated with a water-repellent substance as described in paragraphs [0010] to [0027] of JP-A-2007-302836.

Examples of the method for producing titanium black include a method of heating and reducing a mixture of titanium oxide and titanium metal in a reducing atmosphere (see JP-A-49-5432); reduction of tetrachloro by high temperature reduction in a reducing atmosphere containing hydrogen Method for reducing ultrafine titanium dioxide obtained by titanium (see JP-A-57-205322); method for reducing titanium dioxide or titanium hydroxide at a high temperature in the presence of ammonia (see JP-A-60-65069 and JP-A) -61-201610); and a method of attaching a vanadium compound to titanium oxide or titanium hydroxide, followed by reduction at a high temperature in the presence of ammonia (see JP-A-61-201610), but the method is not construed as merely Limited to this.

The particle diameter of the titanium black particles is not particularly limited, but from the viewpoint of dispersibility and colorability, the particle diameter is preferably from 3 nm to 2,000 nm, more preferably from 10 nm to 500 nm.

The specific surface area of titanium black is not particularly limited, but the value measured by the BET method is usually about 5 square meters / gram to 150 square meters / gram, in order to make titanium black on the surface of the waterproofing agent The treatment may have a predetermined water repellency, preferably from about 20 square meters per gram to 100 square meters per gram.

Regarding the particle diameter of the inorganic pigment used as the other infrared light blocking agent, in terms of the average particle diameter, it is preferably from 3 nm to 0.01 mm, and the dispersibility, the light blocking property, and the depositability with time are increased ( From the viewpoint of sedimentation property, the average particle diameter is preferably from 10 nm to 1 μm.

The infrared light-shielding composition according to the present invention may or may not contain other infrared light blocking agents, and in the case of containing other infrared light blocking agents, the content of the tungsten oxide fine particles containing the alkali metal, the content thereof It is preferably from 5% by mass to 75% by mass, more preferably from 10% by mass to 40% by mass.

[6] Dispersant

In the present invention, a conventional dispersant may be used to disperse the tungsten oxide fine particles containing an alkali metal for the purpose of improving the dispersibility and dispersion stability of the tungsten oxide fine particles in the infrared light-shielding composition.

Dispersing agents which can be used in the present invention include polymeric dispersing agents (for example, polyamidoamine and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyaminocarboxylic acids). Ester, modified polyester, modified poly(meth)acrylate, (meth)acrylic copolymer or naphthalenesulfonic acid-formalin condensate, and surfactant (eg Polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine or alkanolamine.

The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer according to its structure.

Examples of the terminal-modified polymer having an anchor moiety for the surface include, for example, JP-A-3-112992 and JP-T-2003-533455 (the term "JP-T" is used herein. The polymer having a phosphate group at the terminal as described in the published Japanese translation of the PCT patent application; a polymer having a sulfonic acid group at the terminal as described in JP-A-2002-273191; such as JP-A a polymer having an organic dye partial structure or a heterocyclic ring as described in -9-77994; and an oligomer modified by an acid anhydride having a hydroxyl group or an amine group at one end thereof as described in JP-A-2008-29901 Or polymers made from polymers. Polymerization of two or more anchoring moieties (eg, acid groups, bases, organic dye moiety structures or heterocycles) at the end of the polymer is introduced to the surface of the infrared light blocker as described in JP-A-2007-277514 The material is also preferred because of its excellent dispersion stability.

Examples of graft polymers having anchoring moieties for the surface include, for example a reaction product of a poly(lower alkylene imine) and a polyester described in JP-A-54-37082, JP-T-8-507960, and JP-A-2009-258668; such as JP-A-9- a reaction product of a polyallylamine and a polyester as described in 169821; an amphoteric dispersing resins having a base and an acid group as described in JP-A-2009-203462: such as JP-A- a copolymer of a macromonomer and a nitrogen atom-containing monomer described in JP-A-2003-238837, JP-A-2008-9426, and JP-A-2008, as described in JP-A-2003-37986. a graft polymer having an organic dye moiety structure or a heterocycle as described in -81732; and a copolymer of a macromonomer and an acid group-containing monomer as described in JP-A-2010-106268.

The macromonomer is used in the production of a graft polymer having an anchor portion for the surface by radical polymerization, and conventional macromonomers usable and examples thereof include those manufactured by Toagosei Co. Ltd. Giant monomer AA-6 (polymethyl methacrylate with methacryl fluorenyl group at the end), AS-6 (polystyrene with methacryl fluorenyl group at the end), AN-6S (end of methacrylic acid oxime) a copolymer of styrene and acrylonitrile) and AB-6 (polybutyl acrylate having a methacryl fluorenyl group at the end); PLACCEL FM5 (made by Daicel Corp.) 5 molar equivalent of ε-caprolactone (ε-caprolactone and 2-hydroxyethyl methacrylate addition product) and FA10L (10 molar equivalents of ε-caprolactone and 2-hydroxyethyl acrylate The addition product); and the polyester macromonomer as described in JP-A-2-272009. Among them, from the viewpoint of the dispersibility and dispersion stability of the infrared light blocker in the infrared light-shielding composition, it is preferably a polyester giant excellent in flexibility and solvent affinity. The body is preferably a polyester macromonomer represented by a polyester macromonomer as described in JP-A-2-272009.

Preferably, the block polymer having an anchoring moiety for the surface is as The block polymer described in JP-A-2003-49110 and JP-A-2009-52010.

For example, a dispersing agent which can be used can be appropriately selected from conventional dispersing agents and surfactants.

Specific examples thereof include Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylate), 110 (copolymer containing acid group) manufactured by Byk-Chemie, 130 (polyamide), 161, 162, 163, 164, 165, 166 and 170 (high molecular weight copolymer) and BYK-P104 and P105 (high molecular weight unsaturated polycarboxylic acid); by Aijia (EFKA) ) manufactured by Aijia 4047, 4050-4010-4165 (polyurethane), Aijia 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyester phthalamide) ), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), and 6745 (phthalocyanine derivative); (Aji by Ajinomoto Fine-Techno Co., Inc.) AJISPER PB821, PB822, PB880 and PB881; FLOWLEN TG-710 (urethane oligo) manufactured by Kyoeisha Chemical Co., Ltd. , POLYFLOW 50E and 300 (acrylic copolymer); DISPARLON KS-860, 873SN, 874 manufactured by Kusumoto Chemicals, Ltd. , #2150 (fat Group polyvalent carboxylic acid), #7004 (polyether ester), DA-703-50, DA-705 and DA-725; DEMOL RN, N (naphthalene sulfonate) manufactured by Kao Corporation Acid fumarin polycondensate), MS, C, SN-B (aromatic sulfonate fumarate condensate), HOMOGENOL L-18 (polymer polycarboxylic acid), IMUGEN (EMULGEN) 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) and ACETAMIN 86 (stearylamine acetate); manufactured by Lubrizol Japan Ltd. SOSSPERSE 5000 (phthalocyanine derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer with functional moiety at the end), 24000, 28000, 32000, 38500 (graft polymer) NIKKOL T106 (polyoxyethylene sorbitan monooleate) manufactured by Nikko Chemicals, Co., Ltd., MYS-IEX (polyoxyethylene monostearate) Ester); HINOACT T-8000E manufactured by Kawaken Fine Chemicals, Co., Ltd.; manufactured by Shin-Etsu Chemical Co., Ltd. An organic siloxane polymer KP341; a cationic surfactant (for example, W001) manufactured by Yusho Co., Ltd., a nonionic surfactant (for example, polyoxyethylene lauryl ether, poly Oxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol a distearate or sorbitan fatty acid ester) and an anionic surfactant (eg W004, W005 or W017); Aijia-46, Aijia-47, Aijia-47EA, EFKA POLYMER 100, Aijia Polymer 400, Aijia Polymer 401 and Aijia Polymer 450 manufactured by Morishita & Co., Ltd.; Polymer dispersant manufactured by San Nopco Limited (eg DISPERSE AID 6, DSM 8, DS 3 and DS 8100); ADEKA PLURONIC manufactured by ADEKA Corp. L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108 , L121 and P-123; and Inet (IONET) S-20 manufactured by Sanyo Chemical Industries, Ltd.

These dispersing agents can be used singly or in combination of two or more. According to this The dispersing agent of the invention may also be used in combination with an end-modified polymer having an anchoring moiety for the surface of the infrared light blocker, a graft polymer or a block copolymer, and an alkali-soluble resin. Examples of the alkali-soluble resin include (meth)acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer The side chain has an acid cellulose derivative of a carboxylic acid and a resin obtained by a hydroxyl group-containing polymer modified with an acid anhydride, and particularly preferably a (meth)acrylic acid copolymer. Further, it is preferably an N-substituted maleimide monomer which is substituted at the N position as described in JP-A-10-300922, as in JP-A-2004-300204. The ether dimer copolymer described above and an alkali-soluble resin containing a polymerizable group as described in JP-A-7-319161.

From the viewpoint of dispersibility and depositability, the resin described in the following JP-A-2010-106268 is preferred. In particular, from the viewpoint of dispersibility, a polymer dispersant having a polyester chain in its side chain, and a resin having an acid group and a polyester chain are also suitable. With respect to the acid group in the dispersant, the acid group preferably has a pKa of 6 or less, and more preferably a carboxylic acid, a sulfonic acid or a phosphoric acid, from the viewpoint of adsorptivity.

The dispersant resin described in the preferred JP-A-2010-106268 of the present invention is described below.

The dispersing agent is preferably a graft copolymer having a graft chain selected from the group consisting of a polyester structure, a polyether structure, and a polyacrylate structure, wherein the number of atoms other than the hydrogen atom is from 40 to 10,000, and the graft copolymer is preferably. It is preferable that at least the structural unit represented by any one of the following formulas (1) to (4) is contained, and it is more preferable to contain at least the following formula (1A), formula (2A), formula (3A), and formula (3B). And a structural unit represented by any one of the formulas (4).

In the formulae (1) to (4), X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom or a monovalent organic group, and from the viewpoint of limitation on synthesis, hydrogen is preferred. The atom or an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.

In the formulae (1) to (4), W ¹ , W ² , W ³ and W ⁴ are each independently represented as an oxygen atom or NH, and particularly preferably an oxygen atom.

In the formulae (1) to (4), Y ¹ , Y ² , Y ³ and Y ^{4 are} each independently represented as a divalent linking group, and the structure thereof is not particularly limited. Specific examples thereof include the following linking group (Y-1) to a linking group (Y-20). In the following structures, A and B refer to the bonding to the left end group and the right end group in the formulae (1) to (4), respectively. From the viewpoint of easy synthesis, among the structures shown below, (Y-2) and (Y-13) are preferable.

In the formulae (1) to (4), Z ¹ , Z ² , Z ³ and Z ⁴ are each independently represented as a hydrogen atom or a monovalent substituent, and the structure of the substituent is not particularly limited. Specific examples thereof include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amine group. Among them, from the viewpoint of enhancing dispersibility, a substituent having a steric repulsion effect is preferred. The monovalent substituent represented by any one of Z ¹ to Z ³ is preferably an alkyl group having 5 to 24 carbon atoms or an alkoxy group having 5 to 24 carbon atoms, and particularly, preferably having An alkoxy group of a branched alkyl group of 5 to 24 carbon atoms or an alkoxy group having a cycloalkyl group of 5 to 24 carbon atoms. The monovalent substituent represented by any of Z ⁴ is preferably an alkyl group having 5 to 24 carbon atoms, and particularly preferably a branched alkyl group having 5 to 24 carbon atoms or having 5 to A cycloalkyl group of 24 carbon atoms.

In the formulae (1) to (4), n, m, p, and q are each represented as an integer of from 1 to 500.

In the formulas (1) and (2), j and k are each independently represented as an integer of 2 to 8. From the viewpoint of dispersion stability, each of j and k in the formula (1) and the formula (2) is preferably an integer of 4 to 6, and most preferably 5.

In the formula (3), R' represents a branched alkyl group or a linear alkyl group, and R' in the formula (3) is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably has An alkyl group of 2 or 3 carbon atoms.

Further, as for R' in the formula (3), two or more kinds of R' having different structures may be used in the dispersant resin.

In the formula (4), R represents a hydrogen atom or a monovalent organic group and its structure is not particularly limited. R is preferably a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, more preferably a hydrogen atom or an alkyl group. When R is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms or a ring having 5 to 20 carbon atoms. The alkyl group is more preferably a linear alkyl group having 1 to 20 carbon atoms, and particularly preferably a linear alkyl group having 1 to 6 carbon atoms.

Further, regarding R in the formula (4), two types of mixing may be used in the specific resin. R with a different structure.

From the viewpoint of dispersion stability, the structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A).

Further, from the viewpoint of dispersion stability, the structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A).

In the formula ^{(1A), X 1, Y} 1, Z 1 and n in the formula (1) in the X ^1, Y ^1, Z ¹ and n have the same meaning and preferred ranges are also the same.

In formula ^{(2A), X 2, Y} 2, Z 2 and m in the formula (2) in the X ^2, Y ^2, Z ² and m have the same meaning and preferred ranges are also the same.

Further, from the viewpoint of dispersion stability, the structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or (3B):

In formula (3A) or the formula ^{(3B), X 3, Y} 3, Z 3 and p in formula (3) in the X ^3, Y ^3, Z ³ and p have the same meaning and preferred ranges are also the same.

Specific examples thereof include the compounds below. In the compounds below, the value attached to each structural unit (the numerical value of the repeating unit attached to the main chain) means the content (% by mass; expressed by "% by mass") of the structural unit. Repeated connection to the side chain The value of the unit refers to the number of repetitions of the repeating unit.

(Compound 4)

(Compound 35)

(Compound 57)

In the case of using a dispersing agent, it is preferred to improve the dispersibility. To prepare a dispersion composition by using an alkali metal-containing tungsten oxide fine particle (and, if necessary, other infrared light blockers described above), a dispersing agent, and a suitable solvent, and then blending the dispersion composition into infrared light shielding Sexual composition.

The infrared light-shielding composition according to the present invention may or may not contain a dispersing agent, and in the case of containing a dispersing agent, based on the total solid content of the alkali metal-containing tungsten oxide fine particles in the composition, or In the case of using other infrared light blocking agents and using infrared light absorbing inorganic pigments as other infrared light blocking agents, the total solid content and infrared light absorption of the alkali metal-containing tungsten oxide fine particles in the infrared light-shielding composition The content of the dispersant in the composition is preferably from 1% by mass to 90% by mass, and more preferably from 3% by mass to 70% by mass, based on the total of the total solid content of the inorganic pigment.

[7] ultraviolet light absorber

The infrared light-shielding composition according to the present invention may contain an ultraviolet light absorber.

The ultraviolet light absorber is incorporated into, for example, an infrared light-shielding composition as a solder resist, and is coated on the semiconductor substrate of the solid-state image element (where an alignment mark is provided on the surface) by applying the infrared light-shielding composition After the photosensitive layer is formed, exposure and development are performed to form a solder resist layer, whereby it is possible to more reliably produce a "problem caused by reflected light on the surface of the substrate" and ensure alignment of the visible light sensor pair. Mark the detection performance of the solder resist layer.

Providing a photosensitive layer above the surface of the substrate, wherein the substrate is formed of a material having high light reflectivity (for example, metal), since the reflected light from the surface of the substrate becomes considerable when the photosensitive layer is exposed, The profile of the obtained pattern tends to become a skirt profile (ie, the rectangularity of the profile) Easy to damage). On the other hand, when the reflected light is reduced by suppressing the exposure dose, the pattern having a rectangular cross-sectional profile may be difficult to form due to insufficient exposure dose.

However, in the case where the infrared light-shielding composition according to the present invention contains an ultraviolet light absorber, it is irradiated even with an exposure dose necessary (hereinafter also referred to as "adequate exposure amount"). When a pattern having a rectangular cross-sectional profile is obtained, the ultraviolet light absorber absorbs the reflected light, and thus the infrared light-shielding composition containing the ultraviolet light absorber according to the present invention is suitable for forming a pattern having a rectangular cross-sectional profile.

Any compound can be used as the ultraviolet light absorber as long as the above spectral characteristics are satisfied. However, the ultraviolet light absorber refers to a compound which cannot initiate polymerization of a polymerizable compound by light or heat (that is, a compound which does not belong to the category of a polymerization initiator). The term "polymerization incapable of initiating a polymerizable compound" as used herein means that even when the ultraviolet light absorber receives light or heat, it does not produce an active species for initiating polymerization of the polymerizable compound.

More specifically, the ultraviolet light absorber is preferably not photosensitive to ultraviolet rays or visible light (more specifically, light having a wavelength of from 300 nm to 450 nm), and is heat (more specifically, for example, Heat at 150 ° C to 250 ° C) Compounds that do not have thermodynamic sensitivity. The terms "sensitivity" and "temperature sensitivity" as used herein mean a target function exhibited by a change in chemical structure by the action of ultraviolet rays or visible rays or heat.

Further, it is preferred that the ultraviolet light absorber not only fail to initiate polymerization of the polymerizable compound, but also lacks sensitizer properties as described below. The term "sensitizer property" as used herein means that the energy obtained by light absorption of the sensitizer itself is transferred to another material (polymerization initiator, such as a triazine polymerization initiator) and Initial aggregation quality.

The ultraviolet light absorber is preferably a compound having a maximum absorption wavelength ranging from 300 nm to 430 nm, and more preferably a compound having a maximum absorption wavelength ranging from 330 nm to 420 nm.

More preferably, the ultraviolet light absorber has a maximum absorption wavelength in at least one of the following ranges: (I) a range of 340 nm to 380 nm; (II) a range of 380 nm to 420 nm; and (III) ) 420 nm to 450 nm range.

When the photosensitive layer formed by the infrared light-shielding composition according to the present invention is subjected to exposure and development to form a pattern, in the case where the exposure source contains the i-line, the ultraviolet absorption agent preferably has a maximum absorption wavelength of Within the above wavelength range (I).

In the case where the exposure source contains the h line, the ultraviolet absorbing agent preferably has a maximum absorption wavelength within the above wavelength range (II).

In the case where the exposure source contains the g line, the ultraviolet absorber has a maximum absorption wavelength preferably in the above wavelength range (III).

For example, salicylate-based ultraviolet light absorbers, benzophenone ultraviolet light absorbers, benzotriazole-based ultraviolet light absorbers, substituted acrylonitriles (for example) can be used. An acrylonitrile-based ultraviolet light absorber or a triazine-based ultraviolet light absorber is used as an ultraviolet light absorber.

Examples of the salicylate-based ultraviolet light absorber include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Examples of the benzophenone ultraviolet light absorber include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzol Ketone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4- Octyloxybenzophenone. Examples of the benzotriazole ultraviolet light absorber include 2-(2'-hydroxy-3',5'-di-t-butylbenzene. 5-)Chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'- Hydroxy-3'-third amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl -5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy- 3',5'-di-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 2-[2'-hydroxy-5' -(1,1,3,3-tetramethyl)phenyl]benzotriazole.

Examples of the substituted acrylonitrile-based ultraviolet light absorber include ethyl 2-cyano-3,3-diphenylacrylate and 2-cyano-3,3-diphenylacrylate-2-ethylhexyl ester. Examples of the triazine-based ultraviolet light absorber include a mono(hydroxyphenyl)triazine compound (for example, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxybenzene) 4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl) Oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-(2,4-dihydroxyphenyl)- 4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine); bis(hydroxyphenyl)triazine compound (eg 2,4-bis(2-hydroxy-4-) Propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-propoxy Phenyl)-6-(4-methylphenyl)-1,3,5-triazine and 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6- (2,4-dimethylphenyl)-1,3,5-triazine); and tris(hydroxyphenyl)triazine compounds (eg 2,4-bis(2-hydroxy-4-butoxybenzene) 6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1, 3,5-triazine and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine).

Further, diethylamonopnenylsulfonyl pentadienoate-based ultraviolet light absorber (DPO, (by Fujifilm Fine Chemicals Co., Ltd.) can also be suitably used. Manufactured) or the like.

The ultraviolet light absorber is preferably a compound represented by the following formula (A):

In the formula (A), R ₆₁ and R ₆₂ are each independently represented by a hydrogen atom, an alkyl group or an aryl group, or are represented by a combination of R ₆₁ and R ₆₂ to form a 5-membered ring or a 6-membered ring. A necessary non-metal atomic group. Further, any of R ₆₁ and R ₆₂ may be combined with a methine group adjacent to a nitrogen atom to form a 5-membered ring or a 6-membered ring. X ₆₁ and Y ₆₁ are each independently represented by a cyano group, -COOR ₆₃ , -CONR ₆₃ R ₆₄ , -COR ₆₃ , -SO ₂ R ₆₃ or -SO ₂ R ₆₃ R ₆₄ , and R ₆₃ and R ₆₄ are each independently represented as A hydrogen atom, an alkyl group or an aryl group. X ₆₁ and Y ₆₁ can be combined with each other to form a 5-membered ring or a 6-membered ring. Further, any one of R ₆₁ , R ₆₂ , X ₆₁ and Y ₆₁ may be combined with any one of R ₆₁ , R ₆₂ , X ₆₁ and Y ₆₁ in another compound represented by formula (A) to form two Polymer.

In the present invention, various ultraviolet light absorbers may be used singly or in combination of two or more.

The infrared light-shielding composition according to the present invention may or may not contain an ultraviolet light absorber, and in the case of containing an ultraviolet light absorber, the total solid content of the infrared light-shielding composition according to the present invention, its content It is preferably 0.001% by mass to 1% by mass, more preferably 0.01% by mass to 0.3% by mass.

[8] sensitizer

The infrared light-shielding composition according to the present invention may contain a sensitizer for the purpose of increasing the radical generating efficiency of the triazine polymerization initiator and making the photosensitive wavelength longer. The sensitizer which can be used in the present invention is preferably a compound capable of sensitizing the above triazine polymerization initiator by an electron transfer mechanism or an energy transfer mechanism. The sensitizer which can be used in the present invention includes a compound belonging to the following compound group and having an absorption wavelength in a wavelength region of from 300 nm to 450 nm.

Preferred examples of sensitizers include those belonging to the following compound groups and at 330 Nai A compound having an absorption wavelength in a wavelength range from m to 450 nm.

For example, preferred compounds include polynuclear aromatic compounds (e.g., phenanthrene, anthracene, pyrene, Perylene, triphenylene or 9,10-dialkoxy).蒽), xanthene (such as fluorescein, eosin, erythrosine, Rhodamine B or rose Bengal) , thioxanthone-like compounds (2,4-diethylthioxanthone, isopropylthioxanthone, diethylthioxanthone or chlorothioxanthone), cyanine compounds (for example) Thiocarbocyanine or oxacarbocyanine, merocyanine compounds (eg, merocyanine or carbomerocyanine), phthalocyanine, Thiazine compounds (such as thionine, methylene blue or toluidine blue), acridine compounds (such as acridine orange, chloroflavin) (chloroflavin) or acriferlavin, anthraquinone compounds (eg 蒽醌), squarylium Compound (for example, aryl acid phthalocyanine), acridine orange, coumarin compound (for example, 7-diethylamino-4-methylcoumarin), ketocoumarin, phenothiazine a compound, a phenazine compound, a styrylbenzene compound, an azo compound, a diphenylmethane, a triphenylmethane, a distyrylbenzene compound, a carbazole compound, a porphyrin ( Porphyrin), spiro compound, quinacridone, indigo, styryl compound, n-pentanium compound, pyrromethene compound, pyrazolyl Pyrazolotriazole compound, benzothiazole compound, barbituric acid derivative, thiobarbituric acid derivative (thiobarbituric acid derivative), acetophenone, benzophenone, thioxanthone (for example, Kayacure DETX-S, manufactured by Nippon Kayaku Co., Ltd.), An aromatic ketone compound (for example, Michler's ketone) and a heterocyclic compound (for example, N-aryloxazolidinone).

Other examples include compounds as described in European Patent No. 568,993, U.S. Patent No. 4,508,811, U.S. Patent No. 5,227,227, JP-A-2001-125255, and JP-A-11-271969.

The infrared light-shielding composition according to the present invention may or may not contain a sensitizer, and in the case of containing a sensitizer, the content is preferably based on the total solid content of the infrared light-shielding composition according to the present invention. It is from 0.01% by mass to 10% by mass, more preferably from 0.1% by mass to 2% by mass.

[9] Crosslinker

In order to achieve the purpose of increasing the strength of the infrared light-shielding film, the infrared light-shielding composition according to the present invention may further contain a crosslinking agent.

As the crosslinking agent, a compound having a crosslinking group is preferred, and a compound having two or more crosslinking groups is more preferred. Specific examples of the crosslinking group are suitable to include an oxetane group, a cyanate group, and a group of the crosslinking group which these alkali-soluble binders may have. Among them, an epoxy group, an oxetane group, and a cyanate group are preferred. Specifically, the crosslinking agent is particularly preferably an epoxy compound, an oxetane compound or a cyanate compound.

Examples of the epoxy compound which can be suitably used as a crosslinking agent in the present invention include an epoxy compound containing at least two oxiane groups per molecule and at least two epoxy groups per molecule and An epoxy compound having an alkyl group at the β position.

Examples of the epoxy compound having at least two oxirane groups per molecule include a bixylenol-type epoxy compound or a biphenol-type epoxy compound (for example, from Japan) YX4000 manufactured by Japan Epoxy Resins Co., Ltd. or a mixture thereof, a heterocyclic epoxy compound having an isocyanurate skeleton or the like (for example, Nissan Chemical Industry Co., Ltd. (Nissan) TEPIC manufactured by Chemicals Industries, Ltd., ARALDITE PT810 manufactured by BASF Co., Ltd., bisphenol A epoxy compound, novolac-type epoxy compound, bisphenol F epoxy compound, hydrogenated Bisphenol A type epoxy compound, bisphenol S type epoxy compound, phenol novolac type epoxy compound, cresol novolac type epoxy compound, halogenated epoxy compound (for example, low brominated epoxy compound, highly halogenated epoxy) Compound or brominated phenol phenolic resin type epoxy compound), allyl-containing bisphenol A type epoxy compound, trisphenol methane type epoxy compound, diphenyl dimethanol type epoxy compound, phenol extended phenyl group Epoxy compound, dicyclopentadiene type epoxy compound (for example, HP-7200 and HP-7200H manufactured by Dainippon Ink and Chemicals, Inc.), glycidylamine-type (glycidylamine-type) An epoxy compound (for example, a diaminodiphenylmethane-type epoxy compound, a glycidylaniline or a triglycidylaminophenol), or a glycidylester-type (glycidylester- Type) epoxy compound (eg diglycidyl phthalate, diglycidyl adipate, diglycidyl hexahydrophthalate or dibasic fatty acid) Diglycidyl dimerate), hydantoin-type epoxy compound, alicyclic epoxy compound (eg 3,4-epoxycyclohexylmethyl-3', 4'-ring Oxycyclohexane Formate, bis(3,4-epoxycyclohexyl) adipate, dicyclopentadienyl diepoxide or GT-300, GT-400 manufactured by Daicel Corp. And ZEHPE 3150), quinone imine type alicyclic epoxy compound, trishydroxyphenylmethane type epoxy compound, bisphenol A phenolic resin type epoxy compound, tetraphenylolethane-type epoxy compound, adjacent Glycidyl phthalate compound, tetraglycidyl xylenoylethane compound, naphthyl-containing epoxy compound (for example, naphthol aralkyl-type epoxy) a compound, a naphthol phenol resin type epoxy compound or a tetrafunctional naphthalene type epoxy compound, and a commercially available product such as ESN-190 and ESN-360 manufactured by Nippon Steel Chemical Co., Ltd. or by HP-4032, EXA-4750 and EXA-4700 manufactured by Dainippon Ink Chemical Co., Ltd., a reaction product of epichlorohydrin and a polyphenol compound (in which a polyphenol compound is composed of a phenol compound and a diolefin compound (for example, divinylbenzene and two) Addition of cyclopentadiene) a product of a ring-opening polymerization product of 4-vinylcyclohexene-1-oxide epoxidized with peracetic acid or the like, an epoxy compound having a linear phosphorus-containing structure, Epoxy compound having a cyclic phosphorus-containing structure, α-methylstilbene-type liquid crystal epoxy compound, dibenzoyloxybenzene-type liquid crystal epoxy compound, azo group Phenyl liquid crystal epoxy compound, azomethine phenyl-type liquid crystal epoxy compound, binaphthyl liquid crystal epoxy compound, azine-type epoxy compound, glycidyl methacrylate Ester copolymer epoxy compounds (for example, CP-50S and CP-50M manufactured by NOF Corp.), copolymerized epoxy compounds of cyclohexylmaleimide and glycidyl methacrylate, Bis(glycidyloxyphenyl)fluorene-type epoxy compound and bis(glycidol) Oxyphenyl) adamantane type (bis(glycidyloxyphenyl)adamantane-type) epoxy compound. However, the present invention is not construed as being limited thereto, and the epoxy resins may be used singly or in combination of two or more.

In addition to the epoxy compound having at least two ethylene oxide groups per molecule, an epoxy compound having at least two epoxy groups per molecule and an alkyl group at the β-position can be used. Particularly preferred are compounds containing an epoxy group substituted at the β-position with an alkyl group (more specifically, a β-alkyl substituted glycidyl group or the like).

In the epoxy compound containing at least one epoxy group having an alkyl group at the β-position, each of two or more epoxy groups contained in each molecule may be a β-alkyl substituted glycidyl group or at least one ring. The oxy group may be a glycidyl group substituted with a β-alkyl group.

Examples of the oxetane compound include an oxetane resin having at least two oxetanyl groups per molecule.

Specific examples thereof include polyfunctional oxetane such as bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy) Methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxocyclo) Butylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methyl acrylate, (3-ethyl-3-oxetanyl)methyl acrylate, methacrylic acid (3 -methyl-3-oxetanyl)methyl ester, (3-ethyl-3-oxetanyl)methyl methacrylate or an oligomer or copolymer thereof; and having an oxetane An ether compound of a compound having a hydroxyl group, such as a phenol resin, a poly(p-hydroxystyrene), a cardo-type bisphenol, a calixarene, a resorcinol calixarene (calixresorcinarene) Or sesquioxane (silsesquioxane). Other examples include copolymers having an oxetane ring and an alkyl (meth) acrylate unsaturated monomer.

Examples of the bismaleimide compound include 4,4'-diphenylmethane bismale Yttrium, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane and 2,2'-bis[4-(4-maleimide phenoxy) Phenyl]propane.

Examples of the cyanate ester compound include a bis A-type cyanate compound, a double F-type cyanate compound, a cresol novolac type cyanate compound, and a phenol novolac type cyanate compound.

A melamine or melamine derivative can be used as the crosslinking agent.

Examples of the melamine derivative include methylol melamine and alkylated methylol melamine (a compound obtained by etherfiding a methylol group with a methyl group, an ethyl group, a butyl group or the like).

The crosslinking agent may be used singly or in combination of two or more. The crosslinking agent is preferably melamine or alkylated methylol melamine, more preferably hexamethylated methylol melamine, because of its good preservation stability and effective increase of the surface of the photosensitive layer. Hardness or film strength of the infrared light-shielding film (cured film) itself.

The infrared light-shielding composition according to the present invention may or may not contain a crosslinking agent, and in the case of containing a crosslinking agent, the content is preferably based on the total solid content of the infrared light-shielding composition according to the present invention. It is 1% by mass to 40% by mass, more preferably 3% by mass to 20% by mass.

[10] curing accelerator

In order to promote the heat curing of the crosslinking agent (for example, an epoxy compound and an oxetane compound), the infrared light-shielding composition according to the present invention may further contain a curing accelerator.

Examples of the curing accelerator which can be used include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzene Amine, 4-methoxy-N,N-dimethylbenzylamine or 4-methyl-N,N-dimethylbenzylamine), quaternary ammonium compound (eg triethylbenzene chloride) Alkyl ammonium), a blocked isocyanate compound (for example, dimethylamine), an imidazole derivative-dicyclic amidine compound or a salt thereof (for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl) 4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole or 1-(2-cyanoethyl)-2-ethyl-4 -methylimidazole), a phosphorus compound (such as triphenylphosphine), a guanamine compound (such as melamine, guanamine, acetamide or benzoguanamine), and an S-triazine derivative ( For example, 2,4-diamino-6-methacryloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4, 6-Diamino-S-triazine-isocyanuric acid addition product or 2,4-diamino-6-methylpropenyloxyethyl-S-triazine-isocyanuric acid addition product). The curing accelerator is preferably melamine or dicyandiamide.

The curing accelerators may be used singly or in combination of two or more.

The infrared light-shielding composition according to the present invention may or may not contain a curing accelerator, and in the case of containing a curing accelerator, preferably in a total solid content of the infrared light-shielding composition according to the present invention. It is from 0.01% by mass to 15% by mass.

[11] filler

The infrared light-shielding composition according to the present invention may further contain a filler. Fillers useful in the present invention include spherical silica which is surface-treated with a silane coupling agent.

An infrared light-shielding composition containing a filler according to the present invention, which is capable of obtaining an infrared light-shielding film having high durability (particularly, when a solder resist requires high durability (for example, a metal covered with a solder resist) Wire has high wire density The above effects are remarkable and preferred.

By using spherical cerium oxide surface-treated with a decane coupling agent, thermal cycle test resistance and storage stability of the infrared light-shielding composition can be increased, and for example, even subjected to harsh environments (for example, heat) The cycle test) still maintains the same contour as the contour immediately after the pattern is formed.

If the particles are not acicular, cylindrical or amorphous, but rounded, they satisfy the meaning of the "spherical" of the spherical filler, and the particle shape does not have to be certain. It is "true spherical", but the typical "spherical" shape is a "true spherical" shape.

Whether the filler is spherical or not can be determined by observation by a scanning electron microscope (SEM).

The volume average particle diameter of the primary particles of the filler is not particularly limited and may be appropriately selected depending on the purpose, and is preferably from 0.05 μm to 3 μm, and more preferably from 0.1 μm to 1 μm. When the volume average particle diameter of the primary particles of the filler is in the above range, the workability can be suppressed from being reduced due to the occurrence of thixotropy and the maximum particle diameter can be prevented from increasing; and when the volume average particle diameter of the primary particles of the filler is In the above range, it is advantageous to avoid the occurrence of defects due to adhesion of foreign substances to the formed infrared light-shielding film (cured film) or coating unevenness.

The volume average particle diameter of the primary particles of the filler can be measured by a dynamic light scattering particle size distribution measuring device.

The filler can be dispersed by using the above dispersant and a binder. As described above, from the viewpoint of curability, an alkali-soluble binder polymer having a crosslinking group in a side chain is particularly preferable.

- Surface treatment -

The surface treatment of the filler is as follows. The surface treatment of the filler is not particularly limited and may be appropriately selected depending on the purpose, and is preferably a treatment of covering the cerium oxide with a decane coupling agent.

-decane coupling agent -

The decane coupling agent used for the surface treatment of the filler is not particularly limited and may be appropriately selected depending on the purpose, and preferably has at least one selected from the group consisting of an alkoxyalkyl group, a chloroalkyl group, and an ethoxyalkyl group. a functional group (hereinafter, sometimes referred to as a "first functional group") and at least one functional group selected from a (meth) acryloyl group, an amine group, and an epoxy group (hereinafter, sometimes referred to as " Second functional group"). The second functional group is more preferably a (meth)acryl fluorenyl group or an amine group, and still more preferably a (meth) acrylonitrile group. From the standpoint of storage stability and resistance to thermal cycle test, it is advantageous when the second functional group is a (meth) acrylonitrile group.

It is also preferred to use a decane coupling agent described in JP-B-7-68256, wherein the decane coupling agent contains at least one group selected from the group consisting of an alkoxyalkyl group, a chloroalkyl group, and an ethoxyalkyl group. As the first functional group and a group containing at least one selected from the group consisting of imidazolyl, alkylimidazolyl and vinylimidazolyl, as the second functional group.

The decane coupling agent is not particularly limited, and suitable examples thereof include γ-aminopropyltriethoxydecane, N-(β-aminoethyl)-γ-aminopropyltrimethoxydecane, N- (β-Aminoethyl)-γ-aminopropylmethyldimethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropylmethyldimethoxy Decane, γ-methacryloxypropyltrimethoxydecane, γ-methylpropenyloxypropylmethyldimethoxydecane, and α-[[] described in JP-B-7-68256 3-(Trimethoxydecyl)propoxy]methyl]-imidazol-1-ethanol, 2-ethyl-4-methyl-α-[[3-(trimethoxydecyl)propyloxy] Methyl]-imidazol-1-ethanol, 4-vinyl-α-[[3-(trimethoxydecyl)propoxy]methyl]-imidazole-1-ethanol, 2-ethyl-4-methyl Imidazolylpropyltrimethoxydecane and salts thereof, intramolecular condensates and intermolecular condensates; and commercially available product KBM-503 (manufactured by Shin-Etsu Silicone Co., Ltd.) ). The decane coupling agent may be used singly or in combination of two or more.

The surface treatment of spherical cerium oxide with a decane coupling agent may be carried out only for spherical cerium oxide (in this case, hereinafter sometimes referred to as "pretreatment"), or may be used for the infrared light opaque composition. Some or all of the other fillers are included together.

The method of performing the pretreatment is not particularly limited, and examples thereof include a dry method, an aqueous solution method, an organic solvent method, and a spraying method. The temperature at which the pretreatment is carried out is not particularly limited, and is preferably from room temperature to 200 °C.

It is also preferred to add a catalyst at the time of pretreatment. The catalyst is not particularly limited, and examples thereof include an acid, a base, a metal compound, and an organometallic compound.

The amount of the decane coupling agent to be added at the time of pretreatment is not particularly limited, and is preferably from 0.01 part by mass to 50 parts by mass, more preferably from 0.05 part by mass to 50 parts by mass per 100 parts by mass of the spherical cerium oxide. When the amount is in the above range, it is possible to carry out a surface treatment sufficient for the production of the effect, and to suppress a decrease in handling property due to aggregation of the spherical ceria after the treatment.

The decane coupling agent reacts with the active groups in the surface of the substrate, on the surface of the spherical ceria or in the binder, and the second functional group further reacts with the carboxyl group and the ethylenically unsaturated group in the binder. The decane coupling agent has an effect of increasing the adhesion between the substrate and the photosensitive layer. On the other hand, the decane coupling agent has a high Reactivity, therefore, if the decane coupling agent itself is added to the infrared light-shielding composition, in some cases, the second functional group is sometimes mostly reacted or deactivated due to its diffusion during storage, resulting in The shelf life or pot life is shortened.

However, when the above-mentioned spherical cerium oxide pretreated with a decane coupling agent is used, since the diffusion effect is suppressed, the problem of the shelf life or pot life is greatly improved, and it is possible to produce a one-component type composition. Further, in the case where the pretreatment of the spherical ceria is carried out as compared with the addition of the spherical ceria which is not subjected to the pretreatment, since the conditions can be freely selected (for example, stirring conditions, temperature conditions, and use of the catalyst), the cepene couple The reaction ratio between the first functional group of the mixture and the active group in the spherical ceria can be significantly increased. Therefore, excellent results are obtained which are required under severe conditions such as electroless gold plating, electroless solder plating, and humidity resistance load test. . Further, by performing the pretreatment, the amount of the decane coupling agent used can be reduced, and the storage period and the pot life can be further improved.

Examples of the spherical cerium oxide which can be used for the surface treatment of the decane coupling agent in the present invention include the FB series of Denki Kagaku Kogyo Kabushiki Kaisha and the SFP series, Tatsumori Ltd. 1-FX, HSP series of Toagosei Co., Ltd.; and SP series of Fuso Chemical Co., Ltd.

The infrared light-shielding composition according to the present invention may or may not contain a filler, and in the case of containing a filler, although the content of the filler is not particularly limited and may be appropriately selected according to the purpose, it is composed of infrared light-shielding property. Total solids of matter The content is preferably from 1% by mass to 60% by mass. When the amount is in the above range, the linear expansion coefficient is sufficiently lowered, and the formed infrared light-shielding film (cured film) is prevented from being embrittled. Therefore, an infrared light-shielding film is used in forming a wire, and the effect can be fully exerted. The function of the protective film of the wire.

[12] Elastomer

The infrared light-shielding composition according to the present invention may further contain an elastomer.

By incorporating the elastomer, when the infrared light-shielding composition is used as a solder resist, the adhesion to the conductive layer of the printed wiring board can be further increased, and the heat resistance of the infrared light-shielding film (cured film) can be further increased. Properties, heat shock resistance, flexibility, and toughness.

The elastomer which can be used in the present invention is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a styrene elastomer, an olefin elastomer, a urethane elastomer, a polyester elastomer, a polyamine elastomer, an acrylic elastomer, and a silicone-based. ) Elastomers. The elastomer consists of a hard segment component and a soft segment component, wherein in general the former provides heat resistance and strength and the latter provides flexibility and toughness. Among the elastomers, polyester elastomers are advantageous in view of compatibility with other materials.

Examples of the styrene elastomer include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, and a styrene-ethylene-butylene-styrene. Block copolymers and styrene-ethylene-propylene-styrene block copolymers. As a component constituting the styrene elastomer, in addition to styrene, a styrene derivative such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene or 4-cyclohexyl may also be used. Styrene. Specific examples include Tuffrene (TUFPRENE), SOLPRENE T, ASAPRENE T, and Tatek (TUFTEC) (manufactured by Asahi Chemical Industry Co., Ltd.), elastomer AR (manufactured by Aronkasei Co., Ltd.), KRATON G And CALIFLEX (manufactured by Shell Chemicals Japan Ltd.), JSR-TR, TSR-SIS, and Dynaron (by Japan Synthetic Rubber Co., Ltd. (JSR) , manufactured by Japan Synthetic Rubber Co., Ltd.), Denka STR (manufactured by Nippon Denshoku Chemical Co., Ltd.), QUINTAC (manufactured by ZEON Corporation), TPE -SB series (manufactured by Sumitomo Chemical Co., Ltd.), RABALON (manufactured by Mitsubishi Chemical Corporation), SEPTON and HYBRAR (by Kuraray Co., Ltd.) Co., Ltd.), SUMIFLEX (made by Sumitomo Bakelite Co., Ltd.), LEOSTOMER and ACTYMER ) (manufactured by Riken Vinyl Industry Co., Ltd.).

The olefin-based elastomer is a copolymer of an α-olefin having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene or 4-methyl-pentene, and examples thereof include ethylene- Propylene copolymer (ERR) and ethylene-propylene-diene copolymer (EPDM). Other examples of the olefin elastomer include an α-olefin and a non-conjugated diene having 2 to 20 carbon atoms (e.g., dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene origin). Copolymer of methylenenorbornene, ethylidenenorbornene, butadiene or isoprene, and epoxidized polybutadiene. The olefin elastomer further includes, for example, a carboxyl group-modified MBR obtained by copolymerization of methacrylic acid and a butadiene-acrylonitrile copolymer. Further, the olefin elastomer includes, for example, an ethylene-α-olefin copolymer rubber, an ethylene-α-olefin-non-conjugated diene. Copolymer rubber, propylene-α-olefin copolymer rubber, and butene-α-olefin copolymer rubber.

Specific examples of the olefin elastomer include Japan's Mitsui Thermoplastics (MILASTOMER) (manufactured by Mitsui Petrochemical Industries, Ltd.) and Igcot (EXACT) (by Exxon Chemical Company (Exxon) Chemical Corp.), ENGAGE (manufactured by Dow Chemical Co.), hydrogenated styrene-butadiene rubber (DYNABON HSBR, manufactured by Japan Synthetic Rubber Co., Ltd.) Co., Ltd., butadiene-acrylonitrile copolymer (NBR series, manufactured by Nippon Synthetic Rubber Co., Ltd.), butadiene-acrylonitrile copolymerized at both ends via a carboxyl group containing a crosslinking site (XER series, manufactured by Nippon Synthetic Rubber Co., Ltd.) and polybutadiene partially epoxidized epoxidized polybutadiene (BF-1000, manufactured by Nippon Soda Co., Ltd.) ).

The urethane elastomer includes a hard segment composed of a low molecular (short chain) diol and a diisocyanate, and a soft segment composed of a polymer (long chain) diol and a diisocyanate. Examples of the polymer (long-chain) diol include polypropylene glycol, polytetramethylene oxide, poly(adipate-1,4-butylene), poly(adipate (extended ethyl-1) , 4-butylene) ester, polycaprolactone, poly(-1,6-extended hexyl carbonate), and poly(adipate-1,6-exexyl-extension). The number average molecular weight of the polymer (long-chain) diol is preferably from 500 to 10,000. Examples of low molecular (short chain) diols include ethylene glycol, propylene glycol, 1,4-butanediol, and bisphenol A. The number average molecular weight of the short-chain diol is preferably from 48 to 500. Specific examples of the urethane elastomer include PANDEX T-2185 and Pandenx T-2983N (manufactured by Dainippon Ink and Chemicals, Inc.) and MIRACTRAN E790.

The polyester elastomer is obtained by polycondensing a dicarboxylic acid or a derivative thereof with a diol compound or a derivative thereof. Specific examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid or naphthalenedicarboxylic acid, by methyl group, ethyl group, An aromatic dicarboxylic acid formed by substituting a hydrogen atom of an aromatic ring of the above dicarboxylic acid with a phenyl group or the like; an aliphatic dicarboxylic acid having 2 to 20 carbon atoms, such as adipic acid, Sebacic acid or dodecanedicarboxylic acid; and an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid. The dicarboxylic acids may be used singly or in combination of two or more. Specific examples of the diol compound include aliphatic diols or alicyclic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-fluorene. Glycol or 1,4-cyclohexanediol, bisphenol A, bis-(4-hydroxyphenyl)-methane, bis-(4-hydroxy-3-methylphenyl)-propane, and resorcinol ( Resorcin). The diol compounds may be used singly or in combination of two or more. Further, it is possible to use a portion having an aromatic polyester (for example, polybutylene terephthalate) for the hard segment component and a portion for the aliphatic polyester (for example, tetramethylene glycol). Multi-block copolymer for soft segment components. There are various grades of polyester elastomers depending on the type, ratio, and molecular weight difference of the hard section and the soft section or the like. Specific examples of the polyester elastomer include Hytrel (manufactured by Du Pont-Toray Co., Ltd.) and PELPRENE (limited by Toyobo Co., Ltd.) Company (manufactured by Toyobo Co., Ltd.) and ESPEL (manufactured by Hitachi Chemical Co., Ltd.).

Polyamine elastomers include a hard segment composed of polyamine and a polyether Or a soft segment composed of polyester, and the polyamine elastomer is roughly classified into two types: a polyether block guanamine type and a polyether ester block guanamine type. Examples of polyamines include polyamide 6, polyamine 11, and polyamine 12. Examples of the polyether include polyethylene oxide, polypropylene oxide, and polytetramethylene glycol. Specific examples of the polyamine-based elastomer include UBE polyamine elastomer (manufactured by Ube Industries, Ltd.) and DAIAMID (by Daicel-Herss) Ltd. (made by Daicel-Huels Ltd.), PEBAX (made by Toray Industries, Inc.), GRILON ELY (Emans Chemical Trading) (Japan) Co., Ltd. (EMS-CHEMIE (Japan) Ltd.)), NOVAMID (manufactured by Mitsubishi Chemical Corp.), and GRILAX (GRILAX) Made by Dainippon Ink Chemical Industry Co., Ltd.).

The acrylic elastomer is made of an acrylate (such as ethyl acrylate, butyl acrylate, methoxyethyl acrylate or ethoxyethyl acrylate) and an epoxy group-containing monomer (such as glycidyl methacrylate or Obtained by copolymerization of an alkyl glycidyl ether) and/or a vinyl monomer (for example, acrylonitrile or ethylene). Examples of the acrylic elastomer include acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, and acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer.

The anthrone-based elastomer mainly consists of an organic fluorenone, and can be classified into a polydimethyl siloxane type, a polymethylphenyl siloxane type, and a polydiphenyl siloxane type. It is also possible to use an organic fluorenone which has been modified with a vinyl group, an alkoxy group or the like. Specific examples of the anthrone-based elastomer include the KE series (manufactured by Shin-Etsu Chemical Co., Ltd.), the SE series, the CY series, and the SH series (by Dow Corning Toray Silicone Co., Ltd.). ))).

In addition to the above elastomers, a rubber-modified epoxy resin can be used. The rubber-modified epoxy resin can be modified by two carboxyl-modified butadiene-acrylonitrile rubbers, an amine-modified anthrone rubber or the like, for example, the above-mentioned bisphenol F type. Epoxy resin, bisphenol A type epoxy resin, salicylaldehyde type epoxy resin, phenol novolac-type epoxy resin or cresol novolac type epoxy resin (cresol novolac-type) Some or all of the epoxy groups of the epoxy resin are obtained.

In the elastomer, from the viewpoints of shear adhesion and thermal shock resistance, a butadiene-acrylonitrile copolymer having two terminal carboxyl groups modified, and a polyester elastomer having a hydroxyl group (Esperian) are preferred. ESPEL 1612 and Esper 1620, manufactured by Hitachi Chemical Co., Ltd., and epoxidized polybutadiene.

The infrared light-shielding composition according to the present invention may or may not contain an elastomer, and in the case of containing an elastomer, although the content of the elastomer is not particularly limited and may be appropriately selected according to the purpose, it is composed of infrared light-shielding property. The content of the elastomer is preferably from 0.5% by mass to 30% by mass, more preferably from 1% by mass to 10% by mass, particularly preferably from 3% by mass to 8% by mass, based on the total solid content of the substance. When the content is in the above preferred range, it is advantageous in that shear adhesion and thermal shock resistance can be further improved.

[13] surfactants

From the viewpoint of further improving the coatability, various surfactants can be added to the infrared light-shielding composition according to the present invention. A variety of surfactants can be used as the surfactant, such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, or an anthrone-based surfactant.

In particular, by incorporating a fluorine-based surfactant into the infrared according to the present invention The light-shielding composition can further improve the liquid property (especially fluidity) of the coating solution prepared by the infrared light-shielding composition, so as to further improve the uniformity of the coating thickness and the liquid retention efficiency. (liquid saving property).

Specifically, when a coating solution is prepared from an infrared light-shielding composition containing a fluorine-based surfactant and a layer is formed using the coating solution, the interfacial tension between the coated surface and the coating solution Lowering, thereby increasing the wettability of the coated surface and improving the coatability on the coated surface. Therefore, even if only a small amount of solution is used to form a thin layer of about several micrometers, this is effective because a layer having a uniform thickness (small thickness unevenness) can be suitably formed.

The fluorine content of the fluorine-based surfactant is preferably from 3% by mass to 40% by mass, more preferably from 5% by mass to 30% by mass, and particularly preferably from 7% by mass to 25% by mass. A fluorine-based surfactant having a fluorine content in the above range is useful in view of uniformity of coating thickness or liquid retention, and also exhibits good solubility in an infrared light-shielding composition.

Examples of fluorine-based surfactants include MEGAFAC F171, Majia Fike F172, Majia Fike F173, Majia Fike F176, Ma Jiafeike F177, Majia Fike F141, Ma Jiafeike F142, Ma Jiafeike F143, Majia Fike F144, Majia Fick R30 , Ma Jia Fike F437, Ma Jia Fike F475, Ma Jia Fike F479, Ma Jia Fike F482, Ma Jia Fike F554, Ma Jia Fike F780 and Ma Jia Fike F781 (manufactured by DIC Corp.), Fluoride ( FLUORAD) FC430, Fluoride FC431 and Fluoride FC171 (manufactured by Sumitomo 3M Ltd.), and SURFLON S-382, Safluron SC-101, Sa Fluoro SC-103, Safluron SC-104, Safluron SC-105, Safluron SC-1068, Saflu Dragon SC-381, Safron SC-383, Safluron S-393, and Safron KH-40 (manufactured by Asahi Glass Co., Ltd.).

Specific examples of the nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene. Polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate (polyethylene) Glycol distearate) and sorbitan fatty acid esters (for example, PLURONIC L10, L31, L61, L62, 10R5, 17R2 and 25R2, and TETRONIC 304, 701, 704, 901, 904, and 150R1 (manufactured by BASF) and SOLSPERSE 20000 (manufactured by Zeneca).

Specific examples of the cationic surfactant include phthalocyanine derivatives (EFKA-745, manufactured by Morishita Sangyo KK), and organic siloxane polymers KP341 (by Shin-Etsu Chemical Co., Ltd.) (manufactured by the company), (meth)acrylic acid (co)polymer (POLYFLOW No. 75, Baoke No. 90 and Baoke No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (by Yushang) Made by Ltd.).

Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yushang Co., Ltd.).

Examples of anthrone-based surfactants include TORAY SILICONE DC3PA, Torayone SH7PA, Torayone DC11PA, Toray Ketone SH21PA, Torayone SH28PA, Torayone SH29PA, Torayone SH30PA, and Torayone SH8400 (manufactured by Dow Corning Toray Silicone Co., Ltd.); TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (manufactured by Momentive Performance Materials Inc.); KP341, KF6001, and KF6002 (manufactured by Shin-Etsu Chemical Co., Ltd.) ); and BYK307, BYK-323 and BYK-330 (manufactured by BYK Chemicals, Germany).

The surfactants may be used singly or in combination of two or more.

The infrared light-shielding composition according to the present invention may or may not contain a surfactant, and in the case of containing a surfactant, the content is preferably based on the total solid content of the infrared light-shielding composition according to the present invention. It is 0.001% by mass to 1% by mass, more preferably 0.01% by mass to 0.1% by mass.

[14] Other components

In addition to the above-described essential components and the above preferred additives, other components may be appropriately selected and used in the infrared light-shielding composition according to the present invention, as long as the present invention is not impaired.

Examples of other components that can be used include a heat curing accelerator, a thermal polymerization inhibitor, a plasticizer, and a coloring agent (coloring pigment or dye). Further, an adhesion promoter to the surface of the substrate and other auxiliary agents (for example, conductive particles, a filler, a defoaming agent, a flame retardant, a leveling agent) may be used in combination. Leveling agent, release accelerator, antioxidant, perfume, surface tension-controlling agent or chain transfer Agent)).

The properties of the target solder resist (e.g., film stability, photographic properties, or physical properties) can be adjusted by appropriately incorporating this component into the infrared light-blocking composition.

The thermal polymerization inhibitor is described in detail in, for example, paragraphs [0101] and [0102] of JP-A-2008-250074.

Plasticizers are described in detail in, for example, paragraphs [0103] and [0104] of JP-A-2008-250074.

Colorants are described in detail in, for example, paragraphs [0105] and [0106] of JP-A-2008-250074, and paragraphs [0038] and [0039] of JP-A-2009-205029.

The adhesion promoter is described in detail in, for example, paragraphs [0107] to [0109] of JP-A-2008-250074.

Any of the additives described in these patent documents can be used in the infrared light-blocking composition according to the present invention.

The solid content concentration of the infrared light-shielding composition according to the present invention is preferably from 5% by mass to 90% by mass, more preferably from 20% by mass to 80% by mass, and most preferably from 40% by mass to 60% by mass. quality%.

The use of the infrared light-shielding composition according to the present invention is not particularly limited, and examples thereof include a solder resist, an infrared light-shielding film for a rear surface of a substrate of a solid-state image element (infrared light blocking property in a solid-state image element) Solder resist), and an infrared light-shielding film for wafer level lenses. The infrared light-shielding composition according to the present invention is preferably used as a solder resist or an infrared light-shielding solder resist in an infrared light-shielding film solid-state image element for a rear surface of a substrate in a solid-state image sensor.

In the case where the infrared light-shielding composition according to the present invention is used as a solder resist or an infrared light-shielding film (infrared light-shielding solder resist in a solid-state image element) on the rear surface of the substrate of the solid-state image sensor, The coating film having a relatively large thickness preferably has a solid content concentration of from 30% by mass to 80% by mass, more preferably from 35% by mass to 70% by mass, and most preferably from 40% by mass to 60% by mass.

Further, the viscosity of the infrared light-shielding composition according to the present invention is preferably in the range of 1 mPa. Seconds to 3,000 mPa. Seconds, a better range is 10 millipascals. Seconds to 2,000 mPa. Seconds, and the best range is 100 mPa. Seconds to 1,500 mPa. second.

In the case where the infrared light-shielding composition according to the present invention is used as a solder resist or an infrared light-shielding film (infrared light-shielding solder resist in a solid-state image element) on the rear surface of the substrate of the solid-state image sensor, it is thick From the viewpoint of film formability and uniform coatability, the viscosity is preferably in the range of 10 mPa. Seconds to 3,000 mPa. Seconds, a better range is 500 mPa. Seconds to 1,500 mPa. Seconds, the best range is 700 mPa. Seconds to 1,400 mPa. second.

The invention also relates to a photosensitive layer formed from the infrared light-blocking composition according to the present invention. Since the photosensitive layer is formed of the infrared light-shielding composition according to the present invention, the photosensitive layer has high light-shielding property in the infrared light region and high light transmittance in the visible light region, and can form crack suppression and An infrared light-shielding film exhibiting high adhesion and high exposure sensitivity to a substrate. Further, by incorporating an alkali-soluble binder into the infrared light-shielding composition according to the present invention, a pattern having a desired contour having a high squareness can be formed by exposure and alkali development.

Further, the present invention relates to an infrared light-shielding film formed of the infrared light-shielding composition according to the present invention, wherein the infrared light-shielding film is a cured film. The infrared light-shielding film according to the present invention is a cured film, wherein the cured film has an infrared light region High light-shielding property and high light transmittance in the visible light region; occurrence of cracks in the cured film can be suppressed; and the cured film exhibits high adhesion to a substrate and high exposure sensitivity. Further, by incorporating an alkali-soluble binder into the infrared light-shielding composition according to the present invention to form a photosensitive layer, and subjecting the photosensitive layer to exposure and alkali development, a desired profile including high rectangularity can be formed. A pattern of infrared light shielding film.

Furthermore, the present invention also relates to a pattern forming method comprising the steps of forming a photosensitive layer using the infrared light-shielding composition according to the present invention, patterning exposure of the photosensitive layer to cure the exposed region, and borrowing The step of removing the unexposed regions by alkali development to form a pattern.

The pattern forming method will be described in detail below, for example, using the infrared light-shielding composition of the present invention to form a patterned solder resist. However, the description about the kind and amount of the solvent used to prepare the coating solution, the coating method of the coating solution, the thickness of the photosensitive layer, and the exposure step and other steps are not limited to the solder resist. Now, a case where a photosensitive layer (polymerizable composition layer) is formed using an infrared light-shielding composition will be described as an example.

-Photosensitive layer -

To form a patterned solder resist (solder resist pattern), the photosensitive layer is first formed using the infrared light blocking composition according to the present invention. The photosensitive layer is not particularly limited as long as it is a layer formed of an infrared light-shielding composition. The layer thickness, the stacked structure, and the like can be appropriately selected depending on the purpose.

The method of forming the photosensitive layer includes a method of dissolving, emulsifying or dispersing the infrared light-shielding composition according to the present invention in water or a solvent to prepare a coating solution, directly coating the coating solution, and drying the coating.

For the preparation of a coating comprising an infrared light-blocking composition according to the invention The solvent of the solution is not particularly limited, and a solvent capable of uniformly dissolving or dispersing the respective components of the infrared light-shielding composition according to the present invention can be appropriately selected depending on the purpose. Examples thereof include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol or n-hexanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane Ketone, diisobutyl ketone, cyclohexanone or cyclopentanone; esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, benzene Ethyl formate, propylene glycol monomethyl ether acetate (PGMEA) (also known as 1-methoxy-2-ethoxypropane propane) or methoxypropyl acetate; aromatic hydrocarbon , for example, toluene, xylene, benzene or ethylbenzene; halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, dichloromethane or monochlorobenzene; ethers such as tetrahydrofuran , diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol or propylene glycol monomethyl ether (PGME, also known as 1-methoxy-2-propanol); Methylformamide, dimethylacetamide, dimethyl hydrazine, and sulfolane. The solvent may be used singly or in combination of two or more. Further, a conventional surfactant can be added.

From the viewpoint of uniformly dissolving or dispersing the respective components of the infrared light-shielding composition according to the present invention, propylene glycol monomethyl ether acetate (PGMEA) is preferred.

The method of applying the coating solution onto the support is not particularly limited, and may be appropriately selected depending on the purpose, and examples thereof include using a spin coater, a slit spin coater, and a slit spin coater. A method of coating a coating solution by a roll coater, a die coater or a curtain coater.

The drying conditions of the coating may vary depending on the relative components, the type of solvent, the amount used, and the like, and are usually at a temperature of from about 60 ° C to about 150 ° C and about 30. Drying is carried out in seconds to about 15 minutes.

The thickness of the photosensitive layer is not particularly limited and may be appropriately selected depending on the purpose, and is, for example, preferably from 1 μm to 100 μm, more preferably from 2 μm to 50 μm, and particularly preferably from 4 μm to 30 μm.

(Solder resist pattern forming method)

The method of forming the solder resist pattern using the infrared light-shielding composition according to the present invention includes at least an exposure step, and usually further includes a development step and other steps as appropriate, under appropriate selection conditions. The term "exposure" as used in the present invention includes not only exposure to light having various wavelengths but also radiation irradiation such as electron beam or X-ray.

<Exposure step>

The exposing step is a step of exposing the photosensitive layer formed of the infrared light-shielding composition through the mask, and in the step, only the region irradiated with light is cured.

The exposure is preferably carried out by using radiation irradiation, and the radiation usable for exposure is preferably an electron beam, KrF, ArF, ultraviolet light (for example, g-line, h-line or i-line) or visible light. In particular, it is preferably KrF, g-line, h-line or i-line.

Examples of exposure systems include stepper exposure and exposure to high pressure mercury lamps.

The exposure amount is preferably from 5 mJ/cm 2 to 3,000 mJ/cm 2 , more preferably from 10 mJ/cm 2 to 2,000 mJ/cm 2 , and most preferably 50 mJ/cm 2 . Up to 1,000 mJ/cm 2 .

<Development step>

Next, after the exposure step, an alkali development treatment (development step) is performed to dissolve the region not irradiated with light in the exposure step, thereby leaving only the photocured region, and the shape It is a patterned solder resist with infrared light blocking properties.

The developer is preferably an organic alkaline developer which does not damage an underlying circuit or the like. The development temperature is usually from 20 ° C to 40 ° C, and the development time is from 10 seconds to 180 seconds.

As the base used in the developer, for example, an organic base compound (for example, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline) can be used by using pure water. (choline), pyrrole (pyrrole), piperidine (piperidine) and 1,8-diazabicyclo-[5,4,0]-7-undecene) are diluted to a general range of 0.001% by mass to 10% by mass. An aqueous alkali solution which is preferably obtained at a concentration of from 0.01% by mass to 1% by mass. When a developer composed of this aqueous alkali solution is used, it is usually washed (rinsed) with pure water after development.

<other steps>

The other steps are not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a surface treatment step of a substrate, a curing treatment step, and a post-exposure step.

<Curing process step>

The curing treatment step is a step of applying a curing treatment to the photosensitive layer having the formed pattern after the development step, if necessary. By performing the treatment, the mechanical strength of the infrared light-shielding film which is a cured film is enhanced.

The curing treatment step is not particularly limited and may be appropriately selected depending on the purpose, and suitable examples thereof include an integral surface exposure treatment and an integral surface heat treatment.

Examples of the method for the integral surface exposure treatment include a method of exposing the entire surface of the stack having the patterned photosensitive layer formation after the development step. The solidification of the polymerization component in the infrared light-shielding composition of the photosensitive layer is promoted by integral surface exposure, and the infrared light-shielding film (which is a cured film) is further cured, thereby improving mechanical strength and durability.

The apparatus for performing the overall surface exposure is not particularly limited, and may be appropriately selected depending on the purpose, and preferred examples thereof include a UV exposing machine such as an ultrahigh pressure mercury lamp.

Further, the method for integral surface heat treatment includes a method of heating the entire surface of the stack having the patterned photosensitive layer after the developing step. The film strength of the infrared light-shielding film, which is a cured film, is increased by integral surface heating.

The heating temperature in the overall surface heating is preferably from 120 ° C to 250 ° C, and more preferably from 140 ° C to 250 ° C. When the heating temperature is 120 ° C or more, the film strength can be increased by heat treatment, and when the heating temperature is 250 ° C or less, the decomposition of the resin in the infrared light-shielding composition can be prevented, and the film quality is deteriorated and becomes brittle. .

The heating time in the overall surface heating is preferably from 3 minutes to 180 minutes, and more preferably from 5 minutes to 120 minutes.

The apparatus for performing the overall surface heating is not particularly limited, and may be appropriately selected from conventional apparatuses according to the purpose, and examples thereof include a drying oven, a heating plate, and an infrared light heater.

The patterned photoresist thus formed has excellent infrared light blocking properties, and thus has a wide range of applications. Since the infrared light-shielding composition according to the present invention is excellent in light-shielding property in the infrared region and light-transmitting property in the ultraviolet light region to the visible light region, a pattern having an excellent profile is formed, and the patterned infrared light-shielding film is formed. It has excellent infrared light blocking properties, making it suitable for forming solder resists for photodiode elements (especially solid-state imaging elements) having sensitivity to the infrared region.

In view of the above, the infrared light-shielding composition according to the present invention is not only suitable for forming a solder resist, but also for forming an infrared light-shielding film for a rear surface of a germanium substrate in a solid-state image element or infrared light for a wafer level lens. Light-shielding film.

Accordingly, the present invention is also directed to a solid-state image sensor having an infrared light-shielding composition formed from the infrared light-shielding composition according to the present invention.

The solid-state image element according to an embodiment of the present invention is described below with reference to FIGS. 1 and 2, but the present invention is not construed as being limited thereto.

The same reference numeral or sign refers to the same portion between FIG. 1 and FIG. 2.

Moreover, in the specification, the terms "top", "above" and "upper side" refer to one side away from the substrate 10, and the phrase "bottom". "Below" and "lower side" refer to one side of the substrate 10 next to the substrate.

1 is a schematic cross-sectional view showing the structure of a camera module equipped with a solid-state image element according to a specific example of one of the above embodiments.

The camera module 200 shown in FIG. 1 is connected to a circuit board 70 as a mounting substrate through a solder ball 60 as a connecting member.

More specifically, the camera module 200 includes a solid-state image element substrate 100 having an image forming element unit on a first main surface of the substrate, and a glass substrate 30 disposed on an upper side of the first main surface of the solid-state image element substrate 100 ( a light-transmissive substrate; an infrared light-cut filter 42 disposed above the glass substrate 30; a lens having an image lens 40 disposed above the glass substrate 30 and the infrared light-cut filter 42 A lens holder 50; and a light shielding and electromagnetic shielding 44 that surrounds the periphery of the solid-state image element substrate 100 and the glass substrate 30. Each member is adhered using the adhesives 20, 41, 43, and 45.

In the camera module 200, the incident light hν sequentially passes through the image lens 40, the infrared cut filter 42 and the glass substrate 30 from the outside, and reaches the image element unit of the solid-state image element substrate 100.

Further, the camera module 200 is connected to the circuit board 70 through the solder balls 60 (connection materials) on the second main surface side of the solid-state image element substrate 100.

FIG. 2 is an enlarged cross-sectional view of the solid-state image element substrate 100 of FIG. 1.

The solid-state image element substrate 100 includes a substrate 10 as a substrate, an image element 12, an interlayer insulating film 13, a base layer 14, a red filter 15R, a green filter 15G, and a blue filter. The light sheet 15B, the overcoat layer 16, the microlens 17, the light shielding film 18, the insulating film 22, the metal electrode 23, the solder resist layer 24, the internal electrode 26, and the element surface electrode 27.

The solder resist layer 24 can be omitted.

First, the structure on the first main surface side of the solid-state image element substrate 100 will be mainly described below.

As shown in FIG. 2, an image element unit (which is a plurality of image elements 12 arranged in two dimensions (for example, CCD and CMOS) is provided on the first main surface side of the germanium substrate 10 (which is the substrate of the solid-state image element substrate 100). )).

An interlayer insulating film 13 is formed on the image element 12 in the image element unit, and a base layer 14 is formed on the interlayer insulating film 13. Further, a red color filter 15R, a green color filter 15G, and a blue color filter 15B corresponding to the respective image elements 12 are provided on the base layer 14 (hereinafter, these (filters) are collectively referred to as "color filter" sheet 15").

A light shielding film (not shown) may be provided in the boundary between the red color filter 15R, the green color filter 15G, and the blue color filter 15B and around the image element unit. This light shielding film can be manufactured, for example, using a conventional black photoresist.

An overcoat layer 16 is formed on the color filter 15, and a microlens 17 corresponding to the image element 12 (color filter 15) is formed on the overcoat layer 16.

A peripheral circuit (not shown) and an internal electrode 26 are provided on the periphery of the image element on the first main surface side, and the internal electrode 26 is electrically connected to the image element 12 through a peripheral circuit.

Further, the element surface electrode 27 is formed on the internal electrode 26 through the interlayer insulating film 13. In the interlayer insulating film 13 between the internal electrode 26 and the element surface electrode 27, a contact plug (not shown) for electrically connecting these electrodes is formed. The element surface electrode 27 is for applying a voltage or reading a signal passing through the contact plug and the internal electrode 26.

A base layer 14 is formed on the element surface electrode 27, and an overcoat layer 16 is formed on the base layer 14. The base layer 14 and the overcoat layer 16 formed on the element surface electrode 27 are opened to form a pad opening and expose a portion of the element surface electrode 27.

This is the structure of the first main side on the solid-state image element substrate 100.

On the first main side of the solid-state image element substrate 100, an adhesive 20 is provided on the periphery of the image element portion, and the solid-state image element substrate 100 and the glass substrate 30 are adhered through the adhesive 20.

The germanium substrate 10 has a through hole penetrating through the germanium substrate 10, and a through electrode serving as a part of the metal electrode 23 is provided in the through hole (penetrating Electrode). The image element unit and the circuit board 70 are electrically connected by a penetrating electrode.

Next, the structure of the second main surface side of the solid-state image element substrate 100 will be mainly described below.

On the second main surface side, an insulating film 22 is formed from the second main surface to the inner wall of the through hole.

A metal electrode 23 patterned to extend from a region on the second major surface of the substrate 10 into the via hole is provided on the insulating film 22. The metal electrode 23 is an electrode for connecting the image element unit and the circuit board 70 in the solid-state image element substrate 100.

A portion of the metal electrode 23 formed inside the through hole is a penetrating electrode. The penetration electrode passes through the ruthenium substrate 10 and a part of the interlayer insulating film 13, and reaches the lower side of the internal electrode 26, and is electrically connected to the internal electrode 26.

Further, on the second main surface side, a solder resist layer 24 (protective insulating film) is provided which covers the second main surface on which the metal electrode 23 is formed, and has an opening to expose a part of the metal electrode 23.

Further, on the second main surface side, a light shielding film 18 is provided which covers the second main surface on which the solder resist layer 24 is formed, and has an opening to expose a part of the metal electrode 23.

In this structure, (1) the light shielding film 18 and the solder resist layer 24 form a single layer of an infrared light-shielding solder resist layer, wherein the infrared light-shielding solder resist layer can be made of the infrared light-shielding composition according to the present invention. To form, or (2) the light-shielding film 18 and the solder resist layer 24 are individual layers, and the light-shielding film 18 can be formed by the infrared light-shielding composition according to the present invention (in this case, the solder resist layer can be a conventional solder resist) Composition to form).

In FIG. 2, although the light shielding film 18 is patterned to cover a part of the metal electrode 23 and the remaining portion of the exposure, which can still be patterned to expose all of the metal electrodes 23 (also applied to the patterning of the solder resist layer 24).

Also, the solder resist layer 24 may be omitted, and the light shielding film 18 may be directly formed on the second main surface on which the metal electrode 23 is formed.

A solder ball 60 as a connection member is provided on the exposed metal electrode 23, and the metal electrode 23 of the solid-state image sensor substrate 100 and the connection electrode (not shown) of the circuit board 70 are electrically connected through the solder ball 60.

The structure of the solid-state element substrate 100 is described above, but the portions other than the light-shielding film 18 of the solid-state image element substrate 100 can be formed by a conventional method, for example, paragraphs [0033] to [0068] of JP-A-2009-158863. The method described in the paragraph or the method described in paragraph [0036] to [0065] of JP-A-2009-99591.

The light shielding film 18 can be formed by the above-described method of manufacturing the infrared light shielding film according to the present invention.

The interlayer insulating film 13 which is a film of cerium oxide (SiO ₂ ) or a film of tantalum nitride (SiN) is formed, for example, by sputtering or chemical vapor deposition (CVD).

The color filter 15 is formed, for example, by photolithography using a conventional color resist.

The overcoat layer 16 and the base layer 14 are formed, for example, by photolithography using conventional photoresists for forming an organic interlayer film.

The microlens 17 is formed, for example, by photolithography, using a styrenic resin or the like.

In the case where the solder resist layer 24 and the light shielding film 18 are combined to form a single layer of the infrared light-shielding solder resist layer, the layer is preferably covered with the infrared light according to the present invention. A photonic composition is formed.

On the other hand, in the case where the solder resist layer 24 and the light shielding film 18 are individual layers, the solder resist layer 24 is preferably made of, for example, photolithography, using a phenol resin, a polyimide resin, or an amine resin. The conventional solder resist is formed.

The solder ball 60 is formed, for example, by using Sn-Ag, Sn-Cu, and Sn-Ag-Cu or the like to form, for example, Sn-Pb (eutectic), 95Pb-Sn (high-lead high-melting solder), or No Pb solder. The solder ball 60 is formed, for example, into a sphere having a diameter of 100 μm to 1,000 μm (preferably 150 μm to 700 μm in diameter).

The internal electrode 26 and the element surface electrode 27 (for example, a metal electrode (for example, Cu)) are formed by chemical mechanical polishing (CMP) or photolithography and etching.

The metal electrode 23 (for example, a metal electrode such as Cu, Au, Al, Ni, W, Pt, Mo, Cu compound, W compound or Mo compound) is formed by sputtering, photolithography, etching, or electrolytic plating. The metal electrode 23 may have a single layer structure or a multilayer structure composed of two or more layers. The thickness of the metal electrode 23 is, for example, 0.1 μm to 20 μm (preferably 0.1 μm to 10 μm). The ruthenium substrate 10 is not particularly limited, and a ruthenium substrate which is thinned by grinding the rear surface of the substrate can be used. The thickness of the substrate is not particularly limited, and a tantalum wafer having a thickness of 20 μm to 200 μm (preferably 30 μm to 150 μm) is used.

The via hole of the germanium substrate 10 is formed, for example, by photolithography or reactive ion etching (RIE).

The solid-state image element substrate 100 as a specific example of the above embodiment is described with reference to FIGS. 1 and 2, but the above embodiment is not limited to the structural modes of FIGS. 1 and 2, and the structure of the element substrate is not particularly limited as long as it is For the back surface The structure having the metal electrode and the light shielding film on the side may be sufficient.

An example in which an infrared light-shielding film obtained by the infrared light-shielding composition according to the present invention is applied to a light-shielding film of a wafer-level lens will be described below with reference to the drawings.

3 is a plan view showing one example of a wafer level lens array having a plurality of wafer level lenses.

As shown in FIG. 3, the wafer level lens array includes a substrate 410 and a lens 412 arranged on the substrate 410. Although the plurality of lenses 412 are two-dimensionally arranged with respect to the substrate 410 in FIG. 3, they may be one-dimensionally arranged.

Figure 4 is a cross-sectional view taken along line A-A of Figure 3.

As shown in FIG. 4, in the wafer level lens array, a light shielding film 414 for preventing light from transmitting through a portion other than the lens 412 is provided between the plurality of lenses 412 arranged on the substrate 410.

The wafer level lens is composed of a lens 412 present on the substrate 410 and a light shielding film 414 provided on a peripheral portion of the lens circle. This light shielding film 414 is formed using the infrared light blocking composition according to the present invention.

One embodiment of the structure of the wafer level lens array in which the plurality of lenses 412 are two-dimensionally arranged with respect to the substrate 410 as shown in FIG. 3 will be described below.

The lens 412 is generally composed of the same material as the substrate 410 and is a lens integrally molded on the substrate 410 or a lens molded into an individual structure and fixed to the substrate. Although an example is described above, the wafer level lens is not limited to this embodiment, and various embodiments may be employed, such as a multilayer structure or a lens module that is separated by dicing.

Examples of materials for forming the lens 412 include glass. Since there are many kinds of glass and a glass with a high refractive index can be selected, the glass has a large potential Force is applied to the material of the lens. Further, the glass is excellent in heat resistance and has the advantage of being able to withstand reflow mounting on an image unit or the like.

Other examples of materials for forming the lens 412 include a resin. The resin is excellent in processability and is suitable for forming a lens surface simply and inexpensively by using a mold or the like.

In this case, the lens 412 is preferably formed of an energy-curable resin. The energy curable resin may be a resin which can be cured by heat or a resin which can be cured by irradiation with actinic energy ray (for example, irradiation with heat, ultraviolet rays or electron beams).

Any conventional energy curable resin can be used as the energy curable resin, and in view of reflow soldering of the image unit, a resin having a relatively high softening point (for example, a softening point of 200 ° C or higher) is preferred. More preferably, the resin has a softening point of 250 ° C or higher.

[Example]

The invention is described below with reference to the examples, but the invention is not construed as being limited thereto, unless otherwise indicated, "parts" and "%" are by mass.

<Preparation of Filler Dispersion 1>

6.8 parts by mass of a cerium oxide filler (Aerosil 50, manufactured by Nippon Aerosil Co., Ltd., particle size: 30 nm), and 92.9 parts by mass of an alkali-soluble resin (ACA230AA) was previously prepared. , manufactured by Daicel-Cytec Co. Ltd., weight average molecular weight: 14,000 (measured by GPC method and calculated in terms of polystyrene), solid content: 50% by mass , Solvent: PGME) and 0.3 parts by mass of melamine mixed and using zirconia beads of 1.0 mm diameter, by motor grinder M-50 (by Eiger GmbH) (manufactured by Eiger Ltd.) The filler dispersion 1 was prepared by dispersing the mixture at a peripheral speed of 9 m/sec for 1.5 hours.

<Preparation of Filler Dispersion 2>

92.9 parts by mass of a resin obtained by polymerizing a monomer respectively corresponding to the repeating unit shown above at a molar ratio of 65:35 (weight average molecular weight: 10,000, solid content: 39% by mass, solvent: PGME), 6.8 parts by mass of a cerium oxide filler (AEROSIL 50, manufactured by Degussa Co., Ltd., particle size: 30 nm) and 0.3 parts by mass of melamine mixed and using zirconia beads having a diameter of 1.0 mm by A motor mill M-50 (manufactured by Eiger Co., Ltd.) was used to prepare a filler dispersion 2 by dispersing the mixture at a peripheral speed of 9 m/sec for 1.5 hours.

<Preparation of Infrared Light-shielding Composition> Example 1

The infrared light-shielding composition of Example 1 was prepared by mixing and filtering the following compositions. The solid concentration of the infrared light-shielding composition of Example 1 was 47% by mass.

Example 2 to Example 5

The infrared light-shielding composition of Examples 2 to 5 was prepared in the same manner as in the infrared light-shielding composition of Example 1, except that the triazine photopolymerization initiator (Compound A) was replaced with Compound B to Compound E, respectively. Things. The solid concentration of each of the infrared light-shielding compositions of Examples 2 to 5 was 47% by mass.

Example 6

Infrared light-shielding composition with Example 1 except that 58.39 parts by mass of the filler dispersion 1 was replaced with 72.10 parts by mass of the filler dispersion 2, and the amount of PGMEA was changed from 14.10 parts by mass to 0.39 parts by mass. The infrared light-shielding composition of Example 6 was prepared in the same manner. The solid concentration of the infrared light-shielding composition of Example 6 was 43% by mass.

Example 7 to Example 10

Infrared light shading compositions of Examples 7 to 10 were prepared in the same manner as in the infrared light-blocking composition of Example 6, except that the triazine photopolymerization initiator (Compound A) was replaced with Compound B to Compound E, respectively. Things. The solid concentration of each of the infrared light-shielding compositions of Examples 7 to 10 was 43% by mass.

Comparative example 1

An infrared light-shielding composition of Comparative Example 1 was prepared in the same manner as in the infrared light-shielding composition of Example 1, except that the light-shielding particles YMF-02 were replaced by the following titanium black dispersion. The solid concentration of the infrared light-shielding composition of Comparative Example 1 was 47% by mass.

[Preparation of Titanium Black Dispersion] (Manufacture of Titanium Black A)

First, weigh 100 grams of titanium dioxide (titanium) with a particle size of 15 nm. Oxide) (MT-150A, manufactured by Tayca Corp.), 25 g of cerium oxide particles with a BET surface area of 300 m ^ 2 / gram (AEROPERL 300/30, by Evonik Industries ( Evonik Industries) and 100 g of DSM 190 (manufactured by Beque Chemical, Germany), and 71 g of ion-exchanged water was added thereto. The final mixture was treated with MAZERSTAR KK-400W (manufactured by Kurabo Industries Ltd.) at a revolution speed of 1,360 rpm and a rotation speed of 1,047 rpm for 20 minutes to obtain a uniform aqueous mixture. . The aqueous solution mixture was filled in a quartz vessel, and heated in an oxygen atmosphere at 920 ° C using a small rotary kiln (manufactured by Motoyama Co., Ltd.). The atmosphere was replaced with nitrogen, and then ammonia gas was introduced at a rate of 100 ml/min for 5 hours at the same temperature as above to carry out nitrogen reduction treatment. After the treatment, the collected powder was ground in a mortar to obtain Titanium A in powder form.

(Synthesis of Dispersant 1)

600.0 g of ε-caprolactone and 22.8 g of 2-ethyl-1-hexanol were introduced into a 500 mL three-necked flask, and dissolved while stirring with nitrogen gas. Then, 0.1 g of monobutyltin oxide was added to the flask, followed by heating to 100 °C. After 8 hours, the raw material was used up by gas chromatography, and the mixture was cooled to 80 °C. After 0.1 g of 2,6-di-t-butyl-4-methylphenol was added to the flask, 27.2 g of 2-methylpropenyloxyethyl isocyanate was added to the flask. After 5 hours, the raw material was used up by ¹ H-NMR, and the mixture was cooled to room temperature to obtain 200 g of a solid form precursor M1 (having the following structure, n = 30). The precursor M1 was identified by ¹ H-NMR, IR and mass spectrometry.

30.0 g of precursor M1, 70.0 g of NK ESTER CB-1 (2-methylpropenyloxyethyl phthalate, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2.3 g of dodecyl mercaptan, and 233.3 g of propylene glycol Monomethyl ether acetate was introduced into a three-necked flask which was replaced with nitrogen, and the mixture was stirred using a stirrer (three-one motor, manufactured by SHINTO Scientific Co., Ltd.), and nitrogen was introduced into the flask. The inside was heated to 75 ° C at the same time. Then, 0.2 g of 2,2-azobis(2-methylpropionic acid) dimethyl ester (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, followed by The mixture was stirred under heating at 75 ° C for 2 hours. After 2 hours, 0.2 g of V-601 was further added, followed by stirring by heating for 3 hours to obtain a solution of 30% by mass of Dispersant 1 having the following structure.

n=30

Dispersant 1

The composition ratio, acid value, and weight average molecular weight (Mw) of the dispersant 1 are as follows. The weight average molecular weight is measured by gel permeation chromatography (GPC), calculated in terms of polystyrene. Gel permeation chromatography was performed using HLC-8020GPC (manufactured by Tosh Corp.). TSKGEL SUPER HZM-H, TSKGEL SUPER HZ4000, and TSKGEL SUPER HZ200 (manufactured by Tosoh Corporation) were used as the pipe string.

Composition ratio: x = 30% by mass, y = 70% by mass

Acid value: 80 mg KOH / g

Mw: 30,000

(Preparation of titanium black dispersion)

The components in the composition shown below were mixed for 15 minutes using a stirrer (EUROSTAR, manufactured by IKA Works, Ink) to obtain a dispersion.

(composition 1)

The dispersion obtained thereby was subjected to dispersion treatment using ULTRA APEX MILL UAM015 (manufactured by Kotobuki Industries Co., Ltd.) under the following conditions to obtain a titanium black dispersion (solid content concentration) : 18.0% by mass). The particle diameter of the titanium black dispersion (refer to the particle diameter at the maximum of the particle size distribution) was 19 nm.

(dispersion condition)

Bead size: φ0.05 mm

Bead filling ratio: 75% by volume

Grinding machine peripheral speed: 8 meters / sec

Dispersed mixture amount: 500 g

Circulating flow (pump supply): 13 kg / hour

Treatment liquid temperature: 25 ° C ~ 30 ° C

Cooling water: tap water

Bead mill annular passage volume: 0.15 liter

Passes: 90 times

Comparative example 2

The same as the infrared light-shielding composition of Example 6, except that the α-amino ketone polymerization initiator (Yanjiagu 907, manufactured by BASF Corporation, Japan) was used in place of the triazine polymerization initiator (Compound A). The infrared light-shielding composition of Comparative Example 2 was prepared in the same manner. The solid concentration of the infrared light-shielding composition of Comparative Example 2 was 43% by mass.

<Evaluation of infrared light-shielding composition for solder resist> (evaluation of cracks)

The diameters of the wafers are 50 micrometers each and the depth is 70 micrometers each. A plurality of holes of the meter, and the coating conditions for forming a layer having a thickness of 30 μm and having no voids on the wafer were determined. The above-mentioned infrared light-shielding composition was spin-coated under the conditions taken above, and subjected to pre-baking treatment at 100 ° C for 120 seconds, ultraviolet curing treatment, and post-baking at 150 ° C (post) -baking) for 1 hour. The hole portion of the substrate thus obtained was photographed using a cross-sectional scanning electron microscope, and the presence or absence of cracks was visually evaluated. According to the evaluation criteria shown below, five levels (5 to 1) are used for grading. Grades above 4 are acceptable.

[evaluation criteria]

5: 20 holes were observed, and the extent to which cracks were not observed was observed.

4: 20 holes can be observed and the extent to which a crack exists can be identified.

3: 20 holes can be observed and the extent to which the two cracks exist can be identified.

2: 20 holes can be observed, and 3 to 9 cracks can be identified, and the extent of cracks can be observed from the substrate through a microscope.

1: 20 holes can be observed, and 10 or more cracks can be identified, and the extent of cracks can be observed from the substrate through the microscope.

(assessment of adhesion)

A coating condition of forming a layer having a thickness of 10 μm on the tantalum wafer was taken, and the above-mentioned infrared light-shielding composition was spin-coated under the above-mentioned conditions and subjected to prebaking treatment at 100 ° C for 120 seconds, ultraviolet The photocuring treatment was carried out by puddle development at 25 ° C for 40 seconds by using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide. Then, the substrate was washed with a spin shower, washed with pure water, and subjected to post-baking treatment at 150 ° C for 1 hour. The substrate was placed at a temperature of 110 ° C and a humidity of 100% for 7 days, returned to room temperature (27 ° C), and cut into 100 squares by a cutter, wherein the size of the square was 1 mm × 1 mm, and the calculation was not The number of stripped boxes. According to the evaluation criteria shown below, the ranking is performed using five levels (5 to 1). Grades above 3 are acceptable.

[evaluation criteria]

5: No peeling of the square was observed and the extent of the edge of the square was not observed.

4: No peeling of the square was observed, but the degree of the edge of the square in 1 to 10 squares was observed.

3: No peeling of the square was observed, but the degree of the edge of the square in 11 to 100 squares was observed.

2: The degree of peeling of the square was observed.

1: The extent to which all the squares are peeled off.

(Single overall surface exposure sensitivity of solder resist (layer exposure sensitivity))

Each of the infrared light-shielding compositions of Examples 1-10 and Comparative Examples 1 and 2 was coated on a ruthenium wafer by spin coating to obtain a layer thickness of 25 μm, and on a hot plate at 120 Dry at ° C for 2 minutes to obtain a photosensitive layer.

The photosensitive layer was subjected to a single overall surface exposure in an amount of 1,000 mJ using an i-line exposure apparatus. The exposed photosensitive layer was subjected to a cover liquid development at 25 ° C for 40 seconds using N-methyl-2-pyrrolidone (NMP), and the substrate was rinsed with a spin shower. And then washed with pure water. The ratio of the layer thickness after rinsing to the layer thickness after exposure (thickness ratio reduction) was determined and evaluated according to the evaluation criteria shown below.

[evaluation criteria]

5: The thickness ratio is reduced by no more than 5%.

4: The thickness ratio is reduced by 5% or more than 5%, but not more than 10%.

3: The thickness ratio is reduced by 10% or more than 10%, but not more than 20%.

2: The thickness ratio is reduced by 20% or more than 20%, but not more than 30%.

1: The thickness ratio is reduced by more than 30%.

(formation of solder resist pattern)

The infrared light-shielding compositions of Examples 1 to 5 and Comparative Example 1 were patterned.

Specifically, each of the infrared light-shielding compositions of Examples 1 to 5 and Comparative Example 1 was coated on a tantalum wafer by spin coating to have a film thickness of 25 μm and on a hot plate at 120 Dry at ° C for 2 minutes to obtain a photosensitive layer.

Then, using an i-line stepper, a light mask with a circular pattern of 300 micrometers in diameter, at a phase of 50 mJ/cm, in a range of 50 mJ/cm to 2,000 mJ/cm2 The exposure dose is changed internally to illuminate the photosensitive layer.

The exposed photosensitive layer was subjected to puddle development using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide for 60 seconds, rinsed with a spin shower and washed with pure water to obtain an infrared light-shielding solder resist. pattern. The minimum exposure amount (mice/square centimeter) of the obtained circular pattern of 300 micrometers in diameter (pattern exposure sensitivity) was measured when the development step was performed for 60 seconds. The smaller the value, the better the pattern exposure sensitivity. Evaluate according to the guidelines presented below.

[evaluation criteria]

5: The minimum exposure is no more than 200 mJ/cm 2 .

4: The minimum exposure is greater than 200 mJ/cm 2 but not greater than 250 mJ/cm 2 .

3: The minimum exposure is greater than 250 mJ/cm 2 but not more than 300 mJ/cm 2 .

2: The minimum exposure is greater than 300 mJ/cm 2 but not greater than 350 mJ/cm 2 .

1: The minimum exposure is greater than 350 mJ/cm 2 .

(evaluation of pattern outline)

According to the above (formation of the solder resist pattern), the pattern is formed by exposure and development with a minimum exposure amount. The outline of the pattern is evaluated according to the criteria shown below.

[evaluation criteria]

5: The pattern is formed on the substrate with sufficient adhesion and the cross section of the pattern exhibits a good rectangular outline.

4: The pattern was formed on the substrate with sufficient adhesion, but the cross section of the pattern did not exhibit a good rectangular outline.

3: The pattern is formed on the substrate with sufficient adhesion, but the cross section of the pattern has an undercut (undercut) the outline and the outline of the rectangle cannot be displayed.

2: Although a pattern is formed, the adhesion to the substrate is insufficient, and a pattern stably adhered to the substrate cannot be formed.

1: The pattern cannot be parsed.

(Infrared light shading and evaluation of visible light transmittance)

Under the above conditions, an infrared light-shielding composition was spin-coated on a glass substrate to form a coating layer of a photosensitive layer having a layer thickness of 25 μm, and a UV-VIS-NIR spectrophotometer UV-3600 was used (by Shimadzu Corporation ( Shimadzu Corp.) was used to measure the penetration of the coating at a wavelength of 1,200 nm. The smaller the transmittance, the more excellent the infrared light blocking property. Evaluate according to the guidelines presented below.

[evaluation criteria]

5: The penetration rate is not more than 2%.

4: The penetration rate is greater than 2%, but not greater than 3%.

3: The penetration rate is greater than 3%, but not more than 5%.

2: The penetration rate is more than 5%, but not more than 10%.

1: The penetration rate is greater than 10%.

Further, a UV-VIS-NIR spectrophotometer UV-3600 (manufactured by Shimadzu Corporation) was used to measure the transmittance of the coating at a wavelength of 550 nm. The larger the value, the more excellent the visible light transmittance. Evaluate according to the guidelines presented below.

[evaluation criteria]

5: The penetration rate is not less than 30%.

4: The penetration rate is less than 30%, but not less than 25%.

3: The penetration rate is less than 25%, but not less than 20%.

2: The penetration rate is less than 20%, but not less than 15%.

1: penetration rate is less than 15%.

The results of the evaluation are shown in Table 1 below.

Obviously, as shown in Table 1, Comparative Example 1 uses titanium black as an infrared light-shielding agent to show many crack occurrences, which are inferior to substrate adhesion and film exposure sensitivity, and particularly in visible light transmittance. difference. Further, in the case of pattern formation, Comparative Example 1 was inferior in pattern exposure sensitivity and pattern outline.

On the contrary, it can be found that Examples 1 to 5 use tungsten ruthenium oxide particles as an infrared light-shielding agent and use a triazine polymerization initiator to show that no or few cracks occur and adhesion to a substrate, film exposure sensitivity, infrared light Both light blocking properties and visible light transmittance are excellent. It was also found that in the case of pattern formation, Examples 1 to 5 were excellent in pattern exposure sensitivity and pattern outline.

It can be found that Comparative Example 2 uses tungsten cerium oxide particles as an infrared light shielding agent and a polymerization initiator other than a triazine polymerization initiator, which is excellent in adhesion to a substrate, infrared light blocking property, and visible light transmittance. Or at an acceptable level, but the crack and film exposure sensitivity is poor.

Conversely, it can be found that Examples 6 to 10 use yttrium-tungsten oxide particles as an infrared light-shielding agent and use a triazine polymerization initiator to show that no or little cracking occurs, and the adhesion to the substrate is acceptable to the extent that It is excellent in any of film exposure sensitivity, infrared light blocking property, and visible light transmittance.

The present application is based on Japanese Patent Application No. 2011-253228, filed on Jan.

10‧‧‧矽 substrate

12‧‧‧Image components

13‧‧‧Interlayer insulating film

14‧‧‧ grassroots

15B‧‧‧Blue filter

15G‧‧‧Green Filter

15R‧‧‧Red Filter

16‧‧‧Overcoat

17‧‧‧Microlens

18‧‧‧Shade film

20‧‧‧Adhesive

22‧‧‧Insulation film

23‧‧‧Metal electrodes

24‧‧‧Anti-flux layer

26‧‧‧Internal electrodes

27‧‧‧ Component surface electrode

30‧‧‧ glass substrate

60‧‧‧ solder balls

70‧‧‧ circuit board

100‧‧‧Fixed image element substrate

Claims (14)

An infrared light-shielding composition comprising an alkali metal-containing tungsten oxide fine particle, a triazine polymerization initiator, and a polymerizable compound. The infrared light-shielding composition according to claim 1, wherein the triazine polymerization initiator is represented by the following formula (T): Wherein X ¹ and X ² each independently represents a halogen-substituted hydrocarbon group, a hydrogen atom, a halogen atom, dialkylamino, alkyl, alkoxy or cyano group; Y ¹ represents a group -NH- or extending ethyl; B ¹ And B ² each independently represent an aromatic ring group which may have a substituent; and l and m each independently represent an integer selected from 0, 1, and 2. The infrared light-shielding composition according to claim 2, wherein X ¹ and X ² in the formula (T) each independently represent a halogen-substituted hydrocarbon group. The infrared light-shielding composition according to claim 2, wherein in the formula (T), the aromatic ring constituting the aromatic ring group of B ¹ or B ² is a benzene ring. The infrared light-shielding composition according to any one of claims 1 to 3, further comprising an alkali-soluble binder. The infrared light-shielding composition according to claim 5, wherein the alkali-soluble binder has an acid group. The infrared light-shielding composition according to claim 5, wherein the alkali-soluble binder has a crosslinking group. The infrared light-shielding composition according to any one of the items 1 to 3, wherein the alkali metal-containing tungsten oxide fine particles are represented by the following formula (I): M _x W _y O _z ( I) wherein M represents an alkali metal; W represents tungsten; O represents oxygen; x/y 1.1; and 2.2 z/y 3.0. The infrared light-shielding composition according to any one of claims 1 to 3, wherein the polymerizable compound is a polyfunctional polymerizable compound, and the polyfunctional polymerizable compound is in one molecule There are a plurality of polymerizable groups thereon. The infrared light-shielding composition according to any one of claims 1 to 3, which is used as a solder resist or as an infrared light-shielding film on the back side of the substrate in the solid-state image sensor. A photosensitive layer formed of the infrared light-shielding composition according to any one of claims 1 to 10. An infrared light-shielding film which is formed by the infrared light-shielding composition as described in any one of Claims 1 to 10. A solid-state image sensor comprising a substrate and an infrared light-shielding film according to claim 12, wherein an image element unit is formed on one side of the substrate, and the infrared light is as described in claim 12 The light shielding film is disposed on the other surface side of the substrate. A pattern forming method comprising: forming a photosensitive layer as described in claim 11; patterning exposure of the photosensitive layer to cure an exposed region; and removing an unexposed region by alkali development Form a pattern.