TWI569095B - Light-shielding composition, method for producing a light-shielding composition, solder resist, method for forming a pattern, and solid-state imaging device - Google Patents

Description

Light-shielding composition, method for producing light-shielding composition, solder resist, pattern forming method, and solid-state imaging element

The present invention relates to a light-shielding composition, a method for producing a light-shielding composition, a solder resist formed using the light-shielding composition, a method for forming a pattern, and a solid-state image sensor.

Solid-state photographic elements for mobile phones, digital cameras, digital televisions, security cameras, and the like are photoelectric conversion elements that are integrated into circuits using semiconductor component production techniques. According to recent trends in miniaturization and weight reduction of mobile phones and digital cameras, solid-state imaging components are required to be miniaturized.

In order to achieve miniaturization of solid-state imaging elements, a method of applying a through electrode and forming a thin film tantalum wafer has been proposed. The miniaturization of the solid-state imaging element can be achieved by forming a germanium wafer in the form of a thin film through a polishing process. However, although the thin film germanium wafer maintains the light blocking property for light having a wavelength of less than or equal to 800 nm, light having a wavelength greater than or equal to 800 nm tends to be easily transmitted therethrough. It has been found that since a photodiode for a solid-state photographic element can react with light having a wavelength of 800 nm to 1200 nm, light having a wavelength higher than or equal to 800 nm is easily transmitted, and thus image quality deterioration is caused. New problem.

The configuration of the solid state imaging element is as follows. That is, in the solid-state imaging element, a color filter and a lens are disposed on one side of the adjacent photodiode, and the infrared cut filter is located around the color filter or the lens and thus blocks the wavelength from 800 nm to 1200 nm. The light of the meter, while the metal wires, solder resist and the like are located on the opposite side of the color filter. Although metal wires and the like The gap between them is often embedded with solder resist, but there is a problem that infrared light (such as leaking light) incorporated into a cell phone, a digital camera, and the like cannot be blocked. Therefore, a method of forming a light-shielding layer on a solder resist having a poor light-shielding property for infrared light to secure infrared light characteristics is conventionally required.

Currently, an infrared ray blocking layer is separately formed after the solder resist has been formed by a coating method. For this reason, a series of processes including coating, exposure, development, and post-heating processes and the like are required to form a solder resist and an infrared shielding layer. This can complicate the overall process and cause an increase in cost. For this reason, this needs to be improved.

In the infrared ray shielding layer, carbon black can be used (for example, see Japanese Patent Application Laid-Open (JP-A) No. 2009-276406), titanium black (titanium black) (for example, see Japanese Patent Application Laid-Open (JP-A) No. 2009-276406). For example, see JP-A No. 2002-285007, cesium tungsten oxide (for example, see JP-A No. 2009-205029) or the like. However, when any of these techniques is used in the gap between the metal wires to form a filling layer instead of the solder resist, sufficient filling cannot be achieved, and the resulting filled layer has a non-uniform surface and cannot be eliminated by the metal wire and the like. The step (ie, unevenness) caused by the object. That is, the formability of the thick film is low, the surface characteristics of the obtained film are poor, and "thickness uniformity on the uneven surface" is deteriorated.

In an attempt to solve these problems, a method of imparting a solder resist to the infrared light characteristics is considered. For example, a black solder resist composition containing a black colorant, a coloring agent which is not a black colorant, and a polyfunctional epoxy compound is proposed (for example, see JP-A No. 2008-257045). However, due to this composition The content of the black colorant contained in the black colorant is reduced by the combination of the black colorant and the colorant which is not a black colorant, so that the light-shielding property, specifically, the light-shielding property in the infrared range is insufficient, and "thick film formation suitability" Insufficient, making the composition practically unsuitable.

In general, in order to avoid coating unevenness (for example, film thickness unevenness, surface property deterioration, and the like) of a coating film used in a spin coating method for a semiconductor process, it is generally required to be higher than or equal to 900. Transfers per revolution (rpm). However, the unevenness due to the metal wire generally has a height difference of about 20 μm and thus it is necessary to apply a coating film (such as a solder resist layer) having a thickness of greater than or equal to about 24 μm by spin coating (in the present invention) This is called "thick film formation suitability", which means the suitability of the composition to form a thick coating film to flatten the unevenness. Further, the obtained film is required to have a uniform surface (referred to as "coating uniformity" in the present invention).

In addition, it is generally required to cure the coated solder resist by irradiation with UV rays or the like. However, when a solder resist layer having unevenness due to a metal wire and the like is formed on a substrate, the film thickness in the pit area between the metal wires is increased, and thus it is difficult to perform UV against the lowest layer of the solder layer. The light is irradiated, so that the solder resist layer causes problems such as insufficient curing of the lower layer or "film peeling" under the most severe conditions.

Namely, it is required that the film thickness on the gap between the metal wires is substantially the same as the film thickness on the metal wires (in the present invention, it is referred to as "thickness uniformity on the uneven surface").

In addition, the solder resist is required to have high temperature resistance and/or high humidity resistance or no cracks.

The present invention has been made to meet the above-described needs of solder resists and the like and to solve the conventional problems.

That is, an object of the present invention is to provide a light-shielding composition which has a thick film forming suitability, can impart excellent coating uniformity to a film obtained, has thickness uniformity on an uneven surface, and exhibits excellent blocking in an infrared light range. characteristic. Further, another object of the present invention is to provide a method for producing a light-shielding composition, a solder resist, a pattern forming method using a solder resist, and a high-resolution solid-state image sensor.

The aspect of the invention is as follows.

<1> A light-shielding composition comprising: (A) any one of a light-shielding particle or a light-shielding dye; (B) a first filler having a particle diameter of from 100 nm to 3,000 nm, and a particle diameter of the first filler a maximum of the particle diameter distribution; and (C) a second filler having a particle diameter of 5 nm to 90 nm, the particle diameter being the maximum of the particle diameter distribution of the second filler, wherein when the composition is in the light-shielding When (B) the first filler and (C) the second filler are mixed, the particle diameter distribution among the mixed fillers includes a maximum value in the range of 5 nm to 90 nm and 100 nm to 3,000 nm. The maximum value within the range of meters.

<2> The light-shielding composition according to <1>, wherein the light-shielding particles are pigments.

<3> The light-shielding composition according to <1> or <2>, wherein the light-shielding particles are inorganic pigments.

<4> The light-shielding composition according to any one of <1> to <3> wherein the light-shielding particles have a particle diameter of from 5 nm to 100 nm, and the particle diameter is the maximum value of the particle diameter distribution of the light-shielding particles.

<5> The light-shielding composition according to any one of <1> to <4> wherein the light-shielding particles are at least one selected from the group consisting of titanium black, carbon black, and tungsten strontium oxide.

<6> The light-shielding composition according to any one of <1> to <5> wherein at least one of (B) the first filler or (C) the second filler is an inorganic filler.

<7> The light-shielding composition according to any one of <1> to <6> wherein at least one of (B) the first filler or (C) the second filler is cerium oxide.

<8> The light-shielding composition according to any one of <1> to <7> wherein at least one of (B) the first filler or (C) the second filler has a substantially spherical shape.

<9> The light-shielding composition according to any one of <1> to <8>, wherein (B) the content ratio of the first filler to the (C) second filler is 1:30 to 1:2 by mass .

<10> The light-shielding composition according to any one of <1> to <9>, further comprising: (D) a polymerizable compound; and (E) a photopolymerization initiator.

<11> A method for producing a light-shielding composition according to any one of <1> to <10>, comprising: A dispersion containing the light-shielding particles, a dispersion containing the (B) first filler, and a dispersion containing the (C) second filler are prepared by mixing the respective dispersions.

<12> A solder resist comprising the light-shielding composition according to any one of <1> to <10>.

<13> A method of producing a pattern comprising: forming a photosensitive layer on a substrate using a solder resist according to <12>; pattern-exposing the photosensitive layer to cure the exposed region; and performing alkali development on the photosensitive layer after pattern exposure .

<14> A solid-state photographic element having at least one solder resist layer formed using a solder resist according to <12>.

The light-shielding composition according to the aspect of the present invention contains (A) one of light-shielding particles and a light-shielding dye, (B) a first filler, and (C) a second filler, and has a thick film formation suitability, and the resulting The film has excellent coating uniformity as well as excellent thickness uniformity on uneven surfaces.

The reason for this can be considered as follows. Since the light-shielding composition of the present invention contains (B) a first filler having a relatively large particle diameter and a (C) second filler having a relatively small particle diameter, it is assumed that the (B) filler in the light-shielding composition A cross-linking-like structure is formed together with the (C) filler together with the dispersant and the like. By forming a crosslinked-like structure, when a high shear rate is applied during the coating process, even if there is unevenness due to the metal wires and the like, it may be between the metal wires and the metal wires. A thick coating having substantially the same thickness is formed on the gap, and the thick film is improved to form suitability.

In addition, during the drying process, the shear rate is reduced and the resulting coating (having substantially the same film thickness over the gap between the metal wire and the metal wire) does not cause flow and maintains its thickness during drying and thus exhibits Thickness uniformity on a good uneven surface. Moreover, even when the resulting coating is heated for curing and the like, the fluidity is limited by the crosslinked structure, thereby preventing heat slack and maintaining a uniform thickness uniformity on the uneven surface.

Moreover, the resulting film has uniform surface characteristics and exhibits excellent coating uniformity. The reason for this is considered to be densely filling (B) the first filler having a large particle diameter and the (C) second filler having a small particle diameter, thereby producing excellent surface characteristics.

According to an aspect of the present invention, there is provided a light-shielding composition which has a thick film forming suitability, can impart excellent coating uniformity to a film obtained, has thickness uniformity on an uneven surface, and exhibits excellent in an infrared range. Shading characteristics. Further, according to another aspect of the present invention, a method for producing a light-shielding composition, a solder resist, a pattern forming method using a solder resist, and a solid-state image sensor having high resolution are provided.

Hereinafter, the light-shielding composition, the method of producing the light-shielding composition, the solder resist using the light-shielding composition, and the solid-state imaging element according to the present invention will be described in detail.

Further, in the specification of the present invention, the unsubstituted or unsubstituted group (atomic group) which is not disclosed may have no substituent or have one or more substituents. For example, the term "alkyl" embraces an alkyl group having no substituent (ie, an unsubstituted alkyl group) and an alkyl group having one or more substituents (ie, a substituted alkyl group). Further, in the specification of the present invention, the viscosity means a value measured at 25 °C.

The light-shielding composition of the present invention contains at least: (A) any one of light-shielding particles or light-shielding dyes; (B) a first filler having a particle diameter of from 100 nm to 3,000 nm, and the particle diameter is in a particle diameter distribution a maximum amount; and (C) a second filler having a particle diameter of 5 nm to 90 nm, the particle diameter being the maximum of the particle diameter distribution, and optionally containing (D) a polymerizable compound and (E) light A polymerization initiator, an alkali-soluble binder, a dispersant, a sensitizer, a crosslinking agent, a hardening accelerator, an elastomer, a surfactant, and other components.

The light-shielding composition of the present invention is preferably a negative-working composition. Hereinafter, the components of the composition will be described.

Although the description of the constituent elements mentioned below may be based on the exemplary embodiments of the present invention, the present invention is not limited to the embodiments. In addition, in this specification, the range of values indicated by "to" or "... to ..." indicates the value mentioned before "to" and the reference to "to" The values are taken as the range of the lower limit and the upper limit, respectively.

Further, in the specification of the present invention, the term "(meth)acrylate" means acrylate and methacrylate, and the term "(meth)acryloyl amide (( Meth)acryl) means acryl and methacryl, and The term "(meth)acryloyl" means acryloyl and methacryloyl. Further, in the specification of the present invention, the term "monomer compound" is the same as the term "monomer". In the present invention, a monomer 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 present specification, a polymerizable compound means a compound having a polymerizable group and may be a monomer or a polymer. A polymerizable group refers to a group that mediates a polymerization reaction.

(A) shading particles and shading dyes

The light-shielding composition of the present invention contains at least one of (A) light-shielding particles or light-shielding dyes.

Preferably, the light-shielding particles and the light-shielding dye used in the present invention absorb light having a wavelength of from 800 nm to 1,200 nm and exhibit excellent light transmittance to light for exposure.

Further, the light-shielding particles and the light-shielding dye used in the present invention may be light-shielding dyes or light-shielding particles that absorb light having a wavelength of from 800 nm to 1,200 nm. The light-shielding particles are preferred in terms of heat resistance.

Examples of the dye which can be used as the light-shielding dye in the present invention include a cyanine colorant, a phthalocyanine colorant, a nathalocyanine colorant, an imiumium colorant. , an aminium colorant, a quinolium colorant, a pyrylium colorant, and a metal complex colorant (such as a Ni complex colorant).

Further, in terms of heat resistance, the light-shielding particles are preferably made of an organic pigment And a pigment selected from inorganic pigments, and particularly preferably an inorganic pigment.

Examples of the infrared light absorbing inorganic pigment which can be used as the light-shielding particles in the present invention include carbon black, titanium black, tungsten compound, zinc oxide, white lead, zinc antimony white, titanium oxide, chromium oxide, iron oxide, precipitated sulfuric acid. Barium and barite powder, red lead, iron oxide red, lead yellow, zinc chromate (zinc chromate type 1, zinc chromate type 2), ultramarine blue, Prussian blue (Prussian blue) Potassium ferricyanide, zirconium lime, praseodymium yellow, chrome titanate, chrome green, peacock, Victoria green, iron blue (not related to Prussian blue), vanadium Zirconium blue, chromium tin pink, manganese pink, and salmon pink. Additionally, examples of suitable black pigments include metal oxides, metal nitrides, or mixtures thereof, which comprise one or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni. , Sn, Ti and Ag.

Among these inorganic pigments, carbon black, titanium black, and a tungsten compound are preferable in terms of infrared light shielding properties, and titanium black and a tungsten compound are more preferable.

Titanium black refers to black particles having a titanium atom in the present invention. The low oxidation number of titanium oxide, titanium oxynitride or the like is preferred. Surface-modified particles can be used as titanium black particles to improve dispersibility and inhibit aggregation.

For example, surface modification can be carried out by coating one or more selected from the group consisting of cerium oxide, titanium oxide, cerium oxide, aluminum oxide, magnesium oxide, and zirconia. Alternatively, the water resistance disclosed in paragraphs [0010] to [0027] of Japanese Patent Application Laid-Open (JP-A) No. 2007-302836 may be used. (water-repellent) material treatment surface.

Examples of the method of producing titanium black include, but are not limited to, reduction of a mixture of titanium oxide and titanium metal by heating in a reducing atmosphere (see, for example, JP-A No. 49-5432); borrowing in a reducing atmosphere containing hydrogen Reduction of ultrafine titanium dioxide obtained by high-temperature hydrolysis of titanium tetrachloride (see, for example, JP-A No. 57-205322); reduction of titanium dioxide or titanium hydroxide in the presence of ammonia at a high temperature (see, for example, JP-A No. 60- No. 65069 or JP-A No. 61-201610); reduction of a vanadium compound connected to titanium oxide or titanium hydroxide in the presence of ammonia at a high temperature (see, for example, JP-A No. 61-201610) and the like.

Further, the light-shielding particles used in the present invention are more preferably a tungsten compound from the viewpoint of low absorbance of visible light.

The tungsten compound is a light-shielding particle having high absorbance (that is, a high light-shielding property (shielding property) for infrared light) and low absorbance to visible light for infrared light (wavelength of about 800 nm to 1,200 nm). Therefore, when the light-shielding composition of the present invention contains a tungsten compound, a pattern exhibiting high light-shielding characteristics in infrared light and exhibiting high transmission characteristics in visible light will be formed.

In addition, the tungsten compound exhibits a low absorbance for light having a wavelength smaller than that of visible light which is exposed to a high pressure mercury lamp for image formation, KrF, ArF, and the like. Therefore, excellent pattern formability can be obtained by using a tungsten compound in combination with a photopolymerization initiator, a polymerizable compound, and the like.

Examples of the tungsten compound include a tungsten oxide compound, a tungsten boride compound, and a tungsten sulfide compound. The tungsten compound is more preferably a tungsten oxide compound represented by the following formula (I).

MxWyOz (I)

In formula (I), M represents a metal, W represents tungsten and O represents oxygen, and 0.001 x/y 1.1, and 2.2 z/y 3.0.

Examples of the metal represented by M in the formula (I) include an alkali metal, an alkaline earth metal, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd. , Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, and Bi. The metal represented by M may be one type of metal, or may comprise two or more types of the above metals.

M is preferably an alkali metal, more preferably Rb or Cs, and still more preferably Cs.

When x/y is greater than or equal to 0.001, infrared light can be sufficiently shielded, and when x/y is less than or equal to 1.1, formation of impurities in the tungsten compound can be reliably prevented.

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

Specific examples of the tungsten oxide compound represented by the formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ and Ba _0.33 WO ₃ . Further, from the viewpoint of visibility in visible light, Cs _0.33 WO ₃ or Rb _0.33 WO _{3 is} preferable, and Cs _0.33 WO ₃ (tungsten oxide) is more preferable.

Tungsten compounds are commercially available. When the tungsten compound is, for example, a tungsten oxide compound, the tungsten oxide compound can be obtained by heating a tungsten compound under an inert gas atmosphere or under a reducing gas atmosphere (see, for example, Japanese Patent No. 4096205).

In addition, the tungsten oxide compound can be obtained, for example, in the form of a dispersion of tungsten particles. To, for example, YMF-02 (trade name, manufactured by Sumitomo Metal Mining Co., Ltd.).

The light-shielding particles are preferably fine particles, and the particle diameter indicating the maximum value of the particle diameter distribution thereof is preferably from 5 nm to 100 nm, more preferably from 5 nm to 50 nm and most preferably from 5 nm to 30 nm.

When the particle diameter is within the above range, the precipitation of the light-shielding particles with time decreases, and the stability of the light-shielding composition of the present invention further increases with the passage of time.

The particle diameter of the light-shielding particles and the particle diameter distribution of the (B) filler and the (C) filler mentioned below can be measured in such a manner that the light-shielding particles are diluted with propylene glycol monomethyl ether acetate (×100). a dispersion or a dispersion containing (B) a filler and (C) a filler, which is a target for particle diameter distribution measurement; droplets of the diluted dilution are dropped onto a carbon foil, followed by drying; and transmission electron microscopy is used (Transmission electron microscope, TEM) The dried dilution was observed to measure the particle diameter. Particle diameter evaluation was performed by evaluating the particle diameter based on a circular shape; plotting a particle diameter distribution with a sample number of 400, plotting the particle diameter on the horizontal axis, plotting the appearance frequency on the vertical axis, and providing The particle diameter of the maximum value; and the particle diameter is evaluated as "the particle diameter exhibiting the maximum value in the particle diameter distribution".

In addition, the term "particle diameter" means a volume average particle diameter unless otherwise specifically stated in the specification of the present invention.

Two or more types of light-shielding particles and a light-shielding dye can be used in the light-shielding composition of the present invention. In this case, you can use two or super There are two types of shading particles, or two or more types of shading dyes may be used, or one or more types of shading particles may be used in combination with one or more types of shading dyes. Under any circumstances, different types or the same type of shading particles and shading dyes may be used separately.

(A) the content of the light-shielding particles and/or the light-shielding dye (that is, the total content), which is preferably in the range of 3% by mass to 30% by mass, and more preferably the total solid mass of the light-shielding composition of the present invention. It is 5 mass% to 20 mass%.

The total solid mass of the light-shielding composition in the present invention means the total content (mass) of the components in the composition other than the solvent.

(B) first filler and (C) second filler

The light-shielding composition of the present invention contains (B) a first filler having a maximum particle diameter distribution in a particle diameter ranging from 100 nm to 3,000 nm (hereinafter, referred to as "(B) filler" or " a first filler "), and (C) a second filler having a particle diameter of a maximum of a particle diameter distribution in a range of 5 nm to 90 nm (hereinafter, referred to as "(C) filler" or "Second filler").

Hereinafter, (B) a filler and (C) a filler will be described.

The (B) filler and the (C) filler may each be an organic filler, an inorganic filler, an inorganic-organic compound filler or the like, or a combination of both or more. Preferably, at least one of the (B) filler or the (C) filler is an inorganic filler.

Examples of the organic filler include synthetic resin particles as well as natural polymer particles. Preferred examples thereof include acrylic resin, polyethylene, polypropylene, Resin particles of polyethylene oxide, polypropylene oxide, polyethyleneimine, polystyrene, polyurethane, polyurea, polyester, polyamine, polyimine, and the like, and Carboxymethyl cellulose, gelatin, starch, chitin, and polyglucosamine. More preferred are resin particles of acrylic resin, polyethylene, polypropylene, polystyrene, and the like.

Specific examples of commercially available fillers which are preferred as organic fillers include CHEMIPEARL W100, W200, W300, W308, W310, W400, W401, W4005, W410, W500, WF640, W700, W800, W900, W950, WP100 (trade name, manufactured by Mitsui Chemicals, Inc.); MX-150, MX-180, MX-300, MX-500, MX-1000, MX-1500H, MX-2000, MR -2HG, MR-7HG, MR-10HG, MR-3GSN, MR-5GSN, MR-2G, MR-7G, MR-10G, MR-20G, MR-5C, MR-7GC, SX-130H, SX-350H , SX-500H, SGP-50C, SGP-70C (trade name, manufactured by Soken Chemical & Engineering Co., Ltd.); and MBX-5, MBX-8, MBX-12, MBX -15, MBX-20, MB20X-5, MB30X-5, MB30X-8, MB30X-20, SBX-6, SBX-8, SBX-12, SBX-17 (trade name, by Sekisui Plastics Co., Ltd. (Sekisui Plastics Co., Ltd.) and the like.

Examples of inorganic fillers include metals and metal compounds such as oxides, composite oxides, hydroxides, carbonates, sulfates, silicates, phosphates, nitrides, carbides, and sulfides, and at least two classes thereof It combination. Specific examples include cerium oxide, mica compound, glass, zinc oxide, aluminum oxide, zirconium oxide, tin oxide, potassium titanate, barium titanate, aluminum borate, magnesium oxide, magnesium borate, aluminum hydroxide, magnesium hydroxide, hydrogen Calcium oxide, titanium hydroxide, basic magnesium sulfate, calcium carbonate, magnesium carbonate, calcium sulfate, magnesium sulfate, calcium citrate, magnesium citrate, calcium phosphate, tantalum nitride, titanium nitride, aluminum nitride, tantalum carbide, Titanium carbide, zinc sulfide, and compounds of at least two classes thereof.

The inorganic filler is preferably cerium oxide, mica compound, glass, alumina, potassium titanate, barium titanate, aluminum borate, magnesium oxide, calcium carbonate, magnesium carbonate, calcium citrate, magnesium citrate, calcium phosphate, sulfuric acid. Calcium and its analogues.

Among the inorganic fillers, cerium oxide is preferred.

At least one of the (B) filler or the (C) filler is preferably cerium oxide; and more preferably, both the (B) filler and the (C) filler are cerium oxide.

Examples of the form of the filler include a fiber shape, a needle shape, a planar shape, a spherical shape, a quadrangular shape, a balloon shape, and the like. Among them, the spherical shape is preferred.

At least one of the (B) filler or the (C) filler preferably has a spherical shape; and more preferably, both the (B) filler and the (C) filler have a spherical shape.

(B) Indication of Filler (B) The maximum diameter of the particle diameter distribution of the filler is from 100 nm to 3,000 nm. When the particle diameter exceeds the upper limit of the range, the coating uniformity of the light-shielding composition is deteriorated. When the particle diameter is below the lower limit of the range, the moisture resistance of the light-shielding composition is lowered.

(B) The particle diameter of the filler is preferably from 100 nm to 1,600 na M, more preferably from 100 nm to 900 nm; further, more preferably from 100 nm to 500 nm, more preferably from 100 nm to 300 nm, and most preferably from 200 nm to 300 nm .

When the particle diameter is in the above range, the coating uniformity of the light-shielding composition is further improved.

(C) Indication of Filler (C) The maximum diameter of the particle diameter distribution of the filler is from 5 nm to 90 nm. When the particle diameter exceeds the upper limit of the range, the present invention exhibits almost no effect on the thickness uniformity on the uneven surface. In addition, when the particle diameter is lower than the lower limit of the range, the viscosity of the dispersion will excessively increase, and when the dispersion of the filler is prepared, the production efficiency will be remarkably lowered.

The particle diameter of the (C) filler is preferably from 5 nm to 70 nm, more preferably from 5 nm to 50 nm, even more preferably from 5 nm to 40 nm, and most preferably from 5 nm to 35 nm.

When the particle diameter is within the above range, the thickness uniformity of the light-shielding composition on the uneven surface is further improved.

The light-shielding particles and (B) filler and (C) filler (hereinafter, the light-shielding particles, (B) filler, and (C) filler may be collectively referred to as "separate particles") are preferably mentioned below. A surface-treated particle of a decane coupling agent or the like. By using surface treated particles, the thermal cycle test resistance (TCT) and storage stability of the improved shading composition can be made easier, for example, even after rigorous testing (such as thermal cycling testing). The shape is maintained as good as the shape immediately after the pattern is formed.

Decane coupling agent

The decane coupling agent used for the surface treatment of the particles is not particularly limited and may be appropriately selected depending on the purpose. The decane coupling agent preferably has at least one functional group selected from an alkoxyalkyl group, a chlorosilyl group, and an acetoxysilyl group (hereinafter, referred to as a "first functional group"). And at least one functional group selected from a (meth) acrylonitrile group, an amine group, and an epoxy group (hereinafter, referred to as a "second functional group"). The second functional group is more preferably a (meth) acrylonitrile group or an amine group, and the second functional group is even more preferably a (meth) acrylonitrile group. When the second functional group is a (meth) acrylonitrile group, it is advantageous in terms of storage stability or TCT resistance.

Further, a decane coupling agent as disclosed in JP-A No. 7-68256 having at least one functional group selected from an alkoxyalkyl group, a chloroalkyl group and an ethoxylated decyl group is preferably used. The first functional group and at least one functional group selected from an imidazole group, an alkylimidazole group, and a vinylimidazole group are used as the second functional group.

The decane coupling agent is not particularly limited, but examples of preferred decane coupling agents include γ-aminopropyltriethoxydecane, N-(β-aminoethyl)-γ-aminopropyltrimethoxydecane, N-(β-Aminoethyl)-γ-aminopropylmethyldimethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropylmethyldimethyl Oxydecane, γ-methacryloxypropyltrimethoxydecane, γ-methylpropenyloxypropylmethyldimethoxydecane, α disclosed in JP-A No. 7-68256 -[[3-(trimethoxydecyl)propoxy]methyl]-imidazol-1-ethanol, 2-ethyl-4-methyl-α-[[3-(trimethoxydecyl) Propyl]methyl]-imidazol-1-ethanol, 4-vinyl-α-[[3-(trimethoxydecyl)propyloxy]methyl]-imidazol-1-ethanol, 2-ethyl 4-methylimidazolylpropyltrimethoxydecane, as well as salts, intramolecular condensates and intermolecular condensates thereof. These decane coupling agents may be used singly or in combination of two or more types thereof.

The surface treatment of the particles with a decane coupling agent may be carried out only for each individual particle in advance (in this case, hereinafter, may be referred to as "pretreatment"), or may be included in each individual particle together with the light-shielding composition. Some or all of the other fillers are carried out together.

The pretreatment is not particularly limited, but examples thereof include a dry method, an aqueous solution method, an organic solvent method, and a spray method. The temperature of the pretreatment is not particularly limited, but is preferably room temperature to 200 °C.

The pretreatment is preferably carried out together with the addition of a catalyst. 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 in the pretreatment is not particularly limited, but is preferably from 0.01 part by mass to 50 parts by mass, and more preferably from 0.05 part by mass to 50 parts by mass, per 100 parts by mass of each of the respective particles. When the amount of the decane coupling agent to be added is in the above range, surface treatment sufficient to obtain a desired effect is achieved, and operability deterioration caused by aggregation of the respective particles after surface treatment is suppressed.

Since the first functional group in the decane coupling agent reacts with the surface of the matrix material, the surface of the individual particles, and the reactive group of the binder, and the second functional group in the decane coupling agent and the carboxyl group and the olefinic unsaturation of the binder Group The reaction, therefore, the adhesion between the matrix material and the light-shielding composition layer increases. At the same time, since the decane coupling agent has high reactivity, when the decane coupling agent is incorporated into the light-shielding composition, the second functional group will react during storage or lose its activity due to diffusion, and thus shorten the shelf life or pot life. .

However, as described above, when individual particles pretreated with a decane coupling agent are used, diffusion is suppressed and the shelf life or pot life problem is remarkably reduced, and it is possible to use a one-component solution. When the spherical shape of cerium oxide is pretreated, the stirring conditions, temperature conditions, and catalyst use conditions can be freely selected. Therefore, the reactivity between the first functional group in the decane coupling agent and the active group in the spherical shape of cerium oxide can be remarkably increased as compared with the case where the addition is carried out without pretreatment. Therefore, quite good results are obtained especially under strict requirements such as electrodeless gold plating, electrodeless solder plating, and water repellency load testing. Further, by performing the pretreatment, the amount of the decane coupling agent used can be lowered, and the storage period and the pot life can be further improved. Examples of the spherical shape of cerium oxide suitable for the surface treatment of the decane coupling agent of the present invention include the FB series and the SFP series (trade name, manufactured by Denki Kogyo Co., Ltd.), 1 - FX (trade name, manufactured by Tatsumori Co., Ltd.), HSP series (trade name, manufactured by Toagosei Co., Ltd.), and SP series (trademark) Name, manufactured by Fuso Chemical Co., Ltd.).

When (B) the first filler and (C) the second filler are mixed in the light-shielding composition of the present invention, the mixed filler (that is, (B) first filled The particle diameter distribution in the charge and (C) second filler) exhibits a bimodal particle diameter distribution, one of which is in the range of 5 nm to 90 nm and the other is in the range of 100 nm to 3,000 nm. Within the meter range. The technical meanings of the lower limit and the upper limit of the above range are the same as those described for (B) the first filler and (C) the second filler.

In the light-shielding composition of the present invention, the ratio of the (B) filler content to the (C) filler content (i.e., (B) filler: (C) filler) is preferably 1:30 to 1 by weight. : 2, and more preferably from 1:15 to 1:5 by weight. When the ratio is within the above range, the thickness uniformity on the uneven surface will be improved.

The sum of the (B) filler content and the (C) filler content is preferably from 3% by mass to 30% by mass, more preferably from 5% by mass to 20% by mass, and still more preferably 6% by mass based on the total solid content of the light-shielding composition. % by mass to 15% by mass. When the sum is in the above range, the transmittance in the visible light range is further improved.

One or more types of each of (B) fillers and (C) fillers may be provided, or one of them may be of two or more types, or both may be of two or more types.

Preparation of particle dispersion

As described above, the light-shielding particles, (B) the filler, and (C) the filler have been described. It is preferred to disperse each individual particle together with a dispersing agent, an organic solvent, and the like, which will be described later, by a mixing and dispersing process, before using the grinding machine (such as a bead mill or Roller mill) grinding particles to produce a dispersion of light-shielding particles, (B) A dispersion of the filler and (C) a dispersion of the filler. By preparing the respective dispersions before preparing the light-shielding composition, the individual particles can be dispersed into fine particles, and the effect of the present invention can be further achieved.

The shading dye may not be provided in the form of a dispersion, and may be prepared as a light-shielding composition by dissolving it in an organic solvent or without any treatment. The light-shielding particles are preferably prepared in advance as a dispersion. Hereinafter, the case of using the light-shielding particles will be described as an example.

Hereinafter, the dispersion of the light-shielding particles, (B) the dispersion of the filler, and (C) the dispersion of the filler may be collectively referred to as "particle dispersion", and the preparation of the particle dispersion will be described.

Preparation of particle dispersion

In a preferred embodiment for producing the light-shielding composition of the present invention, the dispersion containing the light-shielding particles is prepared by separately dispersing the light-shielding particles, (B) the first filler, and (C) the second filler, and contains (B) a dispersion of the first filler and a dispersion containing the (C) second filler.

Each particle dispersion liquid is obtained by dispersing any one of the light-shielding particles, (B) the first filler, or (C) the second filler in an organic solvent. At this time, a dispersant, a resin or the like may be selectively added. In addition, other components such as pigment derivatives may be selectively added.

As described above, according to the preferred embodiment, the dispersion containing the light-shielding particles and the (B) first filler are prepared by separately dispersing the light-shielding particles, (B) the first filler, and (C) the second filler. a dispersion and a dispersion containing (C) a second filler. Alternatively, (B) the first filler and (C) the second filler may be prepared as a single dispersion, or the shading may be The particles, (B) the first filler, and (C) the second filler are prepared as a single dispersion. In these embodiments, in order to improve the degree of freedom in the design of the treatment (for example, changing the solid content or changing the viscosity to improve the stability over time), it is preferred to separately prepare the dispersion containing (B) the first filler and to contain ( C) A dispersion of the second filler.

The preparation of the particle dispersion is not particularly limited. For example, it can be made by using a vertical or horizontal type sand mill, a pin mill, a cutter, an ultrasonic distributor or the like together with glass, zirconia or the like and having a particle diameter of The beads of 0.01 mm to 1 mm are subjected to fine dispersion treatment of any one of the light-shielding particles, (B) the first filler, and (C) the second filler or the dispersant and the organic solvent to obtain a particle dispersion.

Before the beads are dispersed, by using a two-roll mill, a three-roll mill, a ball mill, a trommel, a disperser, a kneader, a co-twist, a homogenizer, a blender, a single screw An extruder or a twin-screw extruder or the like applies a strong shear force to perform a kneading dispersion treatment.

Details of blending and dispersion are disclosed, for example, in TC Patton, "Paint Flow and Pigment Dispersion" (1964, published by John Wiley and Sons, Corp.) in.

Dispersant

A dispersant preferably contained in each particle dispersion will be described. When the particle dispersions each contain a dispersant, the dispersibility and dispersion stability can be improved.

Examples of the dispersant which can be used in the particle dispersion in the present invention include a polymeric dispersant such as polyamide amine and Salts, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly(meth)acrylates, (meth)acrylic acid a copolymer or a naphthalenesulfonate formalin condensate; and a surfactant such as polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine or alkanolamine.

The polymeric dispersant can be classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer based on the structure.

Examples of the terminal-modified polymer having an anchoring moiety for the surface include polymerization having a terminal phosphate group as disclosed in JP-A No. 3-112992, JP-A No. 2003-533455, and the like. a polymer having a terminal sulfonate group as disclosed in JP-A No. 2002-273191 or the like; an organic pigment as disclosed in JP-A No. 9-77994 or the like. a polymer having a partial skeleton or a heterocyclic ring; and a polymer prepared by modifying an oligomer or polymer having a hydroxyl group or an amine group at one end with an acid anhydride as disclosed in JP-A No. 2008-29901 or the like. . In addition, at least two anchoring moieties for the surface of the infrared ray blocking material (such as an acidic group, a basic group, a partial skeleton of an organic pigment) are introduced at the end of the polymer as disclosed in JP-A No. 2007-277514. The polymer of the or heterocyclic ring is also preferred because it exhibits excellent dispersion stability.

Examples of the graft polymer having an anchoring portion for the surface include those in JP-A No. 54-37082, Japanese National Publication No. 8-507960, JP-A No. 2009-258668, or the like. Exposure a reaction product of a carbon alkylene imine) and a polyester; a reaction product of a polyarylamine and a polyester as disclosed in JP-A No. 9-169821 or the like; for example, JP-A No. 2009-203462 An amphoteric dispersion resin having a basic group and an acidic group as disclosed in the above; a macromonomer as disclosed in JP-A No. 10-339949, JP-A No. 2004-37986 or the like ( a macromonomer) copolymer with a nitrogen atom-containing monomer; as disclosed in JP-A No. 2003-238837, JP-A No. 2008-9426, JP-A No. 2008-81732, or the like, having an organic pigment a graft polymer of a partial skeleton or a heterocyclic ring; and a copolymer of a macromonomer and an acid group-containing monomer as disclosed in JP-A No. 2010-106268 or the like.

The macromonomer used to prepare the graft polymer having an anchoring moiety to the surface by free radical polymerization can be selected from known macromonomers. Examples thereof include a macromonomer AA-6 (poly(methyl methacrylate) having a methacryl fluorenyl group as a terminal group), AS-6 (polystyrene having a methacryl fluorenyl group as a terminal group), AN-6S (copolymer of styrene and acrylonitrile having a methacryl fluorenyl group as a terminal group), AB-6 (poly(butyl acrylate) having a methacryl fluorenyl group as a terminal group) (all are trade names) , manufactured by Toagosei Co., Ltd.; PLACCEL FM5 (addition product of 2-hydroxyethyl methacrylate with 5 molar equivalents of ε-caprolactone), FA10L (addition product of 2-hydroxyethyl acrylate and 10 mol equivalent of ε-caprolactone) (all of which are trade names, manufactured by Daicel Chemical Industries Ltd.); and as JP- A polyester macromonomer as disclosed in A No. 2-272009 and the like. in Among these monomers, in particular, excellent flexibility and excellent solvent affinity are exhibited from the viewpoints of dispersibility and dispersion stability of the infrared ray-blocking material and developability of the light-shielding composition using the infrared ray shielding material. The polyester macromonomer is particularly preferably used in the light-shielding composition, and the polyester macromonomer represented by the polyester macromonomer disclosed in JP-A No. 2-272009 is preferred.

The block polymer having an anchoring portion for the surface is preferably a block polymer as disclosed in JP-A No. 2003-49110, JP-A No. 2009-52010, and the like.

The dispersing agent can, for example, be suitably selected from known dispersing agents or surfactants.

Specific examples thereof include DISPERBYK-101 (polyamido-amine phosphate), dispept-107 (carbonate), and dispept-110 (polymerization with acidic groups) ), Dispick-130 (polyamide), Dispbike-161, Dispbike-162, Dispbike-163, Dispbike-164, Diss Pubike-165, Dispick-166, Dispick-170 (high molecular weight copolymer) (all trade names, manufactured by BYK Japan KK); BYK-P104 and P105 (high molecular weight unsaturated polycarboxylic acid) (both trade names, manufactured by BYK Japan KK); EFKA 4047, Ivka 4050 Afka 4010 to Afka 4165 (polyurethane), Afka 4330 to Afka 4340 (block copolymer), Afka 4400 to Afka 4402 (modified polyacrylate) ), Afka 5010 (polyester phthalamide), Ivka 5765 (high score) Amount of polycarboxylate), Afka 6220 (fatty acid polyester), Afka 6745 (phthalocyanine derivative) (all are trade names, by EFKA Chemicals Co., Ltd.) Manufactured; AJISPER PB821, Espa PB822, Espa PB880, Espa PB881 (all brand names, manufactured by Ajinomoto Fine Techno Co., Inc.) FLUOREN TG-710 (urethane oligo), POLYFLOW 50E, Baoke No. 300 (acrylic copolymer) (all are trademark names, by Kyoeisha Chemical Co., Ltd. (manufactured by Kyoeisha Chemical Co., Ltd.); DISPARLON KS-860, Dishi Baron 873 SN, Di Si Balong 874, Di Si Balong #2150 (aliphatic multi-price Carboxylic acid), Dis Baron #7004 (polyether ester), DA-703-50, DA-705, DA-725 (all are trade names, by Kusumoto Chemicals, Co., Ltd.) Manufacture); DEMOL RN, Demao N (polycondensation of naphthalenesulfonic acid and formalin), Demao MS, Demao C, Demao SN-B (polycondensation of aromatic sulfonic acid and formalin) ), HOMOGENOL L-18 (polycarboxylic acid polymer), Aizujin (EM) ULGEN) 920, Aizujin 930, Aizujin 935, Aizujin 985 (polyoxyethylene nonylphenyl ether), ACEXMIN 86 (octadecyl acetate) (all are trade names) , manufactured by Kao Corporation; SOLSPERS 5000 (phthalocyanine derivatives), Solpus 13240 (polyesteramine), Solps 3000, Solps 17000, Solps 27000 (polymer with functional moiety at the end), Solpus 24000, Solps 28000, Solps 32000, Solps 38500 (graft polymer) (all are trademark names, manufactured by The Lubrizol Corporation); NIKKOL T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) Ester) (all are trade names, manufactured by Nikko Chemicals, Co., Ltd.); HINOACT T-8000 E and its analogues (trade name, by Chuanyan Fine Chemical Co., Ltd. (manufactured by Kawaken Fine Chemicals Co., Ltd.); organic siloxane polymer KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.); W001 (cation Surfactant) (trade name, manufactured by Yusho Co., Ltd.); nonionic surfactant such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyethylene oxide oil Alkenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate or sorbitan fatty acid ester; anion Surfactants such as W004, W005 or W017; polymeric dispersants such as EFKA-46, Ivka-47 Afka-47EA, EFKA POLYMER 100, Afka Polymer 400, Afka Polymer 401, Afka Polymer 450 (all are trade names, by Morishita) & Co., Ltd.); Dispersion Aid (DISPERSE AID) 6, Dispersing Aid 8, Dispersing Aid 15, Dispersing Aid 9100 (all are trade names, by San Nopco Limited) Manufacturing); ADEKA PLURONIC L31, Eddie Plonik F38, Eddie Plonik L42, Eddie Plonik L44, Eddie Plonik L61, Eddie Plonik L64, Ai Dikoplonic F68, Eddie Plonik L72, Eddie Plonik P95, Eddie Plonik F77, Eddie Pluronic P84, Eddie Plonik F87, Eddie Plonik P94, Eddie Plonik L101, Eddie Pluronic P103 , Eddie Plonik F108, Eddie Pluronic L121, Eddie Pluronic P-123 (both trade names, manufactured by ADEKA Corporation); and IONET S -20 (trade name, manufactured by Sanyo Chemical Industries).

The dispersing agents may be used singly or in combination of two or more types. The dispersant of the present invention may be combined with an alkali-soluble resin together with a terminal-modified polymer, graft polymer or block polymer having anchoring moieties for the surface of the light-shielding particles, (B) filler or (C) filler. Use together in combination. Examples of the alkali-soluble resin include a (meth)acrylic copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partially esterified maleene. A diacid copolymer, an acidic cellulose derivative having a carboxylic acid group in a side chain, and a resin having a hydroxyl group modified with an acidic acid anhydride. (Meth)acrylic copolymers are especially preferred. In addition, a N-substituted maleimide monomer copolymer disclosed in JP-A No. 10-300922, such as an ether dimer copolymer disclosed in JP-A No. 2004-300204 Also, an alkali-soluble resin having a polymerizable group as disclosed in JP-A No. 7-319161 is also preferable.

The following resins as disclosed in JP-A No. 2010-106268 are particularly preferred from the viewpoints of dispersibility, developability, and precipitation characteristics. on From the viewpoint of dispersibility, a polymer dispersant having a polyester chain in a side chain is preferred. From the viewpoint of the dispersibility and the resolution of the pattern formed by the photolithography method, a resin having an acidic group and a polyester chain is preferred. From the viewpoint of absorbability, the preferred acidic group which may be contained in the dispersant is preferably an acidic group having a pKa of 6 or less, and particularly, a carboxylic acid, a sulfonic acid and a phosphonic acid are preferred.

Hereinafter, a dispersing agent as disclosed in JP-A No. 2010-106268, which is suitable for the present invention, will be described. The preferred dispersant is a graft copolymer having a number of atoms other than a hydrogen atom and having a graft chain selected from a polyester structure, a polyether structure, and a polyacrylate structure, and preferably contains the following formula. The structural unit represented by at least one of (a) to (d) preferably further contains the following formula (1A), the following formula (2A), the following formula (3A), the following formula (3B) or the following formula (d) A structural unit represented by any of them.

In the formulae (a) to (d), W ¹ , W ² , W ³ and W ⁴ each independently represent an oxygen atom or NH, and particularly preferably represent an oxygen atom.

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

In the formulae (a) to (d), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a divalent linking group, and there is no particular structural limitation. Specific examples of the divalent linking group represented by Y ¹ , Y ² , Y ³ or Y ⁴ include the following linking group (Y-1) to a linking group (Y-21). In the following structures (Y-1) to (Y-21), A indicates between Y ¹ and W ¹ , Y ² and W ² , and Y ³ in the formulae (a) to (d), respectively. a bond between W ^{3 and} between Y ⁴ and W ⁴ , and B indicates that Y ¹ , Y ² , Y ³ , Y ⁴ and W ¹ , W ² , W in the formulae (a) to (b), respectively. ³ , the key between the parts of the W ⁴ alignment. Among the following structures, (Y-2) and (Y-13) are preferred in terms of ease of synthesis.

In the formulae (a) to (d), Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a monovalent organic group and have no particular structural limitations. Specific examples of Z ¹ , Z ² , Z ³ and Z ⁴ include alkyl, hydroxy, alkoxy, aryloxy, heteroaryloxy, alkyl sulfide, aryl sulfide, heteroaryl sulfide Base and amine group. Among them, the monovalent organic group represented by Z ¹ , Z ² , Z ³ and Z ⁴ preferably has a steric hindrance effect from the viewpoint of improving dispersibility. The organic groups represented by Z ¹ to Z ³ each independently represent an alkyl group having 5 to 24 carbon atoms or an alkoxy group having 5 to 24 carbon atoms, preferably each independently representing a branched alkane. And an alkoxy group having 5 to 24 carbon atoms or an alkoxy group having a cyclic alkyl group and having 5 to 24 carbon atoms. Further, the organic groups represented by Z ⁴ each preferably independently represent an alkyl group having 5 to 24 carbon atoms, and specifically, each preferably independently represents a branched chain having 5 to 24 carbon atoms. An alkyl group or a cyclic alkyl group having 5 to 24 carbon atoms.

In the formulae (a) to (d), n, m, p, and q each independently represent an integer of 1 to 500.

In the formulas (a) and (b), j and k each independently represent an integer of 2 to 8. In the formulae (a) and (b), j and k are preferably an integer of 4 to 6 from the viewpoint of dispersion stability and developability, and are most preferably 5.

In the formula (c), R ³ represents a branched chain or a linear alkylene group. In the formula (c), R ^{3 is} preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 to 3 carbon atoms.

In the formula (d), R ⁴ represents a hydrogen atom or a monovalent organic group and the monovalent organic group has no particular structural limitation. In the formula (d), R ^{4 is} preferably a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. In the case where R ⁴ is an alkyl group in the formula (d), 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 having 5 The cyclic alkyl group to 20 carbon atoms 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. In the formula (d), when a plurality of R ⁴ are present in the graft copolymer, the plurality of R ⁴ may be the same or different from each other.

In the graft copolymer, the content of the structural unit represented by any one of the formulae (a) to (d) is preferably from 10% by mass to 90% by mass based on the total mass of the graft copolymer, and More preferably, it is 30% by mass to 70% by mass. When the content of the structural unit represented by any one of the formulae (a) to (d) is within the above range, the dispersibility of the pigment is high, and the developability during formation of the light-shielding film is excellent.

In addition, there may be two or more than two kinds of graft copolymers having different structures from each other.

The structural unit represented by the formula (a) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of dispersion stability and developability.

In addition, the structural unit represented by the formula (b) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of dispersion stability and developability.

X ¹ , Y ¹ , Z ¹ and n in the formula (1A) have the same definitions as X ₁ , Y ¹ , Z ¹ and n in the formula (a), respectively, and a preferred range thereof (including preferred examples) is also the same.

X ² , Y ² , Z ² and m in the formula (2A) have the same definitions as X ² , Y ² , Z ² and m in the formula (b), respectively, and preferred ranges thereof (including preferred examples) are also the same.

The structural unit represented by the formula (c) is more preferably a structural unit represented by the following formula (3A) or the following formula (3B) from the viewpoint of dispersion stability and developability.

X ³ , Y ³ , Z ³ and p in the formula (3A) or the formula (3B) have the same definitions as X ³ , Y ³ , Z ³ and p in the formula (c), respectively, and a preferred range thereof (including The preferred embodiment) is also the same.

The graft copolymer is more preferably a structural unit represented by the above-mentioned formula (1A).

Specific examples of the graft copolymer include the following compounds. In the following exemplary compounds, the numerical values shown together with the respective structural units mean the content of the corresponding structural unit [% by mass, arbitrarily referred to as "(% by weight)"]. The values described next to the repeating units of the side chain each indicate the number of repeats of the repeating unit.

The dispersing agent used in the present invention is preferably a compound having a polyester chain such as exemplified compound 72.

The content of the dispersant used in the preparation of the particle dispersion 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 solid mass of the particle dispersion liquid.

The particle dispersion preferably further contains an organic solvent, and may further optionally contain an alkali-soluble binder, a surfactant, or the like.

When the particle dispersion further contains an organic solvent, the content of the light-shielding particles in the particle dispersion is preferably from 2% by mass to 15% by mass, more preferably from 3% by mass to 10% by mass, and most preferably from 4% by mass to 8% by mass. . When the content is higher than the upper limit of the above range, the dispersion stability of the particles will be deteriorated with time, and when the content is lower than the lower limit of the above range, the light-shielding property will be deteriorated when applied in the form of a light-shielding composition.

Filler dispersion (ie, first filler dispersion) (B) The content of a filler is preferably from 0.1% by mass to 5% by mass, more preferably from 0.1% by mass to 3% by mass, and most preferably from 0.1% by mass to 2% by mass. When the content is higher than the upper limit of the above range, the dispersion stability of the particles deteriorates with time, and when the content is lower than the lower limit of the above range, the thickness uniformity on the uneven surface (i.e., the action of the present invention) is slightly deteriorated.

The content of the (C) second filler in the filler dispersion (that is, the second filler dispersion) is preferably from 1% by mass to 20% by mass, more preferably from 1% by mass to 15% by mass, and most preferably 1% by mass to 10% by mass. When the content is higher than the upper limit of the above range, the dispersion stability of the particles deteriorates with time, and when the content is lower than the lower limit of the above range, the thickness uniformity on the uneven surface (i.e., the action of the present invention) is slightly deteriorated.

Solvent

The solvent to be used for each particle dispersion liquid and the light-shielding composition is not particularly limited. Any solvent may be appropriately selected depending on the intended purpose as long as it can uniformly dissolve or disperse the respective components of the light-shielding composition of the present invention. Examples of suitable solvents 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, Cyclohexanone, diisobutyl ketone, cyclohexanone or cyclopentanone; esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, methyl phthalate, Ethyl benzoate, propylene glycol monomethyl ether acetate or methoxypropyl acetate; aromatic hydrocarbons such as 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, propylene glycol monomethyl ether or dipropylene glycol monomethyl ether; and dimethylformamide, dimethylacetamide, dimethylhydrazine, and cyclobutyl hydrazine.

Particularly preferred is 1-methoxy-2-propanol, propylene glycol monomethyl ether acetate or dipropylene glycol monomethyl ether, and the solvent preferably contains propylene glycol monomethyl ether acetate.

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

The content of the light-shielding particles in the dispersion containing the light-shielding particles is preferably from 30% by mass to 80% by mass, and more preferably from 40% by mass to 70% by mass, based on the total solid content (mass) in the dispersion. When the content of the light-shielding particles is within the above range, the light-shielding particles tend to be easily dispersed and the stability of the resulting dispersion is excellent.

In the dispersion containing (B) the first filler, (B) the content of the first filler and the content of the (C) second filler in the dispersion containing (C) the second filler, B) the total solid content (mass) in the filler dispersion of the first filler (that is, the first filler dispersion), and (B) the content of the first filler is preferably from 20% by mass to 70% by mass. More preferably, it is 30% by mass to 50% by mass, and based on the total solid content (mass) in the filler dispersion liquid (that is, the second filler dispersion liquid) containing (C) the second filler, (C) The content of the second filler is preferably from 3% by mass to 30% by mass, and more preferably from 5% by mass to 20% by mass. When the contents of the first filler and the second filler are respectively within the above ranges, the filler tends to be easily dispersed and the stability of the resulting dispersion is good.

Dispersing agent in each particle dispersion based on the mass of the light-shielding particles contained in the particle dispersion, (B) the first filler or (C) the second filler The content is preferably from 30% by mass to 80% by mass, and more preferably from 40% by mass to 80% by mass. When the content of the dispersant is in the above range, the particles tend to be easily dispersed and the stability of the resulting dispersion is good.

The light-shielding composition of the present invention preferably contains (A) a dispersion of any one of the light-shielding particles or the light-shielding dye, (B) a dispersion of the first filler, and (C) a dispersion of the second filler, and more Containing (D) a polymerizable compound and (E) a photopolymerization initiator. When the light-shielding composition contains these components, the composition is radiation-sensitive and thus capable of forming a pattern or having a curing property.

(D) polymerizable compound

The light-shielding composition of the present invention preferably contains (D) a polymerizable compound.

The polymerizable compound used herein may have a functional group capable of reacting with at least one of an acid, a radical or a heat in a molecule (in the present specification, the functional group may be referred to as a "polymerizable group") Any compound. The polymerizable compound is preferably a polyfunctional polymerizable compound having a plurality of polymerizable groups in the molecule.

Preferred examples of the present invention having a polymerizable compound capable of reacting with at least one of an acid, a radical or a heat include an ethylenically unsaturated group-containing compound containing an ethylenically unsaturated group such as An unsaturated ester functional group, an unsaturated decylamino group, a vinyl ether group or an allyl group; and a methylol compound; a bis-n-butyleneimine compound; a benzocyclobutene compound; a bis(allyl) a bis(allyl)nadimide compound; and a benzoxazine compound.

Examples of polymerizable compounds which can be preferably used in the present invention include general The radical polymerizable compound, and a compound having an ethylenically unsaturated double bond well known in the art can be used without particular limitation. For example, these compounds can have chemical forms such as monomers, prepolymers (i.e., dimers, trimers, and oligomers) or mixtures and copolymers thereof.

Examples of the monomer and its copolymer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid) and esters thereof. The guanamine and the copolymer, and preferably comprise an unsaturated carboxylic acid ester, an ester of an unsaturated carboxylic acid and an aliphatic polyol compound, and a guanamine formed from an unsaturated carboxylic acid and an aliphatic polyvalent amine compound.

In particular, an ester formed of an unsaturated carboxylic acid and an aliphatic polyol compound can impart high hydrophobicity to an exposed region, and thus it is preferable to easily form a pattern having a desired shape by alkali development and obtain high durability. Sexual pattern. In particular, the above effects are remarkable in the case where the wire density of the metal wire coated with the solder resist is high or the solder resist requires a particularly high resistance.

Further, it is preferred to use an addition reaction product of an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group, an amine group or a mercapto group, or a guanamine with a monofunctional or polyfunctional isocyanate or epoxide, or Dehydration condensation reaction product of an unsaturated carboxylic acid ester or decylamine with a monofunctional or polyfunctional carboxylic acid.

Also, among these compounds, an unsaturated carboxylic acid ester having an electrophilic substituent such as an isocyanate group or an epoxy group; an addition reaction product of a guanamine with a monofunctional or polyfunctional alcohol, an amine or a thiol; An unsaturated carboxylic acid ester having a substituent (such as a halogen group and a toluenesulfonyloxy group); A substituted reaction product of an amine with a monofunctional or polyfunctional alcohol, amine or thiol. A compound obtained by replacing the above carboxylic acid with an unsaturated phosphonic acid, styrene, vinyl ether or the like can be used.

The unsaturated carboxylic acid ester is preferably a methacrylate, and examples thereof include tetramethylene glycol dimethacrylate, triethylene golycol dimethacrylate, neopentyl glycol. Neopentyl glycol dimethacrylate, trimethylol propane trimethacrylate, trimethylol ethane trimethacrylate, ethylene glycol dimethyl Ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate (pentaerythritol) Dimethacrylate), pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbus Sugar alcohol three Sorbitol trimethacrylate, sorbitol tetramethacrylate, bis[p-(3-methylpropenyloxy-2-hydroxypropoxy)phenyl]dimethylmethane ( Bis[p-(3-methacryloxy-2-hydroxypropoxy)phenyl]dimethyl methane) and bis[p-(methacryloxyethoxy)phenyl]dimethyl Bis (bis[p-(methacryloxyethoxy)phenyl)dimethyl methane), and its EO-modified compound and PO-modified compound.

The unsaturated carboxylic acid ester is preferably itaconate, and examples thereof include ethylene glycol pentoxide, propylene glycol conjugated acid ester, 1,3-butylene glycol isaconate, and 1,4- Butanediol diitaconate, butanediol diitaconate, pentaerythritol diitaconate, and sorbitol tetraconconate. Examples of the crotonate include ethylene glycol dicrotonate, butanediol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetracrotonate. Examples of the isocrotonate include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleic acid. ester.

Specific examples of the ester monomer formed of the aliphatic polyol compound and the unsaturated carboxylic acid include (meth) acrylate such as ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3-butylene glycol Acrylate, butanediol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris(propylene oxypropyl) ether, trihydroxyl Methyl ethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, tricyclodecane dimethanol diacrylate, tricyclodecane II Methanol dimethacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbose Alcohol pentaacrylate, sorbitol hexaacrylate, tris(propylene methoxyethyl) Cyanurate and polyester acrylate oligomers. Further, an EO-modified compound or a PO-modified compound of these compounds can be used.

Other examples of preferred esters include aliphatic alcohol esters as described in JP-B No. 51-47334 and JP-A No. 57-196231; such as JP-A No. 59-5240, JP-A No. 59- An ester having an aromatic skeleton described in No. 5241 and JP-A No. 2-226149; and an ester having an amine group as described in JP-A No. 1-156613. Mixtures of ester monomers can also be used.

Examples of the guanamine monomer formed by the reaction between the aliphatic polyvalent amine compound and the unsaturated carboxylic acid include methylene bis acrylamide, methylene bis methacrylamide, 1,6-hexamethylene Bis-acrylamide, 1,6-hexamethylene bismethyl acrylamide, di-extension ethyltriamine tripropylene decylamine, xylylene bis acrylamide and xylylene bis methacrylamide. Preferred examples of the other monomer containing a decylamine include a monomer having a cyclohexylene structure as described in JP-B No. 54-21726.

The urethane-containing addition polymerizable compound produced by the addition reaction between an isocyanate and a hydroxyl group is also preferable, and an example thereof is as described in JP-B No. 48-41708 by The addition of a hydroxyl group-containing vinyl monomer shown in E) to a polyisocyanate compound having two or more than two isocyanate groups in the molecule is prepared by containing two or more than two polymerizable vinyl groups in the molecule. Vinyl carbamate compound.

CH ₂ =C(R ⁴ )COOCH ₂ CH(R ⁵ )OH Formula (E)

In the formula (E), R ⁴ and R ⁵ each independently represent H or CH ₃ .

Further, urethane acrylate (such as those described in JP-A No. 51-37193 and JP-B No. 2-32293 and JP-B No. 2-16765) An urethane urethane) and an ethylene oxide skeleton as described in JP-B Nos. 58-49860, 56-17654, 62-39417, and 62-39418 A urethane compound is also preferred. In addition, when an addition polymerizable compound having an amine structure or a sulfide structure in a molecule as described in JP-A Nos. 63-277653, 63-260909, and 1-105238 is obtained, A photopolymerizable composition of excellent photospeed.

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

When a radical polymerizable compound is to be added in the present invention, a polyfunctional polymerizable compound containing two or more ethylenically unsaturated bonds is preferably used from the viewpoint of curing sensitivity, and more preferably contains A polyfunctional polymerizable compound having three or more than one ethylenically unsaturated bond. In particular, a polyfunctional polymerizable compound containing two or more than two (meth) acrylate structures preferably has three or more than three (meth) acrylate structures. The polyfunctional polymerizable compound is more preferable, and the polyfunctional polymerizable compound having four or more (meth) acrylate structures is most preferable.

From the viewpoint of curing sensitivity and developability of an unexposed region, a compound containing an EO-modified compound is preferably used. From the viewpoint of curing sensitivity and strength of the exposed region, a compound containing a urethane bond is preferably used. The acid group-containing compound is preferred from the viewpoint of developability during pattern formation.

From these viewpoints, examples of preferred polymerizable compounds used in the present invention include bisphenol A diacrylate, EO-modified bisphenol A diacrylate, trimethylolpropane triacrylate, trimethylol Propane tris(propylene methoxypropyl)ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate , dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tris(propylene methoxyethyl) Isocyanurate, EO-modified pentaerythritol tetraacrylate, and EO-modified dipentaerythritol hexaacrylate. Further, commercially available polymerizable compound products include urethane oligomers UAS-10, UAB-140 (all of which are trade names, manufactured by Sanyo Kokusaku Pulp Corp.); DPHA-40 H (trade name, manufactured by Nippon Kayaku Co., Ltd.); UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (all are trademarks) Name, manufactured by Kyoeisha Chemical Co., Ltd.).

Among them, EO modified bisphenol A diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tris(propylene oxyethyl) isocyanurate, EO Modified pentaerythritol tetraacrylate and EO-modified dipentaerythritol hexaacrylate are preferred. A more preferable commercial product is DPHA-40H (trade name, manufactured by Nippon Kayaku Co., Ltd.); UA-306H, UA-306T, UA-306I, AH-600, T-600 AI-600 (all of which are trade names, manufactured by Kyoeisha Chemical Co., Ltd.).

The ethylenically unsaturated compound having an acidic group is also preferred, 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 pentafunctional acrylate having a carboxyl group. (All are trademark names, manufactured by Toagosei Co., Ltd.).

Other examples include highly heat resistant polymerizable compounds such as benzocyclobutene (BCB), bis(allyl)nadimide (BANI), benzoxazine, melamine, and the like. Its analogues.

The polymerizable compound may be used in combination of two or more types.

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

When the polymerizable compound is a polymer, the polymerizable compound may be the same as the alkali-soluble binder described in detail below (ie, the polymerizable compound and the alkali solution) The adhesive can be the same component). In this case, the content of the polymerizable compound is preferably from 3% by mass to 80% by mass, and more preferably from 5% by mass to 60% by mass based on the total solid mass of the light-shielding composition of the present invention.

(E) Photopolymerization initiator

The light-shielding composition of the present invention preferably contains (E) a photopolymerization initiator.

In the present invention, any photopolymerization initiator is not particularly limited as long as it can initiate polymerization of the polymerizable compound in response to at least one of light and heat, and can be appropriately selected depending on the purpose. The photopolymerization initiator is preferably a photopolymerizable compound. When it is desired to use light-initiated polymerization, a photopolymerization initiator which is photosensitive to light in the ultraviolet region to the visible region is preferred.

When it is desired to use a thermally initiated polymerization, an initiator which decomposes at 150 ° C to 250 ° C is preferred.

The photopolymerization initiator which can be used in the present invention is preferably a compound having at least one aromatic group, and examples thereof include a mercaptophosphine compound, an acetophenone compound, an α-aminoketone compound, a benzophenone compound, Benzoin ether compound, ketal derivative compound, thioxanthone compound, hydrazine compound, hexaarylbiimidazole compound, trihalomethyl compound, azo compound, organic peroxide; sulfonium salt compound, such as heavy A nitrogen compound, an anthraquinone compound, an anthraquinone compound or an azinium compound; a metallocene compound, an organic boron salt compound, and a diterpene compound.

From the viewpoint of sensitivity, an anthracene compound, an acetophenone compound, an α-aminoketone compound, a trihalomethyl compound, a hexaarylbiimidazole compound, and a thiol compound are preferred.

Hereinafter, although an example of a preferred photopolymerization initiator in the present invention will be described, the invention is not limited to the examples.

Specific examples of the acetophenone compound include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and Dimethylaminoacetophenone, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 1-hydroxy-cyclohexyl-phenyl-one, 2-benzyl-2-dimethylamino 1-(4-morpholinylphenyl)-butanone-1,2-tolyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-A 1-[4-(methylthio)phenyl]-2-morpholinylacetone-1,2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1 -ketone, 2-benzyl-2-ylamino-1-(4-morpholinylphenyl)-butanone-1,2-(dimethylamino)-2-[(4-methyl) Phenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone and 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl Propan-1-one.

More suitable trihalomethyl compounds are at least one mono-halogen, dihalo or trihalogen substituted methyl group bonded to the s-triazine ring s-triazine derivative, and specific examples thereof include 2, 4, 6 -Tris(monochloromethyl)-s-triazine, 2,4,6-tris(dichloromethyl)-s-triazine, 2,4,6-tris(trichloromethyl)-s-three Pyrazine, 2-methyl-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-phenyl-4,6-bis(trichloromethyl)-s-triazine , 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3,4-epoxyphenyl)-4,6-bis(three Chloromethyl)-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-styryl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-isopropoxystyryl)-4,6-bis(trichloro) Methyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenylthio-4,6-bis(trichloromethyl) )-s-triazine, 2-phenylmethylthio-4,6-bis(trichloromethyl)-s-triazine, 2,4,6-tris(dibromomethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine and 2-methoxy-4,6 - bis(tribromomethyl)-s-triazine.

Examples of the hexaarylbiimidazole compound include a plurality of compounds disclosed in JP-A No. 6-29285 and U.S. Patent Nos. 3,479,185, 4,311,783 and 4,622,286, and the like, and specific examples thereof include 2,2 '-Bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-bromophenyl)-4,4',5,5'-four Phenylbiimidazole, 2,2'-bis(o-, p-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-chlorophenyl) -4,4',5,5'-tetrakis(m-methoxyphenyl)biimidazole, 2,2'-bis(o-,o-di-dichlorophenyl)-4,4',5,5' -tetraphenylbiimidazole, 2,2'-bis(o-nitrophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-tolyl)-4 4',5,5'-tetraphenylbiimidazole and 2,2'-bis(o-trifluorophenyl)-4,4',5,5'-tetraphenylbiimidazole.

Examples of bismuth compounds include the British Chemical Society: JC Perkin II (1979), pages 1653 to 1660; British Chemical Society: Berkin Journal, Series 2 (JCS Perkin) II) (1979) pp. 156-162; Journal of Photopolymer Science and Technology (1995), pp. 202-232; and JP-A No. 2000-66385 The compound described, and the compound described in JP-A No. 2000-80068 and Japanese National Publication No. 2004-534797. It is also preferred to use commercially available products such as IRGACURE OXE 01 (1-[4-(phenylthio))-2-(O-) Benzopyridinium)]-1,2-octanedione), Yanjiao OXE 02 (1-[9-ethyl-6-(2-methylbenzimidyl)-9H-carbazole-3 -yl]-1-(O-acetamidoxime)-ethanone), 2-(ethyloxyiminomethyl)thioxanthene-9-one (all trade names, by BASF Japan (BASF) Manufactured by Corporation, Japan).

The cyclic anthraquinone compounds disclosed in JP-A No. 2007-231000 and JP-A No. 2007-322744 are also preferred. The hydrazine compound having a specific substituent as disclosed in JP-A No. 2007-269779 or the sulfonium compound having a thioaryl group disclosed in JP-A No. 2009-191061 is also preferred.

Specifically, the hydrazine compound is preferably a compound represented by the following formula (i). In addition, the ruthenium compound may be an oxime compound of the (E) type in which the NO bond of the ruthenium is (E) type, or the (Z) type ruthenium compound of the ruthenium NO bond may be (E) type and ( Mixture of type Z).

In the formula (i), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.

The monovalent substituent represented by R in the formula (i) is preferably a monovalent non-metal atomic group. Examples of monovalent non-metal radicals include alkyl, aryl, decyl, alkoxycarbonyl, aryloxycarbonyl, heterocyclyl, alkylthiocarbonyl, and arylthiocarbonyl. Additionally, these groups may each have one or more substituents. Further, the substituent may be further substituted with another substituent.

Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a decyloxy group, a decyl group, an alkyl group, and an aryl group.

The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms. Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, second butyl group, and third butyl group. , 1-ethylpentyl, cyclopentyl, cyclohexyl, trifluoromethyl, 2-ethylhexyl, benzamidine methyl, 1-naphthylmethylmethyl, 2-naphthylmethylmethyl , 4-methylthiobenzhydrylmethyl, 4-phenylthiobenzimidylmethyl, 4-dimethylaminobenzimidylmethyl, 4-cyanobenzhydrylmethyl, 4-methylbenzene Formamidine methyl, 2-methylbenzimidylmethyl, 3-fluorobenzhydrylmethyl, 3-trifluoromethylbenzimidylmethyl, and 3-nitrobenzimidylmethyl.

The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms. Specific examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 9-anthyl group. , 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2- 2-azulenyl group, 9-fluorenyl group, terphenyl group, quaterphenyl group, o-tolyl group, m-toluene M-tolyl group, p-tolyl group, xylyl group, o-cumenyl group, m-cumenyl group, P-cumenyl group, mesityl group, pentalenyl group, binaphthyl Binaphthalenyl group, ternaphthalenyl group, quaternaphthalenyl group, heptalenyl group, biphenylenyl group, dicyclopentadiene Indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, phenalenyl group, fluorenyl group, anthryl Group), bianthracenyl group, teranthracenyl group, quateranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl Group), pyrenyl group, chrysenyl group, naphthacenyl group, pleiadenyl group, picenyl group, perylenyl group, lianwu Pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubicenyl group Coron Enyl group), a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalenyl group.

The fluorenyl group which may have a substituent is preferably a fluorenyl group having 2 to 20 carbon atoms. Specific examples thereof include an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, a trifluoroethyl fluorenyl group, a pentamidine group, a benzamyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 4-methylthiophenyl group. Sulfhydryl, 4-phenylthiobenzimidyl, 4-dimethylaminobenzamide Sulfhydryl, 4-diethylaminobenzhydryl, 2-chlorobenzhydryl, 2-methylbenzhydryl, 2-methoxybenzimidyl, 2-butoxybenzimidyl , 3-chlorobenzhydryl, 3-trifluoromethylbenzhydryl, 3-cyanobenzylidene, 3-nitrobenzhydryl, 4-fluorobenzhydryl, 4-cyano Benzopyridinyl and 4-methoxybenzimidyl.

The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms. Specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a hexyloxycarbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethoxycarbonyl group.

Specific examples of the aryloxycarbonyl group which may have a substituent include a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a 4-methylthiophenoxycarbonyl group, a 4-phenylthiophenoxycarbonyl group, and a 4-dimethyl group. Aminophenoxycarbonyl, 4-diethylaminophenoxycarbonyl, 2-chlorophenoxycarbonyl, 2-methylphenoxycarbonyl, 2-methoxyphenoxycarbonyl, 2-butoxyphenoxycarbonyl, 3 -Chlorophenoxycarbonyl, 3-trifluoromethylphenoxycarbonyl, 3-cyanophenoxycarbonyl, 3-nitrophenoxycarbonyl, 4-fluorophenoxycarbonyl, 4-cyanophenoxycarbonyl, and 4-methyl Oxyphenoxycarbonyl.

The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.

Specific examples thereof include a thienyl group, a benzo[b]thienyl group, and a naphtho[2,3-b]thienyl group. , thianthrenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group Phenylthio (phenoxanthiinyl group), 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl Group), pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, 吲哚Indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolizinyl group, isoquinolyl group, quinolinyl group Quinolyl group), phthalazinyl group, naphthyridinyl group, quinoxalinyl group, quinazolinyl group, cinnolinyl group, acridinyl group Pteridinyl group), 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group ), perimidinyl group, phenanthrolinyl group, phenazinyl Inyl group), phenarsazinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazine Phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl (imidazolidinyl group), imidazolinyl group, pyrazolidinyl (pyrazolidinyl group), pyrazolinyl group, piperidyl group, piperazinyl (group), indolinyl group, isoindolinyl group, quinine Quinuclidinyl group, morpholinyl group, and thioxantholyl group.

Specific examples of the alkylthiocarbonyl group which may have a substituent include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a sulfonium carbonyl group, an octadecylthiocarbonyl group, and a trifluoromethylthiocarbonyl group.

Specific examples of the alkylthiocarbonyl group which may have a substituent include 1-naphthalenethiocarbonyl, 2-naphthylthiocarbonyl, 4-methylthiophenylthiocarbonyl, 4-phenylthiophenylthiocarbonyl, 4-dimethylamino Phenylthiocarbonyl, 4-diethylaminophenylthiocarbonyl, 2-chlorophenylthiocarbonyl, 2-methylphenylthiocarbonyl, 2-methoxyphenylthiocarbonyl, 2-butoxybenzenesulfide Carbocarbonyl, 3-chlorophenylthiocarbonyl, 3-trifluoromethylphenylthiocarbonyl, 3-cyanophenylthiocarbonyl, 3-nitrophenylthiocarbonyl, 4-fluorophenylthiocarbonyl, 4- Cyanophenylthiocarbonyl and 4-methoxyphenylthiocarbonyl.

The monovalent substituent represented by B in the formula (i) represents an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group. These groups may have one or more substituents. The substituent may be exemplified as the substituent. Further, the substituent may be further substituted with another substituent.

In particular, the following structures are particularly preferred. In the following structures, Y, X and n have the same definitions as Y, X and n in the formula (ii) described below, respectively, and preferred examples thereof are also the same.

Examples of the divalent organic group represented by A in the formula (i) include an alkylene group, a cyclohexylene group and an alkynylene group each having 1 to 12 carbon atoms. These groups may have one or more substituents. The substituent may be exemplified as the substituent. Further, the substituent may be further substituted with another substituent.

In particular, in terms of enhancing sensitivity and suppressing coloring due to heat aging, A in the formula (i) preferably represents an unsubstituted alkylene group, an alkyl group (such as a methyl group, an ethyl group). a tert-butyl or dodecyl substituted alkyl group, an alkyl group substituted by an alkenyl group such as a vinyl group or an allyl group, and an aryl group such as a phenyl group, a p-tolyl group, or a xylene group. Alkyl, cumyl, naphthyl, anthracenyl, phenanthryl or styryl) substituted alkyl.

The aryl group represented by Ar in the formula (i) is preferably an aryl group having 6 to 30 carbon atoms and may have a substituent. Examples of the substituent include the same substituents as those introduced in the substituted aryl group described above as a specific example of the aryl group which may have a substituent.

In particular, Ar in the formula (i) is preferably a substituted or unsubstituted phenyl group from the viewpoint of enhancing sensitivity and suppressing coloring due to heat aging.

In the formula (i), from the viewpoint of sensitivity, the "SAr" structure formed of Ar and adjacent S is preferably the structure shown below. In this case, "Me" represents a methyl group, and "Et" represents an ethyl group.

The hydrazine compound is preferably a compound represented by the following formula (ii).

In the formula (ii), R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n represents an integer of 0 to 5.

R, A and Ar in the formula (ii) have the same definitions as R, A and Ar in the above formula (i), respectively, and the preferred ranges thereof (including preferred examples) are also the same.

Specific examples of the monovalent substituent represented by X include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a decyloxy group, a decyl group, an alkoxycarbonyl group, an amine group, a heterocyclic group, and a halogen atom. These groups may each have one or more substituents. Examples of the substituent may include the substituents described above. The substituent may be further substituted with another substituent.

Among them, X preferably represents an alkyl group from the viewpoints of solvent solubility and improvement in absorption efficiency in a long wavelength region.

Further, n in the formula (ii) represents an integer of 0 to 5, and preferably represents an integer of 0 to 2.

Examples of the divalent organic group represented by Y in the formula (ii) include the following structures. In the group described below, " ^* " represents a bonding position of a carbon atom adjacent to Y in the above formula (ii).

Among the above structures, the structure shown below is preferable from the viewpoint of enhancing sensitivity.

Further, the ruthenium compound is preferably a compound represented by the following formula (iii).

R, X, A, Ar and n in the formula (iii) have the same definitions as R, X, A, Ar and n in the formula (ii) described above, respectively, and a preferred range thereof (including The example is the same.

While specific examples (C-4) to specific examples (C-13) of the preferred oxime compounds are shown below, it should be understood that the invention is not limited to the examples.

The maximum absorption wavelength of the ruthenium compound is preferably in the wavelength range of from 350 nm to 500 nm, more preferably in the wavelength range of from 360 nm to 480 nm, and particularly preferably at 365 nm and 455 nm. High absorption degree.

From the viewpoint of sensitivity, the molar absorption coefficient of the cerium compound at 365 nm or 405 nm is preferably from 3,000 to 300,000, more preferably from 5,000 to 300,000, and particularly preferably from 10,000 to 200,000.

The molar absorption coefficient of the compound can be measured by a known method. In particular, it is preferably used, for example, an ultraviolet-visible spectrophotometer (trade name: CARRY-5 SPECTROPHOTOMETER, manufactured by Varian) at a concentration of 0.01 g/liter. Next, the molar absorption coefficient was measured using an ethyl acetate solvent.

The photopolymerization initiator is more preferably a compound selected from the group consisting of an anthracene compound, an acetophenone compound, and a mercaptophosphine compound. Specific examples thereof include the amino acetophenone starter disclosed in JP-A No. 10-291969, and in particular, the mercaptophosphine oxide starter disclosed in Japanese Patent No. 4258899 and the prior art An initiator, and in particular, a hydrazine initiator, such as the compound disclosed in JP-A No. 2001-233842.

Examples of the acetophenone starter include commercially available products, Yanjiagu-907, Yanjiagu-369, and Yanjiagu-379 (both trade names, manufactured by BASF Corporation, Japan). Examples of mercaptophosphine starters include mercaptophosphine starters, including commercially available products such as Yanjiao-819 or DAROCURE-TPO (both trade names, by BASF Japan) BASF Corporation, Japan))).

The photopolymerization initiator may be used singly or in combination of two or more types.

Photopolymerization in the shading composition of the present invention based on the total solid mass of the composition The content of the starting agent is preferably from 0.01% by mass to 30% by mass, more preferably from 0.1% by mass to 20% by mass, and particularly preferably from 0.1% by mass to 15% by mass.

Hereinafter, other components preferably contained in the light-shielding composition of the present invention will be described.

Sensitizer

The light-shielding composition of the present invention preferably contains a sensitizer.

When a sensitizer and a photopolymerization initiator are used in combination, a light-shielding composition having high adhesion can be obtained even when the illuminance is relatively low during radiation curing.

Examples of sensitizers include amine compounds as disclosed in the following documents: MR Sander et al., Journal of Polymer Society, Vol. 10, p. 3173 (1972); JP -B No. 44-20189, JP-A No. 51-82102, JP-A No. 52-134692, JP-A No. 59-138205, JP-A No. 60-84305, JP-A No. 62- No. 18537, JP-A No. 64-33104 and Research Disclosure No. 33825. Specific examples thereof include triethanolamine, p-dimethylaminoethyl benzoate, p-mercaptodimethylaniline, and p-methylthiodimethyl.

Other examples of the sensitizer include a thiol and a sulfide, such as a thiol compound disclosed in JP-A No. 53-702, JP-B No. 55-500806, and JP-A No. 5-142772, JP- A disulfide compound disclosed in No. 56-75643 and analogs thereof. Specific examples thereof include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, N-phenylmercaptobenzimidazole, 2-mercapto-4(3H)-quinazoline, and β- Mercaptophthalene.

Other examples thereof include amino acid compounds (for example, N-phenylglycine and the like), and organometallic compounds (for example, tributylacetate and the like) disclosed in JP-B No. 48-42965. A hydrogen donor disclosed in JP-B No. 55-34414, a sulfur compound disclosed in JP-A No. 6-308727 (for example, trithiane and the like), and the like.

From the viewpoint of increasing the curing rate by the balance between the polymer growth rate and the chain transfer, the content of the sensitizer is preferably from 0.1% by mass to 30% by mass based on the total solids of the light-shielding composition, more preferably 1% by mass to 25% by mass, and most preferably 0.5% by mass to 20% by mass.

Alkali-soluble binder

The light-shielding composition of the present invention preferably contains an alkali-soluble binder.

In the case where the light-shielding composition contains an alkali-soluble binder, the unexposed area can be removed by the alkali developing solution at the time of exposure to form a pattern on the film formed of the light-shielding composition, and thus an excellent pattern is formed by alkali development. .

The alkali-soluble binder is not particularly limited as long as it is alkali-soluble, and can be appropriately selected depending on the purpose. Examples thereof include (meth)acrylic resins, urethane resins, polyvinyl alcohol, polyvinyl butyral, polyvinyl formal, polyamine, and polyester. Among them, a (meth)acrylic resin or a urethane resin is preferred.

In particular, the alkali-soluble binder is more preferably a urethane resin from the viewpoint of further improving the heat cycle test resistance (TCT resistance).

The alkali-soluble binder preferably has an acidic group.

Examples of the acidic group include a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, and a phosphoric acid group. Ester group and guanamine group. The acid group is preferably a carboxylic acid group from the viewpoint of availability of the material.

The alkali-soluble binder having an acidic group is not particularly limited and is preferably a polymer obtained by using a polymerizable compound having an acidic group as a monomer component. From the viewpoint of the controllability of the acid value, a copolymer obtained by copolymerizing a polymerizable compound having an acidic group with a polymerizable compound having no acidic group is more preferable.

The polymerizable compound having an acidic group is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, and p-carboxystyrene. Among them, acrylic acid, methacrylic acid and p-carboxystyrene are preferred. These materials may be used singly or in combination of two or more types.

The polymerizable compound having no acidic group is not particularly limited, but preferred examples thereof include a (meth) acrylate such as an alkyl ester, an aryl ester or an arylalkyl ester.

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

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

a monomer corresponding to a polymerizable compound having an acidic group and corresponding a molar ratio of a monomer to a polymerizable compound having no acidic group (that is, a monomer corresponding to a polymerizable compound having an acidic group: a monomer corresponding to a polymerizable compound having no acidic group) It is usually from 1:99 to 99:1, preferably from 30:70 to 99:1, and more preferably from 50:50 to 99:1.

Although the content of the acidic group in the alkali-soluble binder is not particularly limited, it is preferably from 0.5 meq/g to 4.0 meq/g, and more preferably from 1.0 meq/gram to 3.0 meq/g. When the content is higher than or equal to 0.5 meq/g, alkali developability is sufficiently obtained and an excellent pattern is obtained. When the content is less than or equal to 4.0 meq/g, the strength of the permanent pattern is surely prevented from deteriorating.

Preferably, the alkali soluble binder further contains a crosslinkable group. In this case, both the hardening property of the exposed region and the alkali developability of the unexposed region are improved, and a pattern having high durability is obtained (specifically, the wire density of the metal wire coated with the solder resist is high) The above effects are remarkable in the case where the solder resist requires a large resistance. The term "crosslinkable group" refers to a group capable of crosslinking a binder polymer during polymerization which is carried out upon exposure or heating of a photosensitive layer obtained using a light-shielding composition. Any group may be used without particular limitation as long as it has the function, and examples thereof include a functional group capable of addition polymerization, such as an ethylenically unsaturated bond group, an amine group or an epoxy group. In addition, a functional group capable of generating a radical due to light irradiation may be used, and examples of the crosslinkable group include a thiol group and a halogen group. Among them, an ethylenically unsaturated bond group is preferred. The olefinic system is not sufficient from the viewpoint of the balance between the stability of the crosslinkable group and the strength of the permanent pattern before exposure. The bond group and the bond group are preferably a styryl group, a (meth) acrylonitrile group or an allyl group, and more preferably a (meth) acrylonitrile group.

Alkali-soluble binders can be cross-linkable functional groups with free radicals, for example, by polymer chain reaction directly between polymers or via polymerizable compounds (eg, polymerization initiation radicals or during polymerization of polymerizable compounds) The addition reaction occurs between the radicals and forms a crosslink between the polymers to cure. Alternatively, atoms in the polymer (eg, hydrogen atoms on carbon atoms adjacent to the functional crosslinkable group) are released by free radicals to produce polymer radicals and the radicals are bonded to each other to create crosslinks between the polymers. . Thus, the alkali-soluble binder is cured.

Although the content of the crosslinkable group in the alkali-soluble binder is not particularly limited, it 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 It is particularly preferably from 1.5 meq/g to 2.8 meq/g. When the content is higher than or equal to 0.5 meq/g, the amount of the curing component is sufficient to obtain high sensitivity, and when the content is less than or equal to 3.0 meq/g, the storage stability of the shading composition is improved.

Here, the content (milli-eq/g) can be measured by iodine value titration.

The alkali-soluble binder having a crosslinkable group is described in detail in JP-A No. 2003-262958, and the compound described therein can also be used in the present invention.

The alkali-soluble binder containing a crosslinkable group is preferably an alkali-soluble binder having an acid group and a crosslinkable group, and representative examples thereof include the following compounds: (1) A urethane-modified acrylic resin containing a polymerizable double bond, which, for example, is obtained by reacting an isocyanate group with an OH group in advance, retaining an unreacted isocyanate group and containing at least one (methyl) group An acryl-based compound is obtained by reacting a carboxyl group-containing acrylic resin; and (2) an unsaturated group-containing acrylic resin comprising a carboxyl group-containing acrylic resin and having an epoxy group and a polymerizable double bond The compound obtained by the reaction of the compound; (3) an acrylic resin containing a polymerizable double bond, which can be obtained, for example, by reacting an acrylic resin containing an OH group with a dibasic acid anhydride containing a polymerizable double bond.

Among them, (1) a resin and (2) a resin are particularly preferable.

Examples of the alkali-soluble binder containing an acid group and a crosslinkable group include a polymer compound having an acidic group and an ethylenically unsaturated bond in the side chain and having a bisphenol A skeleton and a bisphenol F skeleton, and having an acidity A novolac resin and a resol resin, and the like, and an ethylenically unsaturated bond. These resins can be obtained by the methods described in paragraphs [0008] to [0027] of JP-A No. 11-240930.

As described above, the alkali-soluble binder is preferably a (meth)acrylic resin or a urethane resin. The "(meth)acrylic resin" preferably has (meth)acrylic acid, a (meth) acrylate (such as an alkyl ester, an aryl ester or an arylalkyl ester), (meth) acrylamide or a (meth) An acrylic acid derivative such as a (meth) acrylamide derivative is used as a copolymer of a polymerizable component. Further, the "urethane resin" is preferably a compound containing two or more than two isocyanate groups. A polymer produced by condensation with a compound containing two or more than two hydroxyl groups.

The (meth)acrylic resin is preferably a copolymer having a repeating unit containing an acid group. Examples of the acid group are preferably the acid groups described above. The repeating unit containing an acidic 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 a (n+1)-valent linking group; A represents an oxygen atom or -NR ³ -, wherein R ³ represents a hydrogen atom or A monovalent hydrocarbon group having 1 to 10 carbon atoms; and n represents an integer of 1 to 5.

In the formula (I), the linking group represented by R ² preferably contains one or more selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom. The number of atoms constituting the linking group represented by R ² is preferably from 1 to 80. In particular, examples of the linking group represented by R ² include an alkylene group and an extended aryl group, or may have two or more of these divalent groups via a guanamine bond, an ether bond, or an amine group. A structure in which a formate bond, a urea bond, or an ester bond is bonded. R ^{2 is} preferably a single bond, an alkylene group or a group formed by bonding two or more alkylene groups via a guanamine bond, an ether bond, a urethane bond, a urea bond or an ester bond.

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

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

The alkylene group and the extended aryl group may each have a more substituent, and examples of the substituent include a monovalent non-metal atomic group other than a hydrogen atom, such as a halogen atom (-F, -Br, -Cl, -I), a hydroxyl group, Cyano, alkoxy, aryloxy, fluorenyl, alkylthio, arylthio, alkylcarbonyl, arylcarbonyl, carboxyl and conjugated bases thereof, alkoxycarbonyl, aryloxycarbonyl, aminemethanyl, Aryl, alkenyl and alkynyl groups.

The number of carbon atoms of the hydrocarbon group represented by R ³ is preferably from 1 to 10, more preferably from 1 to 5, and even more preferably from 1 to 3.

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

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

The ratio (mol%) of the repeating unit having an acid group in all the repeating unit components in the (meth)acrylic resin is preferably from 10% to 90% from the viewpoint of developability, and the developability is The balance between the strengths of the permanent patterns is more preferably from 50% to 85%, and particularly preferably from 60% to 80%.

The (meth)acrylic resin preferably further contains a crosslinkable group as described above, and specific examples and contents of the crosslinkable group are the same as described above.

The (meth)acrylic resin group used in the present invention may further contain (meth)acrylic acid in addition to the polymerized unit having an acid group and the polymerizable unit having a crosslinkable group as described above. Polymeric unit of ester or arylalkyl (meth)acrylate, polymerized list of (meth)acrylamide or its derivative A polymeric unit of a meta-, alpha-hydroxy methacrylate or a polymerized unit of a styrene derivative. The alkyl group in the alkyl (meth)acrylate is preferably an alkyl group having 1 to 5 carbon atoms or an alkyl group having 2 to 8 carbon atoms and having the above substituent, and more preferably a methyl group. The aralkyl (meth)acrylate contains, for example, benzyl (meth)acrylate. The (meth)acrylamide derivative includes, for example, N-isopropylacrylamide, N-phenylmethacrylamide, N-(4-methoxycarbonylphenyl)methacrylamide, N, N-Dimethyl acrylamide and morpholinyl acrylamide. The α-hydroxymethyl acrylate includes, for example, α-hydroxyethyl methacrylate and α-hydroxymethyl methacrylate. The styrene derivative contains, for example, styrene and 4-tert-butylstyrene.

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

OCN-X-NCO (1)

HO-L ¹ -OH (2)

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

The at least one diol compound represented by the formula (2) preferably has an acid group. Thus, the alkali-soluble urethane resin is preferably produced as a reaction product between the corresponding diisocyanate compound and the corresponding diol compound by incorporating an acidic group. According to this preparation method, compared to the urethane resin The alkali-soluble urethane resin can be easily produced in the case where it is desired to be substituted with an acid group or incorporated into an acid group on the side chain.

Further, at least one of the diisocyanate compound represented by the formula (1) and the diol compound represented by the formula (2) preferably have a crosslinkable group. Examples of the crosslinkable group include the above crosslinkable group. Thus, the alkali-soluble urethane resin is preferably produced as a reaction product between the corresponding diisocyanate compound and the corresponding diol compound by incorporating a crosslinkable group. According to this production method, a crosslinkable group can be easily produced as compared with a case where a crosslinkable group is substituted or a crosslinkable group is desired on the side chain after the reaction of the urethane resin. A urethane resin.

(1) Diisocyanate compound

In the formula (1), X is preferably a divalent aliphatic group, a divalent aromatic hydrocarbon group or a group formed by the combination thereof, and preferably has 1 to 20 carbon atoms, and more preferably 1 to 2 15. The divalent aliphatic group or the divalent aromatic hydrocarbon group may each further contain a substituent which does not react with an isocyanate group.

Specific examples of the diisocyanate compound represented by the formula (1) include the following compounds.

That is, examples of the diisocyanate compound include an aromatic diisocyanate compound such as 2,4-tolyl diisocyanate, a dimer of 2,4-tolyl diisocyanate, 2,6-tolyl diisocyanate, Xylylene diisocyanate, m-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-anaphthyl diisocyanate and 3,3'-dimethylbiphenyl-4,4' a diisocyanate; an aliphatic diisocyanate compound such as hexamethylene diisocyanate, trimethyl hexane diisocyanate, diisocyanate diisocyanate and Dimer acid diisocyanate; alicyclic diisocyanate compound such as isophorone diisocyanate, 4,4'-methylene bis(cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) a diisocyanate and 1,3-(isocyanatemethyl)cyclohexane; and a diisocyanate compound which is a reaction product between a diol and a diisocyanate, such as 1 molar 1,3-butanediol and 2 moles An adduct of toluene diisocyanate.

When the diisocyanate compound represented by the formula (1) has a crosslinkable group, the diisocyanate compound is, for example, a triisocyanate compound and one equivalent of a crosslinkable group (for example, an ethylenically unsaturated bond group) A product obtained by an addition reaction of a monofunctional alcohol or a monofunctional amine compound. Specific examples of the triisocyanate compound, the monofunctional alcohol or the monofunctional amine compound having a crosslinkable group include paragraphs [0034], [0035], [0037] to [0040] of Japanese Patent No. 4,401,262. The person described in the paragraph, but not limited to the one described.

Specific examples of the diisocyanate compound having a crosslinkable group include those described in paragraphs [0042] to [0049] of Japanese Patent No. 4,401,262, but are not limited thereto.

(2) diol compound

Examples of the diol compound represented by the formula (2) generally include a polyether diol compound, a polyester diol compound, and a polycarbonate diol compound. Examples of the polyether diol compound include a compound represented by the following formula (3), formula (4), formula (5), formula (6), and formula (7), and ethylene oxide and propylene oxide (propylene oxide). a random copolymer having a terminal hydroxyl group.

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 any one of the groups shown below; a, b, c, d, e, f, and g Each independently represents an integer greater than or equal to 2, and preferably represents an integer from 2 to 100; the two ds may be the same or different from each other; and the two X ¹ may be the same or different from each other.

Specific examples of the polyether diol compound represented by the formula (3) or the formula (4) include the following compounds. That is, examples include diethylene glycol, triethylene glycol, Tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, di-1,2-propanediol, tri-1,2-propanediol, tetra-1,2-propanediol, six -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, polyethylene glycol having a weight average molecular weight of 1,000, polyethylene glycol having a weight average molecular weight of 1,500, polyethylene glycol having a weight average molecular weight of 2,000, and a weight average molecular weight of 3,000. Polyethylene glycol, polyethylene glycol having a weight average molecular weight of 7,500, 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, and a weight average molecular weight of 2,000. Propylene glycol, polypropylene glycol having a weight average molecular weight of 3,000, and polypropylene glycol having a weight average molecular weight of 4,000.

Specific examples of the polyether diol compound represented by the formula (5) include the following compounds. That is, examples include PTMG650, PTMG1000, PTMG2000, and PTMG3000 (all of which are trade names, manufactured by Sanyo Chemical Industries, Ltd.).

Specific examples of the polyether diol compound represented by the formula (6) include the following compounds. That is, examples include NEWPOL PE-61, Newpel PE-62, Newpel PE-64, Newpel PE-68, Newpel PE-71, Newpel PE-74, New Zealand Pell PE-75, Neuper PE-78, Neuper PE-108, Neuper PE-128 and Nupel PE-61 (all are trademark names, Sanyo Chemical Industries, Ltd.) Manufacturing).

Specific examples of the polyether diol compound represented by the formula (7) include the following Column of compounds. That is, examples include Newpel BPE-20, Newpel BPE-20F, Newpel BPE-20NK, Newpel BPE-20T, Newpel BPE-20G, Newpel BPE-40, Newpel BPE -60, Newpel BPE-100, Newpel BPE-180, Newpel BPE-2P, Newpel BPE-23P, Newpel BPE-3P and Newpel BPE-5P (both trade names) It is manufactured by Sanyo Chemical Industries, Ltd.).

Specific examples of the random copolymer of a terminal hydroxyl group of ethylene oxide and propylene oxide include the following compounds.

That is, examples include Newpel 50HB-100, Newpel 50HB-260, Newpel 50HB-400, Newpel 50HB-660, Newpel 50HB-2000, and Newpel 50HB-5100 (both trade names) , manufactured by Sanyo Chemical Industries, Ltd.).

Examples of the polyester diol compound include compounds represented by the following formula (8) and formula (9).

In the formulae (8) and (9), L ² , L ³ and L ⁴ each independently represent a divalent aliphatic or 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 from each other. Preferably, L ² to L ⁴ each independently represent an alkylene group, an alkenyl group, an alkynylene group or an extended aryl group, and L ⁵ represents an alkylene group. Further, L ² to L ⁵ may each contain another bond or a functional group which does not react with an isocyanate group, such as an ether bond, a carbonyl bond, an ester bond, a cyano group, an olefin bond, a urethane bond, a guanamine group, Urea group or halogen atom. Further, n1 and n2 each independently represent an integer greater than or equal to 2, and preferably represent an integer from 2 to 100.

Examples of the polycarbonate diol compound include a compound represented by the following formula (10).

In the formula (10), L ⁶ each independently represents a divalent aliphatic or aromatic hydrocarbon group, and may be the same or different from each other. Preferably, L ⁶ represents an alkylene group, an alkenyl group, an alkynylene group or an extended aryl group. Further, L ⁶ may further contain another bond or a functional group which does not react with an 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. Further, 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 following compounds (i.e., the exemplified compound No. 1 to the exemplified compound No. 18). In these particular examples, n represents an integer greater than or equal to two.

A urethane resin can be used in combination with a diol compound The diol compound of the isocyanate-reactive substituent is synthesized. Examples of the diol compound include the following compounds.

HO-L ⁷ -O-CO-L ⁸ -CO-OL ⁷ -OH (11)

HO-L ⁸ -CO-OL ⁷ -OH (12)

In the formulae (11) and (12), L ⁷ and L ⁸ each independently represent a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group or a divalent heterocyclic group, and a plurality of L ⁷ may be the same or different from each other, And a plurality of L ⁸ may be the same or different from each other. L ⁷ and L ⁸ may each be further selected to have another bond or functional group which does not react with an isocyanate group, such as a carbonyl group, an ester bond, a urethane bond, a guanamine bond or a urea group. In addition, L ⁷ and L ⁸ may form a ring.

The divalent aliphatic hydrocarbon group, the aromatic hydrocarbon group or the heterocyclic group may or may not 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 (such as - F, -Cl, -Br or -I).

Further, the at least one diol compound is preferably a diol compound having an acid group in the form of a compound having a substituent which does not react with an isocyanate group. Specific examples of the acid group include the above groups, and a carboxyl group is preferred. Examples of the diol compound having a carboxyl group include the following compounds represented by the formula (13) to the 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 and preferably represents a hydrogen atom having from 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 each may have a substituent, and examples of the substituent include a cyano group, a nitro group, and a halogen atom (such as -F, -Cl, -Br or -I). ), -CONH ₂ , -COOR ¹⁶ , -OR ¹⁶ , -NHCONHR ¹⁶ , -NHCOOR ¹⁶ , -NHCOR ¹⁶ and -OCONHR ¹⁶ (wherein R ¹⁶ represents an alkyl group having 1 to 10 carbon atoms or has 7 to Aralkyl group of 15 carbon atoms).

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

The divalent aliphatic or aromatic hydrocarbon group may or may not 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.

Further, L ⁹ to L ¹¹ may further optionally contain a functional group which does not react with an isocyanate group, such as a carbonyl group, an ester group, a urethane group, a guanamine group, a ureido group or an ether group. In addition, two or three of R ¹⁵ , L ⁷ , L ⁸ and L ⁹ may form a ring.

Ar represents a trivalent aromatic hydrocarbon group which may or may not 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 the following compounds.

That is, examples include 3,5-dihydroxybenzoic acid, 2,2-bis(hydroxymethyl)propionic acid, 2,2-bis(2-hydroxyethyl)propionic acid, 2,2-bis(3-hydroxyl Propyl) propionic acid, bis(hydroxymethyl)acetic acid, bis(4-hydroxyphenyl)acetic acid, 2,2-bis(hydroxymethyl)butyric acid, 4,4-bis(4-hydroxyphenyl)pentane Acid, tartaric acid, N,N-dihydroxyethylglycine and N,N-bis(2-hydroxyethyl)-3-carboxy-propanamide.

The carboxyl group is preferred from the viewpoint of imparting hydrogen bonding property and alkali solubility to the polyurethane resin.

The carboxyl group-containing polyurethane resin having a content of from 0.5 meq/g to 4.0 meq/g, and more preferably from 1.0 meq/gram to 3.0 meq/g is particularly preferably used in the present invention. Polymer.

When the diol compound represented by the formula (2) has a crosslinkable group, it is preferred to use a diol compound containing an unsaturated group to produce a polyurethane resin. The diol compound may be a commercially available product such as trimethylol propyl An alkane monoallyl ether, which can be easily derived from a halogenated diol compound, a triol compound or an amino diol compound, and a carboxylic acid chloride, isocyanate, alcohol, amine, thiol or halogenated alkyl compound containing an unsaturated group. The product produced by the reaction between the two. Specific examples of the diol compound having a crosslinkable group include those described in paragraphs [0057] to [0066] of Japanese Patent No. 4,401,262, but are not limited thereto.

The compound represented by the exemplified compounds No. 13 to No. 17 corresponds to a diol compound represented by the formula (8), the formula (9) or the formula (10), and is a diol compound having a crosslinkable group.

a polyurethane having a crosslinkable group (preferably an ethylenically unsaturated bond group) having a content of greater than or equal to 0.5 meq/g, more preferably from 1.0 meq/g to 3.0 meq/g. The resin is particularly preferred as the binder polymer used in the present invention.

Further, in addition to the diol, the urethane resin may be a compound obtained by ring-opening reaction of a tetracarboxylic dianhydride represented by the following formula (16) to formula (18) with a diol compound. synthesis.

In the formulae (16) to (18), L ¹² represents a single bond, and may have a substituent such as an alkyl group, an aralkyl group, an aryl group, an alkoxy group, a halogen group, an ester group or a decylamino group. a valent aliphatic or aromatic hydrocarbon group, -CO-, -SO-, -SO ₂ -, -O- or S-, and preferably represents a single bond, a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, -CO-, -SO ₂ -, -O- or S-.

The divalent aliphatic or aromatic hydrocarbon group may or may not 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 group (for example, an alkylcarbonyloxy group). Alkyl, alkoxycarbonyl, arylcarbonyloxy or aryloxycarbonyl) and amidino group.

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

Also, two of L ¹² , R ¹⁷ and R ¹⁸ may be bonded together to form a ring.

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

Also, two of L ¹² , R ¹⁹ and R ²⁰ may be bonded together to form a ring.

L ¹³ and L ¹⁴ may be the same or different from each other, and each independently 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 or polynuclear aromatic ring. Preferably, A represents an aromatic ring having 6 to 18 carbon atoms.

Specific examples of the compound represented by the formula (16), the formula (17) or the formula (18) include the following compounds. That is, examples include pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 2, 3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, 2,2-bis (3, 4-Dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 4,4'-[3,3'-(alkylphosphonium diphenyl)-double (Iminocarbonyl)]diphthalic dianhydride; aromatic tetracarboxylic dianhydride, such as hydroquinone diacetate and trimellitic anhydride adduct, diethyl hydrazine diamine and trimellitic anhydride An alicyclic tetracarboxylic dianhydride such as 5-(2,5-di-oxytetrahydrofuranyl)-3-methyl-3-cyclohexyl-1,2-dicarboxylic anhydride (Yibi clone) (EPICLON) B-4400, trade name, manufactured by DIC Corporation, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid Acid dianhydride, tetrahydrofuran tetracarboxylic dianhydride; aliphatic tetracarboxylic dianhydride, such as 1,2,3,4-butane tetracarboxylic dianhydride and 1,2,4,5-pentane tetracarboxylic acid anhydride.

The method of ring-opening a tetracarboxylic dianhydride in a compound with a diol compound and introducing the compound into the polyurethane resin comprises the following method.

a) A method of reacting a compound having an alcohol terminal obtained by ring-opening a tetracarboxylic dianhydride with a diol compound with a diisocyanate compound.

b) A method of reacting a urethane compound having an alcohol terminal and a tetracarboxylic dianhydride obtained by reacting a diisocyanate compound under an excess of a diol compound.

Examples of the diol compound used in the ring opening reaction thus include the following compounds.

That is, examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butylene glycol, 1,6-hexanediol, 2-butene-1,4-diol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-bis-β-hydroxyethoxy Cyclohexane, cyclohexanedimethanol, tricyclodecane dimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, Ethylene oxide adduct of bisphenol F, propylene oxide adduct of bisphenol F, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, hydroquinone Dihydroxyethyl ether, terephthalic acid, dihydroxyacetamidine, bis(2-hydroxyethyl)-2,4-tolyldicarboxylic acid diamine, 2,4-tolyl-bis(2-hydroxyethyl) Methionine), bis(2-hydroxyethyl)-m-xylylene dicarboxylate, and meta-benzene Bis(2-hydroxyethyl) dicarboxylate.

In the above, the urethane resin has been described, and the urethane resin is added to the aprotic solvent by heating the known active catalyst reactive with the diisocyanate compound and the diol compound, followed by heating. synthesis. The molar ratio (Ma:Mb) of the diisocyanate compound to the diol compound for synthesis is preferably from 1:1 to 1.2:1, and by treating the alcohol, the amine or the like without leaving an isocyanate group Analogs, ultimately, can be synthesized with products having desirable physical properties such as molecular weight or viscosity.

Further, the urethane resin preferably has a crosslinkable group (e.g., an unsaturated group) at the terminal or side chain of the polymer. The exchange between the modified polymerizable compound and the urethane resin or the urethane resin is provided by having a crosslinkable group (for example, an unsaturated group) at the terminal or side chain of the polymer. Reacts reactivity and enhances the strength of permanent patterns. Therefore, the unsaturated group particularly preferably has a carbon-carbon double bond from the viewpoint of the possibility of crosslinking.

Examples of the method of introducing a crosslinkable group into a polymer end include the following methods. That is, in the process of synthesizing a polyurethane resin, an alcohol or an amine having a crosslinkable group is used for a process for treating an isocyanate group remaining on a polymer terminal, an alcohol, an amine, and the like. Examples of the compound are the same as the exemplary compounds of a monofunctional alcohol or a monofunctional amine compound having a crosslinkable group.

Further, from the viewpoint of increasing the amount of the crosslinking group and improving the crosslinking reactivity, it is preferred to incorporate the crosslinkable group into the side chain of the polymer instead of the polymer end.

As a method of introducing a crosslinkable group into a main chain, there is a use in A method of synthesizing a polyurethane resin having 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 the following compounds. That is, these compounds are cis-2-butene-1,4-diol, trans-2-butene-1,4-diol, polybutadiene diol, and the like.

In terms of an excellent balance between film strength and developability, an alkali-soluble adhesive which is not a (meth)acrylic resin and a urethane resin is preferably, for example, European Patent No. 993966, European Patent No. 1204000 And a binder polymer having an acid group containing an acetal-modified polyvinyl alcohol as described in JP-A No. 2001-318463. Additionally, other suitable water soluble linear organic polymers include polyvinylpyrrolidone, polyethylene oxide, and the like. Further, in order to improve the strength of the cured film, an alcohol-soluble nylon or a polyether of 2,2-bis-(4-hydroxyphenyl)-propane, epichlorohydrin, and the like are used.

Specifically, in terms of an excellent balance between film strength, sensitivity, and developability, [(meth)acrylic acid benzyl ester/(meth)acrylic acid, another additive selectively exists A polymerizable vinyl monomer] copolymer and a [(meth)acrylic acid aryl ester/(meth)acrylic acid, optionally added polymerizable vinyl monomer] copolymer are preferred.

The alkali-soluble binder which can be used in the light-shielding composition of the present invention preferably has a weight average molecular weight of 3,000 or more, more preferably 5,000 to 300,000, and most preferably 10,000 to 30,000, and preferably has a number average molecular weight of greater than or equal to 1,000, and more preferably 2,000 to 250,000. The degree of polydispersion (i.e., weight average molecular weight / number average molecular weight) is preferably greater than or equal to 1, and more preferably from 1.1 to 10.

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

The alkali-soluble binder can be synthesized by a conventionally known method. Examples of the solvent used for the synthesis include tetrahydrofuran, dichloroethane, 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 types.

The alkali-soluble binder may be used singly or in combination of two or more types.

The content of the alkali-soluble binder is preferably from 5% by mass to 80% by mass, and more preferably from 30% by mass to 70% by mass, based on the total solid mass of the light-shielding composition of the present invention. When the content is in the above range, the exposure sensitivity is good, the processing time is shortened, and excellent TCT resistance is obtained.

UV absorber

The light-shielding composition of the present invention preferably contains an ultraviolet absorber.

In the case where the light-shielding composition contains the ultraviolet absorber, when the light-shielding composition of the present invention is imparted with lithographic characteristics, a rectangular shape pattern can be favorably obtained.

The photosensitive composition of the present invention may contain an ultraviolet absorber.

Examples of the ultraviolet absorber include a salicylate absorber, a benzophenone absorbent, a benzotriazole absorbent, a substituted acrylonitrile absorbent, and a triazine ultraviolet absorber.

Examples of the salicylate ultraviolet absorber include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Examples of the benzophenone ultraviolet absorber include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'- Dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2, 4-dihydroxybenzophenone and 2-hydroxy-4-octyloxybenzophenone. Further, examples of the benzotriazole ultraviolet absorber include 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxyl group -3'-T-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]benzene And triazole.

Examples of the substituted acrylonitrile ultraviolet absorber include 2-cyano-3,3-diphenylacrylic acid and 2-ethylhexyl-2-cyano -3,3-diphenylacrylic acid. Further, examples of the triazine ultraviolet absorber include a mono(hydroxyphenyl)triazine compound such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxybenzene. 4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-trimethoxypropyl)oxy 2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4 , 6-bis(2,4-dimethylphenyl)-1,3,5-triazine; bis(hydroxyphenyl)triazine compound, such as 2,4-bis(2-hydroxy-4-propoxy) Phenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl) -6-(4-methylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2) , 4-dimethylphenyl)-1,3,5-triazine; and a tris(hydroxyphenyl)triazine compound such as 2,4-bis(2-hydroxy-4-butoxyphenyl)- 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.

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

The opacifying composition of the present invention may or may not contain an ultraviolet absorber. When the composition contains the ultraviolet absorber, the content of the ultraviolet absorber is preferably from 0.001% by mass to 1% by mass, and more preferably from 0.01% by mass to 0.8% by mass based on the total solid mass of the light-shielding composition of the present invention.

Surfactant

From the viewpoint of further improving the coating ability, various surfactants can be added to the light-shielding composition of the present invention. Examples of surfactants that can be used include fluorosurfactants, nonionic surfactants, cationic surfactants, anionic surfactants, fluorenone surfactants, and the like.

In particular, an anthrone surfactant and a fluorosurfactant are preferred, and a fluorosurfactant is preferred. When the light-shielding composition contains a surfactant, the uniformity of the light-shielding composition after coating is further improved.

That is, in the case where a film is formed by a coating solution using a light-shielding composition of a fluorine-containing surfactant, the interfacial tension between the surface to be coated and the coating solution is deteriorated, and the surface to be coated is improved. The wettability and thus the coatability of the surface to be coated is improved. For this reason, this is effective because even if a film having a size of several micrometers is formed using a small amount of liquid, it is further preferable to form a film having a uniform thickness having a low thickness unevenness.

The fluorine content in the fluorine-containing surfactant is preferably from 3% by mass to 40% by mass. % is more preferably from 5% by mass to 30% by mass, and particularly preferably from 7% by mass to 25% by mass. When the fluorine content is in the above range, the fluorine-containing surfactant can be effective from the viewpoint of the uniformity of the coating thickness and the liquid-saving property, and the solubility of the light-shielding composition can also be satisfactory.

Examples of fluorosurfactants include MEGAFAC F171, Magafis F172, Magafis F173, Maga Fiss F176, Magafis F177, Magafis F141, Magafis F142, Magafis F143, Maga Fiss F144, Maga Fisi R30 , Ma Jiafeisi F437, Ma Jiafeisi F475, Ma Jiafeisi F479, Ma Jiafeisi F482, Ma Jiafeisi F554, Ma Jiafeisi F780, Ma Jiafeisi F781 (all trademark names, manufactured by DIC Corporation (DIC Corporation)); Fluoride (FLUORAD ) FC430, Fluoride FC431, Fluoride FC171 (both trade names, manufactured by Sumitomo 3M Ltd.); and SURFLON S-382, Safluron SC- 101, Safluron SC-103, Safluron SC-104, Safluron SC-105, Safluron SC1068, Safluron SC-381, Safluron SC-383, Safluron S393, Safluron KH-40 (all of which are trade names, manufactured by Asahi GlasS Co., Ltd.).

Specific examples of the nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene. Octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters, such as Plonik (PLURONIC) L10, Pluronic L31, Pluronic L61, Pluronic L62, Pluronic 10R5, Pluronic 17R2, and Plonik 25R2, as well as TETRONIC 304, Special Window Nick 701, Window Nick 704, Special Window Nick 901, Special Window Nick 904 and Special Window Nick 150R1 (trade name, manufactured by BASF), and Solpus 20000 (trade name, by The Lubrizol Corporation ))).

Examples of the cationic surfactant include a phthalocyanine derivative (trade name: Afka 745, manufactured by Morishita & Co., Ltd.); an organic siloxane polymer KP341 (trade name, (manufactured by Shin-Etsu Chemical Co., Ltd.); (meth)acrylic (co)polymer (trade name: Baoke No. 75, No. 90, No. 95, by co-prosperity Kyoeisha Chemical Co., Ltd.; and W001 (trade name, manufactured by Yusho Co., Ltd.).

Examples of the anionic surfactant include W004, W005, and W017 (trade name, manufactured by Yusho Co., Ltd.).

Examples of the fluorene ketone surfactant include "Toray SILICONE DC3PA", "Torayone SH7PA", "Torayone DC11PA", "Torayone SH21PA", "Torayone SH28PA" "Torayone SH29PA", "Torayone SH30PA" and "Torayone SH8400" (trade name, manufactured by Dow Corning Toray Co., Ltd.); TSF- 4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (trade name, by Momentive High-Tech Materials) (manufactured by Momentive Performance Materials Inc.); KP341, KF6001 and KF6002 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.); and BYK323 and BYK330 (trade name, by Germany) Manufactured by BYK Japan KK.

Only one surfactant may be used, or two or more than two surfactants may be used in combination.

The opacifying composition may or may not contain a surfactant. When the light-shielding composition contains a surfactant, the content of the surfactant is preferably from 0.001% by mass to 1% by mass, more preferably from 0.01% by mass to 0.1% by mass based on the total solid mass of the light-shielding composition of the present invention.

Decane coupling agent

The light-shielding composition of the present invention preferably contains a decane coupling agent.

When the light-shielding composition contains a decane coupling agent, the adhesion between the photosensitive layer (i.e., the light-shielding composition layer) and the substrate is further improved.

Examples of the decane coupling agent which can be used in the light-shielding composition of the present invention include a decane coupling agent for surface treatment of the above respective particles.

The decane coupling agent may be used singly or in combination of two or more types.

Crosslinker

The light-shielding composition of the present invention may further contain a crosslinking agent to improve the strength of the permanent pattern.

The crosslinking agent is preferably a compound having a crosslinkable group and more preferably a compound having two or more than two crosslinkable groups. Crosslinkable group Examples include an oxetane group, a cyanate group, and a crosslinkable group which may be included in the above alkali-soluble binder. Among them, an epoxy group, an oxetanyl group or a cyanate group is preferred. That is, 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 the crosslinking agent of the present invention include an epoxy compound containing at least two oxylane groups per molecule, and each molecule contains at least two in the β-position. An epoxy compound having an epoxy group of an alkyl group, and an analog thereof.

Examples of the epoxy compound containing at least two oxyalkyl groups in the molecule include a bisxylenol epoxy compound or a bisphenol epoxy compound (such as YX4000, trade name, by Japan Epoxy Resin Co., Ltd. (Japan) Epoxy Resin Co., Ltd.) or a mixture thereof, a heterocyclic epoxy compound containing an isocyanurate skeleton (such as TEPIC), trade name, by Nissan Chemical Industries, Inc. Ltd.); ARALDITE PT810, trade name, manufactured by BASF Corporation, Japan, and its analogues), bisphenol A epoxy compound, novolak epoxy compound, bisphenol F Epoxy compound, hydrogen-containing bisphenol A epoxy compound, bisphenol S epoxy compound, phenolic novolac epoxy compound, cresol novolac epoxy compound, halogenated epoxy compound (for example, low brominated epoxy compound, high Halogenated epoxy compound, brominated phenolic novolac type epoxy compound and the like), allyl-containing bisphenol A epoxy compound, trisphenol methane epoxy compound, diphenyl dimethanol epoxy compound, benzene Extending an epoxy compound with diphenyl, dicyclopentadiene epoxy compounds (such as HP-7200, HP-7200H, trade name, manufactured by DIC Corporation (DIC Corporation), glycidylamine epoxy compound (such as diaminodiphenylmethane epoxy compound, diglycidyl aniline, triglycidylamino phenol and An analog thereof), a glycidyl ester epoxy compound (such as diglycidyl phthalate, diglycidyl adipate, diglycidyl hexahydrophthalate, glycidyl dimerate, etc.); Ethyl carbene epoxy resin, alicyclic epoxy resin (such as 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenylcarboxylate); Acid bis(3,4-epoxycyclohexylmethyl) ester, dicyclopentadiene diepoxide, GT-300, GT-400, ZEHPE 3150 (trade name, by Daicel Chemical Industry (manufactured by Daniel Chemical Industries, Ltd.), quinone imine epoxy resin, trihydroxyphenylmethane epoxy resin, bisphenol A novolac epoxy resin, tetraphenol ethane epoxy resin, adjacent Glycidyl phthalate resin, tetraglycidyl xylenol ethane resin, naphthyl-containing epoxy resin (naphthol aralkyl epoxy resin, Naphthol novolac epoxy resin, tetrafunctional naphthalene epoxy resin, and commercially available products include ESN-190, ESN-360 (manufactured by Nippon Steel Chemical Co., Ltd.), HP-4032, EXA No. 4750 , EXA No. 4700 (manufactured by Dainippon Ink and Chemicals, Inc.), etc.; from epichlorohydrin with a phenol compound and a diene compound such as divinylbenzene or a reaction product obtained by a reaction between polyphenol compounds obtained by an addition reaction between dicyclopentadiene); 4-vinylcyclohexene-1-oxide epoxidized by oxyacetic acid and the like Ring-opening polymerization product; ring having a linear phosphorus-containing structure Oxygen resin; epoxy resin having a cyclic phosphorus-containing structure; α-methyl fluorene liquid crystal epoxy resin, benzophenoxy phenyl liquid crystal epoxy resin; azophenyl liquid crystal epoxy resin; Liquid crystal epoxy resin; binaphthyl liquid crystal epoxy resin; pyridazine epoxy resin; glycidyl methacrylate copolymer epoxy resin ("CP-50S" and "CP-50M" (manufactured by NOF Corporation) ), etc., and copolymerized epoxy resin, bis(glycidoxyphenyl)fluoroepoxy resin, and bis(glycidyloxy) between cyclohexylmethyleneimine and glycidyl methacrylate Phenyl) adamantane epoxy resin. However, the crosslinking agent is not limited to the above. These epoxy resins may be used singly or in combination of two or more types.

Further, in addition to the epoxy compound containing at least two oxyalkyl groups per molecule, an epoxy compound having two epoxy groups having an alkyl group at the β-position per molecule may also be used. A compound containing an alkyl group-substituted epoxy group (more specifically, a β-alkyl group-substituted glycidyl group and the like) is particularly preferable.

The epoxy compound containing at least one epoxy group having an alkyl group at the β-position may be as follows, two or more than two epoxy groups contained in one molecule are all β-alkyl-substituted glycidyl groups, or At least one epoxy group is a β-alkyl substituted glycidyl group.

The oxetane compound is, for example, an oxetane resin containing at least two oxetanyl groups per molecule.

Examples of the oxetane compound include 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-double [(3-Ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methyl acrylate, acrylic acid (3-ethyl-3-oxa) Cyclobutyl)methyl ester, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate or oligomerization thereof Or a polyfunctional oxetane such as a copolymer thereof; and a compound having an oxetanyl group and a resin having a hydroxyl group (such as a novolac resin, a poly(p-hydroxystyrene), a shaft bisphenol (cardo) An ether compound prepared between bisphenol), calix-arene, cup-containing resorcinol, and sesquioxane; and an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate a copolymer between esters.

Examples of the bis-m-butylene iminoimide compound include 4,4'-diphenylmethanebis-s-butyleneimine, bis-(3-ethyl-5-methyl-4-cis-butane Iminophenyl)methane, 2,2'-bis-[4-(4-maleoximineiminophenoxy)phenyl]propane and the like.

Examples of the cyanate ester compound include a bisphenol A cyanate compound, a bisphenol F cyanate compound, a cresol novolac cyanate compound, a phenol novolac cyanate compound, and the like.

In addition, melamine or a melamine derivative can be used as a crosslinking agent.

The light-shielding composition contains melamine or a melamine derivative, thereby further improving the adhesion between the light-shielding composition layer and the metal wire (specifically, copper wire).

Examples of melamine derivatives include methylol melamine, alkylated methylol melamine (hydroxymethyl group from methyl, ethyl, butyl and the like) a group of etherified compounds) and analogs thereof. Among them, hexamethoxymethylmelamine is the best in terms of adhesion to metal wires.

The crosslinking agent may be used singly or in combination of two or more types. The crosslinking agent is preferably melamine or alkylated methylol melamine from the viewpoint of excellent storage stability and an effect of improving the surface hardness of the light-shielding composition layer or the film strength of the cured film. In terms of achieving a high level of excellent thick film formation suitability, excellent coating uniformity, excellent thickness uniformity on uneven surface, excellent high temperature resistance, and excellent high humidity resistance, The ligating agent is particularly preferably melamine.

The opacifying composition may or may not contain a crosslinking agent. When the light-shielding composition contains a crosslinking agent, the content of the crosslinking agent is from 1% by mass to 40% by mass, and more preferably from 3% by mass to 20% by mass based on the total solid mass of the light-shielding composition of the present invention.

Curing accelerator

The light-shielding composition of the present invention may contain a curing accelerator to promote thermal curing of a crosslinking agent such as an epoxy compound or an oxetane compound.

Examples of the curing accelerator include an amine compound such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine or 4-methyl-N,N-dimethylbenzylamine); quaternary ammonium compound (such as triethylbenzylammonium chloride); blocked isocyanate compound (such as Dimethylamine); bicyclic guanidine compounds of imidazole derivatives and salts thereof (such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4- Phenyl imidazole, 1-cyanoethyl-2-phenylimidazole or 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole); phosphorus compound (such as triphenyl) Phosphine); a guanamine compound (such as melamine, guanamine, acetamide or benzoguanamine); an S-triazine derivative (such as 2,4-diamino-6-methacryloxyethyl) -S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine-isocyanuric acid adduct or 2 ,4-diamino-6-methacryloxyethyl-S-triazine-isocyanuric acid adduct)

The curing accelerator is preferably melamine or dicyandiamide.

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

The opacifying composition may or may not contain a curing accelerator. When the light-shielding composition contains a curing accelerator, the curing accelerator is generally contained in an amount of from 0.01% by mass to 15% by mass based on the total solids of the light-shielding composition of the present invention.

Elastomer

The light-shielding composition of the present invention may further contain an elastomer.

In the case where the light-shielding composition contains an elastomer, when the composition is used as a solder resist, the adhesion between the printed wiring board and the conductor layer is further enhanced, and then it is possible to further improve the heat resistance and thermal shock resistance of the cured film. 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 polyamide elastomer, an acrylic elastomer, and an anthrone elastomer. These elastomers are formed from hard segment components as well as soft segment components, and the hard segment components contribute to heat resistance and strength, and the soft segment components contribute to flexibility and toughness. Among them, a polyester elastomer is preferred in terms of compatibility with other components.

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 copolymer. And styrene-ethylene-propylene-styrene block copolymers. Examples of the components of the styrene elastomer include a styrene derivative such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene or 4-cyclohexylstyrene in addition to styrene. Specific examples of styrene elastomers include Tuffren (TUFPRENE), SOLPRENE T, ASAPRENE T, and TUFTEC (both trade names, by Asahi Glass Chemical Industry) (made by Asahi Chemical Industries); Elastomer (ELASTOMER) AR (trade name, manufactured by Aron Kasei); KRAYTON G, CALIFLEX (trade name) , manufactured by Shell Japan (Jerly Japan); JSR-TR, TSR-SIS, DAINALON (all brand names, manufactured by Nippon Synthetic Rubber); DENKA STR (trade name, manufactured by Denki Kagaku); QUINTAC (trade name, manufactured by Nippon Zeon); TPE-SB series (trade name, Produced by Sumitomo Chemicals); RUBBERON (trade name, manufactured by Mitsubishi Chemicals); SEPTON, HYBRAR (trade name, Produced by Kuraray); SUMIFLEX (SUMIFLEX) Trade name, manufactured by Sumitomo Bakelite); LEOSTOMER And ACTIMER (trade name, both manufactured by Riken Vinyl Industries).

The olefin 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. Examples thereof include an ethylene-propylene copolymer (EPR) and an ethylene-propylene-diene copolymer (EPDM). Other examples of olefin elastomers include non-conjugated dienes having from 2 to 20 carbon atoms (such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, sub- Copolymers of ethyl norbornene, butadiene and isoprene with alpha-olefins and epoxidized polybutadiene. Further, another olefin elastomer is a carboxyl group-modified NBR which is a copolymer of methacrylic acid and a butadiene-acrylonitrile copolymer. Further, other olefin elastomers are ethylene-α-olefin copolymer rubber, ethylene-α-olefin-non-conjugated diene copolymer rubber, propylene-α-olefin copolymer rubber, and butene-α-olefin copolymer rubber.

Specific examples of olefin elastomers include MILASTOMER (trade name, manufactured by Mitsui Petrochemicals); EXACT (trade name, by Exxon Chemicals) ))) ENGAGE (trade name, manufactured by Dow Chemicals); DYNABON HSBR, hydrogenated styrene-butadiene copolymer, is butadiene An NBR series of an acrylonitrile copolymer, which is a XER series (trade name, manufactured by Dainippon Ink Chemical Industries) having a carboxyl group-modified butadiene-acrylonitrile copolymer having a crosslinking point at both ends. );as well as "BF-1000" (trade name, manufactured by Nippon Soda Co., Ltd.), which is a partially epoxidized polybutadiene of polybutadiene.

The urethane elastomer comprises a structural unit consisting essentially of a hard segment of a low molecular weight (short chain) diol and a diisocyanate and a soft segment of a high molecular weight (long chain) diol and a diisocyanate. Examples of high molecular weight (long chain) diols are polypropylene glycol, polytetramethylene oxide, poly(1,4-butyl butyl adipate), poly(adipic acid ethyl ethene) , 4-butyl butyl ester), polycaprolactone, poly(1,6-carbonic acid hexyl ester), and poly(adipate 1,6-extended hexyl neopentyl ester). The number average molecular weight of the high molecular weight (long chain) diol is preferably from 500 to 10,000. Examples of short chain diols are 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 or Pandenex T-2983N (trade name, manufactured by Dainippon Ink Chemical Industries) and Hikutulan (SIRAKTRAN) E790.

The polyester elastomer is an elastomer obtained by polycondensation of a dicarboxylic acid or a derivative thereof with a diol compound or a derivative thereof. Examples of dicarboxylic acids are terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, and aromatic dicarboxylic acids substituted with methyl, ethyl or phenyl groups; aliphatic groups having 2 to 20 carbon atoms Dicarboxylic acids such as adipic acid, sebacic acid or dodecanedicarboxylic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. One, two or more of these compounds may be used. Examples of diol compounds are aliphatic or alicyclic Alcohols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediol; bisphenol A, Bis-(4-hydroxyphenyl)-methane, bis-(4-hydroxy-3-methylphenyl)-propane, and resorcinol. One, two or more of these compounds may be used. A multi-block copolymer having an aromatic polyester (e.g., polybutylene terephthalate) as a hard segment component and having an aliphatic polyester (e.g., polytetramethylene glycol) as a soft segment component can be used. Polyester elastomers are classified into various grades of polyester elastomers depending on the type of hard section and soft section, the ratio between the two, and the difference in molecular weight therebetween and the like. Commercially available polyester elastomer is HITREL (trade name, manufactured by Dupont-Toray); PELPRENE (trade name, by Toyobo Co., Ltd. (Toyo) Boseki); and ESPEL (trade name, manufactured by Hitachi Chemical Industries).

The polyamide elastomer is an elastomer comprising a hard segment of polyamine and a soft segment of a polyether or polyester, and can be broadly classified into two categories, such as a polyether block guanamine type and a polyether ester block. Amidoxime type. Examples of polyamines are polyamine 6, polyamine 11 and polyamine 12, and examples of polyethers are polyethylene oxide, polypropylene oxide and polybutylene glycol. Specific examples of the polyamine elastomer include UBE polyamine elastomer (trade name, manufactured by Ube Kosan Co., Ltd.); diamides (trade name, by Daicel Fuel Plant) (made by Daicel Fuels); PEBAX (trade name, manufactured by Toray); GRILON ELY (trade name, manufactured by EMS Japan); NOVAMID (trade name, manufactured by Mitsubishi Chemicals); and GRILUX (trade name, manufactured by Dainippon Ink Chemical Industries) ).

The acrylic elastomer is composed of an acrylate such as ethyl acrylate, butyl acrylate, methoxyethyl acrylate and ethoxyethyl acrylate, and a monomer having an epoxy group such as glycidyl methacrylate and alkene. An elastomer obtained by copolymerization of propyl glycidyl ether) and/or a vinyl monomer such as acrylonitrile or ethylene. Examples of the acrylic elastomer include an acrylonitrile-butyl acrylate copolymer, an acrylonitrile-butyl acrylate-ethyl acrylate copolymer, and an acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer.

The fluorenone elastomer is an elastomer containing an organic polysiloxane as a main component and examples thereof include polydimethyl siloxane, polymethyl phenyl siloxane, and polydiphenyl sulfoxanone elastomer. . Elastomers in which the organopolyoxyalkylene is modified with a vinyl or alkoxy group can also be used. Specific examples of the fluorenone-based elastomer include the following fluorenone elastomers: KE series (trade name, manufactured by Shin-Etsu Chemicals Co., Ltd.); SE series, CY series, and SH series (trade name, by Made by Dow Corning Toray Silicones.

In addition to the above elastomers, rubber-modified epoxy resins can also be used. In the rubber-modified epoxy resin, at least bisphenol F epoxy resin, bisphenol A epoxy resin, salicylaldehyde epoxy resin, phenolic novolac epoxy resin, cresol novolac epoxy resin and the like Part of the epoxy group The carboxylate-modified butadiene-acrylonitrile copolymer or the terminally modified amine-modified anthrone rubber is modified at both ends.

As an elastomer, in terms of shear surface adhesion and thermal shock resistance, butadiene-acrylonitrile copolymer modified with carboxyl groups at both ends, Espel (Espel 1612, Espel 1620, trademark Name, manufactured by Hitachi Chemical Industries, which is a polyester elastomer, and epoxidized butadiene are preferred.

The opacifying composition of the present invention may or may not contain an elastomer. When the light-shielding composition contains an elastomer, the content of the elastomer in the light-shielding composition can be appropriately selected depending on the purpose without particular limitation, and is preferably from 0.5% by mass to 30% by mass based on the solid content of the composition, more preferably 1% by mass to 10% by mass, and particularly preferably 3% by mass to 8% by mass. When the content of the elastomer is within the above range, it is advantageous in that the shear surface adhesion and the thermal shock resistance are further improved.

Other components

The light-shielding composition of the present invention may further contain other components in addition to the main component or the preferred additive, as long as the effects of the present invention are not impaired.

Examples of other components which can be used in combination include a thermosetting accelerator, a thermal polymerization inhibitor, a plasticizer, a colorant (coloring pigment), and the like. In addition, adhesion accelerators and other adjuvants such as conductive particles, antifoaming agents, flame retardants, leveling agents, exfoliation accelerators, antioxidants, flavoring, surface tension modifiers, and chain transfer agents can be combined. Used on the surface of the matrix material.

By suitably containing the light-shielding composition of these components, the properties of the desired solder resist film such as stability, photographic properties, and physical properties can be controlled.

The thermal polymerization inhibitor is described in detail, for example, in paragraphs [0101] to [0102] of JP-A No. 2008-250074.

The plasticizer is described in detail, for example, in paragraphs [0103] to [0104] of JP-A No. 2008-250074.

The coloring agent is described in detail in, for example, paragraphs [0105] to [0106] of JP-A No. 2008-250074 or paragraphs [0038] and [0039] of JP-A No. 2009-205029.

The adhesion accelerator is described in detail, for example, in paragraphs [0107] to [0109] of JP-A No. 2008-250074.

All of the additives described in the publication are suitable for use in the sunscreen compositions of the present invention.

The light-shielding composition of the present invention may be obtained by mixing (A) one of light-shielding particles and a light-shielding dye, (B) a first filler, and (C) a second filler, and optionally mixing (D) a polymerizable compound, (E) Photopolymerization initiator and other components are prepared.

For preparing the light-shielding composition of the present invention, it is preferred to prepare a dispersion of the light-shielding particles in advance, (B) a dispersion of the first filler, and (C) a dispersion of the second filler.

The thus obtained light-shielding composition of the present invention is preferably filtered through a filter to remove foreign matter and reduce defects. Any filter can be used without any special restriction as long as it is conventionally used for filtration. Examples of fluororesin (such as polytetrafluoroethylene (PTFE), polyamide resin (such as nylon-6 and nylon-6,6), polyethylene or polyolefin resin (such as polypropylene (PP)) (including A filter composed of a polyolefin resin having a high density and an ultrahigh molecular weight). Among these materials, polypropylene (including high density polypropylene) is preferred.

The microporous diameter of the filter is suitably from about 0.01 microns to about 7.0 microns, preferably from about 0.01 microns to about 2.5 microns, and more preferably from about 0.01 microns to 1.5 microns. When the micropore diameter is within the above range, the fine foreign matter which is mixed in the dissolved pigment or dye and which hinders the preparation of a uniform and uniform light-shielding composition in the following process is reliably removed.

A combination of different filters can be used when using a filter. At this point, the first filter can be used to filter once or twice. In the case where two or more filtration processes are performed by using other filters in combination, the diameter of the pores of the second filter is preferably larger than that of the first filter. In addition, a combination of first filters having micropore diameters within the above range but different from each other may be used. The micropore diameter can be determined based on the nominal value of the filter manufacturer. Examples of commercially available filters include Japan Pole Co., Ltd., ADVANTEC MFS, Inc., and Entegris Inc., Japan. Formerly known as Mykrolis Corporation or various filters manufactured by Kitz Microfilter Corp.

The second filter may be a filter constructed of the same material as the first filter. The second filter has a micropore diameter of from about 0.5 microns to about 7.0 microns, preferably from about 2.5 microns to 7.0 microns, and more preferably from about 4.5 microns to About 6.0 microns. When the pore diameter is within the above range, the foreign matter mixed in the mixed solution and hindering the formation of a uniform and uniform light-shielding composition during the subsequent process is removed while retaining the component particles contained in the light-shielding composition.

For example, the first filter can be used only to filter the dispersion of individual particles, and secondly to filter the opaque composition containing other components.

The solid concentration of the light-shielding composition of 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.

The light-shielding composition of the present invention can be used without any particular limitation, and the composition can be applied to a solder resist, a light-shielding film of a back surface of a germanium substrate in a solid-state image pickup element, a light-shielding film of a wafer level lens, and the like. It is preferably used for solder resists.

When the light-shielding composition of the present invention is used as a solder resist, the solid concentration is preferably 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, A film having a relatively high thickness is formed.

In addition, the viscosity of the light-shielding composition of the present invention is preferably 1 mPa. Seconds to 3,000 mPa. Seconds, more preferably 10 millipascals. Seconds to 2,000 mPa. Seconds, and the best is 100 mPa. Seconds to 1,500 mPa. second.

When the light-shielding composition of the present invention is used as a solder resist, the viscosity is preferably 10 mPa from the viewpoint of film formability and uniform coating. Seconds to 3,000 mPa. Seconds, more preferably 400 mPa. Seconds to 1,500 mPa. Seconds, and the best is 400 mPa. Seconds to 1,000 millipascals. second.

The invention also relates to a photosensitive layer formed from the light-shielding composition of the present invention. Since the photosensitive layer is formed of the light-shielding composition of the present invention, the photosensitive layer can be formed to exhibit excellent barrier properties in the infrared range and exhibit excellent light transmittance in the visible light region, have a desired shape and have excellent durability (for high temperature and high humidity) A pattern of durability or adhesion to a substrate and the like.

In addition, the present invention also relates to a permanent pattern formed from the light-shielding composition of the present invention. The permanent pattern of the present invention can be obtained by subjecting a photosensitive layer formed of the light-shielding composition of the present invention to exposure and alkali development. Due to the use of the light-shielding composition of the present invention, the permanent pattern exhibits excellent barrier properties in the infrared range and exhibits excellent light transmittance in the visible light region, has a desired shape and has excellent durability (for high temperature and high humidity durability) Pattern of or adhesion to the substrate and its similar properties.

The present invention also relates to a method of forming a pattern comprising: forming a photosensitive layer on a substrate using the light-shielding composition of the present invention as a solder resist; exposing the photosensitive layer to cure the exposed region; and developing the exposed photosensitive layer using a base to form a pattern.

Hereinafter, a method of forming a permanent pattern (such as a solder resist pattern) by using the light-shielding composition of the present invention will be described in detail. The following description relating to the type or amount of the solvent used to prepare the coating solution, the coating method of the coating solution, the thickness of the photosensitive layer, the exposure or other processes is not limited to use for the solder resist. In addition, hereinafter, a case where a light-shielding composition is used to form a photosensitive layer (light-shielding composition layer) is provided as an example.

Photosensitive layer

To form a solder resist pattern, first use the shading composition of the present invention Become a photosensitive layer. The photosensitive layer is not particularly limited as long as it contains a light-shielding composition. The film thickness, layer structure and the like can be appropriately determined depending on the purpose.

For example, a coating solution is prepared by dissolving, emulsifying or dispersing the shading composition of the present invention in water or a solvent; coating a coating solution directly on the support; and drying the coated support to form a photosensitive film Floor.

The solvent used to prepare the coating solution is not particularly limited. The solvent is appropriately determined depending on the purpose in a solvent capable of uniformly dissolving or dispersing the respective components of the light-shielding composition of the present invention. 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 or methoxypropyl acetate; aromatic hydrocarbons such as 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; and dimethylformamide, dimethylacetamide, dimethylhydrazine, cyclobutylide, and the like. These solvents may be used singly or in combination of two or more types. In addition, known surfactants may also be added.

The method of applying the coating solution to the support is not particularly limited and may be appropriately selected depending on the purpose. Examples of the method include coating using a spin coater, a slit coater, a slit coater, a roll coater, a die coater, a curtain coater, an inkjet method, or the like. Among these methods, a spin coater is particularly preferred. For the purpose of obtaining "thick film formation suitability" and "thick film formation suitability", it is an object of the present invention.

Further, the drying conditions of the film depend on the type of the respective components and the solvent and the content thereof, and are usually carried out at a temperature of from 60 ° C to 150 ° C for from about 30 seconds to about 15 minutes.

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

Method for forming solder resist pattern

The method of forming a permanent solder resist pattern by using the light-shielding composition for solder resist of the present invention includes at least an exposure process, and may further include a developing process suitably selected as needed, and other processes. In the present invention, the term "light exposure/exposure" as used herein means irradiation with light having any of various wavelengths and irradiation with an electron beam or radiation such as i-ray.

Exposure process

In the exposure process, a photosensitive layer formed of a light-shielding composition layer is exposed using a mask. In this process, only the illuminated area (i.e., the exposed area) is cured.

Exposure is preferably carried out by irradiation with radiation. In particular, examples of preferred types of radiation that can be used for exposure include electron beams, KrF, ArF, ultraviolet light (such as g-rays, h-rays or i-rays), and visible light. In particular, KrF, g-ray, h-ray, and i-ray are preferred.

Can be exposed by using a stepper, using a high pressure mercury lamp or the like It is like a method to perform exposure.

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 from 50 mJ/cm to 1,000 mJ. / square centimeters.

Other processes

Other processes may be appropriately selected depending on the purpose without particular limitation, and examples thereof include a surface treatment process, a development process, a curing process, and a post-exposure process.

Developing process

After the exposure process, an alkali development process is performed, and an unexposed area during the exposure process is dissolved into an aqueous alkali solution. Thus, only the region solidified by exposure (i.e., the exposed region) is left, and a patterned solder resist having light blocking properties is formed.

The developing solution is preferably an organic alkali developing solution which does not cause damage to the underlying circuit. The development temperature is generally from 20 ° C to 40 ° C, and the development time is from 10 seconds to 180 seconds.

Examples of the base used for the developing solution include organic basic compounds such as ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine and 1 , 8-diazabicyclo-[5,4,0]-7-undecene, and preferably an aqueous alkali solution obtained by diluting with pure water, wherein any of the above organic basic compounds in the aqueous alkali solution The concentration is from 0.001% by mass to 10% by mass and preferably from 0.01% by mass to 1% by mass. When the developing solution is the aqueous alkali solution, it is generally washed and developed with pure water after development. Solution.

Curing process

The curing process is a process for curing a photosensitive layer having a pattern which has been formed in a developing process. As a result of this process, the mechanical strength of the permanent pattern will be improved.

The curing treatment process can be appropriately determined depending on the purpose without particular limitation, and a remarkably preferred example thereof includes the entire surface exposure and the entire surface heating.

The entire surface exposure can be performed, for example, by exposing the entire surface of the laminate having the patterned photosensitive layer formed in the development process. As a result of the entire surface exposure, the polymerizable component in the light-shielding composition constituting the photosensitive layer is cured, and the permanent pattern is further cured, and the mechanical strength and durability are improved.

The apparatus for exposing the entire surface can be appropriately selected depending on the purpose without particular limitation, and preferred examples thereof include a UV exposure apparatus such as an ultrahigh pressure mercury lamp.

The entire surface heating process can be performed, for example, by heating the entire surface of the laminate having the patterned photosensitive layer formed in the development process. As a result of the heating of the entire surface, the strength of the patterned film will be improved.

The heating temperature during the entire surface heating is preferably from 120 ° C to 250 ° C, and more preferably from 150 ° C to 220 ° C. When the heating temperature is higher than or equal to 120 ° C, the film strength is improved by heating, and when the heating temperature is less than or equal to 250 ° C, the resin in the light-shielding composition decomposes, and film loss and brittleness are prevented.

The heating time during the entire surface heating is preferably from 3 minutes to 180 minutes. The clock is more preferably 5 minutes to 120 minutes.

The apparatus for heating the entire surface can be appropriately selected from known apparatuses without any particular limitation, and examples thereof include a drying oven, a hot plate, and an IR heater.

The patterned resist film thus formed exhibits excellent infrared light absorbing properties and is therefore suitable for various applications. The light-shielding composition of the present invention exhibits excellent light-shielding properties in the infrared range and exhibits excellent light transmittance in the ultraviolet region to the visible light region, and thus can form a pattern having an excellent shape. In addition, since the formed pattern (that is, the cured film) exhibits excellent infrared light-shielding characteristics, the pattern is suitable for an element having a photodiode and having sensitivity in the infrared range, in particular, for forming a solid-state imaging element. Anti-flux.

As described above, the light-shielding composition of the present invention is suitable for forming a solder resist, and a light-shielding film on the back surface of the substrate and a light-shielding film of the wafer-level lens in the solid-state imaging element.

Accordingly, the present invention is also directed to a solid-state photographic element having a permanent pattern formed from the opaque composition of the present invention.

Although a solid-state imaging element according to an exemplary embodiment of the present invention will be described below with reference to FIGS. 1 and 2, the present invention is not limited to the following specific examples.

In addition, the common components in FIGS. 1 and 2 are represented by common pattern component symbols.

In addition, in the description, "upper", "above", "above" and "upward" mean to be away from the side of the substrate 10, and "below", "below" and "down" mean to be close to the substrate 10 side.

1 is a diagram illustrating solid state photography including an exemplary embodiment in accordance with the present invention. Schematic view of the configuration of the camera module of the shadow component.

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

In particular, the camera module 200 includes: a solid-state photographic element substrate 100 having at least a ruthenium substrate and a photographic element unit provided on a first major surface of the ruthenium substrate; disposed above the first major surface of the solid-state photographic element substrate 100 a glass substrate 30 (translucent substrate); an infrared cut filter 42 disposed above the glass substrate 30; a lens holder 50 including an imaging lens 40 in its internal space and disposed on the glass substrate 30 and infrared cut filter Above the device 42; and a light-shielding electromagnetic shield 44 surrounding the solid-state imaging element substrate 100 and the glass substrate 30. The respective members are connected via an adhesive 20, an adhesive 41, an adhesive 43, and an adhesive 45.

In the camera module 200, light incident from outside (incident light: hν) is sequentially transmitted through the imaging lens 40, the infrared cut filter 42 and the glass substrate 30, and then reaches the photographic element unit of the solid-state photographic element substrate 100. .

The camera module 200 is connected to the circuit substrate 70 via solder balls 60 (connection materials) provided on the second main surface of the solid-state imaging element substrate 100.

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

The solid-state imaging element substrate 100 includes: a ruthenium substrate 10 as a substrate; a photographic element 12; an interlayer insulating film 13; a base layer 14; a red filter 15R; a green filter 15G; a blue filter 15B; an overlying layer 16; Lens 17; light shielding film 18; insulating film 22; metal electrode 23; solder resist layer 24; Electrode 26; and component surface electrode 27.

First, the configuration of the first main surface of the solid-state imaging element substrate 100 is mainly described.

As shown in FIG. 2, a plurality of photographic elements 12 (such as CCD or CMOS) are arranged in two dimensions, and photographic element units are provided on the first main surface side of the ruthenium substrate 10 as a substrate of the solid-state photographic element substrate 100.

On the photographic element 12 in the photographic element unit, an interlayer insulating layer 13 is formed, and a base layer 14 is formed on the interlayer insulating layer 13. Further, a red filter 15R, a green filter 15G, and a blue filter 15B (hereinafter, collectively referred to as "color filter 15" in some cases) are respectively disposed on the base layer 14 to correspond to the photographic element. 12.

A light shielding film (not shown) may be provided at the boundary of the red filter 15R, the green filter 15G, and the blue filter 15B and at the periphery of the photographic element unit. This light shielding film can be produced, for example, from the light-shielding composition of the present invention.

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

Further, a peripheral circuit (not shown) and an internal electrode 126 are provided at the periphery of the photographic element unit on the first main surface, and the internal electrode 26 is connected to the photographic element 12 via a peripheral circuit.

The component surface electrode 27 is formed on the internal electrode 26 via the interlayer insulating layer 13. In the interlayer insulating layer 13, between the internal electrode 26 and the component surface electrode 27, contact plugs (not shown) that electrically connect them to each other are formed. The component surface electrode 27 is used to apply a voltage or read signal via the contact plug and internal electrode 26.

The base layer 14 is formed on the component surface electrode 27. The upper cladding layer 16 is formed on the base layer 14. The base layer 14 and the overlying layer 16 formed on the surface electrode 27 of the component are opened to form a pad void that exposes a portion of the surface electrode 27 of the component.

The above description is the configuration for the first main surface side of the solid-state imaging element substrate 100.

On the first main surface side of the solid-state imaging element substrate 100, an adhesive 20 is provided in the vicinity of the photographic element unit, and the solid-state photographic element substrate 100 is adhered to the glass substrate 30 via the adhesive 20.

The germanium substrate 10 has a through hole penetrating through the germanium substrate 10, and a through electrode as a part of the metal electrode 23 is disposed in the through hole. The photographic element unit is electrically connected to the circuit board 70 via a through electrode.

Next, the configuration of the second main surface side of the solid-state imaging element substrate 100 will be mainly described.

On the second main surface side, the insulating layer 22 is formed by the second main surface passing through the inner wall of the through hole.

On the insulating layer 22, a patterned metal electrode 23 is provided from a region on the second main surface of the substrate 10 to the inside of the via. The metal electrode 23 is an electrode that connects the imaging element unit of the solid-state imaging element substrate 100 to the circuit board 70.

The through electrode is a portion of the metal electrode 23 formed inside the through hole. The through electrode penetrates the germanium substrate 10 and a portion of the interlayer insulating layer, 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 (that is, a protective insulating layer) is provided which covers the second main surface on which the metal electrode 23 is formed, and has There is a void that exposes a portion of the metal electrode 23.

Also, on the second main surface side, a light shielding film 18 covering the second main surface on which the solder resist layer 24 is formed is provided, and having a void exposing a part of the metal electrode 23.

In this configuration, (1) the light-shielding solder resist layer in which the light-shielding film 18 and the solder resist layer 24 are formed as a single layer may be formed of the light-shielding composition of the present invention, or (2) the light-shielding film 18 and the solder resist layer 24 may be formed separately. The layer, and the light shielding film 18 can be formed of the light shielding composition of the present invention.

In FIG. 2, although the light shielding film 18 is patterned to cover a portion of the metal electrode 23 and expose the remaining portion, it may be patterned to expose the entire metal electrode 23 (also applicable to the patterned solder resist layer 24).

The solder ball 60 is provided as a connecting member on the exposed metal electrode 23, and the metal electrode 23 of the solid-state photographic element substrate 100 is electrically connected to the connection electrode (not shown) of the circuit substrate 70 via the solder ball 60.

The solid-state photographic element substrate 100 has been described above. The respective members other than the light shielding film 18 in the solid-state imaging element substrate 100 can be formed by a known method, such as the method disclosed in paragraphs [0033] to [0068] of JP-A No. 2009-158863, Or the method disclosed in paragraphs [0036] to [0065] of JP-A No. 2009-99591.

The light shielding film 18 can be formed by a method for manufacturing a light shielding film according to the present invention.

The interlayer insulating film 13 is, for example, a SiO ₂ film or a SiN film formed by sputtering, chemical vapor deposition (CVD), or the like.

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

The overcoat layer 16 and the base layer 14 are formed by photolithography, for example, using a resist known to form an organic interlayer film.

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

When the light-shielding solder resist layer is formed in a single layer formed by combining the solder resist layer 24 and the light-shielding film 18, the light-shielding solder resist layer can be formed using the light-shielding composition of the present invention.

The solder balls 60 may be formed using Sn-Pb (eutectic), 95 Pb-Sn (high-lead high-melting solder), or Sn-Ag, Sn-Cu, or Sn-Ag-Cu as Pb-free solder. The solder balls 60 may be formed to each have a spherical shape having a diameter of 100 μm to 1,000 μm, and preferably 150 μm to 700 μm.

The internal electrode 26 and the component surface electrode 27 may each be formed in the form of a metal electrode of Cu or the like by chemical mechanical polishing (CMP) or photolithography and etching.

The metal electrode 23 may be a metal electrode formed of Cu, Au, Al, Ni, W, Pt, Mo, Cu compound, W compound, Mo compound or the like by sputtering, photolithography, etching, and/or electroplating. Form formation. The metal electrode 23 may have a single layer structure or a multilayer structure including two or more layers. The film thickness of the metal electrode 23 may be from 0.1 μm to 20 μm, and preferably from 0.1 μm to 10 μm. The ruthenium substrate 10 is not particularly limited, and may be a ruthenium substrate thinned by peeling off its back surface. The thickness of the substrate is not limited, and a thickness of 20 μm to 200 μm, and preferably 30 μm, can be used. 150 micron wafers.

The via holes of the germanium substrate 10 can be formed by photolithography and reactive ion etching (RIE).

As described above, although the solid-state imaging element substrate 100 as a specific example of the embodiment is described with reference to FIGS. 1 and 2, the embodiment of the present invention is not limited to the embodiment illustrated in FIGS. 1 and 2, and the configuration is not It is particularly limited as long as the configuration has a metal electrode and a light shielding film on the back surface side.

Instance

Hereinafter, although examples of the invention will be described, the invention is not limited to the examples. In the following, "parts" and "%" are by mass unless otherwise stated.

Preparation of filler dispersion b-1

First, 31 parts by mass of a cerium oxide filler (SO-C1, trade name, manufactured by Admatechs Co., Ltd.) was premixed; the particle diameter indicating the maximum value in the particle diameter distribution was 250. Nano), 58 parts by mass of resin (ACA230AA, trade name, manufactured by Daicel-cytec Company Ltd.; solid content: 55%; solvent: propylene glycol monomethyl ether) and 11 parts by mass of six Oxymethylmethyl melamine, and then in a motor grinder M-50 (trade name, manufactured by Eiger Co., Ltd.), using a zirconia bead having a diameter of 1.0 mm at 9 m The peripheral speed of /sec was dispersed for 1.5 hours to obtain a filler dispersion b-1.

Preparation of filler dispersion b-2

First, pre-mix 31 parts by mass of cerium oxide filler (SO-C2, Trade name, manufactured by Admatechs Co., Ltd.; particle diameter indicating the maximum of the particle diameter distribution is 500 nm, and 58 parts by mass of resin (ACA230AA, trade name, by Daicel - Manufactured by Daicel-cytec Company Ltd.; solid content: 55%; solvent: propylene glycol monomethyl ether) and 11 parts by mass of hexamethoxymethyl melamine, and then in the motor grinder M-50 (trade name) In the case of Eiger Co., Ltd., zirconia beads having a diameter of 1.0 mm were dispersed at a peripheral speed of 9 m/sec for 1.5 hours to obtain a filler dispersion b-2. .

Preparation of filler dispersion b-3

First, 31 parts by mass of a cerium oxide filler (SO-C3, trade name, manufactured by Admatechs Co., Ltd.) was previously mixed; the particle diameter indicating the maximum value in the particle diameter distribution was 900 奈m), 58 parts by mass of resin (ACA230AA, trade name, manufactured by Daicel-cytec Company Ltd.; solid content: 55%; solvent: propylene glycol monomethyl ether) and 11 parts by mass of hexamethoxy Methyl melamine, and then in a motor grinder M-50 (trade name, manufactured by Eiger Co., Ltd.), using a zirconia bead having a diameter of 1.0 mm at 9 m/ The peripheral speed of the second was dispersed for 1.5 hours to obtain a filler dispersion b-3.

Preparation of filler dispersion b-4

First, 31 parts by mass of a cerium oxide filler (SO-C5, trade name, manufactured by Admatechs Co., Ltd.) was premixed; the particle diameter indicating the maximum value in the particle diameter distribution was 1,600 奈 m), 58 parts by mass of resin (ACA230AA, trade name, manufactured by Daicel-cytec Company Ltd.; solid content: 55%; solvent: propylene glycol monomethyl ether) and 11 parts by mass of hexamethoxy Methyl melamine, and then in a motor grinder M-50 (trade name, manufactured by Eiger Co., Ltd.), using a zirconia bead having a diameter of 1.0 mm at 9 m/ The peripheral speed of the second was dispersed for 1.5 hours to obtain a filler dispersion b-4.

Preparation of filler dispersion b-5

First, 31 parts by mass of a cerium oxide filler (SO-C6, trade name, manufactured by Admatechs Co., Ltd.) was previously mixed; the particle diameter indicating the maximum value in the particle diameter distribution was 2,200 奈m), 58 parts by mass of resin (ACA230AA, trade name, manufactured by Daicel-cytec Company Ltd.; solid content: 55%; solvent: propylene glycol monomethyl ether) and 11 parts by mass of hexamethoxy Methyl melamine, and then in a motor grinder M-50 (trade name, manufactured by Eiger Co., Ltd.), using a zirconia bead having a diameter of 1.0 mm at 9 m/ The peripheral speed of seconds was dispersed for 1.5 hours to obtain a filler dispersion b-5.

Preparation of filler dispersion b-6

First, 31 parts by mass of a cerium oxide filler (QS-04, trade name, manufactured by Mitsubishi Rayon Co., Ltd.) was previously mixed; the particle diameter indicating the maximum value in the particle diameter distribution was 4,000. Nano), 58 parts by mass of resin (ACA230AA, trade name, manufactured by Daicel-cytec Company Ltd.; solid content The amount is 55%; the solvent: propylene glycol monomethyl ether) and 11 parts by mass of hexamethoxymethyl melamine, and then in the motor grinder M-50 (trade name, manufactured by Eiger Co., Ltd.) In the case, zirconia beads having a diameter of 1.0 mm were dispersed at a peripheral speed of 9 m/sec for 1.5 hours to obtain a filler dispersion b-6.

Preparation of filler dispersion b-7

First, 31 parts by mass of a cerium oxide filler (SO-C1, trade name, manufactured by Admatechs Co., Ltd.) was premixed; the particle diameter indicating the maximum value in the particle diameter distribution was 250 奈. m), 58 parts by mass of resin (ACA230AA, trade name, manufactured by Daicel-cytec Company Ltd.; solid content: 55%; solvent: propylene glycol monomethyl ether) and 11 parts by mass of melamine, Then, in a motor grinder M-50 (trade name, manufactured by Eiger Co., Ltd.), zirconia beads having a diameter of 1.0 mm were dispersed at a peripheral speed of 9 m/sec. 1.5 hours, thereby obtaining a filler dispersion b-7.

Preparation of filler dispersion c-1

First, 7 parts by mass of a cerium oxide filler (Aerosil 50), trade name, manufactured by Nippon Aerosil Co., Ltd., is premixed; the maximum value in the particle diameter distribution is indicated. Particle diameter of 17 nm) and 93 parts by mass of resin (ACA230AA, trade name, manufactured by Daicel-cytec Company Ltd.; solid content: 55%; solvent: propylene glycol monomethyl ether) And then in the motor grinding machine M-50 (trade name, by Eiger GmbH (manufactured by Eiger Co., Ltd.), a zirconia bead having a diameter of 1.0 mm was dispersed at a peripheral speed of 9 m/sec for 1.5 hours to obtain a filler dispersion c-1.

Preparation of filler dispersion c-2

First, 100 g of a cerium oxide filler (Australia 300, trade name, manufactured by Nippon Aerosil Co., Ltd.) was weighed; the particle diameter indicating the maximum value in the particle diameter distribution was 7 nm) and 500 grams of ion exchange water. To this was added 1.5 g of a 2.38 mass% aqueous solution of tetramethylammonium hydroxide. The mixture was sonicated for 1 hour using Branson 8510 (trade name, manufactured by Emerson Co., Ltd., Japan). The aqueous solution obtained by using Optimus L-90 K (Optima L-90 K) at 10,000 rpm was separated for 15 minutes, and the supernatant was collected and a rotary evaporator N-1000 (trade name, by Tokyo Physicochemical Co., Ltd. (Tokyo) was used. Rikakikai Co., Ltd.) Distilled off the solvent to obtain a ceria filler having a maximum particle diameter of 4 nm in the particle diameter distribution.

Next, 7 parts by mass of the thus obtained cerium oxide filler and 93 parts by mass of a resin (ACA230AA, trade name, manufactured by Daicel-cytec Company Ltd.) having a solid content of 55% were previously mixed. Solvent: propylene glycol monomethyl ether), and then in a motor grinder M-50 (trade name, manufactured by Eiger Co., Ltd.), zirconia beads having a diameter of 1.0 mm were used. The circumferential speed of 9 meters per second is dispersed. However, since the grinding activity unit of the apparatus is stopped due to the high viscosity of the solution, the treatment is stopped at this stage.

Preparation of filler dispersion c-3

First, 7 parts by mass of a cerium oxide filler (Aesop OX50, trade name, manufactured by Nippon Aerosil Co., Ltd.; particle diameter indicating the maximum value in the particle diameter distribution) is previously mixed. 40 nm) and 93 parts by mass of resin (ACA230AA, as described above), and then used in a motor grinder M-50 (trade name, manufactured by Eiger Co., Ltd.) The zirconia beads having a diameter of 1.0 mm were dispersed at a peripheral speed of 9 m/sec for 1.5 hours to obtain a filler dispersion c-3.

Preparation of filler dispersion c-4

First, 51.15 parts by mass of ACA230AA (trade name, manufactured by Daicel-cytec Company Ltd.; solid content: 55%; solvent: propylene glycol monomethyl ether) was reprecipitated in a solid. The content is 41.85 parts by mass of propylene glycol monomethyl ether acetate and 7 parts by mass of cerium oxide filler (Aussie 50, trade name, manufactured by Nippon Aerosil Co., Ltd.; indication) The particle diameter of the largest of the particle diameter distributions was 17 nm) mixed. Next, in a motor grinder M-50 (trade name, manufactured by Eiger Co., Ltd.), zirconia beads having a diameter of 1.0 mm were dispersed at a peripheral speed of 9 m/sec. The resulting mixture was allowed to stand for 1.5 hours to obtain a filler dispersion c-4.

Preparation of filler dispersion c-5

First, 51.15 parts by mass of ACA230AA (trade name, manufactured by Daicel-cytec Company Ltd.; The content of the solid is 55%; the solvent: propylene glycol monomethyl ether) and the solid content obtained by reprecipitation with 41.85 parts by mass of butyl acetate and 7 parts by mass of cerium oxide filler (Aussie 50, trade name, loved by Japan It was produced by Nippon Aerosil Co., Ltd.; a particle diameter of 17 nm indicating the maximum value in the particle diameter distribution. Next, in a motor grinder M-50 (trade name, manufactured by Eiger Co., Ltd.), zirconia beads having a diameter of 1.0 mm were dispersed at a peripheral speed of 9 m/sec. The resulting mixture was allowed to stand for 1.5 hours to obtain a filler dispersion c-5.

Preparation of filler dispersion c-6

First, 51.15 parts by mass of ACA230AA (trade name, manufactured by Daicel-cytec Company Ltd.; solid content: 55%; solvent: propylene glycol monomethyl ether) was reprecipitated in a solid. Content and 2.15 parts by mass of dipropylene glycol monomethyl ether, 2.2 parts by mass of butyl acetate, 37.5 parts by mass of propylene glycol monomethyl ether acetate and 7 parts by mass of cerium oxide filler (Aussie 50, trade name, loved by Japan It was produced by Nippon Aerosil Co., Ltd.; a particle diameter of 17 nm indicating the maximum value in the particle diameter distribution. Next, in a motor grinder M-50 (trade name, manufactured by Eiger Co., Ltd.), zirconia beads having a diameter of 1.0 mm were dispersed at a peripheral speed of 9 m/sec. The resulting mixture was allowed to stand for 1.5 hours to obtain a filler dispersion c-6.

Preparation of titanium black A

First, 100 g of titanium oxide having a particle diameter of 15 nm (MT-150A, trade name, manufactured by Tayca Corporation) and 25 g of BET surface area of 300 m 2 /g were weighed. 矽 particles (AEROPERL (registered trademark) 300/30, manufactured by Evonik Monosilane Japan Co., Ltd.) and 100 gram Dispick 190 (trade name) , manufactured by BYK Japan KK., a German company. 71 g of ion-exchanged water was added thereto, and MAZERSTAR KK-400W (trade name, manufactured by KURABO Co., Ltd.) was used at a revolution rate of 1,360 rpm and a rotation of 1,047 rpm. The resulting mixture was treated at a rate of 20 minutes to obtain an aqueous solution of a homogeneous mixture. The aqueous solution thus obtained was fed into a quartz vessel, and heated at 920 ° C under an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.). Thereafter, the atmosphere was replaced with nitrogen, and ammonia gas was blown at a rate of 100 ml/min for 5 hours at the same temperature to carry out a nitrogen reduction treatment. After this treatment, the collected powder was ground in a mortar to obtain Titanium Black A in the form of a powder.

Synthesis of Dispersant 1

First, 600.0 g of ε-caprolactone and 22.8 g of 2-ethyl-1-hexanol were placed in a 500 ml three-necked flask, and stirred while stirring under a nitrogen atmosphere. Next, 0.1 g of monobutyltin oxide was added thereto, followed by heating to 100 °C. After 8 hours, the elimination of the starting material was confirmed by gas chromatography, and the mixture was cooled to 80 °C. Next, 0.1 g of 2,6-di-tert-butyl-4-methylphenol was added thereto, followed by the addition of 27.2 g of 2-methylpropenyloxyethyl isocyanate. After 5 hours, the elimination of the starting material was confirmed by 1 H-NMR, and the mixture was cooled to 80 ° C to obtain 200 g of the precursor M1 as a solid form (having the following structure; n = 30). By 1H-NMR, IR and The mass analysis identifies the precursor M1.

Then, 30.0 g precursor M1, 70.0 g NK Ester CB-1 (2-methyl propylene methoxyethyl phthalate; brand name, by Shin-Nakamura Chemical Co., Ltd. (Shin- Nakamura Chemical Co., Ltd.), 2.3 g of dodecanethiol and 233.3 g of propylene glycol monomethyl ether acetate were placed in a three-necked flask replaced with nitrogen, and a stirrer (Thirty-one motor (THREE-) was used. ONE MOTOR), trade name, manufactured by SHINTO Scientific Co., Ltd., was stirred and heated to 75 ° C while blowing nitrogen into the flask. Next, 0.2 g of 2,2-azobis(2-methylpropionic acid) dimethyl ester (V-601, trade name, manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto. Manufactured), followed by stirring at 75 ° C for 2 hours under heating. After 2 hours, 0.2 g of V-601 was further added, followed by stirring under heating for 3 hours, thereby obtaining a solution of 30% by mass of Dispersant 1 having the following structure.

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) and is calculated based on polystyrene. HSK- using TSK Gel Super HZM-H, TSK Gel Super HZ4000, and TSK Gel Super HZ200 (trade name, manufactured by Tosoh Co., Ltd.) as a column 8020 GPC (trade name, manufactured by Tosoh Co., Ltd.) was subjected to GPC.

. Composition ratio: x = 35 (% by mass), y = 65 (% by mass)

. Acid value: 80 mg KOH / g

. Mw: 30,000

Preparation of titanium black dispersion 2

Using a stirrer (EUROSTAR, trade name, manufactured by IKA Co., Ltd.), the components mentioned in "Composition 1" are mixed for 15 minutes to obtain a dispersion. .

(composition 1)

. Titanium black A prepared as above: 25 parts

. Dispersant: Dispersant 1 (30% by mass aqueous solution) prepared as above: 25 copies

. Organic solvent: propylene glycol monomethyl ether acetate (hereinafter, referred to as "PGMEA (propylene glycol monomethyl ether acetate)"): 130 parts

The dispersion thus obtained was subjected to dispersion treatment using an Ultra Apex mill UAM015 (trade name, manufactured by Kotobuki Industries Co., Ltd.) under the conditions mentioned below, thereby Titanium black dispersion 2 (solid concentration: 18.0% by mass) was obtained. The particle diameter of the maximum value indicating the particle diameter distribution of the titanium black dispersion 2 was 19 nm.

(dispersion condition)

. Bead diameter: φ0.05 mm

. Bead filling rate: 75% by volume

. Grinding machine peripheral speed: 8 meters / sec

. The amount of mixed solution to be dispersed: 500 grams

. Circulating flow rate (pump feed amount): 13 kg / hour

. Processing solution temperature: 25 ° C to 30 ° C

. Cooling water: tap water

. The volume of the annular channel of the bead mill: 0.15 liter

. Passes: 90 times

Preparation of carbon black dispersion 3

The following composition I was subjected to high viscosity dispersion treatment using a two-roll mill to obtain a dispersion.

Next, a mixture of the following composition II is added to the fraction thus obtained The resulting mixture was stirred at 3,000 rpm for 3 hours in a dispersion. Using a disperser (trade name: DISPERMAT, manufactured by GETZMANN GmbH), the resulting mixed solution was finely dispersed using zirconia beads having a particle diameter of 0.3 mm for 4 hours. Carbon black dispersion 3 (solid concentration: 18.0% by mass).

(composition I)

. A carbon black having a diameter of 15 nm indicating a maximum value in the particle diameter distribution (Pigment Black 7): 23 parts by mass

. 45 mass% benzyl methacrylate/methacrylic acid copolymer PGMEA solution (copolymerization ratio of benzyl methacrylate/methacrylic acid = 67/33 (mol%), Mw: 28,000): 22 parts by mass

. Solps 5000 (trade name, manufactured by The Lubrizol Corporation): 1.2 parts by mass

(composition II)

. 45 mass % benzyl methacrylate / methacrylic acid copolymer PGMEA solution (benzyl methacrylate unit / methacrylic acid unit = 67 / 33 (mole %), Mw: 28,000): 22 parts by mass

. PGMEA: 176 parts by mass

Example 1

The composition mentioned below was mixed and filtered (under the conditions mentioned below) to obtain the light-shielding composition of Example 1.

. (A) Light-shielding particles: 18.5 mass% of YMF-02 (trade name, manufactured by Sumitomo Metal Mining; strontium oxide tungsten (Cs _0.33 WO ₃ ), a particle indicating the maximum value in the particle diameter distribution) Dispersion with a diameter of 20 nm): 26.97 parts by mass

. (D) Polymerizable compound: A-DCP (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.; difunctional polymerizable compound): 5.2 parts by mass

. (E) Photopolymerization initiator: Yan Jiagu 907 (trade name, manufactured by BASF Corporation, Japan): 1.24 parts by mass

. Sensitizer: KAYACURE DETX-S (thioxanthone compound, trade name, manufactured by Nippon Kayaku Co., Ltd.): 0.37 parts by mass

. UV absorber: DPO (trade name, manufactured by FUJIFILM Fine Chemicals Co., Ltd.): 0.08 parts by mass

.矽 偶 coupling agent: KBM-503 (trade name, manufactured by Shin-Etsu silicone Co., Ltd.): 2.30 parts by mass

. Surfactant: Magogith F-780 (trade name, manufactured by DIC Corporation): 0.14 parts by mass

. (B) filler dispersion b-1 (described above): 1.50 parts by mass

. (C) filler dispersion c-1 (described above): 61.40 parts by mass

Filter condition

In the above filtration treatment, PROFILE-STAR (trade name, manufactured by Poly Corporation, Japan; made of polypropylene; filtration accuracy: 1.5 μm) was used as the first filtration. And use HDC-II (trade name, by Manufactured by Poll Corporation, Japan; made of high density polypropylene; filtration accuracy: 6.0 microns) as a second filter.

Example 2

The light-shielding composition of Example 2 was prepared in the same manner as in Example 1 except that the light-shielding particle dispersion used in Example 1 was changed to titanium black dispersion 2.

Example 3

The light-shielding composition of Example 3 was prepared in the same manner as in Example 1, except that the light-shielding particle dispersion used in Example 1 was changed to carbon black dispersion 3.

Example 4

The light-shielding composition of Example 4 was prepared in the same manner as in Example 1 except that the (B) filler dispersion b-1 used in Example 1 was changed to the filler dispersion b-2.

Example 5

The light-shielding composition of Example 5 was prepared in the same manner as in Example 1 except that the (B) filler dispersion b-1 used in Example 1 was changed to the filler dispersion b-3.

Example 6

The light-shielding composition of Example 6 was prepared in the same manner as in Example 1 except that the (B) filler dispersion b-1 used in Example 1 was changed to the filler dispersion b-4.

Example 7

The light-shielding composition of Example 7 was prepared in the same manner as in Example 1 except that the (B) filler dispersion b-1 used in Example 1 was changed to the filler dispersion b-5.

Example 8

The light-shielding composition of Example 8 was prepared in the same manner as in Example 1 except that the (C) filler dispersion c-1 used in Example 1 was changed to the filler dispersion c-3.

Example 9

The light-shielding composition of Example 9 was prepared in the same manner as in Example 1 except that the (B) filler dispersion b-1 used in Example 1 was changed to the filler dispersion b-7.

Example 10

The light-shielding composition of Example 10 was prepared in the same manner as in Example 9, except that (E) photopolymerization initiator (Yanjiagu 907, trade name, used by BASF Corporation, Japan) was used in Example 9. Manufactured) was changed to photopolymerization initiator Yan Jiagu 369 (trade name, manufactured by BASF Corporation, Japan).

Example 11

The light-shielding composition of Example 11 was prepared in the same manner as in Example 9 except that (E) photopolymerization initiator (Yanjiagu 907, trade name, used by BASF Corporation, Japan) was used in Example 9. Manufactured) was changed to photopolymerization initiator Yanjiagu 379 (trade name, manufactured by BASF Corporation, Japan).

Example 12

The light-shielding composition of Example 12 was prepared in the same manner as in Example 10 except that the (C) filler dispersion c-1 used in Example 10 was changed to the filler dispersion c-4.

Example 13

The light-shielding composition of Example 13 was prepared in the same manner as in Example 10 except that the (C) filler dispersion c-1 used in Example 10 was changed to the filler dispersion c-5.

Example 14

The light-shielding composition of Example 14 was prepared in the same manner as in Example 10 except that the (C) filler dispersion c-1 used in Example 10 was changed to the filler dispersion c-6.

Comparative example 1

The light-shielding composition of Comparative Example 1 was prepared in the same manner as in Example 1 except that the filler dispersion c-1 used in Example 1 was not added.

Comparative example 2

The light-shielding composition of Comparative Example 2 was prepared in the same manner as in Example 1 except that the filler dispersion b-1 used in Example 2 was not added.

Comparative example 3

The light-shielding composition of Comparative Example 3 was prepared in the same manner as in Example 1 except that the (B) filler dispersion b-1 used in Example 1 was changed to the filler dispersion b-6.

The thus obtained light-shielding compositions of Examples 1 to 14 each have a wavelength range as described for (B) the first filler after mixing (B) the first filler and (C) the second filler. The maximum value and the bimodal particle diameter distribution for the maximum value in the wavelength range described by (C) the second filler.

The thus obtained Examples 1 to 14 were evaluated according to the following methods and The light-shielding compositions of Comparative Examples 1 to 3 were compared.

Thick film formation suitability evaluation

Each of the light-shielding compositions was applied to the tantalum wafer at a rate of 900 rpm by spin coating for 25 seconds. Next, the resulting tantalum wafer was heated on a hot plate at 120 ° C for 2 minutes, and then the film thickness was measured by the method described below. The film thickness is considered to be "allowable" in the case where the thickness of the film is higher than or equal to 20 μm.

Method of Measuring Film Thickness: Film thickness was measured using Dektak 6M (trade name, manufactured by ULVAC Corporation; contact surface shape measuring device).

Evaluation of coating uniformity

The coating uniformity of the thus obtained coating film was evaluated by visual observation, and rating was performed using five grades (5 to 1) based on the following evaluation criteria. A rating of "3" above or equal to is considered "acceptable".

Evaluation criteria

5: No roughness was observed on the surface, and there was no problem of surface characteristics.

4: Roughness was hardly observed on the surface, and there was almost no problem of surface characteristics.

3: Roughness was observed on a part of the surface, and the surface characteristics were slightly poor, but at an allowable level.

2:: Roughness was observed on most of the surfaces, and the surface characteristics were poor, and the level was not allowed.

1: roughness is observed on the entire surface, and the surface characteristics are extremely poor. Being at a level that is not allowed.

Evaluate thickness uniformity on uneven surfaces

A simulated uneven pattern was formed on the tantalum wafer, and the simulated uneven pattern was formed by a raised portion having a height of 20 μm and a pitch of 50 μm. The coating conditions for forming a film having a thickness of 10 μm on a germanium wafer having no simulated uneven pattern were separately determined. Each of the light-shielding compositions was spin-coated on a tantalum wafer having a simulated uneven pattern under the above coating conditions, followed by prebaking at 100 ° C for 120 seconds and UV curing. A cross section of the uneven portion of the substrate was photographed using a scanning electron microscope (SEM), and the thinnest thickness of the obtained film in the concave region (ie, the region between the convex portions) was measured, and evaluated. Thickness uniformity on uneven surfaces.

The maximum film thickness of the obtained film in the concave region was evaluated as a relative value assuming a desired thickness of 10 μm of 100 μm. When the value is close to 100, the thickness uniformity on the uneven surface is regarded as good, and when the value is higher than or equal to 130, the value is regarded as "not allowed".

Evaluation of high temperature and high humidity durability (evaluation of insulation reliability): HAST test

Each of the light-shielding compositions is applied to the anode wire made of copper by a spin coating method in a comb form on the tantalum wafer, so that the copper material having a copper thickness of 12 μm has a line/gap of 50 μm/50 μm. On the substrate material, the film thickness on the copper wire (film thickness after prebaking) was adjusted to 20 μm, and then heated at 100 ° C on a hot plate for 2 minutes to obtain a coated film.

Next, the coated film was exposed at 800 mJ/cm 2 using a high pressure mercury lamp.

After the exposure, the coating film was subjected to puddle development using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide at 25 ° C for 40 seconds. Next, the film was washed in a rotary sprinkler, washed with pure water, and heated (post-baked) at 150 ° C for 1 hour to form a solder resist pattern (permanent pattern).

A high-accelerated stress test (HAST) was performed on the formed permanent pattern to evaluate the dendritic structure and the dielectric resistance (ohm). In HAST, a voltage of 10 volts was applied to the electronic component module at a temperature of 130 ° C in an atmosphere of 85% relative humidity for 200 hours and then the dielectric bump of the conductor was measured under the same conditions using a high acceleration rate tester. Resistance (ohms). Next, the dendritic structure of the conductor bumps was observed and evaluated as follows. A rating higher than or equal to 3 is considered acceptable.

Evaluation criteria

5: No changes were observed in the line.

4: No dendritic structure was observed, but slight changes in the anode line were observed.

3: No dendritic structure was observed, but the anode line was invisible.

2: A dendritic structure was observed, and it was difficult to observe the anode line.

1: There is a dendritic structure.

As shown in Table 1, in Examples 1 to 8 using the light-shielding composition of the present invention, a film exhibiting excellent thick film formation suitability and a film thickness of 20 μm or more was obtained, and excellent coating uniformity and excellent unevenness were obtained. The thickness is uniform on the surface, and the film has excellent high temperature and high wet durability. By comparing Example 1 with Example 8, it was found that when the (B) filler having the same particle diameter is used, the thickness of the (C) filler having a relatively small particle diameter is uniform on a thick film forming suitability and uneven surface. Sexuality, coating uniformity Excellent effect in terms of high temperature and high humidity durability.

In contrast, in Comparative Example 1 and Comparative Example 2 in which the light-shielding composition of the present invention was not used, a thick layer could not be formed, and the thickness uniformity on the uneven surface and the high-temperature and high-humidity durability were inferior. In Comparative Example 3, although a relatively thick layer can be formed, high temperature and high humidity durability are inferior.

Japanese Patent Application No. 2011-040505 and Japanese Patent Application No. 2011-102134 are incorporated herein by reference.

All publications, patent applications, and technical standards referred to in this specification are hereby incorporated by reference in their entirety, the extent of the disclosure, the This article is general.

10‧‧‧矽 substrate

12‧‧‧Photographic components

13‧‧‧Interlayer insulating film/interlayer insulating layer

14‧‧‧ grassroots

15‧‧‧Color filter

15R‧‧‧Red Filter

15G‧‧‧Green Filter

15B‧‧‧Blue filter

16‧‧‧Overlay

17‧‧‧Microlens

18‧‧‧Shade film

20‧‧‧Adhesive

22‧‧‧Insulation film/insulation

23‧‧‧Metal electrode / patterned metal electrode

24‧‧‧Anti-flux layer

26‧‧‧Internal electrodes

27‧‧‧Part surface electrode

30‧‧‧ glass substrate

40‧‧‧ imaging lens

41‧‧‧Adhesive

42‧‧‧Infrared cut-off filter

43‧‧‧Adhesive

44‧‧‧Shade electromagnetic shielding

45‧‧‧Adhesive

50‧‧‧Lens Holder

60‧‧‧ solder balls

70‧‧‧Circuit board/circuit board

100‧‧‧Solid photographic element substrate

115‧‧‧Color filter

200‧‧‧ camera module

Hν‧‧‧ incident light

1 is a schematic view illustrating a configuration of a camera module including a solid-state imaging element according to an exemplary embodiment of the present invention.

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

20‧‧‧Adhesive

30‧‧‧ glass substrate

42‧‧‧Infrared cut-off filter

40‧‧‧ imaging lens

41‧‧‧Adhesive

43‧‧‧Adhesive

44‧‧‧Shade electromagnetic shielding

45‧‧‧Adhesive

50‧‧‧Lens Holder

60‧‧‧ solder balls

70‧‧‧Circuit board/circuit board

100‧‧‧Solid photographic element substrate

200‧‧‧ camera module

Hv‧‧‧ incident light

Claims (15)

A light-shielding composition comprising: (A) any one of a light-shielding particle or a light-shielding dye; (B) a first filler having a particle diameter of from 100 nm to 3,000 nm, the particle diameter being the first fill a maximum of the particle diameter distribution of the agent; and (C) a second filler having a particle diameter of 5 nm to 90 nm, the particle diameter being the maximum of the particle diameter distribution of the second filler, Wherein when the (B) first filler and the (C) second filler are mixed in the light-shielding composition, a particle diameter distribution among the mixed fillers includes 5 nm to 90 nm The maximum value in the range of meters and the maximum in the range of 100 nm to 3,000 nm. The light-shielding composition of claim 1, wherein the light-shielding particles comprise a pigment. The light-shielding composition of claim 1, wherein the light-shielding particles comprise an inorganic pigment. The light-shielding composition according to claim 1, wherein the light-shielding particles have a particle diameter of 5 nm to 100 nm, and the particle diameter is a maximum value among particle diameter distributions of the light-shielding particles. The light-shielding composition according to claim 1, wherein the light-shielding particles comprise at least one selected from the group consisting of titanium black, carbon black, and tungsten strontium oxide. The shading composition as described in claim 1 of the patent application, wherein At least one of (B) the first filler or the (C) second filler includes an inorganic filler. The light-shielding composition of claim 1, wherein at least one of the (B) first filler or the (C) second filler comprises cerium oxide. The light-shielding composition of claim 1, wherein at least one of the (B) first filler or the (C) second filler has a substantially spherical shape. The light-shielding composition according to claim 1, wherein the content ratio of the (B) first filler to the (C) second filler is from 1:30 to 1:2 by mass. The light-shielding composition according to claim 1, further comprising: (D) a polymerizable compound; and (E) a photopolymerization initiator. The light-shielding composition according to claim 1, wherein the (B) first filler has a particle diameter of 100 nm to 2200 nm, and the particle diameter is the (B) first filler. a maximum of the particle diameter distribution, and the (C) second filler has a particle diameter of 5 nm to 40 nm, and the particle diameter is in the particle diameter distribution of the (C) second filler The maximum value. A method for producing a light-shielding composition according to any one of claims 1 to 11, comprising: A dispersion comprising the light-shielding particles, a dispersion comprising the (B) first filler, and a dispersion comprising the (C) second filler are mixed into a respective dispersion. A solder resist comprising the light-shielding composition according to any one of claims 1 to 11. A method of manufacturing a pattern comprising: forming a photosensitive layer on a substrate using a solder resist as described in claim 13; patterning the photosensitive layer to cure the exposed region; and after exposing the pattern The photosensitive layer was subjected to alkali development. A solid-state photographic element comprising a solder resist layer formed using a solder resist as described in claim 13 of the patent application.