WO2014104136A1 - 赤外線反射膜形成用の硬化性樹脂組成物、赤外線反射膜及びその製造方法、並びに赤外線カットフィルタ及びこれを用いた固体撮像素子 - Google Patents
赤外線反射膜形成用の硬化性樹脂組成物、赤外線反射膜及びその製造方法、並びに赤外線カットフィルタ及びこれを用いた固体撮像素子 Download PDFInfo
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- WO2014104136A1 WO2014104136A1 PCT/JP2013/084755 JP2013084755W WO2014104136A1 WO 2014104136 A1 WO2014104136 A1 WO 2014104136A1 JP 2013084755 W JP2013084755 W JP 2013084755W WO 2014104136 A1 WO2014104136 A1 WO 2014104136A1
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Definitions
- the present invention relates to a curable resin composition for forming an infrared reflective film, an infrared reflective film and a method for producing the same, an infrared cut filter, and a solid-state imaging device using the same.
- a CCD or CMOS image sensor which is a solid-state image sensor for color images, is used in video cameras, digital still cameras, mobile phones with camera functions, and the like. Since these solid-state imaging devices use silicon photodiodes having sensitivity to near infrared rays in their light receiving portions, it is required to perform visibility correction and use infrared cut filters (for example, see Patent Document 1).
- an infrared cut filter a type using a dielectric multilayer film and a type using an infrared absorber are known.
- an infrared cut filter of a type using a dielectric multilayer film for example, an infrared cut filter using a blue glass substrate as a base material is known.
- an infrared absorber an infrared cut filter in which most of the constituent material is glass is mainly known.
- Patent Document 2 discloses a near infrared absorption filter using a specific copper complex.
- the above-mentioned dielectric multilayer film is known to have infrared reflectivity and conventionally formed by vapor deposition, but vapor deposition requires a high temperature such as 250 ° C.
- vapor deposition requires a high temperature such as 250 ° C.
- forming a dielectric multilayer film on a substrate having a color filter layer has a problem that the color filter layer is denatured or deteriorated by vapor deposition. Therefore, it has been studied to form a functional layer having infrared reflectivity without using vapor deposition.
- a blue glass substrate used for an infrared cut filter of the type using the above-described dielectric multilayer film has a near infrared absorption ability.
- the blue glass substrate is fragile.
- an infrared cut filter using a blue glass substrate is used for manufacturing a solid-state imaging device, there are problems such as inferior manufacturing suitability such that dicing cannot be performed. Therefore, development of an infrared cut filter having a near infrared ray and infrared ray shielding property equal to or higher than that using a blue glass substrate and having an infrared reflection film not using vapor deposition without using a blue glass substrate has been studied. ing.
- the present invention relates to a curable resin composition for forming an infrared reflective film capable of forming an infrared reflective film having an infrared light shielding property without using vapor deposition, an infrared reflective film obtained thereby, a method for producing the same, and a near infrared light shielding property. And it aims at providing the infrared cut filter which has infrared rays light-shielding property.
- the curable resin composition according to the present invention the infrared cut filter and the surface of the substrate in the solid-state imaging device can be brought into close contact with each other without interposing a space, so that the color shading is suppressed.
- An object is to provide an imaging device.
- the two or more high refractive index layers are a plurality of types of layers having different refractive indexes within a refractive index range of 1.65 to 2.00.
- the two or more high refractive index layers are a plurality of types of layers having different film thicknesses within a thickness range of 50 to 250 nm. film.
- the two or more low-refractive index layers are a plurality of types of layers having different refractive indices within a refractive index range of 1.20 to 1.45.
- the infrared reflective film as described.
- the infrared reflection according to any one of [5] to [11], wherein the two or more low refractive index layers are a plurality of types of layers having different film thicknesses within a thickness range of 50 to 250 nm.
- a step of forming a low refractive index layer using a curable resin composition A method for producing an infrared reflective film, wherein the infrared reflective film has two or more high refractive index layers and two or more low refractive index layers.
- the step of forming the high refractive index layer and the step of forming the low refractive index layer are alternately performed, and the high refractive index layer and the low refractive index layer are alternately stacked. Infrared reflective film manufacturing method.
- An infrared cut filter comprising the infrared reflective film according to any one of [13] and a layer containing a dye or a copper complex having a maximum absorption wavelength in the range of 600 nm to 820 nm.
- the dye or copper complex having the maximum absorption wavelength in the range of 600 nm to 820 nm is a cyanine dye, phthalocyanine dye, aminium dye, iminium dye, azo dye, anthraquinone dye, diimonium dye, squarylium dye.
- the infrared cut filter according to [16] which is at least one selected from the group consisting of a porphyrin pigment and a copper complex.
- the solid-state imaging device according to [18], wherein the substrate has a color filter layer.
- the curable resin composition for infrared reflective film formation which can form the infrared reflective film which has an infrared rays light-shielding property without vapor deposition, the infrared reflective film obtained by it, its manufacturing method, and a near infrared ray
- An infrared cut filter having light shielding properties and infrared light shielding properties can be provided.
- the curable resin composition by using the curable resin composition, the infrared cut filter and the surface of the substrate in the solid-state imaging device can be brought into close contact with each other without interposing a space, thereby suppressing color shading.
- a solid-state imaging device can be provided.
- the notation that does not indicate substitution and non-substitution includes not only a substituent but also a substituent.
- the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- a viscosity value points out the value in 25 degreeC.
- the present invention relates to a curable resin composition for forming an infrared reflecting film having a refractive index of 1.65 to 2.00 (hereinafter simply referred to as “curable resin for forming a high refractive index layer”, which can be applied at a film thickness of 50 to 250 nm. It may also be referred to as a “composition”).
- curable resin for forming a high refractive index layer which can be applied at a film thickness of 50 to 250 nm. It may also be referred to as a “composition”).
- the present invention also relates to a curable resin composition for forming an infrared reflective film having a refractive index of 1.20 to 1.45 (hereinafter simply referred to as “for forming a low refractive index layer”, which can be applied at a film thickness of 50 to 250 nm. It may also be referred to as “curable resin composition”.
- any of the curable resin compositions of the present invention may be a thermosetting resin composition or a photocurable resin composition.
- the present invention also includes a step of forming a high refractive index layer having a film thickness of 50 to 250 nm and a refractive index of 1.65 to 2.00 using a curable resin composition, and a film thickness of 50 to 250 nm and a refractive index of 1.
- the present invention also relates to a method for producing an infrared reflective film, wherein the infrared reflective film has two or more high refractive index layers and two or more low refractive index layers.
- the step of forming the high refractive index layer and the step of forming the low refractive index layer are alternately performed, and the high refractive index layer and the low refractive index layer are formed. It is preferable to laminate them alternately.
- FIG. 1 is a schematic sectional view of an infrared reflecting film of the present invention.
- the present invention includes two or more high refractive index layers 2 having a refractive index of 1.65 to 2.00 and low refractive index layers 3 having a refractive index of 1.20 to 1.45, as shown in FIG. It is also related to the infrared reflective film 1 having two or more layers.
- the high refractive index layer and the low refractive index layer are preferably laminated alternately.
- either one of the curable resin composition for forming the high refractive index layer and the curable resin composition for forming the low refractive index layer is water or a hydrophilic solvent. It is a composition to contain, and it is preferable that the other is a composition containing a hydrophobic solvent.
- the high refractive index layer and the low refractive index layer are alternately laminated by collectively drying.
- An infrared reflective film can be manufactured.
- the composition containing water or a hydrophilic solvent contains a fluorine atom-containing compound.
- the composition containing the hydrophobic solvent preferably contains a surface energy adjusting agent.
- the refractive index of the high refractive index layer formed from the curable resin composition for forming the high refractive index layer is preferably 1.85 or more, and more preferably 1.89 or more.
- the refractive index is further preferably 1.95 or less, and more preferably 1.93 or less.
- the refractive index means a value measured by the measurement method shown in the examples below unless otherwise specified.
- the refractive index of the low refractive index layer formed by the curable resin composition for forming the low refractive index layer is 1.20 or more, and preferably 1.25 or more.
- the refractive index is preferably 1.40 or less, and more preferably 1.35 or less.
- the curable resin composition for forming a high refractive index layer preferably contains (A) metal oxide particles, (B) a dispersant, and (C) a binder.
- the metal oxide particles are inorganic particles having a high refractive index, such as titanium (Ti), zirconium (Zr), aluminum (Al), silicon (Si), zinc (Zn) or magnesium ( Mg) oxide particles, and preferably titanium dioxide (TiO 2 ) particles, zirconium dioxide (ZrO 2 ) particles, or silicon dioxide (SiO 2 ) particles.
- titanium dioxide particles hereinafter simply referred to as “titanium dioxide”. It is more preferable that the The colorless or transparent titanium dioxide particles can be represented by the chemical formula TiO 2 , preferably have a purity of 70% or more, more preferably have a purity of 80% or more, and further have a purity of 85% or more. preferable.
- Low-order titanium oxide, titanium oxynitride and the like represented by the general formula Ti n O 2n-1 are preferably 30% by mass or less, and 20% by mass or less. More preferably, the content is 15% by mass or less.
- a titanium dioxide particle the thing of a rutile type crystal
- the primary particle diameter of the metal oxide particles is preferably 1 nm to 100 nm, more preferably 1 nm to 80 nm, and particularly preferably 1 nm to 50 nm. If the primary particle diameter of the metal oxide particles exceeds 100 nm, the refractive index and the transmittance may decrease. When the thickness is less than 1 nm, dispersibility and dispersion stability may be reduced due to aggregation.
- the average particle diameter of the metal oxide particles is determined by the measurement method employed in the examples described later.
- the refractive index of the metal oxide particles is not particularly limited, but is preferably 1.75 to 2.70, more preferably 1.90 to 2.70 from the viewpoint of obtaining a high refractive index.
- This refractive index can be measured with an Abbe refractometer (manufactured by Atago Co., Ltd.) (measurement temperature 25 ° C., wavelength 633 nm).
- the specific surface area of the metal oxide particles is preferably 10 m 2 / g to 400 m 2 / g, more preferably 20 m 2 / g to 200 m 2 / g, and 30 m 2 / g to 150 m 2 / g. Most preferably.
- limiting in particular in the shape of a metal oxide particle for example, it can be a rice grain shape, a spherical shape, a cubic shape, a spindle shape, or an indefinite shape.
- the metal oxide particles may have been surface-treated with an organic compound.
- organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, stearic acid or a silane coupling agent is preferable, and stearic acid is particularly preferable.
- the surface treatment may be carried out by using a single surface treatment agent or a combination of two or more surface treatment agents. It is also preferable that the surface of the metal oxide particles is treated with an oxide such as aluminum, silicon, or zirconia. Thereby, a weather resistance improves.
- titanium dioxide particles As a metal oxide particle, what is marketed can be used preferably.
- examples of commercially available titanium dioxide particles include TTO series (TTO-51 (A), TTO-51 (C), TTO-55 (C), etc.), TTO-S, and V series (TTO) manufactured by Ishihara Sangyo Co., Ltd. -S-1, TTO-S-2, TTO-V-3, etc.) and MT series (MT-01, MT-05, etc.) manufactured by Teika Corporation.
- zirconium dioxide particles examples include UEP (Daiichi Rare Element Chemical Co., Ltd.), PCS (Nippon Denko Co., Ltd.), JS-01, JS-03, JS-04 (Nippon Denko ( And UEP-100 (Daiichi Rare Element Chemical Industries, Ltd.).
- Examples of commercially available silicon dioxide particles include OG502-31 manufactured by Clariant Co. The metal oxide particles may be used alone or in combination of two or more.
- the content of metal oxide particles in the composition is high from the viewpoint of dispersion stability. It is preferably 10 to 90% by mass, more preferably 10 to 50% by mass, and still more preferably 12 to 40% by mass, based on the total solid content of the curable resin composition for layer formation. Preferably, it is 15 to 35% by mass.
- the content of the metal oxide particles exceeds 90% by mass with respect to the total solid content of the curable resin composition for forming the high refractive index layer, it is difficult to cause a sufficient amount of the dispersant to be present. Therefore, dispersibility and dispersion stability are likely to be impaired.
- the curable composition is applied to a large size (for example, 12 inches) wafer, it is difficult to form a film having a small film thickness difference between the central portion and the peripheral portion of the wafer.
- the dispersant used in the curable resin composition for forming the high refractive index layer is preferably a polymer dispersant represented by the following general formula (1).
- R 1 represents a (m + n) -valent linking group
- R 2 represents a single bond or a divalent linking group
- a 1 is an acid group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a heterocyclic group, an alkyloxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonamide group
- the n A 1 and R 2 may be the same or different.
- m represents a positive number of 8 or less
- n represents 1 to 9, and m + n satisfies 3 to 10.
- P 1 represents a polymer chain.
- the m P 1 may be the same or different.
- the dispersing agent represented by the general formula (1) has an acid group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, an alkyloxycarbonyl group, an alkylaminocarbonyl group.
- a monovalent substituent A 1 having at least one group selected from the group consisting of a carboxylate group, a sulfonamide group, a heterocyclic group, an alkoxysilyl group, an epoxy group, an isocyanate group and a hydroxyl group is a metal oxide particle ( Since the dispersant represented by the general formula (1) has n (1 to 9) substituents A 1 , it can strongly interact with the metal oxide particles (A).
- m polymer chains P 1 of the dispersant represented by the general formula (1) can function as a steric repulsion group, and by having m, the metal oxide exhibits a good steric repulsion force.
- the particles (A) can be uniformly dispersed. Further, it is estimated that the dispersant represented by the general formula (1) does not cause adverse effects such as aggregation of particles due to cross-linking between particles, which can be generated by a conventional dispersant having a graft random structure, in terms of molecular structure. Is done.
- a 1 represents an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, an alkyloxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonamide group, an alkoxy group.
- a functional group having an adsorption ability for the metal oxide particles (A) such as a silyl group, an epoxy group, an isocyanate group and a hydroxyl group, and a structure capable of having an adsorption ability for the metal oxide particles (A) such as a heterocyclic structure. It represents a monovalent substituent having at least one kind.
- the site having the ability to adsorb to the metal oxide particles (A) (the functional group and the structure) will be collectively referred to as “adsorption site” as appropriate.
- the adsorption sites are in one A 1, it may be contained at least one, may contain two or more kinds.
- the “monovalent substituent having at least one kind of adsorption site” includes the aforementioned adsorption site, 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, 0 to It is a monovalent substituent formed by bonding up to 100 oxygen atoms, 1 to 400 hydrogen atoms, and a linking group consisting of 0 to 40 sulfur atoms.
- adsorption sites themselves may constitute a monovalent substituent
- adsorption sites themselves may also be a monovalent substituent represented by A 1.
- the adsorption site constituting A 1 will be described below.
- the “acid group” include a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, a monophosphate group, and a boric acid group. Sulfuric acid ester groups, phosphoric acid groups and monophosphoric acid ester groups are more preferred, carboxylic acid groups, sulfonic acid groups and phosphoric acid groups are more preferred, and carboxylic acid groups are particularly preferred.
- Examples of the “urea group” include —NR 15 CONR 16 R 17 (wherein R 15 , R 16 and R 17 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a carbon number of 6 The above aryl group or an aralkyl group having 7 or more carbon atoms may be mentioned as a preferred example, and —NR 15 CONHR 17 (wherein R 15 and R 17 are each independently a hydrogen atom or 1 carbon atom) More preferably an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms.) —NHCONHR 17 (wherein R 17 is a hydrogen atom or 1 to 10 carbon atoms) An alkyl group, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms are particularly preferable.
- Examples of the “urethane group” include —NHCOOR 18 , —NR 19 COOR 20 , —OCONHR 21 , —OCONR 22 R 23 (where R 18 , R 19 , R 20 , R 21 , R 22 and R 23 are Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), and the like.
- R 18 and R 21 each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, or the like, more preferably —NHCOOR 18 , -OCONHR 21 (wherein, R 18, R 21 each independently represents an alkyl group having from 1 to 10 carbon atoms, 6 or more arylene carbon Group, the number 7 or aralkyl group having a carbon.), Etc. are particularly preferred.
- the “group having a coordinating oxygen atom” include an acetylacetonato group and a crown ether.
- Examples of the “group having a basic nitrogen atom” include an amino group (—NH 2 ), a substituted imino group (—NHR 8 , —NR 9 R 10 , wherein R 8 , R 9 , and R 10 Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), a guanidyl group represented by the following formula (a1), Preferred examples include the amidinyl group represented by a2).
- R 11 and R 12 each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.
- R 13 and R 14 each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.
- an amino group (—NH 2 ), a substituted imino group (—NHR 8 , —NR 9 R 10 , wherein R 8 , R 9 , and R 10 are each independently a group having 1 to 10 carbon atoms.
- a guanidyl group represented by the formula (a1) [in the formula (a1), R 11 and R 12 are each independently an alkyl group having 1 to 10 carbon atoms. Represents a phenyl group or a benzyl group.
- An amidinyl group represented by the formula (a2) [in the formula (a2), R 13 and R 14 each independently represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a benzyl group. ] Is more preferable.
- an amino group (—NH 2 ) a substituted imino group (—NHR 8 , —NR 9 R 10 , wherein R 8 , R 9 , and R 10 are each independently an alkyl group having 1 to 5 carbon atoms.
- the alkyl group moiety in the “alkyloxycarbonyl group” is preferably an alkyl group having 1 to 20 carbon atoms, and examples thereof include a methyl group and an ethyl group.
- the alkyl group moiety in the “alkylaminocarbonyl group” is preferably an alkyl group having 1 to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.
- Examples of the “carboxylic acid base” include groups composed of ammonium salts of carboxylic acids.
- a hydrogen atom bonded to a nitrogen atom may be substituted with an alkyl group (such as a methyl group) or an acyl group (such as an acetyl group or a trifluoroacetyl group).
- heterocyclic structure examples include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine , Imide groups such as dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, Preferred examples include acridone and anthraquinone.
- the “heterocyclic structure” may further have a substituent.
- substituents include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group.
- C1-C6 acyloxy groups such as aryl groups having 6 to 16 carbon atoms, such as aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfonylamido groups, and acetoxy groups, methoxy groups, and ethoxy groups
- An alkoxy group having 1 to 20 carbon atoms such as a halogen atom such as chlorine or bromine, an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, or a cyclohexyloxycarbonyl group, a cyano group, t- Examples thereof include carbonate ester groups such as butyl carbonate.
- alkoxysilyl group may be any of monoalkoxysilyl group, dialkoxysilyl group and trialkoxysilyl group, but is preferably trialkoxysilyl group, for example, trimethoxysilyl group, triethoxysilyl group Etc.
- epoxy group include a substituted or unsubstituted oxirane group (ethylene oxide group).
- the linking group bonded to the adsorption site may be a single bond or 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200.
- a linking group consisting of up to hydrogen atoms and 0 to 20 sulfur atoms is preferred, and this organic linking group may be unsubstituted or may further have a substituent.
- a 1 a monovalent group having at least one group selected from the group consisting of an acid group, a urea group, a urethane group, a sulfonamide group, an imide group, and a group having a coordinating oxygen atom.
- a substituent is preferred.
- a 1 has at least one functional group of pKa5-14. It is more preferably a valent substituent.
- pKa has the definition described in Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.).
- Examples of the functional group of pKa5 to 14 include a urea group, a urethane group, a sulfonamide group, an imide group, and a group having a coordinating oxygen atom.
- a urea group about pKa 12 to 14
- a urethane group about pKa 11 to 13
- —COCH 2 CO— about pKa 8 to 10
- a sulfonamide group (About pKa 9 to 11).
- the A 1 is preferably represented as a monovalent substituent represented by the following general formula (4).
- B 1 represents the adsorption site (that is, an acid group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, an alkyloxycarbonyl group, an alkylamino group).
- R 24 represents a single bond or a (a + 1) -valent linking group.
- a represents an integer of 1 to 10
- B 1 existing in the general formula (4) may be the same or different.
- Examples of the adsorption site represented by B 1 include the same adsorption sites as those constituting A 1 in the general formula (1), and preferred examples are also the same. Among them, an acid group, a urea group, a urethane group, a sulfonamide group, an imide group or a group having a coordinating oxygen atom is preferable, and a urea group, a functional group of pKa5 to 14 is more preferable. It is more preferably a urethane group, a sulfonamide group, an imide group or a group having a coordinating oxygen atom.
- R 24 represents a single bond or a (a + 1) -valent linking group, and a represents 1 to 10.
- a is 1 to 7, more preferably a is 1 to 5, and particularly preferably a is 1 to 3.
- (A + 1) valent linking groups include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and Groups consisting of 0 to 20 sulfur atoms are included and may be unsubstituted or further substituted.
- R 24 may be a single bond, or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and (A + 1) valent linking groups consisting of 0 to 10 sulfur atoms are preferred, single bonds or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 More preferred are (a + 1) valent linking groups consisting of up to oxygen atoms, 1 to 50 hydrogen atoms, and 0 to 7 sulfur atoms, a single bond, or 1 to 10 carbons (A + 1) valent linkage consisting of atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms The group is particularly preferred.
- examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group.
- C1-C6 acyloxy groups such as aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups, etc., carbon atoms such as methoxy groups, ethoxy groups, etc.
- R 2 represents a single bond or a divalent linking group.
- n R 2 may be the same or different.
- Divalent linking groups include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 To 20 sulfur atoms are included, which may be unsubstituted or further substituted.
- R 2 includes a single bond or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and Divalent linking groups consisting of 0 to 10 sulfur atoms are preferred, single bonds, or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 More preferred are divalent linking groups consisting of oxygen atoms, 1 to 50 hydrogen atoms, and 0 to 7 sulfur atoms, a single bond or 1 to 10 carbon atoms, 0 Particularly preferred are divalent linking groups consisting of from 1 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms.
- examples of the substituent include carbon numbers such as an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. 1 to 6 carbon atoms such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfonylamido group, acetoxy group, etc. having 6 to 16 carbon atoms, methoxy group, ethoxy group, etc.
- alkoxy groups such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, cyano group, carbonic acid such as t-butyl carbonate, etc.
- An ester group etc. are mentioned.
- R 1 represents an (m + n) -valent linking group.
- m + n satisfies 3 to 10.
- Examples of the (m + n) -valent linking group represented by R 1 include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200. Groups consisting of up to 0 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or further substituted.
- Specific examples of the (m + n) -valent linking group represented by R 1 include specific examples (1) to (17) disclosed in paragraphs 0082 and 008 of JP-A-2007-277514.
- m represents a positive number of 8 or less.
- m is preferably 0.5 to 5, more preferably 1 to 4, and particularly preferably 1 to 3.
- n represents 1 to 9.
- n is preferably 2 to 8, more preferably 2 to 7, and particularly preferably 3 to 6.
- P 1 represents a polymer chain and can be selected from known polymers according to the purpose.
- the m P 1 may be the same or different.
- polymers in order to form a polymer chain, a polymer or copolymer of a vinyl monomer, an ester polymer, an ether polymer, a urethane polymer, an amide polymer, an epoxy polymer, a silicone polymer, and modifications thereof
- copolymer for example, polyether / polyurethane copolymer, copolymer of polyether / vinyl monomer polymer, etc. (any of random copolymer, block copolymer, graft copolymer, etc. May also be included).
- At least one selected from the group consisting of vinyl monomers selected from the group consisting of polymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, and modified products or copolymers thereof. At least one kind is more preferable, and a polymer or copolymer of vinyl monomers is particularly preferable.
- the polymer chain P 1 preferably contains at least one repeating unit.
- the number k of the repeating units of the at least one repeating unit in the polymer chain P 1 is preferably 3 or more, more preferably 5 or more, from the viewpoint of exhibiting steric repulsion and improving dispersibility. Further, from the viewpoint of suppressing the bulk of the dispersant represented by the general formula (1) and causing the titanium dioxide particles (D) to be densely present in the white cured film, the number of repeating units of the at least one repeating unit k is preferably 50 or less, more preferably 40 or less, and still more preferably 30 or less.
- the polymer chain is preferably soluble in an organic solvent.
- the affinity with the organic solvent is low, the affinity with the dispersion medium is weakened, and it may be impossible to secure an adsorption layer sufficient for stabilizing the dispersion.
- the dispersant represented by the following general formula (2) is preferable.
- a 2 represents an acid group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, an alkyloxycarbonyl group, an alkylaminocarbonyl group, or a carboxylic acid. It represents a monovalent substituent having at least one group selected from the group consisting of a base, a sulfonamide group, a heterocyclic group, an alkoxysilyl group, an epoxy group, an isocyanate group and a hydroxyl group.
- a 2 may be the same or different.
- a 2 has the same meaning as the A 1 in the general formula (1), a preferable embodiment thereof is also the same.
- R 4 and R 5 each independently represents a single bond or a divalent linking group.
- the n R 4 s may be the same or different.
- the m R 5 s may be the same or different.
- the divalent linking group represented by R 4 or R 5 the same divalent linking groups as those represented by R 2 in the general formula (1) can be used, and a preferred embodiment Is the same.
- R 3 represents a (m + n) -valent linking group.
- m + n satisfies 3 to 10.
- Examples of the (m + n) -valent linking group represented by R 3 include 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 100. Groups consisting of up to 0 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or further substituted.
- the (m + n) -valent linking group represented by R 3 is the same as the (m + n) -valent linking group represented by R 1 in the general formula (1). Are used, and the preferred embodiments are also the same.
- n represents 1 to 9. n is preferably 2 to 8, more preferably 2 to 7, and particularly preferably 3 to 6.
- P 2 of the general formula (2) represents a polymer chain, can be selected according to the purpose or the like from such known polymers.
- the m P 2 can be the same or different.
- the preferred embodiment of the polymer is the same as P 1 in Formula (1).
- R 3 Specific examples (1), (2), (10), (11), (16), or (17)
- R 4 a single bond or the following structural unit or a combination of the structural units: “1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 carbon atoms A divalent linking group comprising an oxygen atom, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms (which may have a substituent, for example, Alkyl groups having 1 to 20 carbon atoms such as methyl group and ethyl group, aryl groups having 6 to 16 carbon atoms such as phenyl group and naphthyl group, hydroxyl group, amino group, carboxyl group, sulfonamide group, N-sulfonylamide Groups, acyloxy groups having 1 to 6 carbon atoms such as
- R 5 single bond, ethylene group, propylene group, the following group (a), or the following group (b)
- R 12 represents a hydrogen atom or a methyl group
- l represents 1 or 2.
- P 2 Polymer or copolymer of vinyl monomer, ester polymer, ether polymer, urethane polymer, and modified products thereof m: 1 to 3 n: 3-6
- the acid value of the dispersant represented by the general formula (1) or (2) is not particularly limited, but from the viewpoint of dispersibility, the acid value is preferably 400 mgKOH / g or less, and 300 mgKOH / g or less. More preferably, it is particularly preferably 250 mgKOH / g or less.
- the acid value is preferably 400 mgKOH / g or less, and 300 mgKOH / g or less. More preferably, it is particularly preferably 250 mgKOH / g or less.
- limiting in particular as a lower limit of an acid value From a viewpoint of the dispersion stability of a titanium dioxide particle, it is preferable that it is 5 mgKOH / g or more, and it is more preferable that it is 10 mgKOH / g or more.
- the acid value of the dispersant represented by the general formula (1) or (2) is a solid content acid value.
- the acid value of the dispersant represented by the general formula (1) or (2) is, for example, the average content of acid groups in the dispersant represented by the general formula (1) or (2). It can be calculated from the quantity.
- the molecular weight of the dispersant represented by the general formula (1) or (2) is preferably 1000 to 50000, more preferably 3000 to 30000, and particularly preferably 3000 to 20000 in terms of weight average molecular weight.
- the weight average molecular weight is within the above range, the effects of the plurality of adsorption sites introduced at the ends of the polymer are sufficiently exhibited, and performance excellent in adsorptivity to the titanium dioxide particle surface can be exhibited.
- Specific examples of the dispersant represented by the general formula (1) or (2) include polymer compounds C-1 to C-57 disclosed in paragraphs 0316 and after of JP-A-2007-277514. It is done.
- the dispersant represented by the general formula (1) or (2) is not particularly limited, but may be synthesized according to the synthesis method described in JP-A-2007-277514, paragraphs 0114 to 0140 and 0266 to 0348. it can.
- the dispersant used in the curable resin composition for forming the high refractive index layer is preferably a graft copolymer (hereinafter also referred to as “specific resin 2”).
- the graft copolymer has a graft chain in which the number of atoms excluding hydrogen atoms is in the range of 40 to 10,000.
- the graft chain in this case indicates from the base of the main chain of the copolymer (the atom bonded to the main chain in a group branched from the main chain) to the end of the group branched from the main chain.
- the specific resin is a dispersion resin that imparts dispersibility to the metal oxide particles, and has an affinity for the solvent due to the graft chain. Excellent dispersion stability.
- the number of atoms excluding hydrogen atoms per graft chain is preferably 40 to 10,000, more preferably 100 to 500, and still more preferably 150 to 260. . If this number is too small, the graft chain is short, so that the steric repulsion effect is reduced and the dispersibility and dispersion stability may be lowered. On the other hand, if the amount is too large, the graft chain becomes too long, and the adsorptive power to the metal oxide particles may be reduced, resulting in reduced dispersibility and dispersion stability.
- the number of atoms excluding hydrogen atoms per graft chain is included from the base atom bonded to the polymer chain constituting the main chain to the end of the branch polymer branched from the main chain.
- a poly (meth) acrylic structure, a polyester structure, a polyurethane structure, a polyurea structure, a polyamide structure, a polyether structure, etc. can be used, but the interaction between the graft chain and the solvent is improved.
- a graft chain having a poly (meth) acrylic structure, a polyester structure and a polyether structure is preferable, and a polyester structure and a polyether structure are more preferable.
- the graft copolymer preferably has a structural unit having a graft chain (repeating unit), and can be obtained, for example, by polymerizing a macromonomer having a polymer structure as a graft chain based on a conventional method,
- the structure of such a macromonomer is not particularly limited as long as it has a substituent capable of reacting with the polymer main chain and has a graft chain that satisfies the requirements, but preferably a reactive double bond
- a macromonomer having a functional group can be preferably used.
- AA-6 manufactured by Toagosei
- AA-10 manufactured by Toagosei
- AB-6 manufactured by Toagosei
- AS-6 Toagosei
- AN-6 Toagosei
- AW-6 Toagosei
- AA-714 Toagosei
- AY-707 Toagosei
- AY-714 Toagosei
- AK-5 produced by Toagosei Co., Ltd.
- AK-30 produced by Toagosei Co., Ltd.
- AK-32 produced by Toagosei Co., Ltd.
- Blemmer PP-100 manufactured by NOF Corporation
- Blemmer PP- 500 manufactured by NOF Corporation
- AA-6 manufactured by Toagosei
- AA-10 manufactured by Toagosei
- AB-6 manufactured by Toagosei
- AS-6 manufactured by Toagosei
- AN-6 Toagosei Co., Ltd.
- Bremer PME-4000 manufactured by NOF Corporation
- the specific resin 2 preferably includes at least a structural unit represented by any one of the following formulas (1) to (4) as a structural unit having a graft chain.
- 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 synthesis restrictions, a hydrogen atom or an alkyl group having 1 to 12 carbon atoms is preferable, a hydrogen atom or a methyl group is more preferable, and a methyl group is particularly preferable.
- W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH, and particularly preferably an oxygen atom.
- R 3 represents a branched or straight chain alkylene group (the number of carbon atoms is preferably 1 to 10, more preferably 2 or 3, and from the viewpoint of dispersion stability, —CH 2 —CH (CH 3 )).
- a group represented by — or a group represented by —CH (CH 3 ) —CH 2 — is preferred.
- Two or more types of R 3 having different structures may be mixed and used in the specific resin.
- Y 1 , Y 2 , Y 3 , and Y 4 are each independently a divalent linking group and are not particularly limited in structure. Specific examples include the following linking groups (Y-1) to (Y-21). In the following structures, A and B each represent a bond with the left terminal group and the right terminal group in formulas (1) to (4). Of the structures shown below, (Y-2) and (Y-13) are more preferred because of the ease of synthesis.
- Z 1 , Z 2 , Z 3 , and Z 4 are each independently a hydrogen atom or a monovalent substituent, and the structure of the substituent is not particularly limited.
- an alkyl group, a hydroxyl group examples thereof include an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group.
- the monovalent substituents represented by Z 1 to Z 3 are each independently an alkyl group having 5 to 24 carbon atoms or a carbon atom.
- alkoxy group having 5 to 24 carbon atoms is preferable, and an alkoxy group having a branched alkyl group having 5 to 24 carbon atoms or a cyclic alkyl group having 5 to 24 carbon atoms is particularly preferable.
- the monovalent substituent represented by Z 4 is preferably an alkyl group having 5 to 24 carbon atoms, and among them, each independently a branched alkyl group having 5 to 24 carbon atoms or a cyclic group having 5 to 24 carbon atoms. Alkyl groups are preferred.
- n, m, p, and q are each an integer of 1 to 500.
- j and k each independently represents an integer of 2 to 8.
- j and k are preferably integers of 4 to 6, and most preferably 5, from the viewpoint of dispersion stability.
- R 4 represents a hydrogen atom or a monovalent organic group and is not particularly limited in terms of structure, but is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, more preferably a hydrogen atom or an alkyl group. is there.
- the alkyl group may be a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms.
- a linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable.
- Two or more types of R 4 having different structures may be mixed and used in the specific resin.
- the structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) or (2A) from the viewpoint of dispersion stability.
- X 1, Y 1, Z 1 and n are as defined X 1, Y 1, Z 1 and n in Formula (1), and preferred ranges are also the same.
- X 2, Y 2, Z 2 and m are as defined X 2, Y 2, Z 2 and m in the formula (2), and preferred ranges are also the same.
- the specific resin 2 has a structural unit represented by the formula (1A).
- the structural unit (repeating unit) having the graft chain is preferably contained in the range of 10% to 75%, and in the range of 12% to 50%, based on the total mass of the specific resin 2 in terms of mass. It is more preferable that it is contained in a range of 15% to 40%. Within this range, the dispersibility and dispersion stability of the metal oxide particles are high, and the uniformity of the film thickness in the coating film formed using the dispersion composition is further improved.
- the specific resin may be a combination of two or more types of graft copolymers having different structures.
- the specific resin 2 is preferably a polymer having a structural unit (repeating unit) having an acid group in an amount of 25% by mass to 90% by mass with respect to the total mass of the specific resin 2.
- the content of the structural unit having an acid group is more preferably 50% by mass or more and 80% by mass or less, and most preferably 60% by mass or more and 75% by mass or less with respect to the total mass of the specific resin 2.
- the acid value of specific resin can be suitably adjusted in the following preferable range because content of the structural unit which has an acid group exists in the said range.
- the acid group can also function as a functional group capable of forming an interaction with the metal oxide particles in addition to the graft chain.
- the acid group examples include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, and the like.
- the carboxylic acid group It is preferably at least one selected from a group, a sulfonic acid group, and a phosphoric acid group, and a carboxylic acid group is particularly preferable.
- the acid group structure is preferably a structure separated by 5 atoms or more from the main chain of the resin structure. Furthermore, as the acid group, a carboxylic acid bonded to an aromatic ring is most preferable.
- the acid value of the specific resin 2 is preferably in the range of 70 mgKOH / g to 350 mgKOH / g, more preferably in the range of 80 mgKOH / g to 300 mgKOH / g, and still more preferably in the range of 100 mgKOH / g to 250 mgKOH / g. Range.
- the acid value of the specific resin 2 can be calculated from the average content of acid groups in the specific resin, for example. Moreover, resin which has a desired acid value can be obtained by changing content of the monomer unit containing the acid group which comprises specific resin.
- the specific resin 2 may further have a structural unit (repeating unit) having a functional group capable of interacting with the metal oxide particles other than the graft chain and the acid group.
- a structural unit having a functional group capable of forming an interaction with other metal oxide particles is not particularly limited in terms of structure.
- a structural unit having a basic group or a structural unit having a coordinating group And structural units having a reactive group is not particularly limited in terms of structure.
- the basic group examples include a primary amino group, a secondary amino group, a tertiary amino group, a heterocyclic ring containing an N atom, and an amide group. Particularly preferred is a tertiary amino group having good adsorption power to metal oxide particles and high dispersibility and dispersion stability. As said basic group, these can be used individually by 1 type or in combination of 2 or more types.
- the specific resin 2 may or may not contain a structural unit (repeating unit) having a basic group, but when it is contained, the content of the structural unit having a basic group is based on the total mass of the specific resin It is 0.1 mass% or more and 50 mass% or less, Most preferably, it is 0.1 mass% or more and 30 mass% or less.
- Examples of the coordinating group and the reactive group include acetylacetoxy group, trialkoxysilyl group, isocyanate group, acid anhydride residue, acid chloride residue and the like. Particularly preferred is an acetylacetoxy group having good adsorption power to metal oxide particles and high dispersibility and dispersion stability.
- the coordinating group and the reactive group these can be used alone or in combination of two or more.
- the specific resin may or may not contain a structural unit (repeating unit) having a coordinating group or a reactive group, but if included, a structure having a coordinating group or a reactive group.
- the content of the unit is preferably 0.1% by mass or more and 50% by mass or less, and particularly preferably 0.1% by mass or more and 30% by mass or less with respect to the total mass of the specific resin.
- the specific resin 2 can be synthesized by a conventionally known method.
- the solvent used in the synthesis include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy- Examples include 2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate. These solvents may be used alone or in combination of two or more.
- the specific resin 2 include the following exemplary compounds 1 to 32, but the present invention is not limited thereto.
- the numerical value written together with each structural unit represents the content of the structural unit [mass%: described as (wt%)].
- the numerical value written together with the repeating part of the side chain indicates the number of repetitions of the repeating part.
- the weight average molecular weight (polystyrene equivalent value measured by GPC method) of the specific resin 2 is preferably 5,000 or more and 300,000 or less, more preferably 7,000 or more and 100,000 or less. It is especially preferable that it is 50,000 or more and 50,000 or less.
- an oligoimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain is also preferable to use.
- the oligoimine-based dispersant has a repeating unit having a partial structure X having a functional group of pKa14 or less and a side chain containing a side chain Y having 40 to 10,000 atoms, and has a main chain and a side chain.
- a dispersion resin having a basic nitrogen atom in at least one hereinafter referred to as “specific dispersion resin 3” as appropriate
- the basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom.
- the specific resin 3 may have a partial structure W that forms a pair with the partial structure X or the like, and the partial structure W is preferably a structural portion having a nitrogen atom of pK b 14 or less, and pK b 10 It is more preferable to contain the structure which has the following nitrogen atoms.
- the bases strength pK b means a pK b at a water temperature 25 ° C., is one of the index for quantitatively indicating the strength of the base, it is synonymous with basicity constants.
- the W preferably has a structure in which the linking part of the side chain Y is dissociated to become an ion binding site.
- An example of the specific dispersion resin 3 is a resin represented by the following formula [B].
- x, y, and z each represent a polymerization molar ratio of repeating units, and x is preferably 5 to 50, y is 5 to 60, and z is preferably 10 to 90.
- l represents the number of linked polyester chains, and is an integer capable of forming a side chain having 40 to 10,000 atoms. l is preferably 5 to 100,000, more preferably 20 to 20,000, 40 to More preferably, it is 2,000.
- the repeating unit whose copolymerization ratio is defined by x in the formula is the partial structure X
- the repeating unit whose copolymerization ratio is defined by z in the formula is the partial structure Y.
- the specific dispersion resin 3 is composed of (i) a poly (lower alkyleneimine) -based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, a metaxylenediamine-epichlorohydrin polycondensate-based repeating unit, and a polyvinylamine-based repeating unit.
- the specific dispersion resin (B1) has the repeating unit (i). Thereby, the adsorptive power of the dispersed resin to the particle surface can be improved, and the interaction between the particles can be reduced.
- the poly (lower alkyleneimine) may be a chain or a network.
- the lower alkylene imine means an alkylene imine containing an alkylene chain having 1 to 5 carbon atoms.
- the repeating unit (i) preferably forms a main chain portion in the specific dispersion resin.
- the number average molecular weight of the main chain portion that is, the number average molecular weight of the portion excluding the side chain including the side chain Y portion from the specific dispersion resin (B1) is preferably 100 to 10,000, more preferably 200 to 5,000. Is more preferable, and 300 to 2,000 is most preferable.
- the number average molecular weight of the main chain portion can be measured by a polystyrene conversion value by GPC method.
- the specific dispersion resin (B1) includes a repeating unit represented by the following formula (I-1) and a repeating unit represented by the formula (I-2), or a repeating unit represented by the formula (I-1) And a dispersion resin containing a repeating unit represented by the formula (I-2a).
- R 1 and R 2 each independently represents a hydrogen atom, a halogen atom or an alkyl group (preferably having 1 to 6 carbon atoms).
- a independently represents an integer of 1 to 5; * Represents a connecting part between repeating units.
- R 8 and R 9 are the same groups as R 1 .
- L is a single bond, an alkylene group (preferably having 1 to 6 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), an arylene group (preferably having 6 to 24 carbon atoms), a heteroarylene group (having 1 to 6 carbon atoms).
- an imino group preferably having 0 to 6 carbon atoms
- an ether group preferably having 0 to 6 carbon atoms
- a thioether group preferably having a carbonyl group
- a linking group thereof preferably having a single bond or —CR 5 R 6 —NR 7 — (where the imino group is X or Y) is preferable.
- R 5 R 6 each independently represents a hydrogen atom, a halogen atom, or an alkyl group (preferably having 1 to 6 carbon atoms).
- R 7 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- L a is a structural site ring structure formed together with CR 8 CR 9 and N, it is preferable together with the carbon atom of CR 8 CR 9 is a structural site that form a non-aromatic heterocyclic ring having 3 to 7 carbon atoms . More preferably, it is a structural part that forms a 5- to 7-membered non-aromatic heterocycle by combining the carbon atom of CR 8 CR 9 and N (nitrogen atom), and more preferably forms a 5-membered non-aromatic heterocycle It is particularly preferred that it is a structural site that forms pyrrolidine. However, the structural site may further have a substituent such as an alkyl group.
- X represents a group having a functional group of pKa14 or less.
- Y represents a side chain having 40 to 10,000 atoms.
- the specific dispersion resin (B1) preferably further has a repeating unit represented by the formula (I-3), the formula (I-4), or the formula (I-5) as a copolymerization component.
- the specific dispersion resin (B1) includes such a repeating unit, the dispersion performance can be further improved.
- R 1 , R 2 , R 8 , R 9 , L, La, a and * are as defined in the formulas (I-1), (I-2) and (I-2a).
- Ya represents a side chain having 40 to 10,000 atoms having an anionic group.
- the repeating unit represented by the formula (I-3) is reacted by adding an oligomer or polymer having a group that reacts with an amine to form a salt to a resin having a primary or secondary amino group in the main chain.
- Ya is preferably represented by the following formula (III-2).
- R 1 and R 2 are particularly preferably hydrogen atoms.
- a is preferably 2 from the viewpoint of obtaining raw materials.
- the specific dispersion resin (B1) may further contain a lower alkyleneimine containing a primary or tertiary amino group as a repeating unit.
- the group shown by said X, Y, or Ya may couple
- Resins containing both a repeating unit having a group represented by X and a repeating unit having Y bonded to such a main chain structure are also included in the specific dispersion resin (B1).
- the repeating unit represented by the formula (I-1) is preferably contained in an amount of 1 to 80 mol% in all repeating units contained in the specific dispersion resin (B1) from the viewpoint of storage stability and developability. Most preferably, it is contained in an amount of ⁇ 50 mol%.
- the repeating unit represented by the formula (I-2) is preferably contained in an amount of 10 to 90 mol% in all repeating units contained in the specific dispersion resin (B1), and 30 to 70 Most preferably, it is contained in mol%.
- the content ratio [(I-1) :( I-2)] of the repeating unit (I-1) and the repeating unit (I-2) is 10 in terms of molar ratio.
- the range is preferably 1: 1 to 1: 100, and more preferably 1: 1 to 1:10.
- the repeating unit represented by the formula (I-3) used in combination is optionally contained in an amount of 0.5 to 20 mol% from the viewpoint of the effect among all the repeating units contained in the specific dispersion resin (B1).
- the content is preferably 1 to 10 mol%, most preferably.
- Partial structure X The partial structure X in each of the above formulas has a functional group having a pKa of 14 or less at a water temperature of 25 ° C.
- pKa has the definition described in Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.).
- the “functional group of pKa14 or less” is not particularly limited as long as the physical properties satisfy this condition, and examples thereof include known functional groups in which pKa satisfies the above range.
- the following functional groups are preferred, and those having a pKa of 11 or less are particularly preferred. Although there is no particular lower limit, it is practical that it is -5 or more.
- partial structure X examples include, for example, a carboxylic acid group (pKa: about 3 to 5), a sulfonic acid (pKa: about ⁇ 3 to ⁇ 2), —COCH 2 CO— (pKa: about 8 to 10), —COCH 2 CN (pKa: about 8 to 11), —CONHCO—, phenolic hydroxyl group, —R F CH 2 OH or — (R F ) 2 CHOH (R F represents a perfluoroalkylene group or a perfluoroalkyl group.
- PKa About 9 to 11
- sulfonamide groups pKa: about 9 to 11
- carboxylic acid groups pKa: about 3 to 5
- sulfonic acid groups pKa: about -3 to -2
- —COCH 2 CO— pKa: about 8 to 10.
- the partial structure X is preferably directly bonded to the basic nitrogen atom in the repeating unit having the basic nitrogen atom.
- the partial structures X may be linked not only by a covalent bond but also in a form in which a salt is formed by ionic bonding.
- the partial structure X those having a structure represented by the following formula (V-1), formula (V-2) or formula (V-3) are particularly preferable.
- U represents a single bond or a divalent linking group.
- d and e each independently represents 0 or 1;
- Q represents an acyl group or an alkoxycarbonyl group.
- Examples of the divalent linking group represented by U include alkylene (more specifically, for example, —CH 2 —, —CH 2 CH 2 —, —CH 2 CHMe— (Me is a methyl group), — (CH 2 ) 5 —, —CH 2 CH (n—C 10 H 21 ) —, etc.), an oxygen-containing alkylene (more specifically, for example, —CH 2 OCH 2 —, —CH 2 CH 2 OCH 2 CH 2-, etc.), arylene groups (eg, phenylene, tolylene, biphenylene, naphthylene, furylene, pyrrolylene, etc.), alkyleneoxy (eg, ethyleneoxy, propyleneoxy, phenyleneoxy, etc.), etc.
- alkylene more specifically, for example, —CH 2 —, —CH 2 CH 2 —, —CH 2 CHMe— (Me is a methyl group), — (CH 2 ) 5 —, —CH 2
- An alkylene group having 1 to 30 carbon atoms or an arylene group having 6 to 20 carbon atoms is preferable, and an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms is most preferable.
- d is preferably 1, and e is preferably 0.
- Q represents an acyl group or an alkoxycarbonyl group.
- the acyl group for Q is preferably an acyl group having 1 to 30 carbon atoms (eg, formyl, acetyl, n-propanoyl, benzoyl, etc.), and particularly preferably acetyl.
- As the alkoxycarbonyl group in Q Q is particularly preferably an acyl group, and an acetyl group is preferable from the viewpoint of ease of production and availability of a raw material (precursor X a of X).
- the partial structure X is preferably bonded to the basic nitrogen atom in the repeating unit having a basic nitrogen atom. Thereby, the dispersibility and dispersion stability of titanium dioxide particles are dramatically improved. Partial structure X is also considered to contribute to dispersion stability by imparting solvent solubility and suppressing resin precipitation over time. Furthermore, since the partial structure X contains a functional group of pKa14 or less, it also functions as an alkali-soluble group. Thereby, developability is improved, and it is considered that both dispersibility, dispersion stability, and developability can be achieved.
- the content of the functional group of pKa14 or less in the partial structure X is not particularly limited, but is preferably 0.01 to 5 mmol, particularly 0.05 to 1 mmol, with respect to 1 g of the specific dispersion resin (B1). preferable. From the viewpoint of the developability, it is preferable that the acid value of the specific dispersion resin (B1) is contained in an amount of about 5 to 50 mgKOH / g. ⁇ Side chain Y Examples of Y include known polymer chains such as polyester, polyamide, polyimide, and poly (meth) acrylate that can be connected to the main chain portion of the specific dispersion resin (B1). The binding site with the specific dispersion resin (B1) in Y is preferably the terminal of the side chain Y.
- Y is at least one selected from a poly (lower alkyleneimine) -based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, a metaxylenediamine-epichlorohydrin polycondensate-based repeating unit, and a polyvinylamine-based repeating unit. It is preferably bonded to the nitrogen atom of the repeating unit having a nitrogen atom.
- the bonding mode between the main chain portion such as a repeating unit having a nitrogen atom and Y is a covalent bond, an ionic bond, or a mixture of a covalent bond and an ionic bond.
- Y is preferably ionically bonded to the nitrogen atom of the repeating unit having the basic nitrogen atom as an amide bond or carboxylate.
- the number of atoms of the side chain Y is preferably 50 to 5,000, more preferably 60 to 3,000, from the viewpoints of dispersibility, dispersion stability, and developability.
- the number average molecular weight of Y can be measured by the polystyrene conversion value by GPC method. At this time, it is practical to measure the molecular weight of Y before being incorporated into the resin.
- the number average molecular weight of Y is particularly preferably 1,000 to 50,000, and most preferably 1,000 to 30,000 from the viewpoints of dispersibility, dispersion stability, and developability.
- the molecular weight of Y can be specified from the polymer compound used as the raw material for Y, and the measurement method conforms to the measurement conditions by GPC described later. It is preferable that two or more side chain structures represented by Y are connected to the main chain in one molecule of the resin, and more preferably five or more are connected.
- Y preferably has a structure represented by the formula (III-1).
- Z is a polymer or oligomer having a polyester chain as a partial structure, and represents a residue obtained by removing a carboxyl group from a polyester having a free carboxylic acid represented by HO—CO—Z.
- Ya is preferably the formula (III-2).
- Z has the same meaning as Z in formula (III-1).
- the partial structure Y includes a polyester having a carboxyl group at one end, a polycondensation of a carboxylic acid and a lactone, a polycondensation of a hydroxy group-containing carboxylic acid, a polyhydric of a dihydric alcohol and a divalent carboxylic acid (or a cyclic acid anhydride). It can be obtained by condensation or the like.
- Z is preferably-(L B ) nB -Z B.
- Z B represents a hydrogen atom or a monovalent organic group.
- Z B is an organic group, an alkyl group (preferably having 1 to 30 carbon atoms), an aryl group, a heterocyclic group, or the like is preferable.
- Z B may further have a substituent, and examples of the substituent include an aryl group having 6 to 24 carbon atoms and a heterocyclic group having 3 to 24 carbon atoms.
- L B is an alkylene group (having 1 to 6 carbon atoms is preferred), an alkenylene group (2 to 6 carbon atoms is preferred), an arylene group (6 to 24 carbon atoms is preferred), heteroarylene groups (having 1 to 6 carbon atoms Preferred), an imino group (preferably having a carbon number of 0 to 6), an ether group, a thioether group, a carbonyl group, or a combination thereof.
- an alkylene group preferably having 1 to 6 carbon atoms
- an ether group, a carbonyl group, or a linking group relating to a combination thereof is preferable.
- the alkylene group may be branched or linear.
- the alkylene group may have a substituent, and preferred substituents include an alkyl group (preferably 1 to 6 carbon atoms), an acyl group (preferably 2 to 6 carbon atoms), an alkoxy group (preferably 1 to 6 carbon atoms). Or an alkoxycarbonyl group (preferably having 2 to 8 carbon atoms).
- nB is an integer of 5 to 100,000. nB number of L B may have a different structure, respectively.
- p and q represent the number of linked polyester chains, and each independently represents 5 to 100,000.
- R a represents a hydrogen atom or an alkylcarbonyl group.
- the molecular weight of the specific dispersion resin 3 is preferably 3,000 to 100,000 in terms of weight average molecular weight, and if the weight average molecular weight is within the above range, 5,000 to 55,000 is present at the end of the polymer. The effects of the plurality of introduced adsorption sites are sufficiently exhibited, and performance with excellent adsorptivity to the surface of the titanium dioxide particles can be exhibited.
- GPC was measured using HLC-8020GPC (manufactured by Tosoh Corporation) and columns as TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ200 (manufactured by Tosoh Corporation).
- the carrier may be selected as appropriate, but tetrahydrofuran is used as long as it can be dissolved.
- the dispersant may be used alone or in combination of two or more.
- the content of the dispersant with respect to the total solid content of the curable resin composition for forming the high refractive index layer is preferably in the range of 10 to 50% by mass, and 11 to 40% by mass from the viewpoint of dispersibility and dispersion stability.
- the range is more preferable, and the range of 12 to 30% by mass is still more preferable.
- the curable resin composition for forming the high refractive index layer may be referred to as a dispersion resin other than the specific resin (hereinafter referred to as “other dispersion resin”) for the purpose of adjusting the dispersibility of the metal oxide particles. May be contained).
- dispersion resins that can be used in the present invention include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly ( (Meth) acrylate, (meth) acrylic copolymer, naphthalene sulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, pigment derivative and the like.
- Other dispersion resins can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.
- dispersion resins include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide), 161, manufactured by BYK Chemie.
- the curable resin composition for forming the high refractive index layer may or may not contain other dispersion resins, but if included, the other is based on the total solid content of the curable resin composition for forming the high refractive index layer.
- the content of the dispersion resin is preferably in the range of 1 to 20% by mass, and more preferably in the range of 1 to 10% by mass.
- the curable resin composition for the high refractive index layer preferably further contains a binder (C) from the viewpoint of improving the film properties.
- a binder polymer a monomer having a carboxyl group alone or copolymerized, a monomer having an acid anhydride alone or copolymerized to hydrolyze or half-esterify an acid anhydride unit, or Examples thereof include half-amidated resins and epoxy acrylates obtained by modifying epoxy resins with unsaturated monocarboxylic acids and acid anhydrides.
- Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxylstyrene.
- Examples of the monomer having an acid anhydride include maleic anhydride. It is done.
- those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.
- Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
- Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
- Styrenes such as styrene, ⁇ -methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.
- Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
- Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.
- N-vinylpyrrolidone (10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
- Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
- a methacrylic acid monomer having a hetero atom bonded to the ⁇ -position For example, compounds described in JP-A-2002-309057, JP-A-2002-311569 and the like can be mentioned.
- binders include, for example, benzyl methacrylate / methacrylic acid copolymer (copolymerization ratio: 80/20 (mass%), weight average molecular weight: 12,000) manufactured by Fuji Film Fine Chemicals (FFFC), acrylic base (A graft copolymer of benzyl methacrylate / i-butyl methacrylate / 2-hydroxyethyl methacrylate / methacrylic acid copolymer and methoxypolyethylene glycol, manufactured by Fujikura Kasei Co., Ltd.).
- FFFC Fuji Film Fine Chemicals
- the binder preferably includes a repeating unit obtained by polymerizing a monomer component essentially comprising a compound represented by the following general formula (ED) (hereinafter sometimes referred to as “ether dimer”).
- ED general formula
- R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
- the content ratio is not particularly limited, but is 95% by mass. The following is preferable, and it is more preferable that it is 85 mass% or less.
- the weight average molecular weight of the polymer obtained by polymerizing the monomer component containing the compound represented by the general formula (ED) is not particularly limited, but is formed by the viscosity of the colored radiation-sensitive composition and the composition. From the viewpoint of heat resistance of the coating film, it is preferably 2000 to 200000, more preferably 5000 to 100,000, and still more preferably 5000 to 20000.
- the acid value is preferably 30 to 500 mgKOH / g, more preferably 50 It should be ⁇ 400 mg KOH / g.
- a polymer obtained by polymerizing a monomer component containing a compound represented by the general formula (ED) can be easily obtained by polymerizing at least the above-mentioned monomer essentially containing an ether dimer. . At this time, the cyclization reaction of the ether dimer proceeds simultaneously with the polymerization to form a tetrahydropyran ring structure.
- the polymerization method applied to the synthesis of the polymer obtained by polymerizing the monomer component containing the compound represented by the general formula (ED) is not particularly limited, and various conventionally known polymerization methods can be adopted. However, it is particularly preferable to use a solution polymerization method.
- exemplary compounds of a polymer obtained by polymerizing a monomer component containing a compound represented by the general formula (ED) are shown, but the present invention is not limited to these.
- the composition ratio of the exemplary compounds shown below is mol%.
- DM dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate
- BzMA benzyl methacrylate
- MMA methyl methacrylate
- MAA Methacrylic acid
- GMA glycidyl methacrylate
- the molar ratio of DM: BzMA: MMA: MAA: GMA is preferably 5 to 15:40 to 50: 5 to 15: 5 to 15:20 to 30.
- the weight average molecular weight of such a polymer is preferably 9000 to 20000.
- the polymer used in the present invention has a weight average molecular weight (polystyrene conversion value measured by GPC method) of preferably 1000 to 2 ⁇ 10 5 , more preferably 2000 to 1 ⁇ 10 5 , and more preferably 5000 to More preferably, it is 5 ⁇ 10 4 .
- a (meth) acrylic resin having an allyl group, a vinyl ester group, and a carboxyl group in the side chain, and a side chain described in JP-A Nos. 2000-187322 and 2002-62698 are doubled.
- An alkali-soluble resin having a bond and an alkali-soluble resin having an amide group in the side chain described in JP-A No. 2001-242612 are preferable because of excellent balance of film strength, sensitivity, and developability.
- Examples of the above-mentioned polymers include: Dial NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co.
- Japanese Patent Publication No. 7-12004 Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Publication No. 63-287944, Japanese Patent Publication No. 63-287947.
- Urethane binder polymers containing acid groups as described in JP-A-1-271741 and the like, and urethane binders having acid groups and double bonds in side chains as described in JP-A-2002-107918 Since the polymer is very excellent in strength, it is advantageous in terms of film strength.
- Japanese Patent Application Laid-Open No. 2001-318463 is also preferable because of its excellent film strength.
- polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer.
- alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful.
- the weight average molecular weight (polystyrene conversion value measured by GPC method) of the binder polymer that can be used in the curable composition is preferably 5,000 or more, more preferably 10,000 or more and 300,000 or less.
- the number average molecular weight is preferably 1,000 or more, and more preferably 2,000 or more and 250,000 or less.
- the polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably 1.1 or more and 10 or less.
- These binder polymers may be any of random polymers, block polymers, graft polymers and the like.
- the binder polymer can be synthesized by a conventionally known method.
- the solvent used in the synthesis include tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy.
- Examples include -2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, water and the like. These solvents are used alone or in combination of two or more.
- Examples of the radical polymerization initiator used when synthesizing the binder polymer that can be used in the curable composition for forming a high refractive index layer of the present embodiment include known compounds such as an azo initiator and a peroxide initiator. .
- the binder can be used alone or in combination of two or more.
- the content of the binder in the curable resin composition for forming a high refractive index layer is preferably 1% by mass or more and 40% by mass or less, more preferably 3% by mass or more and 30% by mass or less. More preferably, it is at least 20% by mass.
- the method for producing the curable resin composition for forming the high refractive index layer is not particularly limited, and a commonly used method for producing a dispersion composition can be applied.
- a dispersion composition is prepared by mixing metal oxide particles, a dispersant, and a subsequent solvent, and dispersing the mixture using a circulation type dispersion device (bead mill), and then the polymerizable compound composition. It is preferable from the viewpoint of improving dispersibility.
- the curable resin composition for forming a high refractive index layer contains a polymerizable compound (D) and a polymerization initiator, and preferably contains other components as necessary.
- the curable resin composition for forming a high refractive index layer is preferably a transparent composition, and more specifically, a high refractive index layer that is a cured film having a thickness of 1.0 ⁇ m is formed from the composition. When formed, the composition is such that the light transmittance in the thickness direction of the cured film is 90% or more over the entire wavelength region of 400 to 700 nm.
- Such physical properties of light transmittance are achieved by any means as long as the curable resin composition for forming the high refractive index layer contains the polymerizable compound (D) and the polymerization initiator (E). However, it is preferably achieved by adjusting the type and content of the polymerizable compound (D) and the binder (C) that can be further added. Moreover, the said physical property of the light transmittance can be suitably achieved also by adjusting the particle diameter of a metal oxide particle (A), and the kind and addition amount of a dispersing agent (B).
- the light transmittance is 90% over the entire wavelength region of 400 to 700 nm in order to develop the characteristics required for the high refractive index layer. The above is preferable.
- the light transmittance is more preferably 95% or more, further preferably 99% or more, and most preferably 100% over the entire wavelength region of 400 to 700 nm.
- the polymerizable compound is an addition polymerizable compound having a polymerizable group such as at least one ethylenically unsaturated double bond, an epoxy group, or an oxetanyl group. Is selected from compounds having at least 1, preferably 2 or more. Such compounds are widely known in the technical field, and can be used without particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, ie, multimers and oligomers such as dimers and trimers, or mixtures thereof and copolymers thereof.
- Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof.
- unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
- esters and amides thereof examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof.
- an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used.
- an addition reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and A dehydration condensation reaction product with a monofunctional or polyfunctional carboxylic acid is also preferably used.
- a substitution reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a leaving group such as a halogen group or a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. It is.
- the compounds described in paragraph numbers 0095 to 0108 of JP-A-2009-288705 can be preferably used in the present invention.
- a first preferred form of the polymerizable compound is a monomer having at least one ethylenically unsaturated double bond (polymerizable monomer) or an oligomer having a polymerizable group (polymerizable oligomer) (hereinafter, polymerizable with a polymerizable monomer).
- the polymerizable oligomers may be collectively referred to as “polymerizable monomers”.
- the polymerizable monomer or the like is also preferably a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure.
- Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexaned
- polyfunctional acrylate compounds having a (meth) acryloyl group can be used, and examples include NK Ester A-TMMT and A-TMPT, Shin-Nakamura Chemical Co., Ltd.
- a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be used.
- compounds having a fluorene ring and having two or more functional ethylenic groups described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, etc. Polymers can also be used.
- compounds described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof are compounds that have been (meth) acrylated after addition of ethylene oxide or propylene oxide to the polyfunctional alcohol.
- the polymerizable monomer used in the present invention is also preferably a polymerizable monomer represented by the general formulas (MO-1) to (MO-6) described in paragraphs 0297 to 0300 of JP2012-215806A.
- Specific examples of the radical polymerizable monomer represented by the general formulas (MO-1) to (MO-6) include compounds described in paragraph numbers 0248 to 0251 of JP-A No. 2007-26979. It can be suitably used in the present invention.
- dipentaerythritol triacrylate (KAYARAD D-330 as a commercially available product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, KAYARAD D-320; Nippon Kayaku) Dipentaerythritol penta (meth) acrylate (manufactured by Co., Ltd.) (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; Nippon Kayaku Co., Ltd.) Company), and the structure in which these (meth) acryloyl groups are mediated by ethylene glycol and propylene glycol residues, diglycerin EO (ethylene oxide) modified (meth) acrylate (
- the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound.
- a polyfunctional monomer having an acid group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.
- Examples of commercially available products include Aronix series M-305, M-510, and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
- a preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g.
- it is essential that the acid value of the entire polyfunctional monomer is within the above range. It is.
- a polyfunctional monomer having a caprolactone-modified structure described in paragraphs 0306 to 0313 of JP2012-215806A can also be used.
- the polyfunctional monomer having a caprolactone-modified structure is not particularly limited as long as it has a caprolactone-modified structure in the molecule.
- trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane Obtained by esterifying polyhydric alcohol such as pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ⁇ -caprolactone, Mention may be made of functional (meth) acrylates. Among these, a polyfunctional monomer having a caprolactone-modified structure represented by the following formula (1) is preferable.
- R 1 represents a hydrogen atom or a methyl group
- m represents a number of 1 or 2
- “*” represents a bond.
- R 1 represents a hydrogen atom or a methyl group
- “*” represents a bond.
- Such a polyfunctional monomer having a caprolactone-modified structure is commercially available, for example, from Nippon Kayaku Co., Ltd.
- the polyfunctional monomer which has a caprolactone modified structure can be used individually or in mixture of 2 or more types.
- the polymerizable monomer or the like in the present invention is selected from the group of compounds represented by the general formula (Z-4) or (Z-5) described in paragraphs 0314 to 0324 of JP2012-215806A. It is also preferable that it is at least one.
- Examples of commercially available monomers such as polymerizable monomers represented by the general formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, Nippon Kayaku. Examples thereof include DPCA-60, which is a hexafunctional acrylate having 6 pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having 3 isobutyleneoxy chains.
- Examples of the polymerizable monomer include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, and the like. Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Furthermore, as polymerizable monomers, addition polymerizable monomers having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used.
- urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 "(manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA -306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.
- a polyfunctional thiol compound having two or more mercapto (SH) groups in the same molecule described in paragraphs 0216 to 0220 of JP2012-150468A can also be used.
- polymerizable monomer or oligomer having two or more epoxy groups or oxetanyl groups in the molecule as the polymerizable monomer.
- a compound having an epoxy group or an oxetanyl group may be used as the polymerizable compound.
- the compound having an epoxy group or oxetanyl group include a polymer having an epoxy group in the side chain, and a polymerizable monomer or oligomer having two or more epoxy groups in the molecule, and a bisphenol A type epoxy resin, Bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin and the like can be mentioned. These compounds may be used as commercial products or can be obtained by introducing an epoxy group into the side chain of the polymer.
- bisphenol A type epoxy resin JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (manufactured by DIC Corporation), etc.
- bisphenol F type epoxy resin is JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835.
- ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), JER1031S (manufactured by Japan Epoxy Resin Co., Ltd.) and the like.
- polymer having an oxetanyl group in the side chain and the polymerizable monomer or oligomer having two or more oxetanyl groups in the molecule include Aronoxetane OXT-121, OXT-221, OX-SQ, PNOX ( As described above, Toagosei Co., Ltd.) can be used.
- a polymeric compound can be used individually or in combination of 2 or more types.
- the content of the polymerizable compound (D) is preferably in the range of 1% by mass to 50% by mass with respect to the total solid content of the curable resin composition for forming the high refractive index layer.
- the range is more preferably 40% by mass, and further preferably 5% by mass to 30% by mass. Within this range, the curability is good and preferable without lowering the refractive index.
- the curable resin composition for forming the high refractive index layer may or may not contain the polymerization initiator (E).
- the (E) polymerization initiator is a compound that initiates and accelerates the polymerization of the (D) polymerizable compound, and is stable up to 45 ° C., but preferably has a good polymerization initiating ability during high-temperature heating.
- the polymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).
- a polymerization initiator can be used individually or in combination of 2 or more types.
- organic halogenated compounds for example, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds
- examples include hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.
- organic halogenated compound examples include Wakabayashi et al., “Bull. Chem. Soc. Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Examined Patent Publication No. 46-4605, Japanese Laid-Open Patent Publication No. 48-36281, Japanese Laid-Open Patent Publication No. 55-32070, Japanese Laid-Open Patent Publication No. 60-239736, Japanese Laid-Open Patent Publication No. 61-169835, Japanese Laid-Open Patent Publication No. 61-169837, Japanese Laid-Open Patent Publication No. 62-58241. No.
- an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring specifically, for example, 2,4,6- Tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6- Bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- ( ⁇ , ⁇ , ⁇ -trichloroethyl) -4,6-bis (trichloro Methyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (
- Examples of oxydiazole compounds include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, etc. Can be mentioned.
- carbonyl compounds examples include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, benzophenone derivatives such as 2-carboxybenzophenone, 2,2-dimethoxy -2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, ⁇ -hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1 -Hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 2- (dimethylamino) -2-[(4-methylphenol L) methyl] -1- [4- (4-morpholinyl) phenyl] -1
- ketal compound examples include benzyl methyl ketal and benzyl- ⁇ -methoxyethyl ethyl acetal.
- benzoin compound examples include m-benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoylbenzoate and the like.
- acridine compound examples include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane and the like.
- organic peroxide compound examples include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxide).
- Examples of the azo compound include azo compounds described in JP-A-8-108621.
- Examples of coumarin compounds include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl). ) Amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.
- azide compound examples include organic azide compounds described in US Pat. No. 2,848,328, US Pat. No. 2,852,379 and US Pat. No. 2,940,853, 2,6-bis (4-azidobenzylidene) -4 -Ethylcyclohexanone (BAC-E) and the like.
- metallocene compound examples include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705, Various titanocene compounds described in JP-A-5-83588, such as dicyclopentadienyl-Ti-bis-phenyl, dicyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, dicyclopenta Dienyl-Ti-bis-2,4-difluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, dicyclopentadienyl-Ti- Bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluoro Enyl-1-yl
- a hexaarylbiimidazole compound (rophine dimer compound) is preferable.
- the hexaarylbiimidazole compound include lophine dimers described in JP-B-45-37377 and JP-B-44-86516, JP-B-6-29285, US Pat. No. 3,479,185, and the like.
- organic borate compound examples include JP-A-62-143044, JP-A-62-1050242, JP-A-9-188865, JP-A-9-188686, JP-A-9-188710, JP-A-2000. -131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application Laid-Open No. 2001116539, etc., and Kunz, Martin “Rad Tech'98. Proceeding April 19-22, 1998, Chicago”.
- the organic boron iodonium complexes described in JP-A-9-188710, the organic boron phosphonium complexes described in JP-A-9-348710, JP-A-7-128785, JP-A-7-140589, JP-A-7- Specific examples include organoboron transition metal coordination complexes and the like described in JP-A-306527 and JP-A-7-292014.
- Examples of the disulfone compound include compounds described in JP-A Nos. 61-166544 and 2002-328465.
- hydroxyacetophenone compounds As the polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
- hydroxyacetophenone-based initiator IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
- aminoacetophenone-based initiator commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used.
- aminoacetophenone-based initiator a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long-wave light source such as 365 nm or 405 nm can also be used.
- acylphosphine initiator commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.
- the polymerization initiator is preferably an oxime compound from the viewpoints of curability, stability over time, and difficulty in coloring during post-heating.
- oxime compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, Journal of Applied Polymer Science (2012) pp. 725-731, compounds described in JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797, and the like.
- oxime ester compounds other than those described above compounds described in JP-T-2009-519904 in which oxime is linked to carbazole N-position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, A compound described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced into the dye moiety, a ketoxime compound described in International Patent Publication No. 2009-131189, the triazine skeleton and the oxime skeleton are the same A compound described in US Pat. No. 7,556,910 contained in the molecule, a compound described in Japanese Patent Application Laid-Open No. 2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source, and the like may be used. .
- cyclic oxime compounds described in JP 2007-231000 A and JP 2007-322744 A can also be suitably used.
- cyclic oxime compounds in particular, cyclic oxime compounds fused to carbazole dyes described in JP2010-32985A and JP2010-185072A have high light absorptivity and high sensitivity. preferable.
- the compounds described in JP-A-2009-242469 having an unsaturated bond at a specific site of the oxime compound can be preferably used because high sensitivity can be achieved by regenerating the active radical from the polymerization inert radical. it can.
- an oxime compound having a specific substituent described in JP-A-2007-267979 and an oxime compound having a thioaryl group disclosed in JP-A-2009-191061 can be used.
- a compound represented by the following formula (OX-1) is also preferable.
- the oxime N—O bond is an (E) oxime compound or a (Z) oxime compound, It may be a mixture of the (E) body and the (Z) body.
- 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 is preferably a monovalent nonmetallic atomic group.
- the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group.
- these groups may have one or more substituents.
- the substituent mentioned above may be further substituted by another substituent.
- substituents examples include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl 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.
- the aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms.
- the acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms.
- the alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms.
- description in paragraph 0029 of JP2012-032556A can be referred to, and the contents thereof are incorporated in the present specification.
- the aryloxycarbonyl group which may have a substituent the description in paragraph 0030 of JP2012-032556A can be specifically referred to, and the contents thereof are incorporated in the present specification.
- 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.
- the description in Japanese Patent Application Laid-Open No. 2012-032556, paragraph 0031 and the like can be referred to, and the contents thereof are incorporated in the present specification.
- the alkylthiocarbonyl group which may have a substituent the description in paragraph 0032 of JP2012-032556A can be referred to, and the contents thereof are incorporated in the present specification.
- Specific examples of the arylthiocarbonyl group which may have a substituent can be referred to the description in paragraph 0033 of JP2012-032556A, and the contents thereof are incorporated in the present specification.
- the monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
- Y, X, and n have the same meanings as Y, X, and n in formula (OX-2) described later, and preferred examples are also the same.
- examples of the divalent organic group represented by A include an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, and an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent. Among them, A in the formula (OX-1) is an unsubstituted alkylene group, an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, dodecyl) from the viewpoint of increasing sensitivity and suppressing coloring due to heating.
- an alkyl group for example, a methyl group, an ethyl group, a tert-butyl group, dodecyl
- alkylene group alkenyl group (eg vinyl group, allyl group) alkylene group, aryl group (eg phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl) Group, a phenanthryl group, and a styryl group) are preferable.
- alkenyl group eg vinyl group, allyl group
- aryl group eg phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl
- a phenanthryl group e.g., phenanthryl group
- styryl group alkylene group substituted alkylene group
- alkenyl group eg vinyl group, allyl group
- aryl group eg phenyl group, p-tolyl group, xylyl group, cumenyl group, naphth
- the aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent.
- substituents include the same substituents as those introduced into the substituted aryl group mentioned above as specific examples of the aryl group which may have a substituent.
- a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.
- the oxime compound represented by the formula (OX-1) is preferably a compound represented by the following formula (OX-2).
- R and X each independently represent a monovalent substituent
- a and Y each independently represent a divalent organic group
- Ar represents an aryl group
- n represents 0 to (It is an integer of 5.)
- R, A and Ar in the formula (OX-2) have the same meanings as R, A and Ar in the formula (OX-1), and preferred examples are also the same.
- examples of the monovalent substituent represented by X include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an amino group, and a heterocyclic ring.
- X in the formula (OX-2) is preferably an alkyl group from the viewpoints of solvent solubility and improvement in absorption efficiency in the long wavelength region.
- n represents an integer of 0 to 5, and an integer of 0 to 2 is preferable.
- examples of the divalent organic group represented by Y include the structures Sub-1 to Sub-11 shown below.
- “*” represents a bonding position between Y and an adjacent carbon atom in the formula (OX-2).
- the structures Sub-1 and Sub-2 are preferable from the viewpoint of increasing sensitivity.
- the oxime compound represented by the formula (OX-2) is preferably a compound represented by the following formula (OX-3).
- R and X each independently represent a monovalent substituent
- A represents a divalent organic group
- Ar represents an aryl group
- n is an integer of 0 to 5.
- R, X, A, Ar, and n in formula (OX-3) have the same meanings as R, X, A, Ar, and n in formula (OX-2), respectively, and preferred examples are also the same. is there.
- PIox-1 to (PIox-13) of oxime compounds that can be suitably used are shown below, but the present invention is not limited thereto.
- the oxime compound has a function as a thermal polymerization initiator that is decomposed by heat to start and accelerate polymerization.
- the oxime compound preferably has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and has high absorbance at 365 nm and 455 nm. Particularly preferred.
- the molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred. A known method can be used for the molar extinction coefficient of the compound.
- an ultraviolet-visible spectrophotometer (Vary Inc., Carry-5 spectrophotometer) is used with an ethyl acetate solvent. It is preferable to measure at a concentration of / L.
- TRONLY TR-PBG-304 TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD), etc.
- Commercial products can be used.
- the description of the polymerization initiator described in paragraphs 0092 to 0096 of JP2012-113104A can be referred to, and the contents thereof are incorporated in the present specification.
- a resin composition having high curing sensitivity and good developability can be provided.
- the oxime compound is a compound described in paragraphs 0030 and after of JP2012-113104A.
- the general formula is represented by the general formula (I) described in claim 1 of JP2012-113104A, more preferably the general formula (IA) described in claim 3. These descriptions can be referred to, and the contents thereof are incorporated in the present specification.
- commercially available products such as IRGACURE OXE01 and IRGACURE OXE02 (both manufactured by BASF) can also be suitably used.
- onium salt compounds examples include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Bal et al, Polymer, 21, 423 (1980), diazonium salts, US Pat. No. 4,069,055, ammonium salts described in JP-A-4-365049, US Pat. No. 4,069, The phosphonium salts described in the specifications of Nos. 055 and 4,069,056, the specifications of European Patent No. 104,143, and the specifications of JP-A-2-150848 and JP-A-2-296514 And iodonium salts.
- the iodonium salt is a diaryl iodonium salt and is preferably substituted with two or more electron donating groups such as an alkyl group, an alkoxy group, and an aryloxy group from the viewpoint of stability.
- Examples of sulfonium salts include European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, U.S. Pat. Nos. 4,933,377, 4, 760,013, 4,734,444, 2,833,827, German Patent 2,904,626, 3,604,580, 3,604,581
- the sulfonium salt described in the document is mentioned, and from the viewpoint of stability and sensitivity, it is preferably one substituted with an electron withdrawing group.
- the electron withdrawing group preferably has a Hammett value greater than zero.
- Examples of preferable electron withdrawing groups include halogen atoms and carboxylic acid groups.
- sulfonium salts include sulfonium salts in which one substituent of the triarylsulfonium salt has a coumarin structure or an anthraquinone structure and absorbs at 300 nm or more.
- a sulfonium salt in which the triarylsulfonium salt has an allyloxy group or an arylthio group as a substituent and has absorption at 300 nm or more can be mentioned.
- onium salt compounds J. Org. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988) and onium salts such as arsonium salts.
- acylphosphine (oxide) compound examples include Irgacure 819, Darocur 4265, and Darocur TPO manufactured by BASF.
- (E) As a polymerization initiator, from the viewpoint of curability, a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound Oxime compounds, triallylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, 3- Compounds selected from the group consisting of aryl substituted coumarin compounds are preferred.
- trihalomethyltriazine compounds More preferred are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, and trihalo compounds. Most preferred is at least one compound selected from the group consisting of methyltriazine compounds, ⁇ -aminoketone compounds, oxime compounds, triallylimidazole dimers, and benzophenone compounds.
- the content of the (E) polymerization initiator contained in the curable resin composition for forming a high refractive index layer contains (E) a polymerization initiator
- the content of the (E) polymerization initiator contained in the curable resin composition for forming a high refractive index layer is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.3% by mass or more and 8% by mass with respect to the total solid content of the curable composition.
- it is more preferably 0.5% by mass or more and 5% by mass or less. Within this range, good curability can be obtained.
- the curable resin composition for forming a high refractive index layer may further contain optional components described in detail below, if necessary. Hereinafter, optional components that the curable composition may contain will be described.
- the curable resin composition for forming the high refractive index layer preferably contains a solvent.
- the solvent can be constituted using various organic solvents.
- Organic solvents that can be used here include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether.
- the solid content in the curable resin composition for forming the high refractive index layer is preferably 2 to 60% by mass.
- Polymerization inhibitor In order to prevent unnecessary polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during production or storage of the curable composition, it is preferable to add a polymerization inhibitor.
- Polymerization inhibitors include phenolic hydroxyl group-containing compounds, N-oxide compounds, piperidine 1-oxyl free radical compounds, pyrrolidine 1-oxyl free radical compounds, N-nitrosophenylhydroxylamines, diazonium compounds, and cations Examples include dyes, sulfide group-containing compounds, nitro group-containing compounds, transition metal compounds such as FeCl3 and CuCl2.
- the phenolic hydroxyl group-containing compound is hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4-thiobis (3-methyl-6-t-butylphenol), A compound selected from the group consisting of 2,2′-methylenebis (4-methyl-6-t-butylphenol), phenolic resins, and cresol resins is preferred.
- N-oxide compounds include 5,5-dimethyl-1-pyrroline N-oxide, 4-methylmorpholine N-oxide, pyridine N-oxide, 4-nitropyridine N-oxide, 3-hydroxypyridine N-oxide, picoline A compound selected from the group consisting of acid N-oxide, nicotinic acid N-oxide, and isonicotinic acid N-oxide is preferred.
- Piperidine 1-oxyl free radical compounds include piperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-oxo-2,2,6,6-tetramethylpiperidine 1 -Oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-maleimide A compound selected from the group consisting of -2,2,6,6-tetramethylpiperidine 1-oxyl free radical and 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical Is preferred.
- the pyrrolidine 1-oxyl free radical compound is preferably a 3-carboxyproxyl free radical (3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl free radical).
- N-nitrosophenylhydroxylamines are preferably compounds selected from the group consisting of N-nitrosophenylhydroxylamine cerium salts and N-nitrosophenylhydroxylamine aluminum salts.
- the diazonium compound is selected from the group consisting of 4-diazophenyldimethylamine hydrogen sulfate, 4-diazodiphenylamine tetrafluoroborate, and 3-methoxy-4-diazodiphenylamine hexafluorophosphate Is preferred.
- hydroquinone hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4-thiobis (3-methyl-6-t-) are preferable.
- Butylphenol 2,2'-methylenebis (4-methyl-6-t-butylphenol) phenolic hydroxyl group-containing compound, piperidine 1-oxyl free radical or 2,2,6,6-tetramethylpiperidine 1-oxyl free Radical, 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamido-2, 2,6,6-tetramethylpiperidine 1-oxyl free radical , 4-maleimido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and piperidine 1-oxyl free of 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical
- a preferable addition amount of the polymerization inhibitor is preferably 0.01 parts by weight or more and 10 parts by weight or less, and more preferably 0.01 parts by weight or more and 8 parts by weight or less with respect to 100 parts by weight of the polymerization initiator (E). It is preferable that it is in the range of 0.05 parts by mass or more and 5 parts by mass or less. By setting it as the said range, the curing reaction suppression in a non-image part and the curing reaction acceleration in an image part are fully performed, and image forming property and a sensitivity become favorable.
- surfactant Various surfactants may be added to the curable resin composition for forming the high refractive index layer from the viewpoint of further improving the coatability.
- various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
- the curable resin composition for forming a high refractive index layer contains a fluorosurfactant, so that the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved. Thickness uniformity and liquid saving properties can be further improved. That is, in the case of forming a film using a coating liquid to which a photosensitive transparent composition containing a fluorosurfactant is applied, by reducing the interfacial tension between the coated surface and the coating liquid, The wettability is improved, and the coating property to the coated surface is improved. For this reason, even when a thin film of about several ⁇ m is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.
- the fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass.
- a fluorine-based surfactant having a fluorine content in this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in a curable composition. Only one type of surfactant may be used, or two or more types may be combined.
- the curable composition may or may not contain a surfactant.
- the addition amount of the surfactant is 0.001% by mass to 2% with respect to the total mass of the curable composition. It is preferably 0.0% by mass, more preferably 0.005% by mass to 1.0% by mass.
- a known additive such as a plasticizer or a sensitizer may be added to the curable resin composition for forming the high refractive index layer in order to improve the physical properties of the cured film.
- plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. , 10% by mass or less can be added with respect to the total mass of the polymerizable compound and the binder polymer.
- the curable resin composition for forming the high refractive index layer may contain an ultraviolet absorber.
- an ultraviolet absorber a compound represented by the following general formula (I) which is a conjugated diene compound is particularly preferable.
- R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R 1 and R 2 May be the same as or different from each other, but do not represent a hydrogen atom at the same time.
- R 3 and R 4 represent an electron withdrawing group.
- the electron withdrawing group is an electron withdrawing group having a Hammett's substituent constant ⁇ p value (hereinafter, simply referred to as “ ⁇ p value”) of 0.20 or more and 1.0 or less. Preferably, it is an electron withdrawing group having a ⁇ p value of 0.30 or more and 0.8 or less.
- ⁇ p value Hammett's substituent constant
- Hammett's rule was found in 1935 by L. L. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today.
- Substituent constants determined by Hammett's rule include a ⁇ p value and a ⁇ m value, and these values are described in many general books. A. Dean's “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Area of Chemistry”, 122, 96-103, 1979 (Nanedo), Chemical Reviews, 91, 165-195, detailed in 1991. In the present invention, it does not mean that the values known in the literature described in these documents are limited to only certain substituents, but within the range when measured based on Hammett's law even if the value is unknown. Of course, it is included as long as it is included.
- the electron withdrawing group having a ⁇ p value of 0.20 or more and 1.0 or less include an acyl group, an acyloxy group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, Dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, at least An alkyl group substituted with two or more halogen atoms, an alkoxy group substituted with at least two halogen atoms, an aryloxy group substituted with at least two halogen atoms, or at least two hal
- the ultraviolet absorbers represented by the general formula (I) are disclosed in JP-B 44-29620, JP-A 53-128333, JP-A 61-169831, JP-A 63-53543, and JP-A 63-53544. Can be synthesized by the methods described in JP-A 63-56651 and other publications, and WO 2009/123109 pamphlet. Specifically, the exemplified compound (1) can be synthesized by the method described in paragraph No. 0040 of WO2009 / 123109 pamphlet.
- the curable resin composition for forming the high refractive index layer may or may not contain an ultraviolet absorber, but if included, the content of the ultraviolet absorber is based on the total solid content of the composition. 0.1 mass% to 10 mass% is preferable, 0.1 mass% to 5 mass% is more preferable, and 0.1 mass% to 3 mass% is particularly preferable.
- the curable resin composition for forming a high refractive index layer is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects. If it is conventionally used for the filtration use etc., it can use without being specifically limited.
- fluorine resin such as PTFE (polytetrafluoroethylene), polyamide resin such as nylon-6 and nylon-6,6, polyolefin resin such as polyethylene and polypropylene (PP) (including high density and ultra high molecular weight), etc. Filter.
- polypropylene including high density polypropylene is preferable.
- the pore size of the filter is suitably about 0.01 to 7.0 ⁇ m, preferably about 0.01 to 2.5 ⁇ m, more preferably about 0.01 to 1.5 ⁇ m. By setting it as this range, it is possible to surely remove fine foreign matters that are mixed in the dissolved pigment and the like and inhibit the preparation of a uniform and smooth curable composition in the subsequent step.
- different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more. When filtering two or more times by combining different filters, it is preferable that the second and subsequent hole diameters are larger than the first filtering hole diameter. Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above.
- the pore diameter here can refer to the nominal value of the filter manufacturer.
- a commercially available filter for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .
- the second filter a filter formed of the same material as the first filter described above can be used.
- the pore size of the second filter is suitably about 0.5 to 7.0 ⁇ m, preferably about 2.5 to 7.0 ⁇ m, more preferably about 4.5 to 6.0 ⁇ m.
- the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.
- the curable resin composition for forming a low refractive index layer in the present invention preferably contains a curable resin, more preferably contains a siloxane resin or a fluorine-based resin, and further preferably contains a siloxane resin. Moreover, it is preferable to use a hollow particle as a component contained in a composition.
- the siloxane resin can be obtained through hydrolysis reaction and condensation reaction using an alkoxysilane raw material described later. More specifically, in the compound, a part or all of the alkoxy groups of the alkyltrialkoxysilane are hydrolyzed to be converted into silanol groups, and at least a part of the generated silanol groups is condensed to form Si—O—Si. It can be said that a bond is formed.
- the siloxane resin may be a siloxane resin having any silsesquioxane structure such as a cage type, a ladder type, or a random type.
- the “cage type”, “ladder type”, and “random type” can refer to structures described in, for example, the chemistry and application development of silsesquioxane materials (CMC Publishing).
- the siloxane resin preferably has a silsesquioxane structure represented by the following formula (1). -(R 1 SiO 3/2 ) n -Formula (1)
- R 1 represents an alkyl group having 1 to 3 carbon atoms.
- N represents an integer of 20 to 1000.
- the alkyl group represented by R 1 is not particularly limited as long as the carbon number is within the above range, and examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Of these, a methyl group and an ethyl group are preferable, and a methyl group is most preferable.
- the alkyl group represented by R 1 may be an alkyl group having no substituent or an alkyl group having a substituent, but is preferably an alkyl group having no substituent.
- the substituent which the alkyl group represented by R 1 may have is preferably not a halogen atom or a group having an ethylenically unsaturated bond, and an amino group (preferably an amino group having 0 to 20 carbon atoms, For example, amino, N, N-dimethylamino, N, N-diethylamino, N-ethylamino, anilino, etc.), sulfonamide group (preferably a sulfonamide group having 0 to 20 carbon atoms, such as N, N-dimethyl Sulfonamides, N-phenylsulfonamides, etc.), acyloxy groups (preferably acyloxy groups having 1 to 20 carbon atoms, such as acetyloxy, benzoyloxy, etc.), carbamoyl groups (preferably carbamoyl groups having 1 to 20 carbon atoms) N, N-dimethylcarbamoyl, N-phenylcarbamoyl,
- a silicon-containing polymer whose main chain is composed of siloxane bonds is called a polysiloxane or a siloxane resin. Since silicon has four bonds, the basic structural unit of polysiloxane is classified according to the number of organic groups typified by methyl and phenyl groups per silicon atom. It can be divided into two. In the following formula, R is an organic group.
- silsesquioxane means a general term for polysiloxanes whose basic structural units are T units unless otherwise specified. Since silicon in silsesquioxane is bonded to three oxygens and oxygen is bonded to two silicons, the theoretical composition is RSiO 3/2 (the Latin word for three-half is "Sesquix (SESQUI) "). In the present embodiment, it is preferable that R in the formula of the T unit is the R 1 and the silsesquioxane structure site is included at the specific content.
- the siloxane resin is 65% by mass or more and 100% by mass or less of the entire siloxane resin contained in the cured film, that is, 65% by mass or more and 100% by mass or less of the entire siloxane resin contained in the resin composition for forming a light transmissive cured film.
- the silsesquioxane structure This proportion is preferably 80% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and most preferably 100% by mass (however, 100% by mass). Even in this case, other components such as inevitable impurities may be contained within a range that does not impair the desired effect.
- the siloxane resin may contain the specific polysilsesquioxane structure individually by 1 type, or may contain 2 or more types.
- the siloxane resin is preferably a hydrolytic condensate obtained by hydrolytic condensation of alkyltrialkoxysilane.
- an alkoxysilane raw material containing an alkyltrialkoxysilane can be used as a starting raw material.
- the alkoxysilane raw material intends the starting raw material comprised from alkoxysilane (silicon compound which has an alkoxy group).
- An alkyltrialkoxysilane is an organosilicon compound in which one alkyl group and three alkoxy groups are bonded to a silicon atom, and can be represented by the following formula (2).
- Formula (2) R 2 Si (OR 3 ) 3 (R 2 represents an alkyl group having 1 to 3 carbon atoms, an alkoxyalkyl group having 1 to 8 carbon atoms, or a fluoroalkyl group having 1 to 10 carbon atoms, and R 3 represents an alkyl group.)
- the alkyl group of alkyltrialkoxysilane (R 2 in formula (2)) is not particularly limited as long as it is within the above range, and specifically, methyl group, ethyl group, propyl group, isopropyl group, methoxymethyl group, Methoxypropyl group, ⁇ -glycidoxymethyl group, ⁇ -glycidoxypropyl group, trifluoromethyl group, trifluoroethyl group, trifluoropropyl group, perfluoroethyl group, perfluoropropyl group, tridecafluorooctyl group Etc.
- a methyl group, an ethyl group, a ⁇ -glycidoxypropyl group, a trifluoromethyl group, a trifluoropropyl group, and a tridecafluorooctyl group are preferable, and a methyl group is most preferable.
- the alkoxy group of the alkyltrialkoxysilane is not particularly limited, and examples thereof include a methoxy group and an ethoxy group. More specifically, R 3 in the formula (2) is preferably a linear or branched alkyl group having 1 to 20 carbon atoms. Of these, a carbon number of 1 to 10 is preferable, and a carbon number of 1 to 4 is more preferable. In particular, an ethoxy group in which R 3 in the formula (2) is an ethyl group is preferable because the hydrolysis rate can be easily controlled.
- alkyltrialkoxysilane examples include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, and ⁇ -glycidoxypropyl.
- alkyltrialkoxysilane examples include trimethoxysilane, trifluoropropyltrimethoxysilane, and tridecafluorooctyltrimethoxysilane.
- methyltriethoxysilane, ethyltriethoxysilane, and trifluoropropyltrimethoxysilane are preferably used, and methyltriethoxysilane is most preferably used.
- alkyl trialkoxysilane only 1 type may be used and 2 or more types may be used together.
- the alkoxysilane raw material is preferably alkyltrialkoxysilane, more preferably 80% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less. It is preferable that the content is within the range because the light receiving sensitivity is more effectively improved.
- Tetraalkoxysilane As the alkoxysilane raw material, in addition to the trialkoxysilane, other alkoxysilanes can be used, and tetraalkoxysilane is particularly preferable. By containing tetraalkoxysilane, the crosslink density in the hydrolyzed condensate is increased, which is preferable in terms of further improving the electrical insulation, development resistance, and heat resistance of the film obtained by hardening.
- Tetraalkoxysilane is an organosilicon compound in which four alkoxy groups are bonded to a silicon atom, and can be represented by the following formula (3).
- the alkoxy group of tetraalkoxysilane is not particularly limited, and examples thereof include a methoxy group and an ethoxy group. More specifically, R 4 in Formula (3) is preferably a linear or branched alkyl group having 1 to 20 carbon atoms. Of these, a carbon number of 1 to 10 is preferable, and a carbon number of 1 to 4 is more preferable. In particular, an ethoxy group in which R 4 in the formula (3) is an ethyl group is preferable because the hydrolysis rate can be easily controlled.
- tetraalkoxysilane examples include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-tert-butoxysilane, and the like. . Of these, tetramethoxysilane and tetraethoxysilane are preferably used. In addition, as tetraalkoxysilane, only 1 type may be used and 2 or more types may be used together.
- the content of tetraalkoxysilane in the alkoxysilane raw material is not particularly limited, but is preferably 35% by mass or less, more preferably 20% by mass or less, from the viewpoint that the heat resistance of the development resistance film of the composition is more excellent. preferable. Although there is no lower limit in particular, in order to obtain the effect of adding tetraalkoxysilane, it is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more.
- a substituent for which substitution / non-substitution is not specified means that the group may have an arbitrary substituent. This is also synonymous for compounds that do not specify substitution or non-substitution.
- Preferred substituents include the following substituent T.
- substituent T examples include the following.
- An alkyl group preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.
- alkenyl A group preferably an alkenyl group having 2 to 20 carbon atoms such as vinyl, allyl, oleyl and the like
- an alkynyl group preferably an alkynyl group having 2 to 20 carbon atoms such as ethynyl, butadiynyl, phenylethynyl and the like
- a cycloalkyl group preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohex
- a compound or a substituent when a compound or a substituent includes an alkyl group, an alkenyl group, etc., these may be linear or branched, and may be substituted or unsubstituted. When an aryl group, a heterocyclic group, or the like is included, they may be monocyclic or condensed, and may be substituted or unsubstituted.
- the siloxane resin contained in the curable resin composition for forming the low refractive index layer can be obtained through the hydrolysis reaction and the condensation reaction using the alkoxysilane raw material described above.
- a catalyst such as an acid or a base may be used as necessary.
- the catalyst is not particularly limited as long as the pH is changed.
- the acid organic acid, inorganic acid
- the alkali for example, Ammonia, triethylamine, ethylenediamine and the like can be mentioned.
- the amount to be used is not particularly limited as long as the siloxane resin satisfies a predetermined molecular weight.
- a solvent may be added to the reaction system for the hydrolysis reaction and the condensation reaction.
- the solvent is not particularly limited as long as hydrolysis reaction and condensation reaction can be carried out.
- water alcohols such as methanol, ethanol and propanol
- ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monopropyl ether And esters such as methyl acetate, ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate
- ketones such as acetone, methyl ethyl ketone, and methyl isoamyl ketone.
- a solvent different from the solvent containing the siloxane resin described later is preferably used, and an alcohol compound having 1 to 5 carbon atoms or an ether compound having 2 to 6 carbon atoms is more preferably used.
- the conditions for the hydrolysis reaction and condensation reaction are appropriately selected according to the type of material used.
- the weight average molecular weight of the siloxane resin is 1,000 to 50,000. Among these, 2,000 to 45,000 is preferable, 2,500 to 25,000 is more preferable, and 3,000 to 25,000 is particularly preferable. By setting the weight average molecular weight within the above range, it is preferable that the light receiving sensitivity is easily improved.
- a weight average molecular weight is a value when it measures using well-known GPC (gel permeation chromatography), and converts into standard polystyrene. Unless otherwise specified, in the GPC measurement, Waters 2695 and Shodex GPC column KF-805L (3 columns directly connected) were used, and 50 ⁇ l of a tetrahydrofuran solution having a column temperature of 40 ° C.
- Siloxane resins can be used alone or in combination of two or more.
- the content of the siloxane resin in the curable resin composition for forming the low refractive index layer is preferably more than 5% by mass and 50% by mass or less with respect to the total amount of the composition material. Among these, 10 to 45% by mass is more preferable, and 15 to 40% by mass is particularly preferable.
- the content is not less than the above lower limit value or more than the above lower limit value, it is difficult to generate voids, which is particularly good in improving light receiving sensitivity.
- the content is less than or equal to the above upper limit value, the film thickness becomes sufficiently thick and does not cause cracks and the like, and is highly practical.
- the curable resin composition for forming a low refractive index layer in the present invention may contain a curable resin other than a siloxane resin.
- a curable resin other than a siloxane resin examples thereof include a copolymer of methacrylic acid, methyl methacrylate, and a monomer in which an alicyclic glycidyl group is introduced at the carboxylic acid terminal of methacrylic acid.
- Examples of commercially available products include cyclomer P series such as cyclomer P ACA230AA.
- the content of the curable resin other than the siloxane resin is the same as the preferable range described above for the siloxane resin.
- the curable resin composition for forming the low refractive index layer preferably contains a surfactant having a polyoxyalkylene structure.
- the polyoxyalkylene structure refers to a structure in which an alkylene group and a divalent oxygen atom are present adjacent to each other, and specific examples include an ethylene oxide (EO) structure and a propylene oxide (PO) structure.
- EO ethylene oxide
- PO propylene oxide
- the surfactant having a polyoxyalkylene structure various surfactants such as a fluorosurfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant as long as they have the polyoxyalkylene structure.
- Surfactants can be used. Among these, nonionic surfactants, anionic surfactants, and silicone surfactants are preferable, nonionic surfactants and anionic surfactants are more preferable, and anionic surfactants are most preferable.
- the wettability to the coated surface is reduced by reducing the interfacial tension between the coated surface and the coating liquid. Is improved, and the coating property to the coated surface is improved.
- fluorosurfactant examples include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F479, F482, F554, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, S-141, S- 145, SC-101, SC-103, SC-104, SC-105, SC-106, SC1068, SC-381, SC-383, S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.) ), EFtop EF301, EF303, EF351, EF352 (above, manufactured by Gemco), PF636, PF65 , PF6320, PF6520, PF7002 (OMNOVA Co., Ltd.), and the like.
- nonionic surfactant examples include glycerol, trimethylolpropane, trimethylolethane ethoxylate and propoxylate (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether (Emulgen 404 manufactured by Kao Corporation), polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, ELEBASE manufactured by Aoki Oil & Fat Co., Ltd. Examples include BUB-3.
- anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.), EMULSOGEN COL-020, EMULSOGEN COA-070, EMULSOGEN COL-080, manufactured by Clariant Japan Co., Ltd., Daiichi Kogyo Examples include Prisurf A208B manufactured by Pharmaceutical Co., Ltd.
- silicone surfactant examples include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd.
- Examples of the surfactant having a polyoxyalkylene structure include surfactants represented by the following general formula (4).
- Formula (4) R 5 O (R 6 O) m R 7 (In the above formula, R 5 represents an alkyl group having 1 to 20 carbon atoms, R 6 represents an alkylene group having 1 to 4 carbon atoms, and R 7 represents a hydrogen atom, a carboxyl group, or —PO 3 H 2 . M represents an integer of 1 to 8.)
- R 5 in formula (4) may be a linear or branched alkyl group. Of these, 5 to 20 carbon atoms are preferable, and 12 to 18 carbon atoms are more preferable.
- R 6 in the formula (4) may be a linear or branched alkylene group, and examples thereof include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, and an isobutylene group. Among them, an ethylene group and an isopropylene group (a group that forms an adjacent O atom and an ethylene oxide structure or a propylene oxide structure) are preferable.
- R 7 in formula (4) is preferably a hydrogen atom or a carboxyl group, and most preferably a carboxyl group.
- the addition amount of the surfactant is not particularly limited, but as its lower limit, it is preferably added in a range of 1 part by mass or more with respect to 100 parts by mass of the curable resin, and 1.5 parts by mass or more. More preferably, it is most preferably 7.5 parts by mass or more. Although an upper limit is not specifically limited, 30 mass parts or less are preferable and 15 mass parts or less are more preferable.
- surfactants may be used together with or separately from the surfactant having the polyoxyalkylene structure.
- the surfactant those commonly used can be used, and among them, a silicone surfactant is preferably used in combination.
- Preferable silicone-based surfactants include polysiloxane surfactants in which an organic group is introduced into a side chain or a terminal, or a side chain and a terminal.
- examples thereof include a carbinol group, a methacryl group, a polyether group, a mercapto group, a carboxyl group, a phenol group, a silanol group, and a diol group.
- alkoxysilane compound ⁇ an alkylalkoxysilane compound having a specific carbon number
- surfactant having the above polyoxyalkylene structure.
- alkoxysilane compound ⁇ an alkoxysilane compound having an alkyl group having 4 to 12 carbon atoms (more preferably 6 to 10 carbon atoms) is preferably used.
- this is represented by a general formula, it is preferably a compound represented by the following formula (5).
- R 51 is the same group as R 4 .
- R 52 is preferably an alkyl group having 4 to 12 carbon atoms, and more preferably an alkyl group having 6 to 10 carbon atoms.
- n is an integer of 1 to 3.
- the amount of the surfactant used in combination with the surfactant having a polyoxyalkylene structure may be arbitrarily adjusted.
- the surfactant used in combination with 100 parts by mass of the surfactant having a polyoxyalkylene structure is preferably used in an amount of 0.01 to 100 parts by weight, more preferably 1 to 100 parts by weight, and even more preferably 10 to 100 parts by weight.
- the curable resin composition for forming the low refractive index layer preferably contains hollow particles.
- the hollow particles not only hollow structures but also porous fine particles may be used.
- the hollow particle has a structure having a cavity inside and refers to a particle having a cavity surrounded by an outer shell, and the porous particle refers to a porous particle having a large number of cavities.
- the hollow particles or the porous particles are appropriately referred to as “specific particles”.
- the specific particles may be organic particles or inorganic particles.
- the porosity of the specific particles is preferably 10 to 80%, more preferably 20 to 60%, and most preferably 30 to 60%.
- the porosity of the specific particles is preferably in the above range from the viewpoint of reducing the refractive index and maintaining the durability of the particles.
- hollow particles are more preferable, and hollow silica particles are particularly preferable from the viewpoint of easily reducing the refractive index.
- JP-A-2001-233611 As a method for producing hollow particles, for example, the method described in JP-A-2001-233611 can be applied.
- a method for producing porous particles for example, methods described in JP-A Nos. 2003-327424, 2003-335515, 2003-226516, 2003-238140 and the like can be applied.
- the specific particles preferably have an average primary particle diameter of 1 nm to 200 nm, more preferably 10 nm to 100 nm.
- the average primary particle diameter of the specific particles can be determined from the photograph obtained by observing the dispersed particles with a transmission electron microscope. The projected area of the particles is obtained, and the equivalent circle diameter is obtained therefrom, which is the average primary particle diameter.
- the average primary particle diameter in this specification is calculated by measuring the projected area of 300 or more particles and obtaining the equivalent circle diameter.
- the refractive index of the specific particles is preferably 1.10 to 1.40, more preferably 1.15 to 1.35, and most preferably 1.15 to 1.30.
- the refractive index here represents the refractive index of the entire particle, and when the particle is a hollow particle, it does not represent the refractive index of only the outer shell forming the hollow particle.
- the method for measuring the refractive index of the porous particles is the same as that of the metal oxide particles.
- the specific particles are preferably hollow or porous inorganic particles from the viewpoint of lowering the refractive index.
- the inorganic low refractive index particles include particles of magnesium fluoride and silica, and silica particles are more preferable from the viewpoints of low refractive index properties, dispersion stability, and cost.
- the average primary particle diameter of these inorganic particles is preferably 1 nm to 100 nm, and more preferably 1 nm to 60 nm.
- the crystal system may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles that satisfy a predetermined particle diameter.
- the shape is most preferably a spherical shape, but may be a bead shape, a shape having a major axis / minor axis ratio of 1 or more, or an indefinite shape.
- the specific surface area of the inorganic particles is preferably 10 m 2 / g to 2000 m 2 / g, more preferably 20 m 2 / g to 1800 m 2 / g, and 50 m 2 / g to 1500 m 2 / g. Is most preferred.
- Inorganic particles have a physical surface such as plasma discharge treatment or corona discharge treatment in order to stabilize dispersion in the curable resin composition or to increase the affinity and binding properties with the binder component.
- Chemical surface treatment with a treatment, a surfactant, a coupling agent, or the like may be performed.
- the use of a coupling agent is particularly preferred.
- an alkoxy metal compound eg, titanium coupling agent, silane coupling agent
- silane coupling treatment is particularly effective.
- the organosilyl group (monoorganosilyl, diorganosilyl, triorganosilyl group) becomes silica particles by the reaction of the silane compound and the silanol group. It binds to the surface.
- the organic group on the surface of the surface-treated silica particles include saturated or unsaturated hydrocarbon groups having 1 to 18 carbon atoms and halogenated hydrocarbon groups having 1 to 18 carbon atoms.
- the above-mentioned coupling agent may be used as a surface treatment agent for inorganic particles in order to perform surface treatment in advance before the preparation of the coating solution for low refractive index film, or may be further added as an additive during the preparation of the coating solution.
- the inorganic particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.
- a more preferred embodiment of the specific particles is silica particles.
- Commercially available particles can be preferably used as the specific particles made of silica.
- Julia Catalysts Co., Ltd. through rear series hinder particles, isopropanol (IPA) dispersion, 4-methyl-2-pentanone (MIBK) dispersion, etc., such as through rear 2320
- OSCAL series Nissan Chemical Co., Ltd.
- Snowtex series (porous particles, IPA dispersion, ethylene glycol dispersion, methyl ethyl ketone (MEK) dispersion, dimethylacetamide dispersion, MIBK dispersion, propylene glycol monomethyl acetate dispersion, propylene glycol monomethyl ether dispersion, methanol dispersion, ethyl acetate dispersion, butyl acetate) Dispersion, xylene-n-butanol dispersion, toluene dispersion, etc.
- MEK methyl ethyl ketone
- MIBK-SD-L, MIBK-ST, etc. Sirenax (porous particles) manufactured by Nittetsu Mining Co., Ltd., PL manufactured by Fuso Chemical Industry Co., Ltd. series Porous particles, IPA dispersion, toluene dispersion, propylene glycol monomethyl ether dispersion, methyl ethyl ketone dispersion, etc., such as PL-1-IPA, PL-2L-PGME, etc., Aerosil series manufactured by EVONIK (porous particles, propylene glycol acetate dispersion) Silica particles such as ethylene glycol dispersion and MIBK dispersion) can be used.
- Sittetsu Mining Co., Ltd. PL manufactured by Fuso Chemical Industry Co., Ltd. series Porous particles, IPA dispersion, toluene dispersion, propylene glycol monomethyl ether dispersion, methyl ethyl ketone dispersion, etc
- silica particles are added to the photosensitive composition as a dispersion containing silica particles and a particle dispersant (details of the particle dispersant will be described later), the content of silica particles in the silica dispersion is 10 % By mass to 50% by mass is preferable, 15% by mass to 40% by mass is more preferable, and 15% by mass to 30% by mass is still more preferable.
- the specific particles may be one kind or a combination of two or more kinds.
- the content of the specific particles with respect to the total solid content in the curable resin composition for forming the low refractive index layer is preferably 5% by mass to 95% by mass, and more preferably 10% by mass to 90% by mass.
- the content is preferably 20% by mass to 90% by mass.
- the coating amount of the specific particles is preferably 1 mg / m 2 to 100 mg / m 2 , more preferably 5 mg / m 2 to 80 mg. / M 2 , more preferably 10 mg / m 2 to 60 mg / m 2 .
- the coating amount of the specific particles is preferably 1 mg / m 2 to 100 mg / m 2 , more preferably 5 mg / m 2 to 80 mg. / M 2 , more preferably 10 mg / m 2 to 60 mg / m 2 .
- it is 1 mg / m 2 or more, the effect of lowering the refractive index and the effect of improving scratch resistance can be reliably obtained, and when it is 100 mg / m 2 or less, fine irregularities are formed on the surface of the cured film. It is possible to suppress the deterioration of the integrated reflectance due to the fact that
- the curable resin composition for forming the low refractive index layer may contain a fluorine-based resin.
- a fluorine-based siloxane polymer described in JP-A No. 2004-21036 can be mentioned.
- Fluorine-based resin is a resin containing fluorine in a substance molecule.
- polytetrafluoroethylene, polyhexafluoropropylene, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoro examples include alkyl vinyl ether copolymers, tetrafluoroethylene / ethylene copolymers, hexafluoropropylene / propylene copolymers, polyvinylidene fluorides, vinylidene fluoride / ethylene copolymers, among which polytetrafluoroethylene, tetra Fluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, and polyvinylidene fluoride are preferred.
- polytetrafluoroethylene and tetrafluoroethylene / ethylene copolymer are preferred, polytetrafluoroethylene is more preferred, and polytetrafluoroethylene-containing mixed powder comprising polytetrafluoroethylene particles and an organic polymer is also preferred.
- the molecular weight of fluororesin such as polytetrafluoroethylene is preferably in the range of 100,000 to 10,000,000, more preferably in the range of 100,000 to 1,000,000, and is particularly effective for extrusion moldability and flame retardancy.
- polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer
- Metal (registered trademark)” A series from Mitsubishi Rayon Co., Ltd.
- METABBRENE (registered trademark)” A-3800 and the like are commercially available.
- polytetrafluoroethylene “Teflon (registered trademark)” 6-J and the like are prone to agglomerate, and when mixed with other resin compositions mechanically with a Henschel mixer or the like, agglomeration may occur due to aggregation.
- a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer is excellent in handling properties and dispersibility, and is particularly preferably used.
- the polytetrafluoroethylene-containing mixed powder composed of the polytetrafluoroethylene particles and the organic polymer is not limited, but polytetrafluoroethylene disclosed in Japanese Patent Application Laid-Open No. 2000-226523. Examples thereof include polytetrafluoroethylene-containing mixed powder composed of particles and an organic polymer.
- the organic polymer include aromatic vinyl monomers, acrylate monomers, and vinyl cyanide.
- An organic polymer containing 10% by mass or more of a monomer may be a mixture thereof.
- the polytetrafluoroethylene content in the polytetrafluoroethylene-containing mixed powder is 0.1% by mass to 90% by mass. It is preferable that it is mass%.
- fluororesin an amorphous fluororesin, a copolymer oligomer containing a perfluoroalkyl group-containing acrylate or methacrylate, a fluorocoating agent, a fluorosurfactant, an electron beam or an ultraviolet curing component containing an ultraviolet curing component
- fluorine-based surface treatment agent containing an agent and a thermosetting component is also preferable.
- alkyl acrylate or alkyl methacrylate is preferable.
- Examples of the amorphous fluororesin include Lumiflon manufactured by Asahi Glass Co., Ltd. and CYTOP.
- Examples of copolymer oligomers based on perfluoroalkyl group-containing (meth) acrylates and alkyl (meth) acrylates include Nippon Oil & Fats Modiper F series, Daikin Industries Unidyne, Dainippon Ink & Chemicals Examples thereof include F470 series, F480 series, F110 series, and the like, and block copolymerization is more preferable.
- a fluorine-type coating agent Sumitomo 3M EGC1700 is mentioned.
- fluorosurfactant examples include Megafac F114, F410 series, 440 series, 450, 490 series and the like manufactured by Dainippon Ink and Chemicals, Inc.
- fluorine-based surface treating agent containing an electron beam or ultraviolet ray curable component examples include Omnova Solutions Polyfox PF-3320, Unimatec Cheminox FAMAC-8, Sumitomo 3M EGC1720, and the like.
- fluorine-based surface treatment agent containing a thermosetting component examples include EGC1720 manufactured by Sumitomo 3M, NH-10 and NH-15 manufactured by Dainippon Ink and Chemicals, Inc.
- amorphous fluororesins include resins having the following structural formula.
- the fluororesin may be a mixture of a plurality of types of fluorine-containing compounds.
- the addition amount of the fluorine-based resin is not particularly limited, but from the same viewpoint as the siloxane resin, the content is preferably in the same range as the siloxane resin.
- the curable resin composition for forming the low refractive index layer may further contain a polymerization initiator.
- Specific examples and preferred examples of the polymerization initiator include those similar to the specific examples and preferred examples of the polymerization initiator described above in the section of the curable resin composition for forming a high refractive index layer.
- the content of the polymerization initiator contained in the curable resin composition for forming the low refractive index layer (in the case of two or more types)
- the total content) is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.3% by mass or more and 8% by mass or less, and further preferably 0% by mass with respect to the total solid content of the curable composition. It is 5 mass% or more and 5 mass% or less.
- the curable resin composition for forming the low refractive index layer may further contain a curing agent.
- curing agent the hardening
- curing agents can be easily obtained by reacting a metal alkoxide with a chelating agent.
- chelating agents include ⁇ -diketones such as acetylacetone, benzoylacetone, and dibenzoylmethane; ⁇ -keto acid esters such as ethyl acetoacetate and ethyl benzoylacetate.
- metal group chelate compounds include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetyl acetate bis (ethyl acetoacetate), aluminum tris.
- Aluminum chelate compounds such as (acetylacetonate), magnesium chelate compounds such as ethyl acetoacetate magnesium monoisopropylate, magnesium bis (ethylacetoacetate), alkyl acetoacetate magnesium monoisopropylate, magnesium bis (acetylacetonate), zirconium tetra Acetylacetonate, zirconium tributoxyacetylacetonate, di Benzalkonium acetylacetonate bis (ethylacetoacetate), manganese acetylacetonate, cobalt acetylacetonate, copper acetylacetonate, titanium acetylacetonate and titanium oxy acetylacetonate.
- magnesium chelate compounds such as ethyl acetoacetate magnesium monoisopropylate, magnesium bis (ethylacetoacetate), alkyl acetoacetate magnesium monoisopropylate, magnesium bis (acetylaceton
- the total content of the curing agent is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total content of the siloxane resin. Particularly preferred is 0.01 to 0.5 parts by mass.
- the curable resin composition for forming the low refractive index layer can be constituted using an organic solvent.
- the organic solvent is basically not particularly limited as long as the solubility of each component and the applicability of the resin composition for forming a light-transmitting cured film are satisfied. It is preferable to select in consideration.
- organic solvents examples include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate.
- Alkyl oxyacetates eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)
- alkyl 3-oxypropionate Esters eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc.
- 2- Xylpropionic acid alkyl esters eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc.
- ethers For example, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene Glycol mono n-butyl ether, propylene glycol mono tert-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and ketones
- methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like, and aromatic hydrocarbons include, for example, tolulose,
- the solvent to be applied is preferably 50 to 99.9% by mass in the total amount of the curable resin composition for forming the low refractive index layer. More preferably, it is 95% by mass.
- the amount of the compound is equal to or more than the above lower limit value, the coating property is good, which is preferable.
- the amount is less than or equal to the above upper limit value, the coating property is good, which is preferable.
- the viscosity of the curable resin composition for forming a high refractive index layer or for forming a low refractive index layer is preferably adjusted from the viewpoint of forming a good high refractive index layer or a low refractive index layer.
- the specific viscosity range is not particularly limited, but is preferably 1 to 20 cP, more preferably 2 to 15 cP, and particularly preferably 4 to 6 cP. Unless otherwise specified, the viscosity value in this specification is based on the measurement method described later. Measurement method Measured at room temperature (about 25 ° C.) using an E-type viscometer “TV-20 type viscometer / cone plate type TVE-20L” (manufactured by Toki Sangyo). Sampling is the average of the values measured for viscosity 5 times every 100 seconds.
- the curable resin composition for forming the high refractive index layer or the low refractive index layer preferably has a solid content concentration of 10 to 90% by mass from the viewpoint of forming the high refractive index layer or the low refractive index layer. More preferably, it is 20 to 90% by mass, and most preferably 30 to 80% by mass.
- the composition means that two or more components exist substantially uniformly in a specific composition.
- substantially uniform means that each component may be unevenly distributed within the range where the effects of the invention are exerted.
- the composition is not particularly limited as long as the above definition is satisfied, is not limited to a fluid liquid or a paste, and includes a solid or powder composed of a plurality of components. Furthermore, even when there is a sediment, it means that the composition maintains a dispersion state for a predetermined time by stirring.
- the application of the curable resin composition for forming a high refractive index layer or for forming a low refractive index layer according to the present invention is for an infrared reflective film that can be incorporated into an infrared cut filter on the light receiving side of a substrate in a solid-state imaging device (for example For infrared reflection film that can be incorporated into an infrared cut filter for wafer level lenses), for infrared reflection film that can be incorporated into an infrared cut filter on the back side of the substrate (opposite to the light receiving side) in a solid-state imaging device It is preferable for the infrared reflecting film on the light receiving side of the substrate in the solid-state imaging device.
- a curable resin composition for forming a high refractive index layer or a low refractive index layer is directly applied on a support and dried. The method of doing is mentioned.
- the support may be a layer containing a dye or a copper complex having a maximum absorption wavelength in the range of 600 nm to 820 nm, which will be described later, or a substrate in a solid-state imaging device, or a separate substrate provided on the light receiving side of the substrate. Or a layer such as a flattening layer provided on the light receiving side of the substrate in the solid-state imaging device.
- an applicator, a spin coater, a slit spin coater, a slit coater, screen printing or the like is used as a method of applying a curable resin composition for forming a high refractive index layer or a low refractive index layer on a support. It is preferable to apply by a spin coater.
- the drying conditions of the coating film vary depending on each component, the type of solvent, the use ratio, and the like, but are usually 60 ° C. to 150 ° C. for about 30 seconds to 15 minutes.
- the method for forming an infrared cut filter using a curable resin composition for forming a high refractive index layer or a low refractive index layer according to the present invention may include other steps.
- the surface treatment process of a base material a preheating process (prebaking process), a hardening process process, a post-heating process (post-baking) Process.
- the heating temperature in the preheating step and the postheating step is usually 80 ° C. to 200 ° C., preferably 90 ° C. to 150 ° C.
- the heating time in the preheating step and the postheating step is usually 30 seconds to 240 seconds, and preferably 60 seconds to 180 seconds.
- the curing process is a process of curing the formed film as necessary, and the mechanical strength of the infrared cut filter is improved by performing this process.
- limiting in particular as said hardening process Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.
- “exposure” is used to include not only light of various wavelengths but also irradiation of radiation such as electron beams and X-rays.
- the exposure is preferably performed by irradiation of radiation, and as the radiation that can be used for the exposure, ultraviolet rays such as electron beams, KrF, ArF, g rays, h rays, i rays and visible light are particularly preferably used.
- KrF, g line, h line, and i line are preferable.
- Exposure is more preferably 5mJ / cm 2 ⁇ 3000mJ / cm 2 is preferably 10mJ / cm 2 ⁇ 2000mJ / cm 2, and most preferably 50mJ / cm 2 ⁇ 1000mJ / cm 2.
- Examples of the entire surface exposure processing method include a method of exposing the entire surface of the formed film.
- the curable resin composition for forming a high refractive index layer or for forming a low refractive index layer contains a polymerizable compound
- the entire surface exposure promotes curing of the polymerization component in the film formed from the composition, Curing of the film further proceeds, and mechanical strength and durability are improved.
- an apparatus which performs the said whole surface exposure Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.
- a method of the whole surface heat treatment a method of heating the entire surface of the formed film can be mentioned.
- the heating temperature in the entire surface heating is preferably 120 ° C. to 250 ° C., more preferably 120 ° C. to 250 ° C.
- the heating time in the entire surface heating is preferably 3 minutes to 180 minutes, more preferably 5 minutes to 120 minutes.
- the low refractive index layer obtained by the heat treatment is mainly composed of organic silicon oxide (SiOC).
- SiOC organic silicon oxide
- the present invention also relates to an infrared reflective film obtained by using the curable resin composition for forming a high refractive index layer or a low refractive index layer of the present invention.
- the film thickness of each of the two or more high refractive index layers and the two or more low refractive index layers is preferably 50 to 250 nm, and preferably 80 to 180 nm. It is more preferable that In the infrared reflective film of the present invention, the two or more high refractive index layers have different refractive indices within a refractive index range of 1.65 to 2.00 from the viewpoint of reducing vibration (ripple) unnecessary for spectral characteristics.
- the two or more high refractive index layers are preferably a plurality of types of layers having different film thicknesses within a range of 50 to 250 nm from the viewpoint of reducing ripples.
- the two or more low-refractive-index layers are a plurality of types of layers having different refractive indices within a refractive index range of 1.20 to 1.45 from the viewpoint of reducing ripples. It is preferable.
- the two or more low refractive index layers are preferably a plurality of types of layers having different film thicknesses within a range of 50 to 250 nm from the viewpoint of reducing ripples.
- the number of laminated layers of the two or more high refractive index layers and the two or more low refractive index layers is preferably 4 to 60 layers, and preferably 8 to 50 layers. Is more preferable, and 10 to 40 layers are more preferable.
- the total film thickness of the two or more high refractive index layers and the two or more low refractive index layers is preferably 10 ⁇ m or less, and preferably 8 ⁇ m or less. More preferably, it is more preferably 6 ⁇ m or less. Since the infrared reflective film of the present invention is formed from the curable resin composition for forming a high refractive index layer or a low refractive index layer of the present invention, it is excellent in infrared shielding properties.
- the present invention also relates to an infrared cut filter having the above-described infrared reflective film and a layer containing a dye or a copper complex having a maximum absorption wavelength in the range of 600 nm to 820 nm.
- the absorption maximum wavelength in the above dye or copper complex is obtained by applying a spectrophotometer to a film having a thickness of 1 ⁇ m obtained by coating a solution in which the dye or copper complex and the resin are prepared to a solid content of 20% by mass with respect to the total amount of the solution. According to the value obtained using.
- the dye is not particularly limited as long as it has a maximum absorption wavelength ( ⁇ max ) in a wavelength range of 600 nm to 820 nm.
- cyanine dyes, phthalocyanine dyes, quaterylene dyes, aminium dyes, iminium dyes, azo dyes Preferable examples include at least one selected from the group consisting of anthraquinone dyes, diimonium dyes, squarylium dyes, and porphyrin dyes.
- a cyanine dye, a phthalocyanine dye, or a quaterylene dye is preferable, and a cyanine dye or a phthalocyanine dye is more preferable.
- the maximum absorption wavelength is less than 600 nm, or the maximum absorption wavelength is more than 820 nm, the shielding property against near infrared rays in the vicinity of the wavelength of 700 nm is low, and a satisfactory result cannot be obtained. It is preferable to have a maximum absorption wavelength in the range of 640 to 770 nm, and it is particularly preferable to have an absorption maximum in the range of 660 to 720 nm.
- Specific examples of cyanine dyes and quaterylene dyes include compounds described in paragraph 0160 of JP2012-215806A, paragraph 0021 of JP2008-009206A, and the like.
- phthalocyanine compound examples include JP-A-60-224589, JP-T-2005-537319, JP-A-4-23868, JP-A-4-39361, JP-A-5-78364, Japanese Laid-Open Patent Publication No. 5-222047, Japanese Laid-Open Patent Publication No. 5-222301, Japanese Laid-Open Patent Publication No. 5-222302, Japanese Laid-Open Patent Publication No. 5-345561, Japanese Laid-Open Patent Publication No. 6-25548, Japanese Laid-Open Patent Publication No. 6-107663, and Japanese Laid-open Patent Publication No. 6-106663.
- JP-A-6-228533 JP-A-7-118551, JP-A-7-118552, JP-A-8-12186, JP-A-8-225751, JP-A-9-202860.
- No. 10 JP-A-10-120927, JP-A-10-182959, JP-A-11-35838 JP-A-2000-26748, JP-A-2000-63691, JP-A-2001-106689, JP-A-2004-18561, JP-A-2005-220060, JP-A-2007-169343 Compounds.
- azo dyes anthraquinone dyes (anthraquinone compounds), and squarylium dyes (squarylium compounds) include the compounds described in paragraphs 0114 to 0117, 0128, 0129, and 0177 of JP2012-215806A. It is done.
- the above dyes are also commercially available.
- Lumogen IR765, Lumogen IR788 (manufactured by BASF); ABS643, ABS654, ABS667, ABS670T, IRA693N, IRA735 (manufactured by Exciton); SDA3598, SDA6075, SDA8030, SDA8030, SDA8030, SDA8030 SDA8030 SDA3039, SDA3040, SDA3922, SDA7257 (manufactured by HW SANDS); TAP-15, IR-706 (manufactured by Yamada Chemical Co., Ltd.) and the like can be mentioned.
- Daito chmix 1371F manufactured by Daito Chemix
- phthalocyanine dyes include the Excolor series, Excolor TX-EX 720, and 708K (manufactured by Nippon Shokubai). Not but be under it is not limited to this.
- the dye is preferably a fine particle.
- the average particle size of the dye is preferably 800 nm or less, more preferably 400 nm or less, and still more preferably 200 nm or less. When the average particle diameter is in such a range, the dye is less likely to block visible light by light scattering, and thus the translucency in the visible light region can be further ensured. From the viewpoint of avoiding photoacid disturbance, the average particle size is preferably as small as possible. However, for reasons such as ease of handling during production, the average particle size of the dye is usually 1 nm or more.
- the dye having the maximum absorption wavelength within the range of 600 nm to 820 nm in the present invention may be a copper complex.
- the copper complex used in the present invention is not particularly limited as long as it is a copper complex having a maximum absorption wavelength in a wavelength range of 600 nm to 820 nm (near infrared region), but is preferably represented by the following general formula (1). More preferably, it is a phosphorus-containing copper complex.
- L represents a ligand coordinated to copper
- X does not exist or represents a halogen atom, H 2 O, NO 3 , ClO 4 , SO 4 , CN, SCN, BF 4 , PF 6 , BPh 4 (Ph represents a phenyl group) or an alcohol.
- n represents an integer of 1 to 4.
- the ligand L that coordinates to copper is not particularly limited as long as it can be coordinated to a copper ion, but preferably has a substituent containing C, N, O, or S as an atom that can coordinate to copper.
- ligand L phosphoric acid ester, phosphonic acid, phosphonic acid ester, phosphinic acid, carboxylic acid, carbonyl (ester, ketone), amine, amide, sulfonamide, urethane, urea, alcohol
- examples include compounds having thiol and the like.
- phosphoric acid, phosphoric acid ester, phosphonic acid, phosphonic acid ester, and phosphinic acid are preferable.
- compounds disclosed in WO2005 / 030898 can be used.
- the group which can be coordinated is not limited to 1 type in a molecule
- numerator 2 or more types may be included, and dissociation or non-dissociation may be sufficient.
- non-dissociation X is not present.
- —OR 2 represents a polyoxyalkyl group having 4 to 100 carbon atoms, a (meth) acryloyloxyalkyl group having 4 to 100 carbon atoms, or a (meth) acryloyl polyoxyalkyl group having 4 to 100 carbon atoms.
- N represents 1 or 2.
- R 2 may be the same or different.
- the carbon number of the polyoxyalkyl group having 4 to 100 carbon atoms, the (meth) acryloyloxyalkyl group having 4 to 100 carbon atoms, or the (meth) acryloyl polyoxyalkyl group having 4 to 100 carbon atoms is 4 to It is preferably 20, and more preferably 4 to 10.
- one of R 2 is —OR 2 and is a (meth) acryloyloxyalkyl group having 4 to 100 carbon atoms or a (meth) acryloyl polyalkyl having 4 to 100 carbon atoms. It preferably represents an oxyalkyl group, and the other is preferably the aforementioned —OR 2 or an alkyl group.
- the molecular weight of the phosphorus atom-containing compound used in the present invention is preferably 300 to 1500, and more preferably 320 to 900.
- a phosphorus atom-containing compound preferably a phosphate copper complex
- copper complex copper compound
- Copper in the phosphate ester copper complex is divalent copper, and can be produced, for example, by a reaction between a copper salt and a phosphate ester. Therefore, if it is an “infrared absorbing composition containing copper and a phosphate ester compound”, it is predicted that a copper phosphate complex is formed in the composition.
- Specific examples of the compound forming the ligand include the following exemplified compounds (A-1) to (A-219).
- the following phosphate ester is obtained by adding triethylamine to a tetrahydrofuran (THF) solution of 2,4-dimethylpentanol and stirring at 0 ° C. for 5 minutes, dropping phosphorus oxychloride and then stirring at room temperature for 6 hours. The reaction is terminated. After the reaction is completed, the reaction solution is decanted with water so that the temperature does not increase by 30 ° C. or more, liquid separation is performed with chloroform / water, and the solvent in the organic layer is distilled off to obtain the following phosphate ester. it can.
- THF tetrahydrofuran
- phosphonic acids such as phosmer M, phosmer PE, phosmer PP (made by Unichemical Co., Ltd.), as a commercial item, for example.
- the copper salt used here is preferably divalent or trivalent copper, and more preferably divalent copper.
- Copper salts include copper acetate, copper chloride, copper formate, copper stearate, copper benzoate, copper ethyl acetoacetate, copper pyrophosphate, copper naphthenate, copper citrate, copper nitrate, copper sulfate, copper carbonate, copper chlorate Copper (meth) acrylate is more preferable, copper benzoate and copper (meth) acrylate are more preferable.
- the copper complex used in the present invention include the following exemplified compounds (Cu-1) to (Cu-219). Needless to say, the present invention is not limited to these examples.
- the above dyes or copper complexes may be used alone or in combination of two or more, and in the case of two or more, the total amount is in the following range.
- the content of the dye or copper complex is preferably 0.05% by mass or more and 90% by mass or less based on the total solid mass of the curable resin composition for forming the dye or copper complex-containing layer. It is more preferable that it is 0.05 mass% or more and 80 mass% or less, and it is still more preferable that it is 0.5 mass% or more and 30 mass% or less.
- the ⁇ (epsilon) of the dye is high, the content may be small, but when the ⁇ (epsilon) of the dye is low, the content increases.
- the dye is a cyanine dye or a phthalocyanine dye
- the content thereof is preferably 0.01% by mass or more and 20% by mass or less, and 0.5% by mass with respect to the total solid mass of the composition. It is more preferable that it is 10% by mass or more.
- the curable resin composition for forming the dye or copper complex-containing layer preferably contains a dispersant, a binder, and a polymerizable compound in addition to the dye or the copper complex, and if necessary, a polymerization initiator. More preferably, it contains a solvent, a surfactant and the like.
- compositions of a dispersant, a binder, and a polymerizable compound, a polymerization initiator, a solvent, a surfactant and the like that can be contained in the curable resin composition for forming a dye or copper complex-containing layer
- the preferable range of the content in the product) is the dispersant (B), binder (C), polymerizable compound (D), polymerization initiator described above in ⁇ Curable resin composition for forming a high refractive index layer>.
- Specific examples, preferred examples, preferred ranges of the amount used, etc., of (E), solvents, surfactants and the like are the same.
- it can carry out according to the preparation method of the above-mentioned curable resin composition for high refractive index layer formation also as a preparation method of the curable resin composition for pigment
- the light transmittance of the dye or copper complex-containing layer is preferably 90% or more over the entire wavelength region of 400 to 700 nm.
- the light transmittance is more preferably 95% or more over the entire wavelength region of 400 to 700 nm, still more preferably 99% or more, and most preferably 100%.
- the viscosity of the curable resin composition for forming the dye or copper complex-containing layer is adjusted from the viewpoint of forming a good thick dye or copper complex-containing layer.
- the specific viscosity range is not particularly limited, but is preferably 1 to 20 cP, more preferably 2 to 15 cP, and particularly preferably 4 to 6 cP. Unless otherwise specified, the viscosity value in this specification is based on the measurement method described later.
- the thickness of the dye or copper complex-containing layer is preferably 20 ⁇ m or more, more preferably 20 ⁇ m to 200 ⁇ m, still more preferably 30 ⁇ m to 150 ⁇ m, and even more preferably 40 ⁇ m to 120 ⁇ m, from the viewpoint that it can be suitably applied to a solid-state imaging device. Is particularly preferred.
- the film thickness is appropriately adjusted depending on the dye or copper complex to be used, but by applying such a thick film, the type of the dye or copper complex to be used is not limited, and a desired near infrared cut function can be achieved. .
- the curable resin composition for forming the dye or copper complex-containing layer preferably has a solid content concentration of 10 to 90% by mass, more preferably 20 to 90% by mass, from the viewpoint of forming the film thickness. %, Most preferably 30 to 80% by weight.
- dye or a copper complex content layer formation directly on a support body, and making it dry is mentioned.
- the support is provided on the light-receiving side of the substrate in the solid-state imaging device, whether it is a substrate in the solid-state imaging device or another substrate (for example, a glass substrate 30 described later) provided on the light-receiving side of the substrate.
- a layer such as a flattening layer may also be used.
- the method of applying a curable resin composition for forming a dye or copper complex-containing layer on a support can be carried out by using, for example, an applicator, spin coater, slit spin coater, slit coater, screen printing, etc. It is preferable to apply by coating.
- substrate surface treatment process, pre-heating process (pre-baking process), curing process, post-heating process (post-baking process), etc. for forming a high refractive index layer or for forming a low refractive index layer
- the method for forming an infrared cut filter using the curable resin composition can be performed according to the method described above.
- the infrared cut filter of the present invention may be an optical article that is manufactured independently (for example, on a glass substrate) and used for incorporation into any element, but is formed on a substrate in a solid-state image sensor. An infrared cut filter may be used.
- the present invention also relates to a solid-state imaging device having the infrared cut filter of the present invention on a substrate.
- the substrate in the solid-state imaging device of the present invention preferably has a color filter layer, and more preferably has a color filter layer, a microlens, and a planarization layer.
- a camera module according to a preferred embodiment of the solid-state imaging device of the present invention is a camera module having a substrate and the infrared cut filter of the present invention disposed on the light receiving side of the substrate.
- FIGS. 2 and 3 common portions are denoted by common reference numerals.
- “upper”, “upper”, and “upper” refer to the side far from the silicon substrate 10, and “lower”, “lower”, and “lower” are the sides closer to the silicon substrate 10. Point to.
- FIG. 2 is a schematic cross-sectional view showing a configuration of a camera module including a solid-state image sensor according to a preferred embodiment of the solid-state image sensor of the present invention.
- the camera module 200 shown in FIG. 2 is connected to a circuit board 70 that is a mounting board via solder balls 60 that are connection members.
- the camera module 200 includes a substrate 100 having an image sensor portion on a first main surface of a silicon substrate, and a planarization layer 46 (on the light receiving side) provided on the first main surface side (light receiving side) of the substrate 100. (Not shown in FIG.
- an infrared cut filter 42 provided on the planarizing layer 46, a glass substrate 30 (light transmissive substrate) disposed above the infrared cut filter 42, and the glass substrate 30
- a lens holder 50 having an imaging lens 40 disposed in an upper space and a light shielding / electromagnetic shield 44 disposed so as to surround the substrate 100 and the glass substrate 30 is provided. Each member is bonded by an adhesive 20 (not shown in FIG. 2) and 45.
- incident light h ⁇ from the outside passes through the imaging lens 40, the glass substrate 30, the infrared cut filter 42, and the planarization layer 46 in order, and then reaches the imaging element portion of the substrate 100. .
- the camera module 200 is connected to the circuit board 70 via a solder ball 60 (connection material) on the second main surface side of the board 100.
- FIG. 3 is an enlarged cross-sectional view of the substrate 100 in FIG.
- the substrate 100 includes a silicon substrate 10 as a base, an image sensor 12, an interlayer insulating film 13, a base layer 14, a red color filter 15R, a green color filter 15G, a blue color filter 15B, an overcoat 16, a microlens 17,
- the light shielding film 18, the insulating film 22, the metal electrode 23, the solder resist layer 24, the internal electrode 26, and the element surface electrode 27 are configured.
- the solder resist layer 24 may be omitted.
- an image sensor section in which a plurality of image sensors 12 such as CCDs and CMOSs are two-dimensionally arranged is provided on the first main surface side of a silicon substrate 10 that is a base of the substrate 100.
- An interlayer insulating film 13 is formed on the image sensor 12 in the image sensor section, and a base layer 14 is formed on the interlayer insulating film 13.
- a red color filter 15 R, a green color filter 15 G, and a blue color filter 15 B (hereinafter collectively referred to as “color filter 15”) corresponding to the image sensor 12. ) are arranged.
- a light shielding film may be provided around the boundary between the red color filter 15R, the green color filter 15G, and the blue color filter 15B, and the periphery of the imaging element unit.
- This light shielding film can be produced using, for example, a known black color resist.
- An overcoat 16 is formed on the color filter 15, and a microlens 17 is formed on the overcoat 16 so as to correspond to the imaging element 12 (color filter 15).
- the planarizing layer 46 is provided on the microlens 17.
- a peripheral circuit (not shown) and an internal electrode 26 are provided in the periphery of the image sensor section on the first main surface side, and the internal electrode 26 is electrically connected to the image sensor 12 via the peripheral circuit.
- an element surface electrode 27 is formed on the internal electrode 26 with the interlayer insulating film 13 interposed therebetween.
- a contact plug (not shown) for electrically connecting these electrodes is formed.
- the element surface electrode 27 is used for applying a voltage and reading a signal through the contact plug and the internal electrode 26.
- a base layer 14 is formed on the element surface electrode 27.
- An overcoat 16 is formed on the base layer 14. The base layer 14 and the overcoat 16 formed on the element surface electrode 27 are opened to form a pad opening, and a part of the element surface electrode 27 is exposed.
- an adhesive 20 is provided around the imaging element portion, and the substrate 100 and the glass substrate 30 are bonded via the adhesive 20.
- the silicon substrate 10 has a through hole that penetrates the silicon substrate 10, and a through electrode that is a part of the metal electrode 23 is provided in the through hole.
- the imaging element portion and the circuit board 70 are electrically connected by the through electrode.
- an insulating film 22 is formed from the second main surface to the inner wall of the through hole.
- a metal electrode 23 patterned so as to extend from a region on the second main surface of the silicon substrate 10 to the inside of the through hole is provided.
- the metal electrode 23 is an electrode for connecting the image pickup element portion in the substrate 100 and the circuit board 70.
- the through electrode is a portion of the metal electrode 23 formed inside the through hole. The through electrode penetrates part of the silicon substrate 10 and the interlayer insulating film, reaches the lower side of the internal electrode 26, and is electrically connected to the internal electrode 26.
- a solder resist layer 24 (protective layer) is provided on the second main surface side, which covers the second main surface on which the metal electrode 23 is formed and has an opening that exposes a portion on the metal electrode 23. Insulating film). Further, on the second main surface side, there is provided a light shielding film 18 that covers the second main surface on which the solder resist layer 24 is formed and has an opening through which a part of the metal electrode 23 is exposed. It has been. In FIG. 3, the light shielding film 18 is patterned so as to cover a part of the metal electrode 23 and expose the remaining part, but may be patterned so as to expose the entire metal electrode 23. (The same applies to the patterning of the solder resist layer 24). The solder resist layer 24 may be omitted, and the light shielding film 18 may be directly formed on the second main surface on which the metal electrode 23 is formed.
- a solder ball 60 as a connection member is provided on the exposed metal electrode 23, and the metal electrode 23 of the substrate 100 and the connection electrode (not shown) of the circuit board 70 are electrically connected via the solder ball 60. Connected to.
- the configuration of the substrate 100 has been described above.
- Known methods such as the method described in paragraphs 0033 to 0068 in JP2009-158863A and the method described in paragraphs 0036 to 0065 in JP2009-99951A are described.
- the interlayer insulating film 13 is formed as a SiO 2 film or a SiN film by sputtering, CVD (Chemical Vapor Deposition), or the like, for example.
- the color filter 15 is formed by photolithography using a known color resist, for example.
- the overcoat 16 and the base layer 14 are formed, for example, by photolithography using a known organic interlayer film forming resist.
- the microlens 17 is formed by using styrene resin or the like, for example, by photolithography.
- the solder resist layer 24 is preferably formed by photolithography using a known solder resist including, for example, a phenol resin, a polyimide resin, or an amine resin.
- the solder balls 60 are formed using, for example, Sn—Pg (eutectic), 95Pb—Sn (high lead high melting point solder), and Pb free solder using Sn—Ag, Sn—Cu, Sn—Ag—Cu or the like.
- the solder ball 60 is formed in a spherical shape having a diameter of 100 ⁇ m to 1000 ⁇ m (preferably a diameter of 150 ⁇ m to 700 ⁇ m).
- the internal electrode 26 and the element surface electrode 27 are formed as a metal electrode such as Cu by CMP (Chemical Mechanical Polishing) or photolithography and etching, for example.
- the metal electrode 23 is formed as a metal electrode such as Cu, Au, Al, Ni, W, Pt, Mo, Cu compound, W compound, and Mo compound by sputtering, photolithography, etching, and electrolytic plating, for example.
- the metal electrode 23 may have a single layer configuration or a stacked configuration including two or more layers.
- the thickness of the metal electrode 23 is, for example, 0.1 ⁇ m to 20 ⁇ m (preferably 0.1 ⁇ m to 10 ⁇ m).
- the silicon substrate 10 is not particularly limited, but a silicon substrate that is thinned by scraping the back surface of the substrate can be used.
- the thickness of the substrate is not limited.
- a silicon wafer having a thickness of 20 ⁇ m to 200 ⁇ m (preferably 30 to 150 ⁇ m) is used.
- the through hole of the silicon substrate 10 is formed by, for example, photolithography and RIE (Reactive Ion Etching).
- the camera module according to one preferred embodiment of the solid-state imaging device of the present invention has been described above with reference to FIGS. 2 and 3, but the embodiment is not limited to the forms of FIGS. 2 and 3.
- ⁇ Curable resin composition for forming a high refractive index layer> [Preparation of titanium dioxide dispersion (dispersion composition)] Using a NPM manufactured by Shinmaru Enterprises Co., Ltd. as a circulation type dispersion device (bead mill), a mixture treatment having the following composition was subjected to a dispersion treatment as follows to obtain a titanium dioxide dispersion as a dispersion composition. . ⁇ Composition ⁇ Titanium dioxide (Ishihara Sangyo Co., Ltd.
- A-1 has a weight average molecular weight (Mw) of 9000 and a copolymerization ratio (molar ratio) as described above.
- the dispersing device was operated under the following conditions. ⁇ Bead diameter: ⁇ 0.05mm ⁇ Bead filling rate: 60% by volume ⁇ Peripheral speed: 10 m / sec ⁇ Pump supply: 30 kg / hour ⁇ Cooling water: Tap water ⁇ Bead mill annular passage volume: 1.0 L ⁇ Amount of liquid mixture to be dispersed: 10kg
- the average particle size was measured at 30 minute intervals (one pass time). The average particle diameter decreased with the dispersion time (pass number), but the amount of change gradually decreased. Dispersion was terminated when the average particle size change when the dispersion time was extended by 30 minutes became 5 nm or less. The average particle size of the titanium dioxide particles in this dispersion was 40 nm.
- the average particle diameter of titanium dioxide or the like in this example is obtained by diluting a mixture or dispersion containing titanium dioxide 80 times with propylene glycol monomethyl ether acetate, and subjecting the obtained diluted liquid to a dynamic light scattering method. The value obtained by using and measuring. This measurement was performed using Microtrack UPA-EX150 manufactured by Nikkiso Co., Ltd.
- curable resin composition 1 for forming a high refractive index layer -Titanium dioxide dispersion prepared above (dispersion composition)-80.0 parts-Solvent: PGMEA-15 parts-Polymerizable compound: KAYARAD DPHA (Nippon Kayaku Co., Ltd.) ... 3.6 parts Polymerization initiator: OXE-01 (trade name) manufactured by BASF Corporation ...
- Polymer A benzyl methacrylate / methacrylic acid copolymer (Copolymerization ratio: 80/20 (mass%), weight average molecular weight: 12,000) (Manufactured by FFFC) 1.0 parts Surfactant: MegaFuck F-781 (manufactured by DIC Corporation) ... 0.30 parts
- the refractive index of the high refractive index layer was measured using an ellipsometer manufactured by JA Woollam Japan. The measurement conditions were 633 nm, 25 ° C., and an average value of 5 points was adopted. The results are shown in the table below.
- the component ratio in the curable composition to be used is changed to the following composition ratio, and various curable resin compositions for forming a high refractive index layer are formed by the same process as the curable resin composition 1 for forming a high refractive index layer. Prepared.
- the refractive index measurement result of each high refractive index layer is also described.
- n 14
- the polystyrene equivalent weight average molecular weight of the dispersing agent (A-2) is 6400, and the acid value is 80 mgKOH / g.
- Polymer B ... Acrybase (grafted copolymer of benzyl methacrylate / i-butyl methacrylate / 2-hydroxyethyl methacrylate / methacrylic acid copolymer and methoxypolyethylene glycol, manufactured by Fujikura Kasei Co., Ltd.)
- ⁇ Curable resin composition for forming low refractive index layer> [Preparation of siloxane] Hydrolysis / condensation reaction was performed using methyltriethoxysilane (MTES) and / or tetraethoxysilane (TEOS) to obtain hydrolysis condensates S-1, S-2, and S-c1. The solvent used at this time was ethanol. The obtained hydrolysis condensate S-1 had a weight average molecular weight of about 10,000.
- MTES methyltriethoxysilane
- TEOS tetraethoxysilane
- curable resin composition for forming low refractive index layer
- Siloxane Hydrolysis condensate S-1 20 parts
- Solvent propylene glycol monomethyl ether acetate (PGMEA) 62 parts
- Solvent ethyl 3-ethoxypropionate (EEP) 16 parts
- Surfactant EMULSOGEN-COL-020 (Manufactured by Clariant Japan) 2 parts
- the components shown in the following table were blended to prepare curable resin compositions 2 and 3 for forming a low refractive index layer.
- the surfactant (Megafac) is composed of a compound containing a perfluoroalkyl group and having an ethylene oxide chain.
- this curable resin composition 1 for forming a low refractive index layer onto a 4-inch silicon wafer After applying this curable resin composition 1 for forming a low refractive index layer onto a 4-inch silicon wafer, pre-baking (100 ° C. for 2 minutes) and post-baking (230 ° C. for 10 minutes) are performed to form a low refractive index layer. did.
- the curable resin compositions 2 to 4 for forming the low refractive index layer low refractive index layers were prepared in the same manner as the curable resin composition 1 for forming the low refractive index layer.
- the method for measuring the refractive index is the same as the method for measuring the high refractive index layer.
- composition A for dye-containing layer Components of the following composition were mixed with a stirrer to prepare a composition for the dye-containing layer.
- composition C for copper compound-containing layer -149.0 parts by mass of the copper complex-JER157S65 (manufactured by Mitsubishi Chemical Corporation) 24.5 parts by mass (polymerizable compound) Pentaerythritol tetraacrylate 24.5 parts by mass (A-TMMT, Shin-Nakamura Chemical Co., Ltd.) (polymerizable compound) ⁇ Megafac F-781F (manufactured by DIC Corporation) (surfactant) 2.0 parts by mass / PGMEA 200.0 parts by mass
- a dye-containing layer B was obtained in the same manner as the dye-containing layer A, except that the composition A for the dye-containing layer was changed to the composition B for the dye-containing layer.
- a copper complex-containing layer C having a thickness of 50 ⁇ m is obtained in the same manner as the dye-containing layer A, except that the composition A for the dye-containing layer is changed to the composition C for the copper compound-containing layer and applied using an applicator. It was.
- a coating film is formed using a spin coater using the curable resin composition 1 for forming a high refractive index layer prepared above, and then, 100 ° C. for 2 minutes. After preheating, postheating was performed at 140 ° C. for 10 minutes. Next, a coating film is formed on the obtained high refractive index layer using a spin coater using the curable resin composition 1 for forming a low refractive index layer prepared above, and then at 100 ° C. 2 After preheating for 10 minutes, postheating was performed at 140 ° C. for 10 minutes.
- the dye containing layer A is changed to the dye or copper complex containing layer described in the following table, and the curable resin composition 1 for forming the high refractive index layer is used as the curable resin for forming the high refractive index layer shown in the following table.
- Infrared cut filter A-1 except that the curable resin composition 1 for forming the low refractive index layer is changed to the dye-containing curable resin composition for forming the low refractive index layer described in the following table.
- the transmittance at a wavelength of 1300 nm in the infrared cut filter was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). The lower the numerical value, the better the infrared shielding property. It can be said that the infrared ray transmittance is less than 25% and a practically good infrared ray shielding property is exhibited. In any infrared cut filter, a satisfactory result satisfying them was obtained.
- the pixel light receiving unit pitch is 2.0 ⁇ m, and the number of pixels is 2592 (X-axis direction) ⁇ 1944 (Y-axis direction) photodiodes (light receiving unit size 1.0 ⁇ m ⁇ 1.0 ⁇ m).
- CMOS comprising a plurality of light receiving elements arranged two-dimensionally at a pitch, an insulating layer (silicon oxide) having a wiring layer made of Al and a light shielding layer, a passivation layer (silicon nitride), and a waveguide (silicon nitride)
- a wafer on which a sensor was formed was prepared.
- the thickness of the passivation layer is 0.3 ⁇ m
- the thickness of the insulating layer interposed between the passivation layer and the waveguide is 0.3 ⁇ m
- the thickness of the waveguide is 2.1 ⁇ m.
- the entrance plane dimension of the waveguide was 1.5 ⁇ m ⁇ 1.5 ⁇ m
- the exit plane dimension was 1.0 ⁇ m ⁇ 1.0 ⁇ m, similar to the photodiode dimension.
- the refractive index of the passivation layer is 2.0
- the refractive index of the insulating layer is 1.46
- the refractive index of the waveguide is 1.88.
- the refractive index of the insulating layer outside the waveguide was 1.46.
- the value of the refractive index is a value at a wavelength of 550 nm unless otherwise specified, including the following.
- a G material was applied onto the lower planarizing layer, exposed and developed, and then post-baked (220 ° C., 10 minutes) to form a green filter in a checkered pattern.
- an R material was applied so as to cover the green filter, exposed and developed using a photomask, and then post-baked (220 ° C., 10 minutes) to form a red filter.
- the B material was applied so as to cover the red filter and the green filter, and after exposure and development using a photomask, post baking (220 ° C., 10 minutes) was performed to form a blue filter.
- a 50% diluted solution of CD-2000 manufactured by FUJIFILM Electromaterials Co., Ltd. was used as a developer.
- the refractive index of the red filter is 1.59 (wavelength 620 nm)
- the refractive index of the green filter is 1.60 (wavelength 550 nm)
- the blue filter The refractive index was 1.61 (wavelength 450 nm).
- a photocurable acrylic transparent resin material (CT-2020L manufactured by FUJIFILM Electromaterials Co., Ltd.) is spin-coated on the color filter, followed by pre-baking, ultraviolet exposure, and post-baking to form an upper planarizing layer. Formed.
- the formed flattened layer had a thickness of 0.3 ⁇ m, and the refractive index measured in the same manner as described above was 1.56.
- a positive resist (a positive resist PFI-27 for i-line manufactured by Sumitomo Chemical Co., Ltd.) is spin-coated, and after pre-baking, exposure and development are performed using a photomask having a pattern corresponding to the bonding pad portion and the scribe portion. went.
- a resist pattern having openings in the bonding pad portion and the scribe portion was formed, and oxygen ashing was performed using the resist pattern as a mask, and the planarizing layer on the portion was removed by etching.
- the positive resist was removed using a resist stripping solution.
- an infrared reflective film 1-1 having a total film thickness of 2.6 ⁇ m and a total number of stacked layers of 20 formed by alternately stacking high refractive index layers and low refractive index layers was formed.
- the glass substrate was affixed on the pigment-containing layer using an adhesive.
- the wafer was diced and package assembled to produce the solid-state imaging device A of the present invention.
- an infrared cut filter excellent in near-infrared shielding properties and infrared shielding properties can be produced.
- the curable resin composition for forming a high refractive index layer or for forming a low refractive index layer of the present invention can form a high refractive index layer or a low refractive index layer by coating, for example. Since an infrared cut filter can be manufactured without requiring a complicated process, insufficient manufacturing suitability of the above-described conventional infrared cut filter can be improved.
- the curable resin composition for forming a high refractive index layer or a low refractive index layer according to the present invention produces a camera module having a substrate and an infrared cut filter disposed on the light receiving side of the substrate. Suitable for doing.
- the curable resin composition for infrared reflective film formation which can form the infrared reflective film which has an infrared rays light-shielding property without vapor deposition, the infrared reflective film obtained by it, its manufacturing method, and a near infrared ray
- An infrared cut filter having light shielding properties and infrared light shielding properties can be provided.
- the curable resin composition by using the curable resin composition, the infrared cut filter and the surface of the substrate in the solid-state imaging device can be brought into close contact with each other without interposing a space, thereby suppressing color shading.
- a solid-state imaging device can be provided.
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Abstract
Description
このような赤外線カットフィルタとして、誘電体多層膜を用いたタイプのものと、赤外線吸収剤を用いたタイプのものが知られている。
誘電体多層膜を用いたタイプの赤外線カットフィルタとしては、例えば、基材として青ガラス基板を用いた赤外線カットフィルタ等が知られている。
また、赤外線吸収剤を用いたタイプとしては、構成材料の大部分がガラスとされた赤外線カットフィルタが主に知られている。
例えば、特許文献2等には、特定の銅錯体を使用した近赤外線吸収フィルタが開示されている。
しかしながら、青ガラス基板は脆く、例えば、固体撮像素子の製造に青ガラス基板を用いた赤外線カットフィルタを用いる場合、ダイシング等を行うことができないなどの製造適性に劣る等の問題があった。
そこで、青ガラス基板を用いないで、青ガラス基板を用いた場合と同等以上の近赤外線及び赤外線遮光性を有し、かつ蒸着によらない赤外線反射膜を有する赤外線カットフィルタの開発が検討されてきている。
また、固体撮像素子における基板の表面と、赤外線カットフィルタとが空間を挟んで相対していると、固体撮像素子が受光した光の入射角依存性が大きくなり、カラーシェーディングが問題になることがあった。
〔1〕
50~250nmの膜厚で塗布可能な、屈折率1.65~2.00の赤外線反射膜形成用の硬化性樹脂組成物。
〔2〕
上記屈折率1.65~2.00の赤外線反射膜形成用の硬化性樹脂組成物が、金属酸化物粒子、バインダー及び分散剤を含有する、〔1〕に記載の赤外線反射膜形成用の硬化性樹脂組成物。
〔3〕
50~250nmの膜厚で塗布可能な、屈折率1.20~1.45の赤外線反射膜形成用の硬化性樹脂組成物。
〔4〕
上記屈折率1.20~1.45の赤外線反射膜形成用の硬化性樹脂組成物が、シロキサン樹脂を含有する、〔3〕に記載の赤外線反射膜形成用の硬化性樹脂組成物。
〔5〕
支持体上に、屈折率1.65~2.00の赤外線反射膜形成用の硬化性樹脂組成物を塗布してなる膜厚50~250nmの高屈折率層を2層以上と、
屈折率1.20~1.45の赤外線反射膜形成用の硬化性樹脂組成物を塗布してなる膜厚50~250nmの低屈折率層を2層以上とを有する赤外線反射膜。
〔6〕
上記高屈折率層と、上記低屈折率層とが交互に積層している、〔5〕に記載の赤外線反射膜。
〔7〕
前記屈折率1.65~2.00の赤外線反射膜形成用の硬化性樹脂組成物と、前記屈折率1.20~1.45の赤外線反射膜形成用の硬化性樹脂組成物とのいずれか一方が水ないしは親水性溶剤を含有する組成物であり、他方が疎水性溶剤を含有する組成物である、〔5〕に記載の赤外線反射膜。
〔8〕
上記水ないしは親水性溶剤を含有する組成物がフッ素原子含有化合物を含有し、上記疎水性溶剤を含有する組成物が表面エネルギー調整剤を含有する、〔7〕に記載の赤外線反射膜。
〔9〕
上記2層以上の高屈折率層が、屈折率1.65~2.00の範囲内で互いに異なる屈折率を有する複数種の層である、〔5〕~〔8〕のいずれか1項に記載の赤外線反射膜。
上記2層以上の高屈折率層が、膜厚50~250nmの範囲内で互いに異なる膜厚を有する複数種の層である、〔5〕~〔9〕のいずれか1項に記載の赤外線反射膜。
〔11〕
上記2層以上の低屈折率層が、屈折率1.20~1.45の範囲内で互いに異なる屈折率を有する複数種の層である、〔5〕~〔10〕のいずれか1項に記載の赤外線反射膜。
〔12〕
上記2層以上の低屈折率層が、膜厚50~250nmの範囲内で互いに異なる膜厚を有する複数種の層である、〔5〕~〔11〕のいずれか1項に記載の赤外線反射膜。
〔13〕
上記2層以上の高屈折率層と、上記2層以上の低屈折率層との積層数が4~60層である、〔5〕~〔12〕のいずれか1項に記載の赤外線反射膜。
〔14〕
膜厚50~250nmで屈折率1.65~2.00の高屈折率層を、硬化性樹脂組成物を用いて形成する工程、及び
膜厚50~250nmで屈折率1.20~1.45の低屈折率層を、硬化性樹脂組成物を用いて形成する工程を有し、
前記赤外線反射膜が2層以上の高屈折率層と2層以上の低屈折率層とを有する赤外線反射膜の製造方法。
〔15〕
上記高屈折率層を形成する工程と、上記低屈折率層を形成する工程とを交互に行い、上記高屈折率層と上記低屈折率層とを交互に積層させる、〔14〕に記載の赤外線反射膜の製造方法。
〔16〕
〔5〕~〔13〕のいずれか1項に記載の赤外線反射膜と600nm~820nmの範囲内に極大吸収波長を有する色素又は銅錯体を含有する層とを有する赤外線カットフィルタ。
〔17〕
上記600nm~820nmの範囲内に極大吸収波長を有する色素又は銅錯体がシアニン系色素、フタロシアニン系色素、アミニウム系色素、イミニウム系色素、アゾ系色素、アンスラキノン系色素、ジイモニウム系色素、スクアリリウム系色素、ポルフィリン系色素及び銅錯体からなる群から選択される少なくとも1種である、〔16〕に記載の赤外線カットフィルタ。
〔18〕
基板上に、〔16〕又は〔17〕に記載の赤外線カットフィルタを有する固体撮像素子。
〔19〕
上記基板がカラーフィルタ層を有する、〔18〕に記載の固体撮像素子。
また、本発明によれば、上記硬化性樹脂組成物を用いることにより、赤外線カットフィルタと、固体撮像素子における基板の表面とを空間を挟まずに密着させることができ、これによりカラーシェーディングが抑制された固体撮像素子を提供することができる。
また、本発明は、50~250nmの膜厚で塗布可能な、屈折率1.20~1.45の赤外線反射膜形成用の硬化性樹脂組成物(以下、単に「低屈折率層形成用の硬化性樹脂組成物」ということもある。)に関するものでもある。
本発明の硬化性樹脂組成物はいずれも、熱硬化性の樹脂組成物であってもよいし、光硬化性の樹脂組成物であってもよい。
また、本発明は、膜厚50~250nmで屈折率1.65~2.00の高屈折率層を硬化性樹脂組成物を用いて形成する工程、及び
膜厚50~250nmで屈折率1.20~1.45の低屈折率層を硬化性樹脂組成物を用いて形成する工程を有し、
前記赤外線反射膜が2層以上の高屈折率層と2層以上の低屈折率層とを有する赤外線反射膜の製造方法に関するものでもある。
本発明の赤外線反射膜の製造方法において、上記高屈折率層を形成する工程と、上記低屈折率層を形成する工程とを交互に行い、上記高屈折率層と上記低屈折率層とを交互に積層させることが好ましい。
そして、本発明は、図1に示すような、屈折率1.65~2.00の高屈折率層2を2層以上と、屈折率1.20~1.45の低屈折率層3を2層以上とを有する赤外線反射膜1に関するものでもある。
本発明の赤外線反射膜において、上記高屈折率層と、上記低屈折率層とが交互に積層していることが好ましい。
これにより、高屈折率層形成用又は低屈折率層形成用の硬化性樹脂組成物を塗布後、各層ごとに乾燥工程を経ないでも、上記高屈折率層形成用の組成物と、上記低屈折率層形成用の組成物とを交互に塗布して乾燥しないで積層しても、高屈折率層形成用の組成物と、低屈折率層形成用の組成物とが混じり合うことを防止することができる。これにより、高屈折率層と、低屈折率層とを塗布により交互に積層した後、一括して乾燥することにより、高屈折率層と、上記低屈折率層とが交互に積層している赤外線反射膜を製造することができる。
同様の観点から、上記疎水性溶剤を含有する組成物が表面エネルギー調整剤を含有することが好ましい。
高屈折率層形成用の硬化性樹脂組成物は、(A)金属酸化物粒子、(B)分散剤及び(C)バインダーを含有することが好ましい。
金属酸化物粒子としては、屈折率の高い無機粒子であり、チタン(Ti)、ジルコニウム(Zr)、アルミニウム(Al)、ケイ素(Si)、亜鉛(Zn)又はマグネシウム(Mg)の酸化物粒子が挙げられ、二酸化チタン(TiO2)粒子、二酸化ジルコニウム(ZrO2)粒子又は二酸化珪素(SiO2)粒子であることが好ましく、中でも二酸化チタン粒子(以下、単に「二酸化チタン」ということもある)であることがより好ましい。
無色又は透明な二酸化チタン粒子としては、化学式TiO2で表すことができ、純度が70%以上であることが好ましく、純度80%以上であることがより好ましく、純度85%以上であることが更に好ましい。一般式TinO2n-1(nは2~4の数を表す。)で表される低次酸化チタン、酸窒化チタン等は30質量%以下であることが好ましく、20質量%以下であることがより好ましく、15質量%以下であることが更に好ましい。また、二酸化チタン粒子としては、ルチル形結晶のものが好ましい。
前記金属酸化物粒子の一次粒子径は1nm~100nmが好ましいが、1nm~80nmであることがより好ましく、1nm~50nmであることが特に好ましい。金属酸化物粒子の一次粒子径が100nmを超えると屈折率及び透過率が低下することがある。また1nm未満の場合には、凝集により分散性や分散安定性が低下する場合がある。
金属酸化物粒子の平均粒子径は、後記実施例で採用した測定方法によるものとする。
また金属酸化物粒子の比表面積は、10m2/g~400m2/gであることが好ましく、20m2/g~200m2/gであることが更に好ましく、30m2/g~150m2/gであることが最も好ましい。
また金属酸化物粒子の形状には特に制限はない。例えば、米粒状、球形状、立方体状、紡錘形状あるいは不定形状であることができる。
表面処理は、1種単独の表面処理剤でも、2種類以上の表面処理剤を組み合わせて実施してもよい。
また金属酸化物粒子の表面が、アルミニウム、ケイ素、ジルコニアなどの酸化物により処理されていることもまた好ましい。これにより、耐候性が向上する。
二酸化チタン粒子の市販物としては、例えば石原産業(株)製TTOシリーズ(TTO-51(A)、TTO-51(C)、TTO-55(C)など)、TTO-S、Vシリーズ(TTO-S-1、TTO-S-2、TTO-V-3など)、テイカ(株)製MTシリーズ(MT-01、MT-05など)などを挙げることができる。
二酸化ジルコニウム粒子の市販物としては、例えば、UEP(第一稀元素化学工業(株)製)、PCS(日本電工(株)製)、JS-01、JS-03、JS-04(日本電工(株)製)、UEP-100(第一稀元素化学工業(株)製)などを挙げることができる。
二酸化珪素粒子の市販物としては、例えば、OG502-31クラリアント社(Clariant Co.)製などを挙げることができる。
金属酸化物粒子は、1種単独でも、2種以上を組み合わせて用いてもよい。
また、金属酸化物粒子の含有量が、高屈折率層形成用の硬化性樹脂組成物の全固形分に対して90質量%を超えると、充分な量の分散剤を存在させにくい等の理由から、分散性及び分散安定性が損なわれやすい。更に、硬化性組成物が大サイズ(例えば12インチ)のウエハーに塗布した場合に、ウエハーの中心部と周辺部での膜厚差が小さい膜を形成しにくくなる。
高屈折率層形成用の硬化性樹脂組成物に用いられる分散剤として、下記一般式(1)で表される高分子分散剤であることが好ましい。
R1は、(m+n)価の連結基を表し、R2は単結合又は2価の連結基を表す。A1は酸基、ウレア基、ウレタン基、配位性酸素原子を有する基、塩基性窒素原子を有する基、複素環基、アルキルオキシカルボニル基、アルキルアミノカルボニル基、カルボン酸塩基、スルホンアミド基、アルコキシシリル基、エポキシ基、イソシアネート基及び水酸基よりなる群から選択される基を少なくとも1種有する1価の置換基を表す。n個のA1及びR2は、それぞれ、同一であっても、異なっていてもよい。
mは8以下の正の数、nは1~9を表し、m+nは3~10を満たす。
P1はポリマー鎖を表す。m個のP1は、同一であっても、異なっていてもよい。
前記A1は、酸基、塩基性窒素原子を有する基、ウレア基、ウレタン基、配位性酸素原子を有する基、アルキルオキシカルボニル基、アルキルアミノカルボニル基、カルボン酸塩基、スルホンアミド基、アルコキシシリル基、エポキシ基、イソシアネート基及び水酸基のような金属酸化物粒子(A)に対する吸着能を有する官能基、複素環構造のような金属酸化物粒子(A)に対する吸着能を有し得る構造を少なくとも1種有する1価の置換基を表す。
なお、以下、この金属酸化物粒子(A)に対する吸着能を有する部位(上記官能基及び構造)を、適宜、「吸着部位」と総称して、説明する。
また、本発明において、「吸着部位を少なくとも1種有する1価の置換基」は、前述の吸着部位と、1から200個までの炭素原子、0個から20個までの窒素原子、0個から100個までの酸素原子、1個から400個までの水素原子、及び0個から40個までの硫黄原子から成り立つ連結基とが結合してなる1価の置換基である。なお、吸着部位自体が1価の置換基を構成しうる場合には、吸着部位そのものがA1で表される1価の置換基であってもよい。
まず、前記A1を構成する吸着部位について以下に説明する。
前記「ウレア基」として、例えば、-NR15CONR16R17(ここで、R15、R16、及びR17は各々独立に、水素原子、炭素数1から20までのアルキル基、炭素数6以上のアリール基、又は炭素数7以上のアラルキル基を表す。)が好ましい例として挙げられ、-NR15CONHR17(ここで、R15及びR17は各々独立に、水素原子あるいは、炭素数1から10までのアルキル基、炭素数6以上のアリール基、炭素数7以上のアラルキル基を表す。)がより好ましく、-NHCONHR17(ここで、R17は水素原子あるいは、炭素数1から10までのアルキル基、炭素数6以上のアリール基、炭素数7以上のアラルキル基を表す。)が特に好ましい。
前記「ウレタン基」として、例えば、-NHCOOR18、-NR19COOR20、-OCONHR21、-OCONR22R23(ここで、R18、R19、R20、R21、R22及びR23は各々独立に、炭素数1から20までのアルキル基、炭素数6以上のアリール基、炭素数7以上のアラルキル基を表す。)などが好ましい例として挙げられ、-NHCOOR18、-OCONHR21(ここで、R18、R21は各々独立に、炭素数1から20までのアルキル基、炭素数6以上のアリール基、炭素数7以上のアラルキル基を表す。)などがより好ましく、-NHCOOR18、-OCONHR21(ここで、R18、R21は各々独立に、炭素数1から10までのアルキル基、炭素数6以上のアリール基、炭素数7以上のアラルキル基を表す。)などが特に好ましい。
前記「配位性酸素原子を有する基」としては、例えば、アセチルアセトナト基、クラウンエーテルなどが挙げられる。
式(a2)中、R13及びR14は各々独立に、炭素数1から20までのアルキル基、炭素数6以上のアリール基、炭素数7以上のアラルキル基を表す。
特に、アミノ基(-NH2)、置換イミノ基(-NHR8、-NR9R10、ここで、R8、R9、及びR10は各々独立に、炭素数1から5までのアルキル基、フェニル基、ベンジル基を表す。)、前記式(a1)で表されるグアニジル基〔式(a1)中、R11及びR12は各々独立に、炭素数1から5までのアルキル基、フェニル基、ベンジル基を表す。〕、前記式(a2)で表されるアミジニル基〔式(a2)中、R13及びR14は各々独立に、炭素数1から5までのアルキル基、フェニル基、ベンジル基を表す。〕などが好ましく用いられる。
前記「アルキルオキシカルボニル基」におけるアルキル基部分としては、炭素数1から20までのアルキル基であることが好ましく、例えば、メチル基、エチル基等が挙げられる。
前記「アルキルアミノカルボニル基」におけるアルキル基部分としては、炭素数1から20までのアルキル基であることが好ましく、例えば、メチル基、エチル基、プロピル基等が挙げられる。
前記「カルボン酸塩基」としては、カルボン酸のアンモニウム塩からなる基などが挙げられる。
前記「スルホンアミド基」としては、窒素原子に結合する水素原子がアルキル基(メチル基等)、アシル基(アセチル基、トリフルオロアセチル基など)等で置換されていてもよい。
前記「エポキシ基」としては、置換又は無置換のオキシラン基(エチレンオキシド基)が挙げられる。
特に、金属酸化物粒子(A)との相互作用を良好にし、屈折率を向上し、かつ組成物の粘度を低減する観点から、A1は、pKa5~14の官能基を少なくとも1種有する1価の置換基であることがより好ましい。
ここでいう「pKa」とは、化学便覧(II)(改訂4版、1993年、日本化学会編、丸善株式会社)に記載されている定義のものである。
上記pKa5~14の官能基としては、ウレア基、ウレタン基、スルホンアミド基、イミド基又は配位性酸素原子を有する基が挙げられる。
具体的には、例えば、ウレア基(pKa 12~14程度)、ウレタン基(pKa 11~13程度)、配位性酸素原子としての-COCH2CO-(pKa 8~10程度)、スルホンアミド基(pKa 9~11程度)等が挙げられる。
中でも、酸基、ウレア基、ウレタン基、スルホンアミド基、イミド基又は配位性酸素原子を有する基であることが好ましく、pKa5~14の官能基であることがより好ましい観点から、ウレア基、ウレタン基、スルホンアミド基、イミド基又は配位性酸素原子を有する基であることがより好ましい。
(a+1)価の連結基としては、1から100個までの炭素原子、0個から10個までの窒素原子、0個から50個までの酸素原子、1個から200個までの水素原子、及び0個から20個までの硫黄原子から成り立つ基が含まれ、無置換でも置換基を更に有していてもよい。
2価の連結基としては、1から100個までの炭素原子、0個から10個までの窒素原子、0個から50個までの酸素原子、1個から200個までの水素原子、及び0個から20個までの硫黄原子から成り立つ基が含まれ、無置換でも置換基を更に有していてもよい。
前記R1で表される(m+n)価の連結基としては、1から100個までの炭素原子、0個から10個までの窒素原子、0個から50個までの酸素原子、1個から200個までの水素原子、及び0個から20個までの硫黄原子から成り立つ基が含まれ、無置換でも置換基を更に有していてもよい。
前記一般式(1)中、mは8以下の正の数を表す。mとしては、0.5~5が好ましく、1~4がより好ましく、1~3が特に好ましい。
また、前記一般式(1)中、nは1~9を表す。nとしては、2~8が好ましく、2~7がより好ましく、3~6が特に好ましい。
ポリマーの中でも、ポリマー鎖を構成するには、ビニルモノマーの重合体若しくは共重合体、エステル系ポリマー、エーテル系ポリマー、ウレタン系ポリマー、アミド系ポリマー、エポキシ系ポリマー、シリコーン系ポリマー、及びこれらの変性物、又は共重合体〔例えば、ポリエーテル/ポリウレタン共重合体、ポリエーテル/ビニルモノマーの重合体の共重合体など(ランダム共重合体、ブロック共重合体、グラフト共重合体のいずれであってもよい。)を含む。〕からなる群より選択される少なくとも一種が好ましく、ビニルモノマーの重合体若しくは共重合体、エステル系ポリマー、エーテル系ポリマー、ウレタン系ポリマー、及びこれらの変性物又は共重合体からなる群より選択される少なくとも一種がより好ましく、ビニルモノマーの重合体若しくは共重合体が特に好ましい。
ポリマー鎖P1における、前記少なくとも1種の繰り返し単位の繰り返し数kが、立体反発力を発揮し分散性を向上する観点から、3以上であることが好ましく、5以上であることがより好ましい。
また、前記一般式(1)で表される分散剤の嵩張りを抑え、白色硬化膜中に二酸化チタン粒子(D)を密に存在させる観点から、前記少なくとも1種の繰り返し単位の繰り返し単位数kは、50以下であることが好ましく、40以下であることがより好ましく、30以下であることが更に好ましい。
なお、A2は、前記一般式(1)における前記A1と同義であり、好ましい態様も同様である。
R4、R5で表される2価の連結基としては、前記一般式(1)のR2で表される2価の連結基として挙げられたものと同様のものが用いられ、好ましい態様も同様である。
前記R3で表される(m+n)価の連結基としては、1から60個までの炭素原子、0個から10個までの窒素原子、0個から50個までの酸素原子、1個から100個までの水素原子、及び0個から20個までの硫黄原子から成り立つ基が含まれ、無置換でも置換基を更に有していてもよい。
前記R3で表される(m+n)価の連結基として、具体的には、前記一般式(1)のR1で表される(m+n)価の連結基として挙げられたものと同様のものが用いられ、好ましい態様も同様である。
また、前記一般式(2)中、nは1~9を表す。nとしては、2~8が好ましく、2~7がより好ましく、3~6が特に好ましい。
R3:前記具体例(1)、(2)、(10)、(11)、(16)、又は(17)
R4:単結合、又は、下記の構造単位若しくは該構造単位が組み合わさって構成される「1から10個までの炭素原子、0個から5個までの窒素原子、0個から10個までの酸素原子、1個から30個までの水素原子、及び0個から5個までの硫黄原子」から成り立つ2価の連結基(置換基を有していてもよく、該置換基としては、例えば、メチル基、エチル基等の炭素数1から20までのアルキル基、フェニル基、ナフチル基等の炭素数6から16までのアリール基、水酸基、アミノ基、カルボキシル基、スルホンアミド基、N-スルホニルアミド基、アセトキシ基等の炭素数1から6までのアシルオキシ基、メトキシ基、エトキシ基等の炭素数1から6までのアルコキシ基、塩素、臭素等のハロゲン原子、メトキシカルボニル基、エトキシカルボニル基、シクロヘキシルオキシカルボニル基等の炭素数2から7までのアルコキシカルボニル基、シアノ基、t-ブチルカーボネート等の炭酸エステル基等が挙げられる。)
なお、下記基中、R12は水素原子又はメチル基を表し、lは1又は2を表す。
m:1~3
n:3~6
なお、酸価の下限値としては特に制限はないが、二酸化チタン粒子の分散安定性の観点から、5mgKOH/g以上であることが好ましく、10mgKOH/g以上であることがより好ましい。
本発明において、前記一般式(1)又は(2)で表される分散剤の酸価は、例えば、前記一般式(1)又は(2)で表される分散剤中における酸基の平均含有量から算出することができる。
前記一般式(1)又は(2)で表される分散剤の分子量としては、重量平均分子量で、1000~50000が好ましく、3000~30000がより好ましく、3000~20000が特に好ましい。重量平均分子量が前記範囲内であると、ポリマーの末端に導入された複数の前記吸着部位の効果が十分に発揮され、二酸化チタン粒子表面への吸着性に優れた性能を発揮し得る。
前記一般式(1)又は(2)で表される分散剤の具体例としては、特開2007-277514号公報の段落0316以降に開示されている高分子化合物C-1~C-57が挙げられる。
前記一般式(1)又は(2)で表される分散剤は、特に制限されないが、特開2007-277514号公報段落0114~0140及び0266~0348に記載の合成方法に準じて合成することができる。
(以下、「特定樹脂2」ともいう)であることも好ましい。前記グラフト共重合体は、水素原子を除いた原子数が40~10000の範囲であるグラフト鎖を有している。この場合のグラフト鎖とは、共重合体の主鎖の根元(主鎖から枝分かれしている基において主鎖に結合する原子)から、主鎖から枝分かれしている基の末端までを示す。分散組成物において、この特定樹脂は、金属酸化物粒子に分散性を付与する分散樹脂であり、グラフト鎖による溶媒との親和性を有するために、金属酸化物粒子の分散性、及び、経時後の分散安定性に優れる。また、分散組成物としたとき、グラフト鎖と溶媒とが良好な相互作用を示すことにより、塗布膜における膜厚の均一性が悪化することが抑制されるものと考えられる。
W1、W2、W3、及び、W4はそれぞれ独立に酸素原子或いはNHを表し、特に酸素原子が好ましい。
n、m、p、及び、qはそれぞれ1~500の整数である。
j及びkは、それぞれ独立に、2~8の整数を表す。
j及びkは、分散安定性の観点から、4~6の整数が好ましく、5が最も好ましい。
式(2A)中、X2、Y2、Z2及びmは、式(2)におけるX2、Y2、Z2及びmと同義であり、好ましい範囲も同様である。
また、酸基を有する構造単位の含有量が上記範囲内であることにより、特定樹脂の酸価を下記の好ましい範囲内に好適に調整できる。
特定樹脂2は、塩基性基を有する構造単位(繰り返し単位)を含有してもしなくても良いが、含有する場合、塩基性基を有する構造単位の含有量は、特定樹脂の総質量に対し0.1質量%以上50質量%以下であり、特に好ましくは、0.1質量%以上30質量%以下である。
特定樹脂は、配位性基又は反応性を有する基を有する構造単位(繰り返し単位)を含有してもしなくても良いが、含有する場合、配位性基又は反応性を有する基を有する構造単位の含有量は、特定樹脂の総質量に対し好ましくは、0.1質量%以上50質量%以下であり、特に好ましくは、0.1質量%以上30質量%以下である。
特定樹脂3としては、前記部分構造X等と対をなす部分構造Wを有していてもよく、部分構造WはpKb14以下の窒素原子を有する構造部であることが好ましく、pKb10以下の窒素原子を有する構造を含有することがより好ましい。塩基強度pKbとは、水温25℃でのpKbをいい、塩基の強さを定量的に表すための指標のひとつであり、塩基性度定数と同義である。塩基強度pKbと、後述の酸強度pKaとは、pKb=14-pKaの関係にある。なお、部分構造Xと部分構造Wとが対になって塩構造を形成しているときには、それぞれが解離した構造を想定し、そこにプロトン(H+)ないし水酸化物イオン(OH-)がイオン結合した化合物として、そのpKa及びpKbを評価する。部分構造Xについては、更にその詳細を後記にて説明する。
部分構造Xについてその好ましい範囲の詳細は後述する部分構造Xと同義である。また、前記側鎖Yについても、同様に、その好ましい範囲の詳細は後述する側鎖Yと同義である。上記Wは、側鎖Yの連結部が解離しイオン結合性の部位となった構造であることが好ましい。
特定分散樹脂(B1)は、前記繰り返し単位(i)を有する。これにより、粒子表面へ分散樹脂の吸着力が向上し、かつ粒子間の相互作用が低減できる。ポリ(低級アルキレンイミン)は鎖状であっても網目状であってもよい。ここで、低級アルキレンイミンとは、炭素数1~5のアルキレン鎖を含むアルキレンイミンを意味する。前記繰り返し単位(i)は、特定分散樹脂における主鎖部を形成することが好ましい。該主鎖部の数平均分子量、すなわち、特定分散樹脂(B1)から前記側鎖Y部分を含む側鎖を除いた部分の数平均分子量は、100~10,000が好ましく、200~5,000が更に好ましく、300~2,000が最も好ましい。主鎖部の数平均分子量は、GPC法によるポリスチレン換算値により測定することができる。
特定分散樹脂(B1)としては、下記式(I-1)で表される繰り返し単位及び式(I-2)で表される繰り返し単位、又は、式(I-1)で表される繰り返し単位及び式(I-2a)で表される繰り返し単位を含む分散樹脂であることが好ましい。
R8及びR9はR1と同義の基である。
Lは単結合、アルキレン基(炭素数1~6が好ましい)、アルケニレン基(炭素数2~6が好ましい)、アリーレン基(炭素数6~24が好ましい)、ヘテロアリーレン基(炭素数1~6が好ましい)、イミノ基(炭素数0~6が好ましい)、エーテル基、チオエーテル基、カルボニル基、又はこれらの組合せに係る連結基である。なかでも、単結合若しくは-CR5R6-NR7-(イミノ基がX若しくはYの方になる)であることが好ましい。ここで、R5R6は各々独立に、水素原子、ハロゲン原子、アルキル基(炭素数1~6が好ましい)を表す。R7は水素原子又は炭素数1~6のアルキル基である。
LaはCR8CR9とNとともに環構造形成する構造部位であり、CR8CR9の炭素原子と合わせて炭素数3~7の非芳香族複素環を形成する構造部位であることが好ましい。更に好ましくはCR8CR9の炭素原子及びN(窒素原子)を合わせて5~7員の非芳香族複素環を形成する構造部位であり、より好ましくは5員の非芳香族複素環を形成する構造部位であり、ピロリジンを形成する構造部位であることが特に好ましい。ただし、当該構造部位は更にアルキル基等の置換基を有していてもよい。
XはpKa14以下の官能基を有する基を表す。
Yは原子数40~10,000の側鎖を表す。
なお、上記式(I-2)の共重合比に関する説明は、式(I-2a)、式(I-4)、式(I-5)で表される繰り返し単位についても同義であり、両者を含むときにはその総量を意味する。
上記各式中の部分構造Xは、水温25℃でのpKaが14以下の官能基を有する。ここでいう「pKa」とは、化学便覧(II)(改訂4版、1993年、日本化学会編、丸善株式会社)に記載されている定義のものである。「pKa14以下の官能基」は、物性がこの条件を満たすものであれば、その構造などは特に限定されず、公知の官能基でpKaが上記範囲を満たすものが挙げられるが、特にpKaが12以下である官能基が好ましく、pKaが11以下である官能基が特に好ましい。下限値は特にないが、-5以上であることが実際的である。部分構造Xとして具体的には、例えば、カルボン酸基(pKa:3~5程度)、スルホン酸(pKa:-3~-2程度)、-COCH2CO-(pKa:8~10程度)、-COCH2CN(pKa:8~11程度)、-CONHCO-、フェノール性水酸基、-RFCH2OH又は-(RF)2CHOH(RFはペルフルオロアルキレン基若しくはペルフルオロアルキル基を表す。pKa:9~11程度)、スルホンアミド基(pKa:9~11程度)等が挙げられ、特にカルボン酸基(pKa:3~5程度)、スルホン酸基(pKa:-3~-2程度)、-COCH2CO-(pKa:8~10程度)が好ましい。
d及びeは、それぞれ独立して0又は1を表す。
Qはアシル基又はアルコキシカルボニル基を表す。
また、生産性の観点から、dは1が好ましく、また、eは0が好ましい。
・側鎖Y
Yとしては、特定分散樹脂(B1)の主鎖部と連結できるポリエステル、ポリアミド、ポリイミド、ポリ(メタ)アクリル酸エステル等の公知のポリマー鎖が挙げられる。Yにおける特定分散樹脂(B1)との結合部位は、側鎖Yの末端であることが好ましい。
Yは、前記塩基性窒素原子を有する繰り返し単位の前記窒素原子とアミド結合、又はカルボン酸塩としてイオン結合していることが好ましい。
また、Yの数平均分子量はGPC法によるポリスチレン換算値により測定することができる。このとき、Yは樹脂に組み込む前の状態でその分子量を測定することが実際的である。Yの数平均分子量は、特に1,000~50,000が好ましく、1,000~30,000が分散性・分散安定性・現像性の観点から最も好ましい。Yの分子量は、Yの原料となる高分子化合物から特定することができ、その測定方法は後記GPCによる測定条件に順ずるものとする。
Yで示される側鎖構造は、主鎖連鎖に対し、樹脂1分子中に、2つ以上連結していることが好ましく、5つ以上連結していることが特に好ましい。
ZBは、水素原子又は1価の有機基を表す。ZBが有機基であるとき、アルキル基(好ましくは炭素数1~30)、アリール基、複素環基などが好ましい。ZBは更に置換基を有していてもよく、当該置換基としては、炭素数6~24のアリール基、炭素数3~24の複素環基が挙げられる。
LBは、アルキレン基(炭素数1~6が好ましい)、アルケニレン基(炭素数2~6が好ましい)、アリーレン基(炭素数6~24が好ましい)、ヘテロアリーレン基(炭素数1~6が好ましい)、イミノ基(炭素数0~6が好ましい)、エーテル基、チオエーテル基、カルボニル基、又はこれらの組合せに係る連結基である。なかでも、アルキレン基(炭素数1~6が好ましい)、エーテル基、カルボニル基、又はこれらの組合せに係る連結基であることが好ましい。アルキレン基は分岐でも直鎖であってもよい。アルキレン基は置換基を有していてもよく、好ましい置換基としては、アルキル基(好ましい炭素数1~6)、アシル基(好ましい炭素数2~6)、アルコキシ基(好ましい炭素数1~6)、又はアルコキシカルボニル基(好ましい炭素数2~8)である。nBは5~100,000の整数である。nB個のLBはそれぞれ異なる構造であってもよい。
前記特定分散樹脂3の分子量としては、重量平均分子量で、3,000~100,000であることが好ましく、5,000~55,000重量平均分子量が前記範囲内であると、ポリマーの末端に導入された複数の前記吸着部位の効果が十分に発揮され、二酸化チタン粒子表面への吸着性に優れた性能を発揮し得る。なお、本明細書において、GPCは、特に断らない限り、HLC-8020GPC(東ソー(株)製)を用い、カラムをTSKgel SuperHZM-H、TSKgel SuperHZ4000、TSKgel SuperHZ200(東ソー社製)として測定した。キャリアは適宜選定すればよいが、溶解可能であるかぎり、テトラヒドロフランを用いることした。
高屈折率層形成用の硬化性樹脂組成物において、分散剤は、1種単独で、あるいは2種以上を組み合わせて用いることができる。
高屈折率層形成用の硬化性樹脂組成物には、金属酸化物粒子の分散性を調整する等の目的で、上記特定樹脂以外の分散樹脂(以下、「その他の分散樹脂」と称する場合がある)が含有されていてもよい。
本発明に用いることができるその他の分散樹脂としては、高分子分散剤〔例えば、ポリアミドアミンとその塩、ポリカルボン酸とその塩、高分子量不飽和酸エステル、変性ポリウレタン、変性ポリエステル、変性ポリ(メタ)アクリレート、(メタ)アクリル系共重合体、ナフタレンスルホン酸ホルマリン縮合物〕、及び、ポリオキシエチレンアルキルリン酸エステル、ポリオキシエチレンアルキルアミン、アルカノールアミン、顔料誘導体等を挙げることができる。
その他の分散樹脂は、その構造から更に直鎖状高分子、末端変性型高分子、グラフト型高分子、ブロック型高分子に分類することができる。
これらのその他の樹脂は、単独で使用してもよく、2種以上を組み合わせて使用してもよい。
高屈折率層用の硬化性樹脂組成物は、皮膜特性向上などの観点から、更にバインダー(C)を含むことが好ましい。
前記バインダー(以下、バインダーポリマーともいう)としてはカルボキシル基を有するモノマーを単独あるいは共重合させた樹脂、酸無水物を有するモノマーを単独あるいは共重合させ酸無水物ユニットを加水分解若しくはハーフエステル化若しくはハーフアミド化させた樹脂、エポキシ樹脂を不飽和モノカルボン酸及び酸無水物で変性させたエポキシアクリレート等が挙げられる。カルボキシル基を有するモノマーとしては、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、マレイン酸、フマル酸、4-カルボキシルスチレン等があげられ、酸無水物を有するモノマーとしては、無水マレイン酸等が挙げられる。
また、同様に側鎖にカルボン酸基を有する酸性セルロース誘導体がある。この他に水酸基を有する重合体に環状酸無水物を付加させたものなどが有用である。
(2)アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸イソブチル、アクリル酸アミル、アクリル酸ヘキシル、アクリル酸2-エチルヘキシル、アクリル酸オクチル、アクリル酸ベンジル、アクリル酸-2-クロロエチル、グリシジルアクリレート、3,4-エポキシシクロヘキシルメチルアクリレート、ビニルアクリレート、2-フェニルビニルアクリレート、1-プロペニルアクリレート、アリルアクリレート、2-アリロキシエチルアクリレート、プロパルギルアクリレート等のアルキルアクリレート。
(4)アクリルアミド、メタクリルアミド、N-メチロールアクリルアミド、N-エチルアクリルアミド、N-ヘキシルメタクリルアミド、N-シクロヘキシルアクリルアミド、N-ヒドロキシエチルアクリルアミド、N-フェニルアクリルアミド、N-ニトロフェニルアクリルアミド、N-エチル-N-フェニルアクリルアミド、ビニルアクリルアミド、ビニルメタクリルアミド、N,N-ジアリルアクリルアミド、N,N-ジアリルメタクリルアミド、アリルアクリルアミド、アリルメタクリルアミド等のアクリルアミド若しくはメタクリルアミド。
(6)ビニルアセテート、ビニルクロロアセテート、ビニルブチレート、安息香酸ビニル等のビニルエステル類。
(7)スチレン、α-メチルスチレン、メチルスチレン、クロロメチルスチレン、p-アセトキシスチレン等のスチレン類。
(8)メチルビニルケトン、エチルビニルケトン、プロピルビニルケトン、フェニルビニルケトン等のビニルケトン類。
(9)エチレン、プロピレン、イソブチレン、ブタジエン、イソプレン等のオレフィン類。
(11)マレイミド、N-アクリロイルアクリルアミド、N-アセチルメタクリルアミド、N-プロピオニルメタクリルアミド、N-(p-クロロベンゾイル)メタクリルアミド等の不飽和イミド。
(12)α位にヘテロ原子が結合したメタクリル酸系モノマー。例えば、特開2002-309057号、特開2002-311569号等の各公報に記載の化合物を挙げる事ができる。
バインダーの市販品としては、例えば、富士フイルムファインケミカルズ社(FFFC社)製ベンジルメタクリレート/メタクリル酸共重合体(共重合比:80/20(質量%)、重量平均分子量:12,000)、アクリベース(ベンジルメタクリレート/i-ブチルメタクリレート/2-ヒドロキシエチルメタクリレート/メタクリル酸共重合体とメトキシポリエチレングリコールとのグラフト共重合物、藤倉化成(株)製)等が挙げられる。
また、一般式(ED)で表される化合物を含む単量体成分を重合してなる重合体が酸基を有する場合には、酸価が、好ましくは30~500mgKOH/g、より好ましくは50~400mgKOH/gであるのがよい。
一般式(ED)で表される化合物を含む単量体成分を重合してなる重合体の合成に適用される重合方法としては、特に制限はなく、従来公知の各種重合方法を採用することができるが、特に、溶液重合法によることが好ましい。詳細には、例えば、特開2004-300204号公報に記載されるポリマー(a)の合成方法に準じて、一般式(ED)で表される化合物を含む単量体成分を重合してなる重合体を合成することができる
本発明で用いる重合体は、重量平均分子量(GPC法で測定されたポリスチレン換算値)が1000~2×105であることが好ましく、2000~1×105であることがより好ましく、5000~5×104であることが更に好ましい。
また、欧州特許第993966号、欧州特許第1204000号、特開2001-318463号公報等に記載の酸基を有するアセタール変性ポリビニルアルコール系バインダーポリマーも、膜強度に優れており、好適である。
更にこの他に水溶性線状有機ポリマーとして、ポリビニルピロリドンやポリエチレンオキサイド等が有用である。また硬化皮膜の強度を上げるためにアルコール可溶性ナイロンや2,2-ビス-(4-ヒドロキシフェニル)-プロパンとエピクロロヒドリンのポリエーテル等も有用である。
これらのバインダーポリマーは、ランダムポリマー、ブロックポリマー、グラフトポリマー等いずれでもよい。
本実施形態の高屈折率層形成用硬化性組成物において用いうるバインダーポリマーを合成する際に用いられるラジカル重合開始剤としては、アゾ系開始剤、過酸化物開始剤等公知の化合物が挙げられる。
高屈折率層形成用の硬化性樹脂組成物において、バインダーは、1種単独で、あるいは2種以上を組み合わせて用いることができる。
また、高屈折率層形成用の硬化性樹脂組成物は、透明な組成物であることが好ましく、より具体的には、組成物により膜厚1.0μmの硬化膜である高屈折率層を形成した時、該硬化膜の厚み方向に対する光透過率が、400~700nmの波長領域全域に渡って90%以上となるような組成物である。
このような光透過率の物性は、高屈折率層形成用の硬化性樹脂組成物が、重合性化合物(D)及び重合開始剤(E)を含有する限りにおいて、どのような手段によって達成されても良いが、例えば、重合性化合物(D)や、更に添加され得るバインダー(C)の種類及び含有量の調整することにより、好適に達成される。また、金属酸化物粒子(A)の粒子径や、分散剤(B)の種類及び添加量を調整することによっても、上記光透過率の物性を好適に達成できる。
高屈折率層形成用の硬化性樹脂組成物及び高屈折率層に関し、高屈折率層として求められる特性を発現するために上記光透過率が、400~700nmの波長領域全域に渡って90%以上であることが好ましい。
(D)重合性化合物は、少なくとも1個のエチレン性不飽和二重結合、エポキシ基、オキセタニル基などの重合性基を有する付加重合性化合物であり、これらの重合性基を少なくとも1個、好ましくは2個以上有する化合物から選ばれる。このような化合物は当該技術分野において広く知られるものであり、本発明においてはこれらを特に限定無く用いることができる。
これらは、例えばモノマー、プレポリマー、すなわち2量体、3量体などの多量体及びオリゴマー、又はそれらの混合物並びにそれらの共重合体などの化学的形態をもつ。モノマー及びその共重合体の例としては、不飽和カルボン酸(例えば、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、イソクロトン酸、マレイン酸など)や、そのエステル類、アミド類が挙げられ、好ましくは、不飽和カルボン酸と脂肪族多価アルコール化合物とのエステル、不飽和カルボン酸と脂肪族多価アミン化合物とのアミド類が用いられる。また、ヒドロキシル基やアミノ基、メルカプト基等の求核性置換基を有する不飽和カルボン酸エステル類あるいは不飽和カルボン酸アミド類と単官能若しくは多官能イソシアネート類あるいはエポキシ類との付加反応物、及び単官能若しくは、多官能のカルボン酸との脱水縮合反応物等も好適に使用される。また、イソシアネート基や、エポキシ基等の親電子性置換基を有する不飽和カルボン酸エステルあるいは不飽和カルボン酸アミド類と単官能若しくは多官能のアルコール類、アミン類、チオール類との付加反応物;更にハロゲン基や、トシルオキシ基等の脱離性置換基を有する不飽和カルボン酸エステルあるいは不飽和カルボン酸アミド類と単官能若しくは多官能のアルコール類、アミン類、チオール類との置換反応物も好適である。また、別の例として、上記の不飽和カルボン酸の代わりに、不飽和ホスホン酸、スチレン、ビニルエーテル等に置き換えた化合物群を使用することも可能である。これらの具体的な化合物としては、特開2009-288705号公報の段落番号0095~段落番号0108に記載されている化合物を本発明においても好適に用いることができる。
(メタ)アクリロイル基を有する多官能アクリレート系化合物類は市販されているものを用いることもでき、新中村化学工業(株)NKエステル A-TMMT、同A-TMPT等を挙げることができる。
多官能カルボン酸にグリシジル(メタ)アクリレート等の環状エーテル基とエチレン性不飽和基を有する化合物を反応させ得られる多官能(メタ)アクリレートなども挙げることができる。
また、その他の好ましい重合性モノマー等として、特開2010-160418、特開2010-129825、特許4364216等に記載される、フルオレン環を有し、エチレン性重合性基を2官能以上有する化合物、カルドポリマーも使用することが可能である。
本発明で用いる重合性モノマーは、更に、特開2012-215806号公報段落0297~0300に記載の一般式(MO-1)~(MO-6)で表される重合性モノマーであることも好ましい。
一般式(MO-1)~(MO-6)で表される、ラジカル重合性モノマーの具体例としては、特開2007-269779号公報の段落番号0248~段落番号0251に記載されている化合物も本発明においても好適に用いることができる。
例えば、RP-1040(日本化薬株式会社製)などが挙げられる。
酸基を有する多官能モノマーの好ましい酸価としては、0.1~40mg-KOH/gであり、特に好ましくは5~30mg-KOH/gである。異なる酸基の多官能モノマーを2種以上併用する場合、或いは酸基を有しない多官能モノマーを併用する場合、全体の多官能モノマーとしての酸価が上記範囲に入るように調製することが必須である。
カプロラクトン変性構造を有する多官能性単量体としては、その分子内にカプロラクトン変性構造を有する限り特に限定されるものではないが、例えば、トリメチロールエタン、ジトリメチロールエタン、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、グリセリン、ジグリセロール、トリメチロールメラミン等の多価アルコールと、(メタ)アクリル酸及びε-カプロラクトンをエステル化することにより得られる、ε-カプロラクトン変性多官能(メタ)アクリレートを挙げることができる。なかでも下記式(1)で表されるカプロラクトン変性構造を有する多官能性単量体が好ましい。
このようなカプロラクトン変性構造を有する多官能性単量体は、例えば、日本化薬(株)からKAYARAD DPCAシリーズとして市販されており、DPCA-20(上記式(1)~(3)においてm=1、式(2)で表される基の数=2、R1が全て水素原子である化合物)、DPCA-30(同式、m=1、式(2)で表される基の数=3、R1が全て水素原子である化合物)、DPCA-60(同式、m=1、式(2)で表される基の数=6、R1が全て水素原子である化合物)、DPCA-120(同式においてm=2、式(2)で表される基の数=6、R1が全て水素原子である化合物)等を挙げることができる。
本発明において、カプロラクトン変性構造を有する多官能性単量体は、単独で又は2種以上を混合して使用することができる。
一般式(Z-4)、(Z-5)で表される重合性モノマー等の市販品としては、例えばサートマー社製のエチレンオキシ鎖を4個有する4官能アクリレートであるSR-494、日本化薬株式会社製のペンチレンオキシ鎖を6個有する6官能アクリレートであるDPCA-60、イソブチレンオキシ鎖を3個有する3官能アクリレートであるTPA-330などが挙げられる。
重合性モノマー等の市販品としては、ウレタンオリゴマーUAS-10、UAB-140(山陽国策パルプ社製)、UA-7200」(新中村化学社製、DPHA-40H(日本化薬社製)、UA-306H、UA-306T、UA-306I、AH-600、T-600、AI-600(共栄社製)などが挙げられる。
これらの化合物は、市販品を用いてもよいし、ポリマーの側鎖へエポキシ基を導入することによっても得られる。
(D)重合性化合物は、単独で、又は2種以上を併用して用いることができる。
この範囲内であると、屈折率を低下させることなく、硬化性が良好で好ましい。
高屈折率層形成用の硬化性樹脂組成物は、重合開始剤(E)を含有していても含有していなくてもよい。
(E)重合開始剤は、(D)重合性化合物の重合を開始、促進する化合物であり、45℃までは安定であるが高温加熱時の重合開始能が良好であることが好ましい。
また、前記重合開始剤は、約300nm~800nm(330nm~500nmがより好ましい。)の範囲内に少なくとも約50の分子吸光係数を有する化合物を、少なくとも1種含有していることが好ましい。
また、重合開始剤は、単独で、又は2種以上を併用して用いることができる。
ヘキサアリールビイミダゾール化合物としては、例えば、特公昭45-37377号公報、特公昭44-86516号公報記載のロフィンダイマー類、特公平6-29285号公報、米国特許第3,479,185号、同第4,311,783号、同第4,622,286号等の各明細書に記載の種々の化合物、具体的には、2,2’-ビス(o-クロロフェニル)-4,4’,5,5’-テトラフェニルビイミダゾール、2,2’-ビス(o-ブロモフェニル))4,4’,5,5’-テトラフェニルビイミダゾール、2,2’-ビス(o,p-ジクロロフェニル)-4,4’,5,5’-テトラフェニルビイミダゾール、2,2’-ビス(o-クロロフェニル)-4,4’,5,5’-テトラ(m-メトキシフェニル)ビイジダゾール、2,2’-ビス(o,o’-ジクロロフェニル)-4,4’,5,5’-テトラフェニルビイミダゾール、2,2’-ビス(o-ニトロフェニル)-4,4’,5,5’-テトラフェニルビイミダゾール、2,2’-ビス(o-メチルフェニル)-4,4’,5,5’-テトラフェニルビイミダゾール、2,2’-ビス(o-トリフルオロフェニル)-4,4’,5,5’-テトラフェニルビイミダゾール等が挙げられる。
ヒドロキシアセトフェノン系開始剤としては、IRGACURE-184、DAROCUR-1173、IRGACURE-500、IRGACURE-2959,IRGACURE-127(商品名:いずれもBASF社製)を用いることができる。アミノアセトフェノン系開始剤としては、市販品であるIRGACURE-907、IRGACURE-369、及び、IRGACURE-379(商品名:いずれもBASF社製)を用いることができる。アミノアセトフェノン系開始剤として、365nm又は405nm等の長波光源に吸収波長がマッチングされた特開2009-191179公報に記載の化合物も用いることができる。また、アシルホスフィン系開始剤としては市販品であるIRGACURE-819やDAROCUR-TPO(商品名:いずれもBASF社製)を用いることができる。
オキシム化合物としては、J.C.S.Perkin II(1979)1653-1660)、J.C.S.Perkin II(1979)156-162、Journal of Photopolymer Science and Technology(1995)202-232、Journal of Applied Polymer Science(2012年)pp.725-731、特開2000-66385号公報記載の化合物、特開2000-80068号公報、特表2004-534797号公報記載の化合物等が挙げられる。
また、オキシム化合物の特定部位に不飽和結合を有する特開2009-242469号公報に記載の化合物も、重合不活性ラジカルから活性ラジカルを再生することで高感度化を達成でき好適に使用することができる。
具体的には、下記式(OX-1)で表される化合物も好ましい。なお、オキシムのN-O結合が(E)体のオキシム化合物であっても、(Z)体のオキシム化合物であっても、
(E)体と(Z)体との混合物であってもよい。
前記式(OX-1)中、Rで表される一価の置換基としては、一価の非金属原子団であることが好ましい。
前記一価の非金属原子団としては、アルキル基、アリール基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、複素環基、アルキルチオカルボニル基、アリールチオカルボニル基等が挙げられる。また、これらの基は、1以上の置換基を有していてもよい。また、前述した置換基は、更に他の置換基で置換されていてもよい。
置換基としてはハロゲン原子、アリールオキシ基、アルコキシカルボニル基又はアリールオキシカルボニル基、アシルオキシ基、アシル基、アルキル基、アリール基等が挙げられる。
置換基を有していてもよいアリール基としては、炭素数6~30のアリール基が好ましい。具体的には、特開2012-032556号公報段落0027等の記載を参酌でき、これらの内容は本願明細書に組み込まれる。
置換基を有していてもよいアシル基としては、炭素数2~20のアシル基が好ましい。具体的には、特開2012-032556号公報段落0028等の記載を参酌でき、これらの内容は本願明細書に組み込まれる。
置換基を有していてもよいアルコキシカルボニル基としては、炭素数2~20のアルコキシカルボニル基が好ましい。具体的には、特開2012-032556号公報段落0029等の記載を参酌でき、これらの内容は本願明細書に組み込まれる。
置換基を有していてもよいアリールオキシカルボニル基としては、具体的には、特開2012-032556号公報段落0030等の記載を参酌でき、これらの内容は本願明細書に組み込まれる。
置換基を有していてもよい複素環基としては、窒素原子、酸素原子、硫黄原子若しくはリン原子を含む、芳香族又は脂肪族の複素環が好ましい。
具体的には、具体的には、特開2012-032556号公報段落0031等の記載を参酌でき、これらの内容は本願明細書に組み込まれる。
置換基を有していてもよいアルキルチオカルボニル基として具体的には、特開2012-032556号公報段落0032等の記載を参酌でき、これらの内容は本願明細書に組み込まれる。
置換基を有していてもよいアリールチオカルボニル基として具体的には、特開2012-032556号公報段落0033等の記載を参酌でき、これらの内容は本願明細書に組み込まれる。
下記の構造中、Y、X、及び、nは、それぞれ、後述する式(OX-2)におけるY、X、及び、nと同義であり、好ましい例も同様である。
中でも、式(OX-1)におけるAとしては、感度を高め、加熱経時による着色を抑制する点から、無置換のアルキレン基、アルキル基(例えば、メチル基、エチル基、tert-ブチル基、ドデシル基)で置換されたアルキレン基、アルケニル基(例えば、ビニル基、アリル基)で置換されたアルキレン基、アリール基(例えば、フェニル基、p-トリル基、キシリル基、クメニル基、ナフチル基、アンスリル基、フェナントリル基、スチリル基)で置換されたアルキレン基が好ましい。
なかでも、感度を高め、加熱経時による着色を抑制する点から、置換又は無置換のフェニル基が好ましい。
式(OX-2)におけるR、A、及びArは、前記式(OX-1)におけるR、A、及びArと同義であり、好ましい例も同様である。
また、式(2)におけるnは、0~5の整数を表し、0~2の整数が好ましい。
中でも、高感度化の観点から、構造Sub-1及びSub-2が好ましい。
式(OX-3)におけるR、X、A、Ar、及び、nは、前記式(OX-2)におけるR、X、A、Ar、及び、nとそれぞれ同義であり、好ましい例も同様である。
オキシム化合物は、365nm又は405nmにおけるモル吸光係数は、感度の観点から、1,000~300,000であることが好ましく、2,000~300,000であることがより好ましく、5,000~200,000であることが特に好ましい。化合物のモル吸光係数は、公知の方法を用いることができるが、具体的には、例えば、紫外可視分光光度計(Varian社製Carry-5 spectrophotometer)にて、酢酸エチル溶媒を用い、0.01g/Lの濃度で測定することが好ましい。
また、IRGACURE OXE01、及び、IRGACURE OXE02などの市販品(いずれも、BASF社製)も好適に使用できる。
また、その他の好ましいスルホニウム塩としては、トリアリールスルホニウム塩の1つの置換基がクマリン構造又はアントアキノン構造を有し、300nm以上に吸収を有するスルホニウム塩が挙げられる。別の好ましいスルホニウム塩としては、トリアリールスルホニウム塩が、アリロキシ基、アリールチオ基を置換基に有する300nm以上に吸収を有するスルホニウム塩が挙げられる。
高屈折率層形成用の硬化性樹脂組成物は溶媒を含むことが好ましい。該溶媒は種々の有機溶剤を用いて構成することができる。
ここで使用できる有機溶剤としては、アセトン、メチルエチルケトン、シクロヘキサン、酢酸エチル、エチレンジクロライド、テトラヒドロフラン、トルエン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、アセチルアセトン、シクロヘキサノン、ジアセトンアルコール、エチレングリコールモノメチルエーテルアセテート、エチレングリコールエチルエーテルアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテルアセテート、3-メトキシプロパノール、メトキシメトキシエタノール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、3-メトキシプロピルアセテート、N,N-ジメチルホルムアミド、ジメチルスルホキシド、γ-ブチロラクトン、乳酸メチル、乳酸エチルなどがある。
これらの有機溶剤は、単独あるいは混合して使用することができる。高屈折率層形成用の硬化性樹脂組成物における固形分の濃度は、2~60質量%であることが好ましい。
硬化性組成物の製造中あるいは保存中において重合可能なエチレン性不飽和二重結合を有する化合物の不要な重合を阻止するために、重合禁止剤を添加することが好ましい。
重合禁止剤としては、フェノール系水酸基含有化合物、N-オキシド化合物類、ピペリジン1-オキシルフリーラジカル化合物類、ピロリジン1-オキシルフリーラジカル化合物類、N-ニトロソフェニルヒドロキシルアミン類、ジアゾニウム化合物類、及びカチオン染料類、スルフィド基含有化合物類、ニトロ基含有化合物類、FeCl3、CuCl2等の遷移金属化合物類が挙げられる。
フェノール系水酸基含有化合物が、ハイドロキノン、p-メトキシフェノール、ジ-t-ブチル-p-クレゾール、ピロガロール、t-ブチルカテコール、ベンゾキノン、4,4-チオビス(3-メチル-6-t-ブチルフェノール)、2,2’-メチレンビス(4-メチル-6-t-ブチルフェノール)、フェノール樹脂類、及びクレゾール樹脂類からなる群より選択される化合物であるのが好ましい。
上記範囲とすることで、非画像部における硬化反応抑制及び画像部における硬化反応促進が充分おこなわれ、画像形成性及び感度が良好となる。
高屈折率層形成用の硬化性樹脂組成物は、塗布性をより向上させる観点から、各種の界面活性剤を添加してもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種界面活性剤を使用できる。
即ち、フッ素系界面活性剤を含有する感光性透明組成物を適用した塗布液を用いて膜形成する場合においては、被塗布面と塗布液との界面張力を低下させることにより、被塗布面への濡れ性が改善され、被塗布面への塗布性が向上する。このため、少量の液量で数μm程度の薄膜を形成した場合であっても、厚みムラの小さい均一厚の膜形成をより好適に行える点で有効である。
界面活性剤は、1種のみを用いてもよいし、2種類以上を組み合わせてもよい。
更に、高屈折率層形成用の硬化性樹脂組成物に対しては、硬化皮膜の物性を改良するために可塑剤や感脂化剤等の公知の添加剤を加えてもよい。
可塑剤としては、例えば、ジオクチルフタレート、ジドデシルフタレート、トリエチレングリコールジカプリレート、ジメチルグリコールフタレート、トリクレジルホスフェート、ジオクチルアジペート、ジブチルセバケート、トリアセチルグリセリン等があり、バインダーポリマーを使用した場合、重合性化合物とバインダーポリマーとの合計質量に対し10質量%以下添加することができる。
高屈折率層形成用の硬化性樹脂組成物は、紫外線吸収剤を含有してもよい。紫外線吸収剤としては、共役ジエン系化合物である下記一般式(I)で表される化合物が特に好ましい。
ハメット則は、ベンゼン誘導体の反応又は平衡に及ぼす置換基の影響を定量的に論ずるために、1935年にL. P. Hammettにより提唱された経験則であるが、これは今日広く妥当性が認められている。ハメット則により求められた置換基定数には、σp値とσm値とがあり、これらの値は多くの一般的な成書に記載があるが、例えば、J.A. Dean編「Lange’s Handbook of Chemistry」第12版、1979年(Mc Graw-Hill)や「化学の領域増刊」、122号、96~103頁、1979年(南江堂)、Chemical Reviews, 91巻、165頁~195頁、1991年に詳しい。本発明では、これらの成書に記載の文献既知の値がある置換基にのみ限定されるという意味ではなく、その値が文献未知であってもハメット則に基づいて測定した場合にその範囲内に含まれる限り包含されることは勿論である。
フィルタの孔径は、0.01~7.0μm程度が適しており、好ましくは0.01~2.5μm程度、更に好ましくは0.01~1.5μm程度である。この範囲とすることにより、溶解した顔料等に混入しており、後工程において均一及び平滑な硬化性組成物の調製を阻害する、微細な異物を確実に除去することが可能となる。
フィルタを使用する際、異なるフィルタを組み合わせても良い。その際、第1のフィルタでのフィルタリングは、1回のみでもよいし、2回以上行ってもよい。異なるフィルタを組み合わせて2回以上フィルタリングを行う場合は1回目のフィルタリングの孔径より2回目以降の孔径が大きい方が好ましい。また、上述した範囲内で異なる孔径の第1のフィルタを組み合わせてもよい。ここでの孔径は、フィルタメーカーの公称値を参照することができる。市販のフィルタとしては、例えば、日本ポール株式会社、アドバンテック東洋株式会社、日本インテグリス株式会社(旧日本マイクロリス株式会社)又は株式会社キッツマイクロフィルタ等が提供する各種フィルタの中から選択することができる。
第2のフィルタは、上述した第1のフィルタと同様の材料等で形成されたものを使用することができる。第2のフィルタの孔径は、0.5~7.0μm程度が適しており、好ましくは2.5~7.0μm程度、更に好ましくは4.5~6.0μm程度である。この範囲とすることにより、混合液に含有されている成分粒子を残存させたまま、混合液に混入しており、後工程でおいて均一及び平滑な硬化性組成物の調製を阻害する異物を除去することができる。
例えば、第1のフィルタでのフィルタリングは、分散液のみで行い、他の成分を混合した後で、第2のフィルタリングを行ってもよい。
本発明における低屈折率層形成用の硬化性樹脂組成物は、硬化性樹脂を含有することが好ましく、シロキサン樹脂又はフッ素系樹脂を含有することがより好ましく、シロキサン樹脂を含有することが更に好ましい。また、組成物に含有させる成分として中空粒子を用いることが好ましい。
シロキサン樹脂は下記式(1)で表されるシルセスキオキサン構造を有することが好ましい。
-(R1SiO3/2)n- 式(1)
(上記式(1)中、R1は炭素数1~3のアルキル基を表す。nは20~1000の整数を表す。)
上記R1が示すアルキル基は上記炭素数の範囲であれば特に制限されないが、例えばメチル基、エチル基、プロピル基、イソプロピル基などが挙げられる。中でもメチル基、エチル基が好ましく、最も好ましいのはメチル基である。また、R1が示すアルキル基は置換基を有さないアルキル基でも置換基を有するアルキル基でもよいが、置換基を有さないアルキル基であることが好ましい。
(2分の3を示すラテン語は「セスキ(SESQUI)」である。)。本実施形態においては、上記T単位の式においてRが上記R1であり、このシルセスキオキサン構造部位が上記特定の含有率で含まれていることが好ましい。
上記加水分解縮合物を製造するために、出発原料として、アルキルトリアルコキシシランを含むアルコキシシラン原料を使用することができる。なお、アルコキシシラン原料とは、アルコキシシラン(アルコキシ基を有するケイ素化合物)から構成される出発原料を意図する。原料としてアルキルトリアルコキシシランを使用することにより、得られる加水分解縮合物の構造がよりフレキシブルとなり、更に有機成分の存在により基板に対する濡れ性を高めることができる。
式(2):R2Si(OR3)3
(R2は炭素数1~3のアルキル基、炭素数1~8のアルコキシアルキル基、炭素数1~10のフルオロアルキル基、を表し、R3はアルキル基を表す。)
アルコキシシラン原料としては上記のトリアルコキシシラン以外に、他のアルコキシシランを使用することができ、なかでもテトラアルコキシシランが好ましい。テトラアルコキシシランを含むことにより、加水分解縮合物中の架橋密度が増加し、硬膜して得られる皮膜の電気的絶縁性、耐現像性、耐熱性がより向上する点で好ましい。
式(3):Si(OR4)4
(R4は、それぞれ独立にアルキル基を表す。)
なお、テトラアルコキシシランとしては、1種のみを使用してもよいし、2種以上を併用してもよい。
アルキル基(好ましくは炭素原子数1~20のアルキル基、例えばメチル、エチル、イソプロピル、t-ブチル、ペンチル、ヘプチル、1-エチルペンチル、ベンジル、2-エトキシエチル、1-カルボキシメチル等)、アルケニル基(好ましくは炭素原子数2~20のアルケニル基、例えば、ビニル、アリル、オレイル等)、アルキニル基(好ましくは炭素原子数2~20のアルキニル基、例えば、エチニル、ブタジイニル、フェニルエチニル等)、シクロアルキル基(好ましくは炭素原子数3~20のシクロアルキル基、例えば、シクロプロピル、シクロペンチル、シクロヘキシル、4-メチルシクロヘキシル等)、アリール基(好ましくは炭素原子数6~26のアリール基、例えば、フェニル、1-ナフチル、4-メトキシフェニル、2-クロロフェニル、3-メチルフェニル等)、ヘテロ環基(好ましくは炭素原子数2~20のヘテロ環基、例えば、2-ピリジル、4-ピリジル、2-イミダゾリル、2-ベンゾイミダゾリル、2-チアゾリル、2-オキサゾリル等)、アルコキシ基(好ましくは炭素原子数1~20のアルコキシ基、例えば、メトキシ、エトキシ、イソプロピルオキシ、ベンジルオキシ等)、アリールオキシ基(好ましくは炭素原子数6~26のアリールオキシ基、例えば、フェノキシ、1-ナフチルオキシ、3-メチルフェノキシ、4-メトキシフェノキシ等)、アルコキシカルボニル基(好ましくは炭素原子数2~20のアルコキシカルボニル基、例えば、エトキシカルボニル、2-エチルヘキシルオキシカルボニル等)、アミノ基(好ましくは炭素原子数0~20のアミノ基、例えば、アミノ、N,N-ジメチルアミノ、N,N-ジエチルアミノ、N-エチルアミノ、アニリノ等)、スルホンアミド基(好ましくは炭素原子数0~20のスルホンアミド基、例えば、N,N-ジメチルスルホンアミド、N-フェニルスルホンアミド等)、アシルオキシ基(好ましくは炭素原子数1~20のアシルオキシ基、例えば、アセチルオキシ、ベンゾイルオキシ等)、カルバモイル基(好ましくは炭素原子数1~20のカルバモイル基、例えば、N,N-ジメチルカルバモイル、N-フェニルカルバモイル等)、アシルアミノ基(好ましくは炭素原子数1~20のアシルアミノ基、例えば、アセチルアミノ、ベンゾイルアミノ等)、シアノ基、又はハロゲン原子(例えばフッ素原子、塩素原子、臭素原子、ヨウ素原子等)であり、より好ましくはアルキル基、アルケニル基、アリール基、ヘテロ環基、アルコキシ基、アリールオキシ基、アルコキシカルボニル基、アミノ基、アシルアミノ基、シアノ基又はハロゲン原子であり、特に好ましくはアルキル基、アルケニル基、ヘテロ環基、アルコキシ基、アルコキシカルボニル基、アミノ基、アシルアミノ基又はシアノ基が挙げられる。
低屈折率層形成用の硬化性樹脂組成物中に含まれるシロキサン樹脂は、上述したアルコキシシラン原料を用いて、加水分解反応及び縮合反応を介して得ることができる。
加水分解反応及び縮合反応としては公知の方法を使用することができ、必要に応じて、酸又は塩基などの触媒を使用してもよい。触媒としてはpHを変更させるものであれば特に制限がなく、具体的には、酸(有機酸、無機酸)としては、例えば硝酸、シュウ酸、酢酸、蟻酸、塩酸など、アルカリとしては、例えばアンモニア、トリエチルアミン、エチレンジアミンなどが挙げられる。使用する量は、シロキサン樹脂が所定の分子量を満たせば、特に限定されない。
なお、重量平均分子量は、公知のGPC(ゲル浸透クロマトグラフィー)を用いて測定し、標準ポリスチレンに換算したときの値である。特に断らない限り、GPC測定においては、カラムとしてWaters2695及びShodex製GPCカラムKF-805L(カラム3本を直結)を使用し、カラム温度40℃、試料濃度0.5質量%のテトラヒドロフラン溶液を50μl注入し、溶出溶媒としてテトラヒドロフランを毎分1mlの流量でフローさせ、RI検出装置(Waters2414)及びUV検出装置(Waters2996)にて試料ピークを検出することで行った。
低屈折率層形成用の硬化性樹脂組成物中における上記シロキサン樹脂の含有量は、全組成物質量に対して、5質量%超50質量%以下であることが好ましく。なかでも、10~45質量%がより好ましく、15~40質量%が特に好ましい。含有量が上記下限値以上ないし超の場合、ボイドを発生させにくく受光感度の良化において特に良い。含有量が上記上限値以下の場合、膜厚が十分に厚くなりクラック等の発生原因とならず実用性に富む。
また、本発明における低屈折率層形成用の硬化性樹脂組成物は、シロキサン樹脂以外の硬化性樹脂を含有していてもよい。例えば、メタクリル酸とメタクリル酸メチルとメタクリル酸のカルボン酸末端に脂環式グリシジル基を導入したモノマーとの共重合物等が挙げられる。市販品としてはサイクロマーP ACA230AA等のサイクロマーPシリーズ等が挙げられる。
シロキサン樹脂以外の硬化性樹脂の含有量としては、シロキサン樹脂について前述した好ましい範囲と同様である。
低屈折率層形成用の硬化性樹脂組成物は、ポリオキシアルキレン構造を有する界面活性剤を含有することが好ましい。ポリオキシアルキレン構造とは、アルキレン基と二価の酸素原子が隣接して存在している構造のことをいい、具体的にはエチレンオキサイド(EO)構造、プロピレンオキサイド(PO)構造などが挙げられる。ポリオキシアルキレン構造を有する界面活性剤としては、該ポリオキシアルキレン構造を有する限りにおいてフッ素系界面活性剤、ノニオン界面活性剤、カチオン界面活性剤、アニオン界面活性剤、シリコーン系界面活性剤などの各種界面活性剤を使用できる。これらの中でもノニオン界面活性剤、アニオン界面活性剤、及びシリコーン系界面活性剤が好ましく、ノニオン界面活性剤、及びアニオン界面活性剤が更に好ましく、アニオン界面活性剤が最も好ましい。
界面活性剤は、1種のみを用いてもよいし、2種類以上を組み合わせてもよい。
式(4):R5O(R6O)mR7
(上記式中、R5は炭素数1~20のアルキル基を表し、R6は炭素数1~4のアルキレン基を表し、R7は水素原子、カルボキシル基、又は-PO3H2を表す。mは1~8の整数を表す。)
式(5):Si(OR51)n-4(R52)n
ここで、R51は前記R4と同義の基である。R52は炭素数4~12のアルキル基であることが好ましく、炭素数6~10のアルキル基であることがより好ましい。nは1~3の整数である。
低屈折率層形成用の硬化性樹脂組成物は、中空粒子を含むことが好ましい。中空粒子としては、中空構造はもちろん多孔質の微粒子を使用してもよい。中空粒子は、内部に空洞を有する構造のものであり、外郭に包囲された空洞を有する粒子を指し、多孔質粒子は、多数の空洞を有する多孔質の粒子を指す。以下、中空粒子又は多孔質粒子を、適宜「特定粒子」と称する。特定粒子は、有機粒子であっても、無機粒子であってもよい。
特定粒子の中でも、屈折率を低下しやすい観点から、中空粒子であることがより好ましく、中空シリカ粒子であることが特に好ましい。例えば、中空粒子をシリカで構成した場合には、中空シリカ粒子は、屈折率の低い空気(屈折率=1.0)を有しているため、その屈折率は、通常のシリカ(屈折率=1.6)と比較して著しく低くなる。
特定粒子の平均一次粒子径は、分散した粒子を透過型電子顕微鏡により観察し、得られた写真から求めることができる。粒子の投影面積を求め、そこから円相当径を求め平均一次粒子径とする。本明細書における平均一次粒子径は、300個以上の粒子について投影面積を測定して、円相当径を求めて算出する。
ここでの屈折率は粒子全体として屈折率を表し、粒子が中空粒子である場合、中空粒子を形成している外殻のみの屈折率を表すものではない。粒子が多孔質粒子である場合、多孔質粒子の屈折率の測定方法は、前記金属酸化物粒子と同じである。
これらの無機粒子の平均一次粒子径は、1nm~100nmであることが好ましく、1nm~60nmであることがより好ましい。
無機粒子は、必要な空隙率を満たす限りにおいて、結晶系は、結晶質でも、アモルファスのいずれでもよく、また単分散粒子でも、所定の粒子径を満たすならば凝集粒子でも構わない。形状は、球形状が最も好ましいが、数珠状、長径と短径の比が1以上の形状、あるいは不定形状であってもよい。
すなわち、無機粒子がシリカ粒子であり、カップリング剤がシラン化合物である場合、シラン化合物とシラノール基との反応により、オルガノシリル基(モノオルガノシリル、ジオルガノシリル、トリオルガノシリル基)がシリカ粒子の表面に結合するものである。表面処理されたシリカ粒子がその表面に有する有機基としては、飽和又は不飽和の炭素数1~18の炭化水素基、炭素数1~18のハロゲン化炭化水素基などが挙げられる。
上記カップリング剤は、無機粒子の表面処理剤として低屈折率膜用塗布液の調製以前にあらかじめ表面処理を施すために用いられても、塗布液調製時に更に添加剤として添加してもよい。
無機粒子は、表面処理前に、媒体中に予め分散されていることが、表面処理の負荷軽減のために好ましい。
シリカからなる特定粒子としては市販されているものを好ましく用いることができる。
例えば、日揮触媒化成(株)製スルーリアシリーズ(中空粒子、イソプロパノール(IPA)分散、4-メチル-2-ペンタノン(MIBK)分散など。例えばスルーリア2320など。)、OSCALシリーズ、日産化学(株)製スノーテックスシリーズ(多孔質粒子、IPA分散、エチレングリコール分散、メチルエチルケトン(MEK)分散、ジメチルアセトアミド分散、MIBK分散、プロピレングリコールモノメチルアセテート分散、プロピレングリコールモノメチルエーテル分散、メタノール分散、酢酸エチル分散、酢酸ブチル分散、キシレン-n-ブタノール分散、トルエン分散など。例えばMIBK-SD-L、MIBK-STなど。)、日鉄鉱業(株)製シリナックス(多孔質粒子)、扶桑化学工業(株)製PLシリーズ(多孔質粒子、IPA分散、トルエン分散、プロピレングリコールモノメチルエーテル分散、メチルエチルケトン分散など。例えばPL-1-IPA、PL-2L-PGMEなど。)、EVONIK社製アエロジルシリーズ(多孔質粒子、プロピレングリコールアセテート分散、エチレングリコール分散、MIBK分散など)などのシリカ粒子を用いることができる。
特定粒子は、1種類であっても、2種以上を併用してもよい。
低屈折率層形成用の硬化性樹脂組成物は、フッ素系樹脂を含んでいてもよい。例えば特開2004-21036号公報に記載のフッ素系のシロキサンポリマーが挙げられる。
フッ素系樹脂の添加量は、特に限定されないが、前記シロキサン樹脂と同様の観点から、前記シロキサン樹脂と同様の含有率の範囲であることが好ましい。
低屈折率層形成用の硬化性樹脂組成物は、更に重合開始剤を含有しても良い。
重合開始剤の具体例、好ましい例としては、高屈折率層形成用の硬化性樹脂組成物の項において前述した重合開始剤の具体例、好ましい例と同様のものが挙げられる。
低屈折率層形成用の硬化性樹脂組成物が重合開始剤を含有する場合、低屈折率層形成用の硬化性樹脂組成物に含有される重合開始剤の含有量(2種以上の場合は総含有量)は、硬化性組成物の全固形分に対し0.1質量%以上10質量%以下であることが好ましく、より好ましくは0.3質量%以上8質量%以下、更に好ましくは0.5質量%以上5質量%以下である。
(硬化剤)
低屈折率層形成用の硬化性樹脂組成物は、更に硬化剤を含有しても良い。硬化剤としては、Al、Mg、Mn、Ti、Cu、Co、Zn、Hf及びZrよりなる硬化剤が好ましく、これらを併用することもできる。
低屈折率層形成用の硬化性樹脂組成物は、一般には、有機溶剤を用いて構成することができる。有機溶剤は、各成分の溶解性や光透過性硬化膜形成用樹脂組成物の塗布性を満足すれば基本的には特に制限はないが、特に、バインダーの溶解性、塗布性、安全性を考慮して選ばれることが好ましい。また、低屈折率層形成用の硬化性樹脂組成物を調製する際には、2種類の有機溶剤を含んでもよい。
特に好ましくは、上記の3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、3-メトキシプロピオン酸メチル、2-ヘプタノン、シクロヘキサノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールメチルエーテル、ジプロピレングリコールジメチルエーテル、プロピレングリコールモノn-ブチルエーテル、プロピレングリコールモノtert-ブチルエーテル、及びプロピレングリコールメチルエーテルアセテートである。
高屈折率層形成用ないしは低屈折率層形成用の硬化性樹脂組成物は、良好な高屈折率層ないしは低屈折率層を形成する観点から、その粘度が調節されていることが好ましい。具体的な粘度の範囲は特に限定されないが、1~20cPであることが好ましく、2~15cPであることがより好ましく、4~6cPであることが特に好ましい。本明細書における粘度の値は、特に断らない限り、後記の測定方法によるものとする。
・測定方法
E型粘度計「TV-20形粘度計・コーンプレートタイプ TVE-20L」(東機産業製)を用いて、室温(約25℃)で測定する。サンプリングは100秒ごとに5回粘度を測定した値の平均とする。
高屈折率層形成用ないしは低屈折率層形成用の硬化性樹脂組成物を支持体上に塗布する方法は、例えば、アプリケータ、スピンコーター、スリットスピンコーター、スリットコーター、スクリーン印刷等を用いることにより実施でき、スピンコーターによる塗布であることが好ましい。
また、塗膜の乾燥条件としては、各成分、溶媒の種類、使用割合等によっても異なるが、通常60℃~150℃の温度で30秒間~15分間程度である。
前加熱工程及び後加熱工程における加熱温度は、通常、80℃~200℃であり、90℃~150℃であることが好ましい。
前加熱工程及び後加熱工程における加熱時間は、通常、30秒~240秒であり、60秒~180秒であることが好ましい。
硬化処理工程は、必要に応じ、形成された前記膜に対して硬化処理を行う工程であり、この処理を行うことにより、赤外線カットフィルタの機械的強度が向上する。
前記硬化処理工程としては、特に制限はなく、目的に応じて適宜選択することができるが、例えば、全面露光処理、全面加熱処理などが好適に挙げられる。ここで、本発明において「露光」とは、各種波長の光のみならず、電子線、X線などの放射線照射をも包含する意味で用いられる。
露光は放射線の照射により行うことが好ましく、露光に際して用いることができる放射線としては、特に、電子線、KrF、ArF、g線、h線、i線等の紫外線や可視光が好ましく用いられる。好ましくは、KrF、g線、h線、i線が好ましい。
露光方式としては。ステッパー露光や、高圧水銀灯による露光などが挙げられる。
露光量は5mJ/cm2~3000mJ/cm2が好ましく10mJ/cm2~2000mJ/cm2がより好ましく、50mJ/cm2~1000mJ/cm2が最も好ましい。
前記全面露光を行う装置としては、特に制限はなく、目的に応じて適宜選択することができるが、例えば、超高圧水銀灯などのUV露光機が好適に挙げられる。
また、全面加熱処理の方法としては、形成された前記膜の全面を加熱する方法が挙げられる。全面加熱により、パターンの膜強度が高められる。
全面加熱における加熱温度は、120℃~250℃が好ましく、120℃~250℃がより好ましい。該加熱温度が120℃以上であれば、加熱処理によって膜強度が向上し、250℃以下であれば、前記膜中の成分の分解が生じ、膜質が弱く脆くなることを防止できる。
全面加熱における加熱時間は、3分~180分が好ましく、5分~120分がより好ましい。
全面加熱を行う装置としては、特に制限はなく、公知の装置の中から、目的に応じて適宜選択することができ、例えば、ドライオーブン、ホットプレート、IRヒーターなどが挙げられる。
本発明の赤外線反射膜において、上記2層以上の高屈折率層と、上記2層以上の低屈折率層との各層の膜厚は、それぞれ、50~250nmであることが好ましく、80~180nmであることがより好ましい。
本発明の赤外線反射膜において、上記2層以上の高屈折率層が、分光特性に不要な振動(リップル)を低減する観点から、屈折率1.65~2.00の範囲内で互いに異なる屈折率を有する複数種の層であることが好ましい。
また、上記2層以上の高屈折率層が、リップルを低減する観点から、膜厚50~250nmの範囲内で互いに異なる膜厚を有する複数種の層であることも好ましい。
本発明の赤外線反射膜において、上記2層以上の低屈折率層が、リップルを低減する観点から、屈折率1.20~1.45の範囲内で異なる屈折率を有する複数種の層であることが好ましい。
上記2層以上の低屈折率層が、リップルを低減する観点から、膜厚50~250nmの範囲内で互いに異なる膜厚を有する複数種の層であることも好ましい。
本発明の赤外線反射膜において、上記2層以上の高屈折率層と、上記2層以上の低屈折率層との積層数が4~60層であることが好ましく、8~50層であることがより好ましく、10~40層であることが更に好ましい。
本発明の赤外線反射膜において、上記2層以上の高屈折率層と、上記2層以上の低屈折率層との積層の総膜厚としては、10μm以下であることが好ましく、8μm以下であることがより好ましく、6μm以下であることが更に好ましい。
本発明の赤外線反射膜は、本発明の高屈折率層形成用ないしは低屈折率層形成用の硬化性樹脂組成物より形成されているので、赤外線遮蔽性に優れる。
本発明は、上述の赤外線反射膜と600nm~820nmの範囲内に極大吸収波長を有する色素又は銅錯体を含有する層とを有する赤外線カットフィルタに関するものでもある。
上記色素又は銅錯体における吸収極大波長は、色素又は銅錯体及び樹脂を溶液全量に対して固形分20質量%に調製した溶液を塗工することにより得られる膜厚1μmの膜を、分光光度計を用いて得られる値に準ずる。
上記色素は、波長600nm~820nmの範囲内に極大吸収波長(λmax)を有する限り特に限定されないが、シアニン系色素、フタロシアニン系色素、クアテリレン系色素、アミニウム系色素、イミニウム系色素、アゾ系色素、アンスラキノン系色素、ジイモニウム系色素、スクアリリウム系色素及びポルフィリン系色素からなる群から選択される少なくとも1種などを好適に挙げることができる。その中でも、シアニン系色素、フタロシアニン系色素、又はクアテリレン系色素であることが好ましく、シアニン系色素、又はフタロシアニン系色素であることがより好ましい。
640~770nmの範囲に極大吸収波長を有することが好ましく、660~720nmの範囲に吸収極大を有することが特に好ましい。
シアニン系色素、クアテリレン系色素の具体例としては特開2012-215806号公報の段落0160、特開2008-009206号公報の段落0021等に記載の化合物が挙げられる。
フタロシアニン化合物の具体例としては、特開昭60-224589号公報、特表2005-537319号公報、特開平4-23868号公報、特開平4-39361号公報、特開平5-78364号公報、特開平5-222047号公報、特開平5-222301号公報、特開平5-222302号公報、特開平5-345861号公報、特開平6-25548号公報、特開平6-107663号公報、特開平6-192584号公報、特開平6-228533号公報、特開平7-118551号公報、特開平7-118552号公報、特開平8-120186号公報、特開平8-225751号公報、特開平9-202860号公報、特開平10-120927号公報、特開平10-182995号公報、特開平11-35838号公報、特開2000-26748号公報、特開2000-63691号公報、特開2001-106689号公報、特開2004-18561号公報、特開2005-220060号公報、特開2007-169343号公報記載の化合物が挙げられる。
本発明で用いる銅錯体は、波長600nm~820nmの範囲内(近赤外線領域)に極大吸収波長を有する銅錯体であれば特に制限はないが、下記一般式(1)で表されることが好ましく、リン含有銅錯体であることがより好ましい。
Cu(L)n・X 一般式(1)
(上記一般式(1)中、
Lは、銅に配位する配位子を表し、
Xは、存在しないか、ハロゲン原子、H2O、NO3、ClO4、SO4、CN、SCN、BF4、PF6、BPh4(Phはフェニル基を表す)又はアルコールを表す。nは、1~4の整数を表す。)
銅に配位する配位子Lとしては銅イオンと配位結合可能であれば特に限定されないが、好ましくは銅に配位可能な原子としてC、N、O、Sを含む置換基を有するものであり、更に好ましくはNやO、Sなどの孤立電子対を持つ基を有するものである。
配位子Lを形成する化合物の種類としては、リン酸エステル、ホスホン酸、ホスホン酸エステル、ホスフィン酸、カルボン酸、カルボニル(エステル、ケトン)、アミン、アミド、スルホンアミド、ウレタン、ウレア、アルコール、チオールなどを有する化合物が挙げられる。これらの中でも、リン酸、リン酸エステル、ホスホン酸、ホスホン酸エステル、ホスフィン酸が好ましく、具体的にはWO2005/030898号に開示の化合物を使用することができる。
また、配位可能な基は分子内に1種類に限定されず、2種以上を含んでも良く、解離しても非解離でも良い。非解離の場合、Xは存在しない。
一般式(2)
(HO)n-P(=O)-(OR2)3-n
(上記一般式(2)中、R2は炭素数1~18のアルキル基、炭素数6~18のアリール基、炭素数1~18のアラルキル基、又は炭素数1~18のアルケニル基を表すか、-OR2が、炭素数4~100のポリオキシアルキル基、炭素数4~100の(メタ)アクリロイルオキシアルキル基、又は、炭素数4~100の(メタ)アクリロイルポリオキシアルキル基を表し、nは1又は2を表す。)
nが1のとき、R2はそれぞれ同一でもよいし、異なっていてもよい。
本発明では、nが1のとき、R2の一方は、-OR2であって、炭素数4~100の(メタ)アクリロイルオキシアルキル基、又は、炭素数4~100の(メタ)アクリロイルポリオキシアルキル基を表すことが好ましく、他方は、前記-OR2であるか、アルキル基であることが好ましい。
赤外線吸収物質としてリン原子含有化合物(好ましくはリン酸エステル銅錯体)は中心金属の銅にリン酸エステルが配位した銅錯体(銅化合物)の形態となっている。リン酸エステル銅錯体における銅は2価の銅であり、例えば、銅塩とリン酸エステルとが反応して生成し得る。よって、「銅とリン酸エステル化合物とを含有する赤外線吸収組成物」であれば、組成物中でリン酸銅錯体を形成していることが予見される。
ここで用いる銅塩は、2価又は3価の銅が好ましく、2価の銅がより好ましい。銅塩としては、酢酸銅、塩化銅、ギ酸銅、ステアリン酸銅、安息香酸銅、エチルアセト酢酸銅、ピロリン酸銅、ナフテン酸銅、クエン酸銅、硝酸銅、硫酸銅、炭酸銅、塩素酸銅、(メタ)アクリル酸銅がより好ましく、安息香酸銅、(メタ)アクリル酸銅が更に好ましい。
色素のε(イプシロン)が高い場合にはその含有量は少なくてよいが、色素のε(イプシロン)が低い場合にはその含有量は多くなる。また上記色素がシアニン系色素やフタロシアニン系色素などの場合その含有量は、組成物の全固形分質量に対して、0.01質量%以上20質量%以下であることが好ましく、0.5質量%以上10質量%以下であることがより好ましい。
色素又は銅錯体含有層形成用の硬化性樹脂組成物に含有され得る分散剤、バインダー、及び重合性化合物、重合開始剤、溶剤、界面活性剤等の具体例、好ましい例、及び使用量(組成物中における含有量)の好ましい範囲等としては<高屈折率層形成用の硬化性樹脂組成物>で前述した分散剤(B)、バインダー(C)、重合性化合物(D)、重合開始剤(E)、溶剤、界面活性剤等についての具体例、好ましい例、及び使用量の好ましい範囲等と同様である。
また、色素又は銅錯体含有層形成用の硬化性樹脂組成物の調製方法としても、上述の高屈折率層形成用の硬化性樹脂組成物の調製方法に準じて行うことができる。
上記光透過率は、400~700nmの波長領域全域に渡って、95%以上であることがより好ましく、99%以上であることが更に好ましく、100%であることが最も好ましい。
色素又は銅錯体含有層形成用の硬化性樹脂組成物は、厚みのある良好な色素又は銅錯体含有層を形成する観点から、その粘度が調節されていることが好ましい。具体的な粘度の範囲は特に限定されないが、1~20cPであることが好ましく、2~15cPであることがより好ましく、4~6cPであることが特に好ましい。本明細書における粘度の値は、特に断らない限り、後記の測定方法によるものとする。
また、色素又は銅錯体含有層形成用の硬化性樹脂組成物は、上記膜厚を形成し得る観点から、固形分濃度は10~90質量%であることが好ましく、より好ましくは20~90質量%、最も好ましくは30~80質量%である。
支持体としては、固体撮像素子における基板であっても、基板の受光側に設けられた別の基板(例えば後述のガラス基板30)であっても、固体撮像素子における基板の受光側に設けられた平坦化層等の層であっても良い。
塗膜の乾燥条件、基材の表面処理工程、前加熱工程(プリベーク工程)、硬化処理工程、後加熱工程(ポストベーク工程)などについては、高屈折率層形成用ないしは低屈折率層形成用の硬化性樹脂組成物を用いて赤外線カットフィルタを形成する方法について前述した方法に準じて行うことができる。
本発明は、基板上に本発明の赤外線カットフィルタを有する固体撮像素子にも関する。
本発明の固体撮像素子における基板は、カラーフィルタ層を有することが好ましく、カラーフィルタ層、マイクロレンズ及び平坦化層を有することがより好ましい。
以下、本発明の固体撮像素子の好ましい1つの実施形態としてのカメラモジュールについて説明する。
本発明の固体撮像素子の好ましい1つの実施形態に係るカメラモジュールとしては、基板と、前記基板の受光側に配置された本発明の赤外線カットフィルタとを有するカメラモジュールである。
なお、図2及び図3にわたり、共通する部分には共通する符号を付す。
また、説明に際し、「上」、「上方」及び「上側」は、シリコン基板10から見て遠い側を指し、「下」、「下方」及び「下側」は、はシリコン基板10に近い側を指す。
図2に示すカメラモジュール200は、実装基板である回路基板70に接続部材であるハンダボール60を介して接続されている。
詳細には、カメラモジュール200は、シリコン基板の第1の主面に撮像素子部を備えた基板100と、基板100の第1の主面側(受光側)に設けられた平坦化層46(図2には不図示)と、平坦化層46の上に設けられた赤外線カットフィルタ42と、赤外線カットフィルタ42の上方に配置されるガラス基板30(光透過性基板)と、ガラス基板30の上方に配置され内部空間に撮像レンズ40を有するレンズホルダー50と、基板100及びガラス基板30の周囲を囲うように配置された遮光兼電磁シールド44とを備えて構成されている。各部材は、接着剤20(図2には不図示)、45により接着されている。
カメラモジュール200では、外部からの入射光hνが、撮像レンズ40、ガラス基板30、赤外線カットフィルタ42、平坦化層46を順次透過した後、基板100の撮像素子部に到達するようになっている。
また、カメラモジュール200は、基板100の第2の主面側で、ハンダボール60(接続材料)を介して回路基板70に接続されている。
基板100は、基体であるシリコン基板10、撮像素子12、層間絶縁膜13、ベース層14、赤色のカラーフィルタ15R、緑色のカラーフィルタ15G、青色のカラーフィルタ15B、オーバーコート16、マイクロレンズ17、遮光膜18、絶縁膜22、金属電極23、ソルダレジスト層24、内部電極26、及び素子面電極27を備えて構成されている。
但し、ソルダレジスト層24は省略されていてもよい。
図3に示すように、基板100の基体であるシリコン基板10の第1の主面側に、CCDやCMOS等の撮像素子12が2次元に複数配列された撮像素子部が設けられている。
撮像素子部における撮像素子12上には層間絶縁膜13が形成されており、層間絶縁膜13上にはベース層14が形成されている。更にベース層14上には、撮像素子12に対応するように、赤色のカラーフィルタ15R、緑色のカラーフィルタ15G、青色のカラーフィルタ15B(以下、これらをまとめて「カラーフィルタ15」ということがある)がそれぞれ配置されている。
赤色のカラーフィルタ15R、緑色のカラーフィルタ15G、青色のカラーフィルタ15Bの境界部、及び撮像素子部の周辺には、図示しない遮光膜が設けられていてもよい。この遮光膜は、例えば、公知のブラックのカラーレジストを用いて作製できる。
カラーフィルタ15上にはオーバーコート16が形成され、オーバーコート16上には撮像素子12(カラーフィルタ15)に対応するようにマイクロレンズ17が形成されている。
そして、マイクロレンズ17の上には、前記平坦化層46が設けられている。
更に、内部電極26上には、層間絶縁膜13を介して素子面電極27が形成されている。内部電極26と素子面電極27間の層間絶縁膜13内には、これら電極間を電気的に接続するコンタクトプラグ(不図示)が形成されている。素子面電極27は、コンタクトプラグ、内部電極26を介して電圧の印加及び信号の読み出しなどに使用される。
素子面電極27上には、ベース層14が形成されている。ベース層14上にはオーバーコート16が形成されている。素子面電極27上に形成されたベース層14及びオーバーコート16が開口されて、パッド開口部が形成され、素子面電極27の一部が露出している。
基板100の第1の主面側において、撮像素子部の周辺には接着剤20が設けられ、この接着剤20を介し、基板100とガラス基板30とが接着される。
該第2の主面側には、第2の主面上から貫通孔の内壁にわたり絶縁膜22が形成されている。
絶縁膜22上には、シリコン基板10の第2の主面上の領域から貫通孔の内部に至るようにパターニングされた金属電極23が設けられている。金属電極23は、基板100中の撮像素子部と回路基板70との接続用の電極である。
前記貫通電極は、この金属電極23のうち、貫通孔の内部に形成された部分である。貫通電極は、シリコン基板10及び層間絶縁膜の一部を貫通して内部電極26の下側に至り、該内部電極26に電気的に接続されている。
更に、第2の主面側には、ソルダレジスト層24が形成された第2の主面上を覆い、かつ、該金属電極23上の1部が露出する開口部を有する遮光膜18が設けられている。
なお、図3では、遮光膜18は、金属電極23の1部を覆い、残りの部分を露出させるようにパターニングされているが、金属電極23の全部を露出させるようにパターニングされていてもよい(ソルダレジスト層24のパターニングについても同様である)。
また、ソルダレジスト層24は省略されていてもよく、金属電極23が形成された第2の主面上に、遮光膜18が直接形成されていてもよい。
層間絶縁膜13は、例えば、スパッタやCVD(Chemical vapor deposition)等によりSiO2膜又はSiN膜として形成する。
カラーフィルタ15は、例えば、公知のカラーレジストを用い、フォトリソグラフィーにより形成する。
オーバーコート16及びベース層14は、例えば、公知の有機層間膜形成用レジストを用い、フォトリソグラフィーにより形成する。
マイクロレンズ17は、例えば、スチレン系樹脂等を用い、フォトリソグラフィー等により形成する。
ソルダレジスト層24は、例えばフェノール系樹脂、あるいはポリイミド系樹脂、アミン系樹脂を含む公知のソルダレジストを用い、フォトリソグラフィーにより形成されることが好ましい。
ハンダボール60は、例えば、Sn-Pb(共晶)、95Pb-Sn(高鉛高融点半田)、Pbフリー半田として、Sn-Ag、Sn-Cu、Sn-Ag-Cuなどを用いて形成する。ハンダボール60は、例えば、直径100μm~1000μm(好ましくは直径150μm~700μm)の球状に形成する。
内部電極26及び素子面電極27は、例えば、CMP(Chemical Mechanical Polishing)、又はフォトリソグラフィー及びエッチングにより、Cu等の金属電極として形成する。
金属電極23は、例えば、スパッタ、フォトリソグラフィー、エッチング、及び電解めっきにより、Cu、Au、Al、Ni、W、Pt、Mo、Cu化合物、W化合物、Mo化合物等の金属電極として形成する。金属電極23は、単層構成でも2層以上からなる積層構成であってもよい。金属電極23の膜厚は、例えば、0.1μm~20μm(好ましくは0.1μm~10μm)とする。シリコン基板10としては特に限定されないが、基板裏面を削ることによって薄くしたシリコン基板を用いることができる。基板の厚さは限定されないが、例えば、厚み20μm~200μm(好ましくは30~150μm)のシリコンウエハーを用いる。
シリコン基板10の貫通孔は、例えば、フォトリソグラフィー及びRIE(Reactive Ion Etching)により形成する。
[二酸化チタン分散液(分散組成物)の調製]
下記組成の混合液に対し、循環型分散装置(ビーズミル)として、シンマルエンタープライゼス株式会社製NPMを用いて、以下のようにして分散処理を行い、分散組成物として二酸化チタン分散液を得た。
~組成~
・二酸化チタン(石原産業(株)製 TTO-51(C)):150.0部
(結晶形:ルチル、TiO2純度(%):79~85%、Al2O3及びステアリン酸で表面処理、比表面積50~60m2/g、一次粒子径10~30nm、吸油量24~30g/100g)
・下記分散樹脂A-1(固形分20%PGMEA溶液) :165.0部
・プロピレングリコールモノメチルエーテルアセテート(PGMEA)
:142.5部
・ビーズ径:φ0.05mm
・ビーズ充填率:60体積%
・周速:10m/秒
・ポンプ供給量:30kg/時間
・冷却水:水道水
・ビーズミル環状通路内容積:1.0L
・分散処理する混合液量:10kg
平均粒子径は分散時間(パス回数)とともに減少していったが、次第にその変化量が少なくなっていった。分散時間を30分間延長したときの平均粒子径変化が5nm以下となった時点で分散を終了した。なお、この分散液中の二酸化チタン粒子の平均粒子径は40nmであった。
この測定は、日機装株式会社製マイクロトラックUPA-EX150を用いて行った。
・上記で調製した二酸化チタン分散液(分散組成物) ・・・80.0部
・溶剤:PGMEA ・・・15部
・重合性化合物:KAYARAD DPHA
(日本化薬(株)製) ・・・3.6部
・重合開始剤:OXE-01(商品名)BASF社製 ・・・0.10部
・ポリマーA:ベンジルメタクリレート/メタクリル酸共重合体
(共重合比:80/20(質量%)、重量平均分子量:12,000)
(FFFC社製) ・・・1.0部
・界面活性剤:メガファックF-781(DIC(株)製)
・・・0.30部
前記高屈折率層形成用の硬化性樹脂組成物1をシリコンウエハー上に塗布後、プリベーク(100℃2分)、ポストベーク(230℃10分)を実施して高屈折率層1を形成した。
前記高屈折率層の屈折率を、ジェー・エー・ウーラム・ジャパン社製エリプソメーターを用いて測定した。測定条件は、633nmで、25℃とし、5点の平均値を採用した。結果を下記表に示した。
使用する硬化性組成物中の成分比率を下記組成比に変更し、高屈折率層形成用の硬化性樹脂組成物1と同様の工程により各種高屈折率層形成用の硬化性樹脂組成物を調製した。なお、各高屈折率層の屈折率測定結果も合わせて記す。
(分散剤)
A-2・・下記式で表される分散剤。
(重合性化合物)
1031S・・・JER1031S(三菱化学(株)製)
157S65・・・JER157S65(三菱化学(株)製)
(バインダー)
ポリマーB・・・アクリベース
(ベンジルメタクリレート/i-ブチルメタクリレート/2-ヒドロキシエチルメタクリレート/メタクリル酸共重合体とメトキシポリエチレングリコールとのグラフト共重合物、藤倉化成(株)製)
[シロキサンの調製]
メチルトリエトキシシラン(MTES)及び/又はテトラエトキシシラン(TEOS)を用いて、加水分解・縮合反応を行い、加水分解縮合物S-1、S-2、S-c1を得た。このときに用いた溶媒は エタノールである。得られた加水分解縮合物S-1は重量平均分子量 約10000であった。
以下の成分を配合して、低屈折率層形成用の硬化性樹脂組成物1を調製した。
・シロキサン:上記加水分解縮合物S-1 ・・・20部
・溶剤:プロピレングリコールモノメチルエーテルアセテート
(PGMEA) ・・・62部
・溶剤:3-エトキシプロピオン酸エチル(EEP) ・・・16部
・界面活性剤:EMULSOGEN-COL-020
(クラリアントジャパン製) ・・・2部
また、下記表の成分を配合して、低屈折率層形成用の硬化性樹脂組成物2、3を調製した。
また、以下の成分を配合して、低屈折率層形成用の硬化性樹脂組成物4を調製した。
・中空粒子:スルーリア2320(日揮触媒化成(株)製)・・・35部
・硬化性樹脂:サイクロマーP ACA230AA(略称:230AA)
(ダイセル化学(株)製) ・・・26部
・重合開始剤:OXE-01(BASF製) ・・・0.05部
・界面活性剤:メガファックF-781
(DIC(株)製) ・・・0.01部
・溶剤:PGMEA ・・・38.94部
低屈折率層形成用の硬化性樹脂組成物2~4についても低屈折率層形成用の硬化性樹脂組成物1と同様に低屈折率層を作製した。屈折率の測定方法は、高屈折率層の測定方法と同じである。
(色素含有層用の組成物A)
下記組成の成分を攪拌機で混合し、色素含有層用の組成物を調製した。
・フタロシアニン系色素A(日本触媒製 Excolor TX-EX 720;極大吸収波長(λmax)=720nm(膜))
149.0質量部
・前記JER157S65(三菱化学(株)製) 24.5質量部
(重合性化合物)
・ペンタエリスリトールテトラアクリレート 24.5質量部
(新中村化学工業株式会社製A-TMMT)(重合性化合物)
・メガファックF-781F(DIC株式会社製)(界面活性剤)
2.0質量部
・PGMEA 200.0質量部
フタロシアニン系色素Aに代えて、フタロシアニン系色素B(日本触媒製 Excolor TX-EX 708K;極大吸収波長(λmax)=755nm(膜))を用いた以外は、色素含有層用の組成物Aと同様とすることにより、色素含有層用の組成物Bを調製した。
無水安息香酸銅(関東化学(株)製)5g、及びメタクリロイルオキシエチルホスフェート(城北化学工業社製)7gをアセトン25ml中に溶解し、室温で4時間攪拌しながら反応を進行させた。得られた反応生成物を、ヘキサン溶剤中に滴下し、沈殿物を濾過により抽出、乾燥することで銅錯体を得た。
下記組成の成分を攪拌機で混合し、銅化合物含有層用の組成物Cを調製した。
(銅化合物含有層用の組成物C)
・前記銅錯体 149.0質量部
・JER157S65(三菱化学(株)製) 24.5質量部
(重合性化合物)
・ペンタエリスリトールテトラアクリレート 24.5質量部
(新中村化学工業株式会社製A-TMMT)(重合性化合物)
・メガファックF-781F(DIC株式会社製)(界面活性剤)
2.0質量部
・PGMEA 200.0質量部
色素含有層用の組成物Aを銅化合物含有層用の組成物Cに変更しアプリケータを用いて塗布する以外は色素含有層Aと同様にして、膜厚50μmの銅錯体含有層Cを得た。
上記得られた色素含有層A上に、前述で調製した高屈折率層形成用の硬化性樹脂組成物1を用いて、スピンコーターを用いて塗布膜を形成し、次いで、100℃2分の前加熱を行った後、140℃10分の後加熱を行った。
次に、得られた高屈折率層上に、前述で調製した低屈折率層形成用の硬化性樹脂組成物1を用いて、スピンコーターを用いて塗布膜を形成し、次いで、100℃2分の前加熱を行った後、140℃10分の後加熱を行った。
以降、同様に、高屈折率層形成用の硬化性樹脂組成物1による高屈折率層の形成と、低屈折率層形成用の硬化性樹脂組成物1による低屈折率層の形成とを繰り返し、高屈折率層と低屈折率層とが交互に積層されてなり、総積層数20の総膜厚2.6μmの赤外線反射膜1-1を上記色素含有層A上に形成した赤外線カットフィルタA-1を形成した。
(近赤外線遮蔽性評価、赤外線遮蔽性評価)
上記のようにして得た赤外線カットフィルタの波長700nmの透過率を、紫外可視近赤外分光光度計UV3600(島津製作所製)を用いて測定した。数値が低いほど近赤外線遮蔽性に優れると評価する。波長700nmの透過率に関しては、可視光透過率が10%以下で実用上良好な近赤外線遮蔽性を示すといえる。
更に、上記赤外線カットフィルタにおける波長1300nmの透過率を分光光度計U-4100(日立ハイテクノロジーズ社製)を用いて測定した。数値が低いほど赤外線遮蔽性に優れると評価する。赤外線透過率が25%未満で実用上良好な赤外線遮蔽性を示すといえる。いずれの赤外線カットフィルタにおいても、それらを満たす良好な結果が得られた。
まず、画素受光部ピッチ2.0μm、画素数2592個(X軸方向)×1944個(Y軸方向)のフォトダイオード(受光部サイズ1.0μm×1.0μm)からなり、基板に一定の配置ピッチで2次元配置された複数の受光素子と、Alからなる配線層と遮光層を有する絶縁層(酸化珪素)と、パッシベーション層(窒化珪素)と、導波路(窒化珪素)とを備えたCMOSセンサーを形成したウェハを用意した。このCMOSセンサーでは、パッシベーション層の厚みを0.3μm、パッシベーション層と導波路との間に介在する絶縁層の厚みを0.3μm、導波路の厚みが2.1μmとした。導波路の入口平面寸法は1.5μm×1.5μm、出口平面寸法はフォトダイオード寸法と同じく1.0μm×1.0μmとした。また、パッシベーション層、絶縁層、導波路の屈折率を分光エリプソメータにより測定した結果、パッシベーション層の屈折率は2.0、絶縁層の屈折率は1.46、導波路の屈折率は1.88、導波路の外側の絶縁層の屈折率は1.46であった。なお、屈折率の値は、以降も含めて、特に波長に指定のない限り、波長550nmでの値である。
パッシベーション層上に、光硬化型アクリル系透明樹脂材料(富士フイルムエレクトロニクスマテリアルズ(株)製CT-2020L)をスピン塗布し、次いで、プリベーク、紫外線全面露光、ポストベークを行って下平坦化層(厚み0.3μm)を形成した。この下平坦化層について、上記と同様に屈折率を測定した結果、1.56であった。
ネガ型感光性の赤色材料(R用材料)、緑色材料(G用材料)、青色材料(B用材料)として以下の材料を用意した。
R用材料:富士フイルムエレクトロマテリアルズ(株)製SR-4000L
G用材料:富士フイルムエレクトロマテリアルズ(株)製SG-4000L
B用材料:富士フイルムエレクトロマテリアルズ(株)製SB-4000L
G、R、Bの形成順序に、上記材料をスピン塗布し、プリベーク、1/5縮小型のi線ステッパーによる露光、現像、ポストベークを行って、カラーフィルタ(膜厚0.8μm)を形成した。すなわち、まず、下平坦化層上にG用材料を塗布し、露光、現像した後、ポストベーク(220℃、10分間)を行って、市松状に緑色フィルタを形成した。次に、この緑色フィルタを被覆するようにR用材料を塗布し、フォトマスクを用いて露光、現像した後、ポストベーク(220℃、10分間)を行って赤色フィルタを形成した。次いで、赤色フィルタ、緑色フィルタを被覆するようにB用材料を塗布し、フォトマスクを用いて露光、現像した後、ポストベーク(220℃、10分間)を行って、青色フィルタを形成した。
なお、現像液として、富士フイルムエレクトロマテリアルズ(株)製CD-2000の50%希釈液を使用した。
形成したカラーフィルタの各色フィルタについて、上記と同様に屈折率を測定した結果、赤色フィルタの屈折率は1.59(波長620nm)、緑色フィルタの屈折率は1.60(波長550nm)、青色フィルタの屈折率は1.61(波長450nm)であった。
カラーフィルタ上に、光硬化型アクリル系透明樹脂材料(富士フイルムエレクトロマテリアルズ(株)製CT-2020L)をスピン塗布し、次いで、プリベーク、紫外線全面露光、ポストベークを行って上平坦化層を形成した。形成した上平坦化層の厚みは0.3μmであり、上記と同様に測定した屈折率は1.56であった。
上平坦化層に、マイクロレンズ材料としてJSR(株)製MFR401Lをスピン塗布し、プリベーク、1/5縮小型のi線ステッパーによる露光、現像、後露光、ポストベークによるメルトフローを行って、マイクロレンズ(高さ0.675μm)を形成した。形成したマイクロレンズの屈折率を上記と同様に測定した結果、1.61であった。なお、現像液として、TMAH(テトラメチルアンモニウムハイドロオキサイド)の1.19質量%溶液を使用した。
得られた固体撮像素子上に、前述で調製した色素含有層用の組成物Aを用いて、3000rpmでスピン塗布(MIKASA Co.,LTD製のMIKASA SPINCOATER 1H-D7を使用)し、塗布膜を形成し、次いで、100℃2分の前加熱を行った後、140℃10分の後加熱を行った。膜厚約2μmの色素含有層を得た。
またガラス基板上に、前述で調製した高屈折率層形成用の硬化性樹脂組成物1を用いて、スピンコーターを用いて塗布膜を形成し、次いで、100℃2分の前加熱を行った後、140℃10分の後加熱を行った。
次に、得られた高屈折率層上に、前述で調製した低屈折率層形成用の硬化性樹脂組成物1を用いて、スピンコーターを用いて塗布膜を形成し、次いで、100℃2分の前加熱を行った後、140℃10分の後加熱を行った。
以降、同様に、高屈折率層形成用の硬化性樹脂組成物1による高屈折率層の形成と、低屈折率層形成用の硬化性樹脂組成物1による低屈折率層の形成とを繰り返し、高屈折率層と低屈折率層とが交互に積層されてなる総積層数20の総膜厚2.6μmの赤外線反射膜1-1を形成した。
そのガラス基板を色素含有層上に接着剤を用いて貼り付けた。
次いで、ウェハのダイシングを行い、パッケージ組立を行って、本発明の固体撮像素子Aを作製した。
(入射角依存性の測定及び評価)
このように作製した固体撮像素子にカメラレンズを組み合わせ、有効撮像領域の中(主光線入射角度0°)での感度を100%としたときの、主光線入射角度が5°、10°、15°、20°、25°、30°の各グリーン画素での相対感度を測定した。その結果から、シェーディングが抑制されていることが確認された。
また、本発明の高屈折率層形成用ないしは低屈折率層形成用の硬化性樹脂組成物は、例えば塗布により高屈折率層ないしは低屈折率層を形成することができるので、この点において、赤外線カットフィルタを煩雑な工程を要することなく製造できるため、上記した従来の赤外線カットフィルタにおける不充分な製造適性を改善することができる。
このように、本発明の高屈折率層形成用ないしは低屈折率層形成用の硬化性樹脂組成物は、基板と、前記基板の受光側に配置された赤外線カットフィルタとを有するカメラモジュールを作製するのに適する。
また、本発明によれば、上記硬化性樹脂組成物を用いることにより、赤外線カットフィルタと、固体撮像素子における基板の表面とを空間を挟まずに密着させることができ、これによりカラーシェーディングが抑制された固体撮像素子を提供することができる。
本出願は、2012年12月28日出願の日本特許出願(特願2012-288696)に基づくものであり、その内容はここに参照として取り込まれる。
2 高屈折率層
3 低屈折率層
10 シリコン基板
12 撮像素子
13 層間絶縁膜
14 ベース層
15 カラーフィルタ
16 オーバーコート
17 マイクロレンズ
18 遮光膜
20 接着剤
22 絶縁膜
23 金属電極
24 ソルダレジスト層
26 内部電極
27 素子面電極
30 ガラス基板
40 撮像レンズ
42 赤外線カットフィルタ
44 遮光兼電磁シールド
45 接着剤
46 平坦化層
50 レンズホルダー
60 ハンダボール
70 回路基板
100 基板
200 カメラモジュール
Claims (19)
- 50~250nmの膜厚で塗布可能な、屈折率1.65~2.00の赤外線反射膜形成用の硬化性樹脂組成物。
- 上記屈折率1.65~2.00の赤外線反射膜形成用の硬化性樹脂組成物が、金属酸化物粒子、バインダー及び分散剤を含有する、請求項1に記載の赤外線反射膜形成用の硬化性樹脂組成物。
- 50~250nmの膜厚で塗布可能な、屈折率1.20~1.45の赤外線反射膜形成用の硬化性樹脂組成物。
- 上記屈折率1.20~1.45の赤外線反射膜形成用の硬化性樹脂組成物が、シロキサン樹脂を含有する、請求項3に記載の赤外線反射膜形成用の硬化性樹脂組成物。
- 支持体上に、屈折率1.65~2.00の赤外線反射膜形成用の硬化性樹脂組成物を塗布してなる膜厚50~250nmの高屈折率層を2層以上と、
屈折率1.20~1.45の赤外線反射膜形成用の硬化性樹脂組成物を塗布してなる膜厚50~250nmの低屈折率層を2層以上とを有する赤外線反射膜。 - 上記高屈折率層と、上記低屈折率層とが交互に積層している、請求項5に記載の赤外線反射膜。
- 前記屈折率1.65~2.00の赤外線反射膜形成用の硬化性樹脂組成物と、前記屈折率1.20~1.45の赤外線反射膜形成用の硬化性樹脂組成物とのいずれか一方が水ないしは親水性溶剤を含有する組成物であり、他方が疎水性溶剤を含有する組成物である、請求項5に記載の赤外線反射膜。
- 上記水ないしは親水性溶剤を含有する組成物がフッ素原子含有化合物を含有し、上記疎水性溶剤を含有する組成物が表面エネルギー調整剤を含有する、請求項7に記載の赤外線反射膜。
- 上記2層以上の高屈折率層が、屈折率1.65~2.00の範囲内で互いに異なる屈折率を有する複数種の層である、請求項5~8のいずれか1項に記載の赤外線反射膜。
- 上記2層以上の高屈折率層が、膜厚50~250nmの範囲内で互いに異なる膜厚を有する複数種の層である、請求項5~9のいずれか1項に記載の赤外線反射膜。
- 上記2層以上の低屈折率層が、屈折率1.20~1.45の範囲内で互いに異なる屈折率を有する複数種の層である、請求項5~10のいずれか1項に記載の赤外線反射膜。
- 上記2層以上の低屈折率層が、膜厚50~250nmの範囲内で互いに異なる膜厚を有する複数種の層である、請求項5~11のいずれか1項に記載の赤外線反射膜。
- 上記2層以上の高屈折率層と、上記2層以上の低屈折率層との積層数が4~60層である、請求項5~12のいずれか1項に記載の赤外線反射膜。
- 膜厚50~250nmで屈折率1.65~2.00の高屈折率層を、硬化性樹脂組成物を用いて形成する工程、及び
膜厚50~250nmで屈折率1.20~1.45の低屈折率層を、硬化性樹脂組成物を用いて形成する工程を有し、
前記赤外線反射膜が2層以上の高屈折率層と2層以上の低屈折率層とを有する赤外線反射膜の製造方法。 - 上記高屈折率層を形成する工程と、上記低屈折率層を形成する工程とを交互に行い、上記高屈折率層と上記低屈折率層とを交互に積層させる、請求項14に記載の赤外線反射膜の製造方法。
- 請求項5~13のいずれか1項に記載の赤外線反射膜と600nm~820nmの範囲内に極大吸収波長を有する色素又は銅錯体を含有する層とを有する赤外線カットフィルタ。
- 上記600nm~820nmの範囲内に極大吸収波長を有する色素又は銅錯体がシアニン系色素、フタロシアニン系色素、アミニウム系色素、イミニウム系色素、アゾ系色素、アンスラキノン系色素、ジイモニウム系色素、スクアリリウム系色素、ポルフィリン系色素及び銅錯体からなる群から選択される少なくとも1種である、請求項16に記載の赤外線カットフィルタ。
- 基板上に、請求項16又は17に記載の赤外線カットフィルタを有する固体撮像素子。
- 上記基板がカラーフィルタ層を有する、請求項18に記載の固体撮像素子。
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JP6140604B2 (ja) | 2017-05-31 |
SG11201505047WA (en) | 2015-08-28 |
TW201431682A (zh) | 2014-08-16 |
EP2940090A1 (en) | 2015-11-04 |
US20150293281A1 (en) | 2015-10-15 |
CN105102560A (zh) | 2015-11-25 |
KR20150090142A (ko) | 2015-08-05 |
EP2940090A4 (en) | 2016-01-06 |
JP2014142628A (ja) | 2014-08-07 |
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