JP5044908B2 - Non-photosensitive resin composition and optical element using the same - Google Patents

Description

  The present invention relates to a non-photosensitive resin composition and an optical element using the same. More specifically, the present invention relates to a condensing lens used for a solid-state imaging device and the like, and a non-photosensitive resin composition for forming the condensing lens.

  In recent years, with the rapid development of digital cameras, camera-equipped mobile phones, and the like, there has been a demand for downsizing and increasing the number of pixels of solid-state imaging devices. Since downsizing of the solid-state imaging device causes a decrease in sensitivity, a condensing lens is disposed between the light receiving unit and the color filter or above the color filter to efficiently collect light and prevent a decrease in sensitivity. As a general manufacturing method of this condensing lens, there are a method of processing an inorganic film formed by a CVD method or the like by dry etching, and a method of applying and processing a resin. The former method is currently attracting attention because it is difficult to obtain a refractive index of 1.78 to 1.90 optimum for a lens.

  For example, a curable composition containing a hydroxyl group-containing resin such as polyvinyl butyral resin, titanium oxide particles, a curable compound, and a curing catalyst is disclosed (for example, see Patent Document 1). Although a cured film having a high refractive index can be obtained, since the viscosity is not sufficiently high, it is difficult to obtain a film thickness of 1 μm or more optimum for a lens. Further, when the viscosity is increased, there is a problem that when the dispersibility between the particles and the resin is not sufficient, the particles are aggregated to become a foreign substance, and the transmittance is reduced when the film thickness is 1 μm or more.

Further, a positive photosensitive resin composition containing a photosensitive resin and metal particles is disclosed (for example, see Patent Document 2). In this method, particularly when the film thickness exceeds 1 μm, the transmittance is lowered, and a sufficient film for use in an optical element cannot be obtained.
JP 2004-169018 A JP 2003-75997 A

  An object of the present invention is to provide a non-photosensitive resin composition that forms a cured film having a moderately high refractive index, a high transmittance, and no cracks even after a heat cycle.

In order to solve the above problems, the present invention mainly has the following configuration. That is, (a) one or more polymers selected from the group consisting of polyimide, polybenzoxazole, polyimide benzoxazole and their precursors, and (b) aluminum compound sol, silicon compound sol, tin compound sol, titanium compound sol A thermally crosslinkable compound having an inorganic particle having an average particle diameter of 1 to 30 nm containing at least one compound sol selected from zirconium compound sol , and (c1) at least two groups represented by the general formula (1) And / or (c2) a non-photosensitive resin composition comprising a thermally crosslinkable compound having a urea organic group represented by the general formula (2).

(In the formula, R ^{1 s} may be the same or different and each represents a hydrogen atom or a monovalent organic group.)

  The non-photosensitive resin composition of the present invention has a high refractive index and transmittance, and can form a good cured film in which cracks do not occur even after a heat cycle. The cured film can be suitably used for a microlens for a solid-state imaging device.

The non-photosensitive resin composition of the present invention contains (a) a polymer, (b) inorganic particles, and (c) a thermally crosslinkable compound.

  The polymer (a) used in the present invention is selected from polyimide or a precursor thereof, polybenzoxazole or a precursor thereof, polyimide benzoxazole or a precursor thereof, and a structural unit represented by the following general formula (3): It is preferable to have.

In the formula, R ² represents a divalent to octavalent organic group having at least 2 carbon atoms, and R ³ represents a divalent to hexavalent organic group having at least 2 carbon atoms. R ⁴ represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. n is an integer of 10 to 100,000, m is an integer of 0 to 2, and p and q are integers of 0 to 4.

R ^{2 in the} general formula (3) represents a structural component of acid dianhydride. R ² preferably contains an aromatic ring, and more preferably a trivalent or tetravalent organic group having 6 to 30 carbon atoms. p is preferably 1 to 4.

Specifically, a structure in which R ² (COOR ⁴ ) m (OH) p in the general formula (3) is represented by the general formula (4) is preferable. In this case, R ⁵ and R ⁷ represent a divalent to tetravalent organic group having 2 to 20 carbon atoms, but those containing an aromatic ring are preferred from the viewpoint of heat resistance of the obtained polymer, and among them, particularly Preferred structures include trimellitic acid, trimesic acid and naphthalene tricarboxylic acid residues. R ⁶ represents a C 3-20 trivalent organic group. Furthermore, the hydroxyl group is preferably located adjacent to the amide bond. Examples of acid dianhydrides having such a structure include fluorine atoms containing bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-hydroxy-4-aminophenyl) hexafluoropropane, No fluorine atom, bis (3-amino-4-hydroxyphenyl) propane, bis (3-hydroxy-4-aminophenyl) propane, 3,3′-diamino-4,4′-dihydroxybiphenyl, 3,3 Mention of amino group of '-diamino-4,4'-dihydroxybiphenyl, 2,4-diamino-phenol, 2,5-diaminophenol, 1,4-diamino-2,5-dihydroxybenzene, etc. Can do.

Moreover, ^{R 8} and ^{R 9} in the general formula (4) represents an organic group of a hydrogen atom or a C 1-20. In the general formula (4), o and s represent integers of 0 to 2, and 0 ≦ o + s ≦ 2. r represents an integer of 1 to 4.

  Among the structures represented by the general formula (4), examples of preferable structures include those shown below, but are not limited thereto.

  Moreover, tetracarboxylic acid and dicarboxylic acid which do not have a hydroxyl group can also be added as a copolymerization component. Examples of this include aromatic tetracarboxylic acids such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, and diphenylsulfone tetracarboxylic acid, and two carboxyl groups thereof as methyl or ethyl groups. Diester compounds, aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and cyclopentanetetracarboxylic acid, diester compounds in which two carboxyl groups are methyl or ethyl groups, terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalene dicarboxylic acid Examples thereof include aromatic dicarboxylic acids such as acids, and aliphatic dicarboxylic acids such as adipic acid.

R ^{3 in the} general formula (3) represents a structural component of diamine. Preferred examples of diamines include those having an aromatic ring and a hydroxyl group from the viewpoint of the heat resistance of the resulting polymer, and specific examples include bis (amino-hydroxy-phenyl) having a fluorine atom. ) Hexafluoropropane, compounds having no fluorine atom, such as diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxy-diamino-pyrimidine, diaminophenol, dihydroxybenzidine. Also, ^R 3 (OH) q is of the general formula (3) (5), (6), may be mentioned those having the structure shown in (7).

^{Wherein, R 10} and ^{R 12} represents a 3-4 valent organic group having 2 to 20 carbon atoms. R ¹¹ represents a divalent organic group having 2 to 30 carbon atoms. t and u represent 1 or 2.

^{Wherein, R 13} and ^{R 15} is a divalent organic group having 2 to 20 carbon atoms. R ¹⁴ represents a C 3-20 trivalent organic group. v represents an integer of 1 to 4.

In the formula, R ¹⁶ represents a divalent organic group having 2 to 20 carbon atoms. R ¹⁷ represents a C 3-20 trivalent organic group. w shows the integer of 1-4.

  Specific examples of the structure represented by the general formula (5) are shown below.

  Specific examples of the structure represented by the general formula (6) are shown below.

  Specific examples of the structure represented by the general formula (7) are shown below.

In the general formula (5), R ¹⁰ and R ¹² are preferably those having an aromatic ring in view of heat resistance of 3-4 monovalent indicates an organic group, the resulting polymer having 2 to 20 carbon atoms. ^{R 10 - (OH) t,} R 12 - (OH) Specific examples of u is hydroxyphenyl group, dihydroxyphenyl group, hydroxynaphthyl group, dihydroxynaphthyl group, hydroxy biphenyl group, dihydroxybiphenyl group, a bis (hydroxyphenyl) Examples thereof include a hexafluoropropane group, a bis (hydroxyphenyl) propane group, a bis (hydroxyphenyl) sulfone group, a hydroxydiphenyl ether group, and a dihydroxydiphenyl ether group. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used. R ¹¹ represents a divalent organic group having 2 to 30 carbon atoms. From the viewpoint of the heat resistance of the resulting polymer, a divalent group having an aromatic ring is preferable, and examples thereof include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group. In addition, an aliphatic cyclohexyl group and the like can also be used.

In the general formula (6), R ¹³ and R ¹⁵ represent a divalent organic group having 2 to 20 carbon atoms. From the viewpoint of the heat resistance of the resulting polymer, a divalent group having an aromatic ring is preferable, and examples thereof include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group. In addition, an aliphatic cyclohexyl group and the like can also be used. R ¹⁴ represents a C 3-20 trivalent organic group and preferably has an aromatic ring from the viewpoint of the heat resistance of the polymer obtained. Specific examples of R ^14- (OH) v include hydroxyphenyl group, dihydroxyphenyl group, hydroxynaphthyl group, dihydroxynaphthyl group, hydroxybiphenyl group, dihydroxybiphenyl group, bis (hydroxyphenyl) hexafluoropropane group, bis (Hydroxyphenyl) propane group, bis (hydroxyphenyl) sulfone group, hydroxydiphenyl ether group, dihydroxydiphenyl ether group and the like can be mentioned. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used.

In the general formula (7), R ¹⁶ represents a divalent organic group having 2 to 20 carbon atoms. From the viewpoint of the heat resistance of the resulting polymer, a divalent group having an aromatic ring is preferable, and examples thereof include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group. In addition, an aliphatic cyclohexyl group and the like can also be used. R ¹⁷ represents a C 3-20 trivalent organic group and preferably has an aromatic ring from the viewpoint of the heat resistance of the resulting polymer. Specific examples of R ^17- (OH) w include hydroxyphenyl group, dihydroxyphenyl group, hydroxynaphthyl group, dihydroxynaphthyl group, hydroxybiphenyl group, dihydroxybiphenyl group, bis (hydroxyphenyl) hexafluoropropane group, bis (hydroxy Phenyl) propane group, bis (hydroxyphenyl) sulfone group, hydroxydiphenyl ether group, dihydroxydiphenyl ether group and the like. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used.

  Moreover, the diamine component which has structures other than general formula (5)-(7) can also be added as a copolymerization component. Examples include phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone or their fragrances. Examples thereof include aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and the like, such as compounds in which an aromatic ring is substituted with an alkyl group or a halogen atom.

R ^{4 in the} general formula (3) represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. In the present invention, a hydrogen atom and an alkyl group can be mixed, and R ⁴ preferably contains at least one hydrocarbon group having 1 to 16 carbon atoms, and the others are hydrogen atoms.

Furthermore, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with R ² and R ³ in the general formula (3) as long as the heat resistance is not lowered. Specifically, examples of the diamine component include those obtained by copolymerizing 1 to 10 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane, and the like.

  The polymer containing the structural unit represented by the general formula (3) of the present invention may be composed only of the structural unit or may be a copolymer with another structural unit. In that case, it is preferable to contain 90 mol% or more of the structural unit represented by General formula (3). The type and amount of the structural unit used for copolymerization can be selected within a range that does not significantly reduce the refractive index, transmittance, and film properties of the cured film obtained by the final heat treatment.

  The polyimide, polybenzoxazole, polyimide benzoxazole, and their precursors used in the present invention can be obtained by condensing a diamine compound with dicarboxylic acid or acid dianhydride. For example, as a method for synthesizing polyhydroxyamide, which is a polybenzoxazole precursor, there is a method in which a bisaminophenol compound and a dicarboxylic acid are subjected to a condensation reaction. Specifically, a dehydration condensing agent such as dicyclohexylcarbodiimide (DCC) is reacted with an acid, and a bisaminophenol compound is added thereto, or a solution of a bisaminophenol compound added with a tertiary amine such as pyridine is added to a dicarboxylic acid. For example, a solution of acid dichloride is dropped.

  The polymer containing the structural unit represented by the general formula (3) of the present invention is, for example, a method of reacting a tetracarboxylic dianhydride and a diamine compound at a low temperature, a diester by a tetracarboxylic dianhydride and an alcohol. And then reacting in the presence of an amine and a condensing agent, obtaining a diester with tetracarboxylic dianhydride and alcohol, and then synthesizing the remaining dicarboxylic acid with acid chloride and reacting with an amine. Can do.

The inorganic particles of component (b) used in the present invention, aluminum compounds, silicon compounds, tin compounds, titanium compounds, and the particle element of zirconium compound. More specifically, aluminum complexes, aluminum oxide particles, tin oxide-aluminum oxide composite particles, silicon oxide-aluminum oxide composite particles, zirconium oxide-aluminum oxide composite particles, tin oxide-silicon oxide composite particles, zirconium oxide-silicon oxide Composite particles, etc., tin complexes, tin oxide particles, zirconium oxide-tin oxide composite particles, etc., titanium complexes, titanium oxide particles, tin oxide-titanium oxide composite particles, silicon oxide-titanium oxide composite particles, zirconium oxide-titanium oxide composite particles And the like, zirconium complexes, zirconium oxide particles and the like. Of these, preferably, tin oxide-aluminum oxide composite particles, zirconium oxide-aluminum oxide composite particles, zirconium oxide-silicon oxide composite particles, etc., tin oxide particles, zirconium oxide-tin oxide composite particles, etc., titanium oxide particles, oxidation Examples thereof include tin-titanium oxide composite particles, silicon oxide-titanium oxide composite particles, zirconium oxide-titanium oxide composite particles, and zirconium oxide particles. Particularly preferred are tin oxide-titanium oxide composite particles, silicon oxide-titanium oxide composite particles, titanium oxide particles, zirconium oxide-tin oxide composite particles, zirconium oxide-silicon oxide composite particles, and zirconium oxide particles. In particular, for titanium oxide particles, the photocatalytic reaction can be reduced by covering the surface with other substances. The particles, Ru sol der in terms of easiness of dispersion into the polymer.

  The average particle diameter of these inorganic particles is 1 to 30 nm, preferably 1 to 15 nm. The average particle diameter here means number average. The average particle diameter can be measured by a gas adsorption method, a dynamic light scattering method, an X-ray small angle scattering method, a method of directly measuring the particle size using a transmission electron microscope, or the like. The particle diameter obtained by these measurement methods may be a volume average or a mass average, but can be converted to a number average by assuming that the particle shape is spherical. When the average particle diameter exceeds 30 nm, light is irregularly reflected by the particles and the transparency is remarkably lowered. Further, by using particles having a particle size distribution maximum in each of particle sizes 1 to 9 nm and 10 to 30 nm, the particle content per unit volume can be reduced without impairing the dispersibility of the particles and the transmittance of the cured film. It becomes possible to improve. As a result, a good cured film having a higher refractive index can be obtained.

  There is no restriction | limiting in particular in content of these inorganic particles. However, although depending on the type of polymer and particles and the surface treatment conditions of the particles, if the content of particles is large, uniform dispersion may be difficult, so the amount should be 500 parts by weight or less with respect to 100 parts by weight of the polymer. Is preferred. More preferably, it is 300 parts by weight or less. Moreover, since a high refractive index cannot be obtained if the content of the particles is small, the amount is preferably 50 parts by weight or more with respect to 100 parts by weight of the polymer.

  These inorganic particles can be used as single particles or composite particles. Further, these inorganic particles can be used in a mixture of two or more. Commercially available inorganic particles include “Optlake TR-502” and “Optlake TR-504” of tin oxide-titanium oxide composite sol, and “Optrake TR-503” of silicon oxide-titanium oxide composite sol. , "Op-tray TR-505" of titanium oxide particle sol (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.), zirconium oxide particle sol (manufactured by Kojundo Chemical Laboratory Co., Ltd.), tin oxide-zirconium oxide composite Examples thereof include particle sol (manufactured by Catalyst Chemical Industry Co., Ltd.), tin oxide particle sol (manufactured by Kojundo Chemical Laboratory Co., Ltd.) and the like.

The thermally crosslinkable compound having at least two groups represented by the general formula (1) used in the present invention (c1), for example, a group represented by the general formula (1) as having two DM-BI25X-F, 46DMOC, 46DMOIPP, 46DMOEP (trade name, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP , DML-34X, DML-EP, DML-POP, DML-OC, dimethylol-Bis-C, dimethylol-BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z, DML-PFP, DML-PSBP, DML -MB25, DML-MTrisPC, DML-Bis25X-34XL, DML-Bis25X- CHP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nicalak MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6- TriML-P, TriML-35XL, TriML-TrisCR-HAP (named above, trade name, Honshu Chemical Industry Co., Ltd.) having three such as dimethoxymethyl-p-cresol and 2,6-diacetoxymethyl-p-cresol TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP ( As mentioned above, there are 6 such as trade name, manufactured by Honshu Chemical Industry Co., Ltd., Nikarac MX-280, Nikalac MX-270 (above, trade name, manufactured by Sanwa Chemical Co., Ltd.) As HML-TPPHBA, HML-TPHAP (or more, trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and the like.

  Among these, in the present invention, those containing 2 to 4 groups represented by the general formula (1) are preferred, and particularly preferred are those having 46 DMOC, 46DMOEP (above, trade names, Asahi Organic Materials Co., Ltd.). Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML- PFP, DML-PSBP, DML-MTrisPC (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nicalak MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4- There are three such as t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc. TriML-P, TriML-35XL (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) as a thing, TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), TML- pp-BPF, TML-BPA, TMOM-BP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nikarac MX-280, Nikalac MX-270 (above, trade name, manufactured by Sanwa Chemical Co., Ltd.) is there. More preferably, DML-PC, DML-PTBP, Nicalak MX-270, Nicalak MX-280 (above, trade names, Sanwa Chemical Co., Ltd.), which are compounds having the group represented by the general formula (2) Manufactured) and the like.

  By containing these thermally crosslinkable compounds, the resulting non-photosensitive resin composition has a strong bond between the film and the particles due to crosslinking, so the film properties are improved and cracks occur even in thick films of 1 μm or more. do not do.

  In particular, in the case where the thermally crosslinkable compound is a thermally crosslinkable compound (c2) having a urea-based organic group represented by the general formula (2), the absorption with respect to light is extremely higher than that of an aromatic thermally crosslinkable compound. small. Moreover, since it is an alicyclic system compared with an aliphatic system, it is excellent in heat resistance.

  These thermally crosslinkable compounds are crosslinked by a reaction mechanism that directly adds to the benzene ring as follows.

  The structures of typical heat crosslinkable compounds particularly preferred for use in the present invention are shown below.

  The non-photosensitive resin composition of the present invention may contain both a heat crosslinkable compound (c1) and a heat crosslinkable compound (c2).

  In addition, surfactants, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, cyclohexanone, methyl isobutyl are used for the purpose of improving the paintability between the non-photosensitive resin composition and the substrate as necessary. Ketones such as ketones and ethers such as tetrahydrofuran and dioxane may be mixed.

  Further, in order to improve the adhesion to the base substrate such as a silicon wafer, a silane coupling agent or the like is added to the varnish of the non-photosensitive resin composition, or the base substrate is made of such a chemical solution. It can also be pre-processed.

  When added to the varnish, a silane coupling agent such as methylmethacryloxydimethoxysilane and 3-aminopropyltrimethoxysilane and an aluminum chelating agent are added in an amount of 0.5 to 10% by weight based on the polymer in the varnish.

  When the substrate is treated, the coupling agent described above is added to a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate and the like in an amount of 0.5-20. Surface treatment is performed by spin coating, dipping, spray coating, steam treatment, etc. on the solution in which the weight% is dissolved. Depending on the case, reaction of a board | substrate and the said coupling agent is advanced by applying the temperature to 50-300 degreeC after that.

In order for this non-photosensitive resin composition to maintain high transmittance, the particles themselves do not aggregate and it is necessary to maintain dispersion stability. The dispersibility of the particles in the non-photosensitive resin composition can be evaluated by measuring the Casson yield value of the non-photosensitive resin composition. The Casson yield value was measured by measuring the shear stress for various shear rates with a viscometer, and Casson's formula S ^1/2 = a × D ^1/2 + b (S: shear stress (Pa), D: shear rate (1 / s), a ² : Residual viscosity (Pa · s) Viscosity when shear rate is infinite, b ² : Casson yield value (Pa) Stress when shear rate is zero). The Casson yield value is preferably 1 × 10 ⁻² Pa or less, more preferably 1 × 10 ⁻³ Pa or less. In particular, when using a high-viscosity non-photosensitive resin composition to form a resin film having a thickness of 1 μm or more, the Cason yield value tends to increase. This is because the particle surface is coated with an organic substance. It can be improved by adding a dispersant. Examples of the method of coating the particle surface with an organic material include a method of modifying the particle surface using a silane coupling agent or the like.

  Next, a method for forming a cured film using the non-photosensitive resin composition of the present invention will be described.

  A non-photosensitive resin composition is applied onto a substrate to obtain a coating film. A silicon wafer, ceramics, gallium arsenide, or the like is used as the substrate, but is not limited thereto. Examples of the application method include spin coating using a spinner, spray coating, and roll coating. Moreover, although a coating film thickness changes with application methods, solid content concentration of composition, viscosity, etc., it is normally applied so that the film thickness after drying becomes 0.1 to 150 μm. Moreover, you may pre-bake after application | coating. As a pre-baking condition, it is common to carry out at 90-120 degreeC for several minutes with a hotplate.

  Next, it is cured by applying heat at 80 to 400 ° C. to convert it into a cured film. This heat treatment may be performed by selecting the temperature and raising the temperature stepwise, or by selecting a certain temperature range and continuously raising the temperature for 5 minutes to 5 hours. As an example, a method of performing heat treatment at 130 ° C., 200 ° C., and 350 ° C. for 30 minutes each, or linearly raising the temperature from room temperature to 400 ° C. over 2 hours may be mentioned.

The cured film formed from the non-photosensitive resin composition of the present invention is used for applications such as a high refractive interlayer film for optical elements, a microlens, and an antireflection film .

To made create the shape of the microlens, dry non-photosensitive resin composition to heat treatment after coating a photoresist of the present invention, an exposure, after forming the micro lens pattern by developing, the resist pattern as an etching mask There are methods such as etching to transfer a pattern .

  Hereinafter, the present invention will be described with reference to examples and techniques, but the present invention is not limited to these examples. In addition, evaluation of the non-photosensitive resin composition in an Example was performed with the following method.

Preparation of cured film A 6-inch silicon wafer and a 6-inch glass substrate were coated with a non-photosensitive resin composition (hereinafter referred to as varnish) so that the film thickness after pre-baking would be 1.2 μm, and then hot plate The coating film was obtained by prebaking at 120 degreeC for 3 minutes using (Dainippon Screen Manufacturing Co., Ltd. SCW-636). This coating film was heated and cured at 230 ° C. for 60 minutes under a nitrogen atmosphere (oxygen concentration 300 ppm) in a clean oven (CLH-21CD manufactured by Koyo Thermo System Co., Ltd.) to obtain a cured film.

Measurement of thickness of cured film Using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd., the thickness of the cured film was measured at a refractive index of 1.78.

Calculation of transmittance For a cured film having a film thickness of 1.0 μm produced on a 6-inch glass substrate, the transmittance at 400 nm and 450 nm was measured using an ultraviolet-visible spectrophotometer UV-260 (manufactured by Shimadzu Corporation). It was measured.

Measurement of refractive index Film surface at 633 nm (using He-Ne laser) at 20 ° C. using a prism coupler (manufactured by Metricon) for a cured film having a film thickness of 1.5 μm produced on a 6-inch silicon wafer The refractive index (TM) in the vertical direction was measured.

Measurement of crack generation A cured film with a thickness of 1.5 μm produced on a 6-inch silicon wafer was subjected to a heat cycle test three times at 230 ° C. for 3 minutes and at room temperature (23 ° C.) for 3 minutes. The presence or absence was confirmed.

Synthesis Example 1 Synthesis of hydroxyl group-containing acid anhydride (a) In a dry nitrogen stream, 18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) 34.2 g (0.3 mol) of allyl glycidyl ether was dissolved in 100 g of gamma butyrolactone (GBL) and cooled to −15 ° C. To this, 22.1 g (0.11 mol) of trimellitic anhydride chloride dissolved in 50 g of GBL was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After completion of dropping, the mixture was stirred at 0 ° C. for 4 hours. This solution was concentrated by a rotary evaporator and charged into 1 l of toluene to obtain an acid anhydride (a).

Synthesis Example 2 Synthesis of hydroxyl group-containing diamine compound (b) 18.3 g (0.05 mol) of BAHF was dissolved in 100 ml of acetone and 17.4 g (0.3 mol) of propylene oxide, and cooled to -15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride in 100 ml of acetone was added dropwise thereto. After completion of dropping, the mixture was stirred at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 ° C.

  30 g of the obtained solid was put in a 300 ml stainless steel autoclave, dispersed in 250 ml of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated by confirming that the balloons did not squeeze any more. After completion of the reaction, the palladium compound as a catalyst was removed by filtration, and concentrated by a rotary evaporator to obtain a diamine compound (b). The obtained solid was used for the reaction as it was.

Synthesis Example 3 Synthesis of hydroxyl group-containing diamine compound (c) 2-Amino-4-nitrophenol (15.4 g, 0.1 mol) was dissolved in acetone (50 ml) and propylene oxide (30 g, 0.34 mol) at -15 ° C. Cooled to. A solution prepared by dissolving 11.2 g (0.055 mol) of isophthalic acid chloride in 60 ml of acetone was gradually added dropwise thereto. After completion of dropping, the mixture was stirred at −15 ° C. for 4 hours. Thereafter, the precipitate formed by returning to room temperature was collected by filtration.

  This precipitate was dissolved in 200 ml of GBL, 3 g of 5% palladium-carbon was added, and the mixture was vigorously stirred. A balloon filled with hydrogen gas was attached thereto, and stirring was continued until the balloon of hydrogen gas did not contract any further at room temperature, and further stirred for 2 hours with the balloon of hydrogen gas attached. After completion of the stirring, the palladium compound was removed by filtration, and the solution was concentrated to half by a rotary evaporator. Ethanol was added thereto and recrystallization was performed to obtain crystals of the target compound.

Synthesis Example 4 Synthesis of Hydroxyl Group-Containing Diamine Compound (d) 2-Amino-4-nitrophenol (15.4 g, 0.1 mol) was dissolved in acetone (100 ml) and propylene oxide (17.4 g, 0.3 mol). Cooled to 15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride in 100 ml of acetone was gradually added dropwise thereto. After completion of dropping, the mixture was stirred at −15 ° C. for 4 hours. Thereafter, the precipitate formed by returning to room temperature was collected by filtration. Thereafter, the target compound crystal was obtained in the same manner as in Synthesis Example 2.

Synthesis Example 5 Synthesis of quinonediazide compound (1) TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 15.31 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 40. 28 g (0.15 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system would not be 35 ° C. or higher. After dropping, the mixture was stirred at 30 ° C. for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (1).

Example 1
Under a dry nitrogen stream, 4.1 g (0.0205 mol) of 4,4′-diaminodiphenyl ether and 1.24 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were added to N-methyl. It was dissolved in 50 g of 2-pyrrolidone (NMP). 21.4 g (0.03 mol) of the hydroxyl group-containing acid anhydride (a) obtained in Synthesis Example 1 was added thereto together with 14 g of NMP and reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. . Thereafter, a solution prepared by diluting 7.14 g (0.06 mol) of N, N-dimethylformamide dimethylacetal with 5 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours.

  To 40.0 g of the obtained solution, 70 g of “Optlake TR-502” (trade name, manufactured by Catalytic Chemical Industry Co., Ltd.) and 5 g of DML-PC (manufactured by Honshu Chemical Industry Co., Ltd.) were added to the varnish. A was obtained. The obtained varnish was applied on a silicon wafer and a glass substrate by the above procedure and thermally cured, and the transmittance, refractive index, and generation of cracks of the cured film were evaluated.

Example 2
Under a dry nitrogen stream, 13.6 g (0.0225 mol) of diamine (b) obtained in Synthesis Example 2, and 4-ethynylaniline (trade name: P-APAC, Fuji Photo Film Co., Ltd.) as a terminal blocking agent 0.29 g (0.0025 mol) was dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). 17.5 g (0.025 mol) of a hydroxyl group-containing acid anhydride (a) was added thereto together with 30 g of pyridine, and reacted at 60 ° C. for 6 hours. After completion of the reaction, the solution was poured into 2 liters of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80 ° C. for 20 hours.

  15 g of the polymer solid thus obtained was weighed, and 50 g of “OPTRAIK TR-502” (trade name, manufactured by Catalytic Chemical Industry Co., Ltd.) having a particle diameter of 5 nm and DML-PTBP (manufactured by Honshu Chemical Industry Co., Ltd.) 2 g and 1 g of vinyltrimethoxysilane were dissolved in 30 g of gamma butyrolactone to obtain varnish B. The obtained varnish was applied on a silicon wafer and a glass substrate by the above procedure and thermally cured, and the transmittance, refractive index, and generation of cracks of the cured film were evaluated.

Example 3
Under a dry nitrogen stream, 20.78 g (0.055 mol) of the diamine compound (c) obtained in Synthesis Example 3 and 1.24 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane ) Was dissolved in 50 g of NMP. To this, 13.95 g (0.045 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic anhydride was added together with 21 g of NMP and reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 2 hours. . After stirring at 50 ° C. for 2 hours, a solution obtained by diluting 14.7 g (0.1 mol) of N, N-dimethylformamide diethyl acetal with 5 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours.

  To 30 g of the obtained solution, 85 g of “Optlake TR-505” (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) having a particle diameter of 10 nm and 3 g of Nicalac MX-270 (manufactured by Sanwa Chemical Co., Ltd.) were dissolved to make a varnish. C was obtained. The obtained varnish was applied on a silicon wafer and a glass substrate by the above procedure and thermally cured, and the transmittance, refractive index, and generation of cracks of the cured film were evaluated.

Example 4
Under a dry nitrogen stream, 6.08 g (0.025 mol) of the diamine compound (d) obtained in Synthesis Example 4, 4.21 g (0.021 mol) of 4,4′-diaminodiphenyl ether, 1,3-bis ( 3-aminopropyl) tetramethyldisiloxane 0.806 g (0.00325 mol) was dissolved in 70 g NMP. Hydroxyl group-containing acid anhydride (a) 24.99 g (0.035 mol), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride 4.41 g (0.015 mol) together with NMP 25 g at room temperature In addition, the mixture was stirred at room temperature for 1 hour and then at 50 ° C. for 2 hours. Then, a solution obtained by diluting 17.6 g (0.2 mol) of glycidyl methyl ether with 10 g of NMP was added and stirred at 70 ° C. for 6 hours.

  In 40 g of this polymer solution, 150 g of “Optlake TR-503” (trade name, manufactured by Catalytic Chemical Industry Co., Ltd.) having a particle diameter of 8 nm and 5 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.) are dissolved to prepare varnish D. Obtained. The obtained varnish was applied on a silicon wafer and a glass substrate by the above procedure and thermally cured, and the transmittance, refractive index, and generation of cracks of the cured film were evaluated.

Example 5
In a dry nitrogen stream, 16.93 g (0.04625 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 50 g of N-methyl-2-pyrrolidone (NMP), and glycidyl methyl ether 26. 4 g (0.3 mol) was dissolved, and the temperature of the solution was cooled to −15 ° C. A solution prepared by dissolving 7.38 g (0.025 mol) of diphenyl ether dicarboxylic acid dichloride and 5.08 g (0.025 mol) of isophthalic acid dichloride in 25 g of gamma butyrolactone was added dropwise so that the internal temperature did not exceed 0 ° C. did. After completion of the dropwise addition, stirring was continued for 6 hours at -15 ° C.

  After completion of the reaction, the solution was poured into 3 l of water to collect a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 ° C. for 20 hours.

  10 g of the polymer powder thus obtained was added to 140 g of “Optlake TR-504” (trade name, manufactured by Catalytic Chemical Industry Co., Ltd.), TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.) 0 Varnish E was obtained by dissolving 1 g in 30 g of NMP. The obtained varnish was applied on a silicon wafer and a glass substrate by the above procedure and thermally cured, and the transmittance, refractive index, and generation of cracks of the cured film were evaluated.

Example 6
Under a dry nitrogen stream, 13.6 g (0.0225 mol) of the diamine (b) obtained in Synthesis Example 2, and 4- (3-aminophenyl) -2-methyl-3-butyne-2 as an end-capping agent -All (trade name: M-APACB, manufactured by Fuji Photo Film Co., Ltd.) (0.44 g, 0.0025 mol) was dissolved in N-methyl-2-pyrrolidone (NMP) (50 g). 17.5 g (0.025 mol) of a hydroxyl group-containing acid anhydride (a) was added thereto together with 30 g of pyridine, and reacted at 60 ° C. for 6 hours. After completion of the reaction, the solution was poured into 2 liters of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80 ° C. for 20 hours.

  10 g of the polymer solid thus obtained was weighed, 1 g of vinyltrimethoxysilane, 140 g of “Optlake TR-504” (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) with a particle diameter of 5 nm, Nicalac MX-280 ( Varnish F was obtained by dissolving 0.5 g of Sanwa Chemical Co., Ltd. in 30 g of gamma butyrolactone. The obtained varnish was applied on a silicon wafer and a glass substrate by the above procedure and thermally cured, and the transmittance, refractive index, and generation of cracks of the cured film were evaluated.

Example 7
The addition amount of “Optlake TR-502” (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) having a particle diameter of 5 nm in Example 2 was changed from 50 g to 140 g, and the rest was performed in the same manner as in Example 2 except that varnish G Got. Using the obtained varnish, as described above, a resin film was applied on a silicon wafer and a glass substrate, thermally cured, and the transmittance, refractive index, and generation of cracks of the cured film were evaluated.

Example 8
The addition amount of “Optlake TR-502” (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) having a particle diameter of 5 nm in Example 2 was changed to 40 g, and the rest was performed in the same manner as in Example 2 except that varnish H Obtained. The obtained varnish was applied on a silicon wafer and a glass substrate by the above procedure and thermally cured, and the transmittance, refractive index, and generation of cracks of the cured film were evaluated.

Example 9
The “Optlake TR-502” (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) having a particle diameter of 5 nm in Example 1 was changed to 10 g of zirconium oxide particles (manufactured by Kojundo Chemical Laboratory Co., Ltd.) having a particle diameter of 5 nm. The others were carried out in the same manner as in Example 1 to obtain Varnish I. The obtained varnish was applied on a silicon wafer and a glass substrate by the above procedure and thermally cured, and the transmittance, refractive index, and generation of cracks of the cured film were evaluated.

Example 10
“Optlake TR-505” (trade name, manufactured by Catalytic Chemical Industry Co., Ltd.) having a particle diameter of 10 nm in Example 3 was used as a tin oxide-zirconium oxide composite particle sol (manufactured by Catalytic Chemical Industry Co., Ltd.) having a particle diameter of 25 nm. The others were carried out in the same manner as in Example 3 to obtain varnish J. The obtained varnish was applied on a silicon wafer and a glass substrate by the above procedure and thermally cured, and the transmittance, refractive index, and generation of cracks of the cured film were evaluated.

Example 11
Varnish K was obtained by changing “Optlake TR-502” (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) having a particle diameter of 5 nm in Example 2 to an aluminum oxide-titanium oxide composite particle sol having a particle diameter of 15 nm. The obtained varnish was applied on a silicon wafer and a glass substrate by the above procedure and thermally cured, and the transmittance, refractive index, and generation of cracks of the cured film were evaluated.

Example 12
The 16.3-g 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane of Example 5 was changed to 18.3 g (0.05 mol), and “OPTRAIK TR-504 having a particle size of 5 nm” was used. "(Trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) was changed to 20 g of tin oxide particles having a particle diameter of 10 nm (manufactured by Kojundo Chemical Laboratory Co., Ltd.). L was obtained. The obtained varnish was applied on a silicon wafer and a glass substrate by the above procedure and thermally cured, and the transmittance, refractive index, and generation of cracks of the cured film were evaluated.

Example 13
A varnish M was obtained in the same manner as in Example 2 except that 100 g of aluminum oxide-zirconium oxide sol having a particle diameter of 25 nm was further added to Example 2. The obtained varnish was applied on a silicon wafer and a glass substrate by the above procedure and thermally cured, and the transmittance, refractive index, and generation of cracks of the cured film were evaluated.

Example 14
50 g of aluminum oxide-titanium oxide sol having a particle diameter of 15 nm was further added to Example 3, and the others were performed in the same manner as Example 2 to obtain varnish N. The obtained varnish was applied on a silicon wafer and a glass substrate by the above procedure and thermally cured, and the transmittance, refractive index, and generation of cracks of the cured film were evaluated.

Example 15
Varnish O was obtained in the same manner as in Example 1 except that “Optlake TR-502” (trade name, manufactured by Catalyst Chemical Industry Co., Ltd.) having a particle diameter of 5 nm in Example 1 was changed to 300 g. Using the obtained varnish in the above procedure, as described above, a resin film was applied on a silicon wafer and a glass substrate, thermally cured, and evaluation of the transmittance, refractive index, and generation of cracks of the cured film was performed. .

Example 16
Varnish P was obtained in the same manner as in Example 3 except that the amount of MX-270 added in Example 3 was changed to 10 g. Using the obtained varnish in the above procedure, as described above, applying a resin film on a silicon wafer and a glass substrate, thermosetting, and generating the transmittance, refractive index and cracks of the cured film high refractive index resin Evaluation was performed.

Comparative Example 1
Varnish Q was obtained in the same manner as in Example 1 except that “Optlake TR-502” (trade name, manufactured by Catalyst Chemical Industry Co., Ltd.) having a particle diameter of 5 nm in Example 1 was not used. The obtained varnish was applied on a silicon wafer and a glass substrate by the above procedure and thermally cured, and the transmittance, refractive index, and generation of cracks of the cured film were evaluated.

Comparative Example 2
“Optlake TR-502” (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) having a particle diameter of 5 nm in Example 2 and “Optlake TR-506” (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) having a particle diameter of 60 nm. The others were carried out in the same manner as in Example 2 to obtain varnish R. The obtained varnish was applied on a silicon wafer and a glass substrate by the above procedure and thermally cured, and the transmittance, refractive index, and generation of cracks of the cured film were evaluated.

Comparative Example 3
“Optlake TR-505” (trade name, manufactured by Catalytic Kasei Kogyo Co., Ltd.) having a particle diameter of 10 nm in Example 3 and “Optlake TR-509” (trade name, manufactured by Catalytic Chemical Industries, Ltd.) having a particle diameter of 35 nm. The others were carried out in the same manner as in Example 3 to obtain varnish S. The obtained varnish was applied on a silicon wafer and a glass substrate by the above procedure and thermally cured, and the transmittance, refractive index, and generation of cracks of the cured film were evaluated.

Comparative Example 4
Varnish T was obtained in the same manner as in Example 3 except that MX-270 of Example 3 was not added. The obtained varnish was applied on a silicon wafer and a glass substrate by the above procedure and thermally cured, and the transmittance, refractive index, and generation of cracks of the cured film were evaluated.

Comparative Example 5
A photosensitive resin composition was obtained in the same manner as in Example 2 except that 2 g of the quinonediazide compound (1) obtained in Synthesis Example 5 was added to Example 2. The obtained photosensitive resin composition was applied onto a silicon wafer and a glass substrate by the above procedure and thermally cured, and the transmittance, refractive index, and generation of cracks of the cured film were evaluated.

  The evaluation results of Examples 1 to 16 and Comparative Examples 1 to 5 are shown in Tables 1 and 2.

Claims (11)

(A) one or more polymers selected from the group consisting of polyimide, polybenzoxazole, polyimide benzoxazole and their precursors; and (b) aluminum compound sol, silicon compound sol, tin compound sol, titanium compound sol, zirconium Inorganic particles having an average particle diameter of 1 to 30 nm containing at least one compound sol selected from compound sols, and (c1) a thermally crosslinkable compound having at least two groups represented by the general formula (1) and / or (C2) A non-photosensitive resin composition comprising a thermally crosslinkable compound having a urea organic group represented by the general formula (2).

(In the formula, R ^{1 s} may be the same or different and each represents a hydrogen atom or a monovalent organic group.) (B) Inorganic particles having an average particle diameter of 1 to 30 nm containing at least one compound sol selected from aluminum compound sol, silicon compound sol, tin compound sol, titanium compound sol, and zirconium compound sol have a particle diameter of 1 to 9 nm. non-photosensitive resin composition according to claim 1 Symbol mounting, characterized in that those having a maximum particle diameter distribution to each 10~30nm with. The non-photosensitive resin composition according to claim 1 or 2 , wherein the component (a) is a polymer containing a structural unit represented by the general formula (3).

(Wherein R ² represents a divalent to octavalent organic group having at least 2 carbon atoms, and R ³ represents a divalent to hexavalent organic group having at least 2 carbon atoms. R ⁴ represents hydrogen. An atom or a C1-C20 organic group is shown, n is an integer of 10-100,000, m is an integer of 0-2, p and q show an integer of 0-4.) Formula ^{(3) R 2 (COOR 4} ) m (OH) p of the non-photosensitive resin composition according to claim 3, characterized by being represented by the general formula (4).

(In the formula, R ⁵ and R ⁷ represent a C 2-20 divalent organic group. R ⁶ represents a C 3-20 trivalent organic group. R ⁸ and R ^9. Represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, o and s are each an integer of 0 to 2, satisfying 0 ≦ o + s ≦ 2, and r represents an integer of 1 to 4. Non-photosensitive resin composition of the R ^{3 (OH)} q is, according to claim 3, characterized by being represented by the general formula (5) of the general formula (3).

(In the formula, R ¹⁰ and R ¹² represent a C 3-20 tetravalent organic group. R ¹¹ represents a C 2-30 divalent organic group. T and u are 1 or 2. Is shown.) R ^{3 (OH)} q is a non-photosensitive resin composition according to claim 3, characterized by being represented by the general formula (6) of the general formula (3).

(In the formula, R ¹³ and R ¹⁵ represent a divalent organic group having 2 to 20 carbon atoms. R ¹⁴ represents a 3 to 6-valent organic group having 3 to 20 carbon atoms. V is an integer of 1 to 4. Is shown.) Non-photosensitive resin composition of the R ^{3 (OH)} q is, according to claim 3, characterized by being represented by the general formula (7) of the general formula (3).

^{(Wherein, R 16} represents an integer of .w is 1 to 4 ^{.R 17} showing a divalent organic group having 2 to 20 carbon atoms which indicates a trivalent to hexavalent organic group having 3 to 20 carbon atoms. ) 100 parts by weight of component (a), (b) 50 to 300 parts by weight of components, according to claim 1-7, characterized in (c1) and (c2) contain 0.5 to 50 parts by weight of components in a total amount Any non-photosensitive resin composition. Claim 1-8 or non-photosensitive resin composition refractive index 1.78 or more cured film obtained by curing the description. A laminate formed by forming a cured film having a refractive index of 1.78 or more and a cured film having a refractive index of 1.45 or less according to claim 9 on a substrate. An optical element having the cured film according to claim 9 .