JP6433110B2 - Optical member and manufacturing method thereof - Google Patents

Description

  The present invention relates to an optical member having antireflection performance and a method for manufacturing the same, and more particularly to an optical member exhibiting high antireflection performance from the visible region to the near infrared region and a method for manufacturing the same.

  Polyimide has been used for electronic and electric parts because of its excellent heat resistance and electrical insulation. Furthermore, highly transparent polyimides introduced with an aliphatic structure or fluorine alkyl are also used in optical applications such as liquid crystal display elements and optical waveguides.

  On the other hand, an optical member having excellent antireflection performance can be obtained by depositing fine particles of metal oxide or fluoride or forming a fine periodic structure of a wavelength or less on the outermost surface. In particular, by forming a fine periodic structure with an appropriate pitch and height, it exhibits excellent antireflection performance in a wide wavelength region. Among these, it is known that a concavo-convex structure made of boehmite of aluminum oxide grown on a substrate can obtain a high antireflection effect. The concavo-convex structure made of boehmite is obtained by subjecting an aluminum oxide film formed by a liquid phase method (sol-gel method) or the like to steam treatment or hot water immersion treatment (see Non-Patent Document 1). Furthermore, it is also known that a higher antireflection effect is exhibited by providing a layer having a refractive index intermediate between the base material and the concavo-convex structure between the base material and the concavo-convex structure made of boehmite.

  Polyimide can impart transparency and change the refractive index, and is also known to have an effect of suppressing damage to the glass substrate caused by moisture or water vapor (see Patent Document 1). Furthermore, in order to obtain an optical member having a low reflectivity, an optical thin film having a small variation in film thickness and optical characteristics at the time of the thin film is required.

JP 2008-233880 A

K. Tadanaga, N .; Katata, and T.K. Minami: “Super-Water-Repellant Al 2 O 3 Coating Films with High Transparency,” J. Am. Ceram. Soc. , 80 [4] 1040 to 42 (1997)

  A porous film with fine particles deposited on the surface layer as an antireflection film and a concavo-convex structure formed by growing alumina boehmite on a substrate have simple and high productivity and excellent optical performance. . However, when the refractive index difference between these layers and the substrate is large, a sufficient antireflection effect cannot be obtained. Therefore, the antireflection effect can be enhanced by providing a layer having an intermediate refractive index between the substrate and the porous film or the layer having a concavo-convex structure. However, since the substrate is selected from a wide range of refractive indexes according to the application, a thin film material that can easily provide a refractive index and a film thickness that match the refractive index of the substrate is desired. Further, there is a demand for an optical member with an antireflection film that has high performance and low in-plane variation in antireflection performance.

  The present invention has been made in view of such a background art, and provides an optical member having high antireflection performance and small in-plane variation in antireflection performance, and a method for manufacturing the same.

An optical member that solves the above-described problems is an optical member in which a laminate for suppressing light reflection is formed on a substrate surface, and the outermost surface of the laminate has a void due to a porous or uneven structure. And at least one layer of the laminate is a layer containing polyimide as a main component, and the layer containing polyimide as a main component is 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic in the main chain. Acid dianhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, bicyclo [2.2.2] octane- 2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro Furyl) -3-methyl Derived from 3-cyclohexene-1,2-dicarboxylic anhydride or 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride Polyimide 1 having an acid dianhydride residue, an aromatic diamine residue, and an alicyclic diamine residue, and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride in the main chain , 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, bicyclo [2.2.2] octane-2,3 , 5,6-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl)- 3-methyl -3-Cyclohexene-1,2-dicarboxylic acid anhydride or 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride dianhydride residues are derived from having a contact and aromatic diamine residue, and the content of the aromatic diamine residue containing different polyimides 2 polyimide 1, of the polyimide 1 and the polyimide 2 The imidation ratio is 90% or more.
An optical member that solves the above-described problems is an optical member in which a laminate for suppressing light reflection is formed on the surface of a substrate, and the outermost surface of the laminate is a void due to a porous or uneven structure. And at least one layer of the laminate is a layer containing polyimide as a main component, and the layer containing the polyimide as a main component is 3,3 ′, 4,4′-diphenylsulfone in the main chain. Tetracarboxylic dianhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, bicyclo [2.2.2] Octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-di Oxotetrahydrofuryl) -3- Tyl-3-cyclohexene-1,2-dicarboxylic anhydride or 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride Polyimide 1 having acid dianhydride residue, aromatic diamine residue, and alicyclic diamine residue, and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid in the main chain Dianhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, bicyclo [2.2.2] octane-2 , 3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) ) -3 Methyl-3-cyclohexene-1,2-dicarboxylic anhydride or 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride A polyimide 2 having an acid dianhydride residue derived from a product and an alicyclic diamine residue and no aromatic diamine residue, the imidization ratio of the polyimide 1 and the polyimide 2 being 90 % Or more.

A method for manufacturing an optical member that solves the above-described problem is an optical member in which a laminate for suppressing light reflection is formed on a substrate surface, and at least one layer of the laminate is composed of a layer mainly composed of polyimide. A manufacturing method of
1) At least aromatic diamine, alicyclic diamine, and acid dianhydride are reacted in a solvent, and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride in the main chain, 4 '-(hexafluoroisopropylidene) diphthalic anhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, bicyclo [2.2.2] octane-2,3,5,6 -Tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl- Derived from 3-cyclohexene-1,2-dicarboxylic anhydride or 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride Is acid two Anhydride residue, an aromatic diamine residue, and having an alicyclic diamine residue, a step of imidization to synthesize polyimide 1 90% or more,
2) at least aromatic diamines Contact and acid dianhydride was reacted in a solvent, in the main chain, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 4,4'- (Hexafluoroisopropylidene) diphthalic anhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic Acid dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene An acid derived from -1,2-dicarboxylic anhydride or 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride dianhydride residue, Oyo Have aromatic diamine residue, a is the imidization of 90% or more, and the step of the content of the aromatic diamine residue to synthesize different polyimide 2 polyimide 1,
3) A step of preparing a polyimide solution by dissolving the polyimide 1 and the polyimide 2 in a solvent,
4) A step of applying the polyimide solution on a substrate or a thin film provided on the substrate,
5) A step of drying and / or firing the applied polyimide solution to form a layer mainly composed of polyimide,
It is characterized by having.
In addition, in the method for manufacturing an optical member that solves the above-described problem, a laminated body for suppressing light reflection is formed on a substrate surface, and at least one layer of the laminated body includes a layer mainly composed of polyimide. A method for manufacturing a member,
1) At least aromatic diamine, alicyclic diamine, and acid dianhydride are reacted in a solvent, and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride in the main chain, 4 '-(hexafluoroisopropylidene) diphthalic anhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, bicyclo [2.2.2] octane-2,3,5,6 -Tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl- Derived from 3-cyclohexene-1,2-dicarboxylic anhydride or 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride Is acid two Anhydride residue, an aromatic diamine residue, and having an alicyclic diamine residue, a step of imidization to synthesize polyimide 1 90% or more,
2) At least alicyclic diamine and acid dianhydride are reacted in a solvent, and 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 4,4 ′-( Hexafluoroisopropylidene) diphthalic anhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid Dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene- 1,2-dicarboxylic anhydride, or 2- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride Anhydride residues, and Has a cycloaliphatic diamine residue, and free of aromatic diamines, process for imidation ratio to synthesize a polyimide 2 is 90% or more,
3) A step of preparing a polyimide solution by dissolving the polyimide 1 and the polyimide 2 in a solvent,
4) A step of applying the polyimide solution on a substrate or a thin film provided on the substrate,
5) A step of drying and / or firing the applied polyimide solution to form a layer mainly composed of polyimide,
It is characterized by having.

  According to the present invention, it is possible to provide an optical member having a high antireflection performance and a small in-plane variation in the antireflection performance and a method for manufacturing the same.

It is the schematic which shows one embodiment of the transparent member for optics of this invention. It is the schematic which shows one embodiment of the transparent member for optics of this invention. It is the schematic which shows the refractive index distribution of one embodiment of the transparent member for optics of this invention. It is the schematic which shows one embodiment of the transparent member for optics of this invention. It is the schematic which shows one embodiment of the transparent member for optics of this invention. It is a graph which shows the relationship between the content rate of the polyimide a in the mixed film of the polyimide b or the polyimide c and the polyimide a in Example 1 and Example 2, and the refractive index of a mixed film. It is a graph which shows the relationship between the content rate of the polyimide a in the mixed film of the polyimide d or the polyimide e in Example 3 and Example 4, and the polyimide a, and the refractive index of a mixed film. It is a graph which shows the relationship between the content rate of the polyimide f in the mixed film of the polyimide g or the polyimide h in Example 5 and Example 6, and the polyimide f, and the refractive index of a mixed film. It is a graph which shows the relationship between the content rate of the polyimide a in the mixed film of the polyimide g or the polyimide h in Example 7 and Example 8, and the polyimide a, and the refractive index of a mixed film. 6 is a graph showing the relationship between the content of polyimide d in the mixed film of polyimide d and polyimide e and the refractive index of the mixed film in Comparative Example 1. It is a graph which shows the absolute reflectance of the glass A surface where the polyimide film in which the refractive index was adjusted to 1.58 in Example 9 and the alumina uneven structure were laminated | stacked. It is a graph which shows the absolute reflectance of the glass A surface in which the polyimide film in which the refractive index was adjusted to 1.64 in Example 10, and the alumina uneven structure were laminated | stacked.

  Hereinafter, the present invention will be described in detail.

  The optical member according to the present invention is an optical member in which a laminated body for suppressing light reflection is formed on the surface of a substrate, and the outermost surface of the laminated body is a layer having a void due to a porous or concavo-convex structure. And at least one layer of the laminate is a layer containing polyimide as a main component, and the polyimide main component is a polyimide 1 having an aromatic diamine residue and an alicyclic diamine residue in the main chain, And a polyimide 2 having an aromatic diamine residue and / or an alicyclic diamine residue in the main chain and having a content of the aromatic diamine residue different from that of the polyimide 1.

  FIG. 1 is a schematic schematic cross-sectional view showing an optical member according to this embodiment. In FIG. 1, the optical member of the present invention is formed by sequentially laminating a layer 2 mainly composed of polyimide and a low refractive index layer 3 composed of a layer having a porous or uneven structure on the surface of a substrate 1. ing.

  The laminated body which consists of the layer 2 which has the polyimide as a main component of this invention, and the low refractive index layer 3 can suppress reflection of the light which generate | occur | produces on the base-material 1 surface. The layer 2 mainly composed of polyimide is a layer composed of polyimide alone or a component other than polyimide and a small amount of polyimide. Components other than polyimide are complementary to polyimide as a main component, and can be dissolved, mixed, and dispersed in polyimide as long as the characteristics are not impaired. Examples of components other than polyimide include silane coupling agents. The content of polyimide contained in the polyimide-based layer is 80% by weight or more, preferably 90% by weight or more and 100% by weight or less.

  When there is a large refractive index difference between the substrate 1 and the low refractive index layer 3, a large antireflection effect cannot be expected due to strong reflection at the interface. By providing the layer 2 mainly composed of polyimide between the base material 1 and the low refractive index layer 3, a higher antireflection effect can be obtained than when the low refractive index layer 3 is formed directly on the base material 1. It is a feature. Therefore, the film thickness of the layer 2 containing polyimide as a main component is in the range of 10 nm to 100 nm, and is changed in this range in accordance with the refractive index of the substrate. When the film thickness is less than 10 nm, the antireflection effect is not different from the case where there is no layer 2 containing polyimide as a main component. On the other hand, when the film thickness exceeds 100 nm, the antireflection effect is significantly reduced.

  The polyimide constituting the layer 2 mainly composed of polyimide includes polyimide 1 having an aromatic diamine residue and an alicyclic diamine residue in the main chain, and an aromatic diamine residue and / or in the main chain. It is a mixture with polyimide 2 having an alicyclic diamine residue and having a molar content of aromatic diamine residue different from polyimide 1.

Polyimide 1 and polyimide 2 constituting layer 2 containing polyimide as a main component are synthesized by a polymerization (polyaddition) reaction and an imidization (dehydration condensation) reaction of diamine and acid dianhydride. Therefore, the polyimide is composed of a repeating unit in which one diamine residue R ₁₂ and acid dianhydride residue R ₁₁ are alternately connected as represented by the following general formula.

  The aromatic diamine residue in the main chain of polyimides 1 and 2 has the effect of increasing the refractive index of the polyimide. On the other hand, since the alicyclic diamine residue has the effect of lowering the refractive index of the polyimide, the refractive index of the polyimide can be changed by changing the molar ratio of the aromatic diamine residue and the alicyclic diamine residue.

  On the other hand, introducing an aromatic diamine residue and an alicyclic diamine residue into the main chain of polyimide 1 has an effect of improving compatibility with polyimide 2 as well as adjusting the refractive index of polyimide. Thereby, the uniformity of the mixture of polyimide 1 and polyimide 2 is dramatically increased.

The refractive index ni of the layer 2 containing polyimide as a main component is intermediate between the refractive index n _P1 of the polyimide ₁ and the refractive index n _P2 of the polyimide 2. Further, when the uniformity of the mixture of polyimide 1 and polyimide 2 increases, the refractive index n _{P2 of} polyimide 2 = xn _P1 + (1-x) n _P2 (where x is the weight ratio of polyimide 1 in the polyimide mixture) Get closer. Therefore, the refractive index can be easily predicted from the mixing ratio of the polyimide 1 and the polyimide 2, and the accuracy of the refractive index ni of the layer 2 containing polyimide as a main component can be increased. On the other hand, when polyimides are not uniformly mixed, a portion containing a large amount of polyimide and a portion containing a small amount of polyimide are formed, resulting in in-plane variations in the film thickness and refractive index ni of the layer 2 containing polyimide as a main component. In the portion where the film thickness and refractive index ni of the layer 2 containing polyimide as a main component deviate from appropriate values, the antireflection effect cannot be sufficiently obtained, and the antireflection performance also varies in-plane.

When mixing the polyimide 1 and the polyimide 2 to adjust the refractive index ni, the refractive index difference between the refractive index n _P1 of the polyimide ₁ and the refractive index n _P2 of the polyimide 2 is preferably 0.01 or more. If it is less than 0.01, the adjustment range of the refractive index is narrow, and it becomes difficult to obtain a desired refractive index.

  Specifically, the mixing ratio of polyimide 1 and polyimide 2 is preferably in the range of 5 wt% or more and 95 wt% or less for polyimide 1 and 5 wt% or more and 95 wt% or less for polyimide 2. More preferably, the polyimide 1 is in the range of 10% by weight to 90% by weight with respect to the polyimide 1 of 10% by weight to 90% by weight.

  The diamine residue in the main chain of the polyimide 1 contains an aromatic diamine residue and an alicyclic diamine residue and, if necessary, other diamine residues. The molar content of the aromatic diamine residue and the alicyclic diamine residue when the total diamine residue in the main chain of the polyimide 1 is 100 mol% is 10 mol% or more and 90 mol% or less. Furthermore, the molar content of the aromatic diamine residue is preferably greater than 35 mol% and less than 65 mol%, and exhibits high compatibility even when the refractive index difference with polyimide 2 is large. When the molar content of the aromatic diamine residue is 35 mol% or less or 65 mol% or more, a uniform mixture may not be obtained due to insufficient compatibility with the polyimide 2.

  On the other hand, the molar content of the aromatic diamine residue in the main chain of polyimide 2 may be different from that of polyimide 1. When the molar content of the aromatic diamine residue is the same, there is almost no refractive index difference between the polyimide 1 and the polyimide 2, and the effect of mixing does not appear.

  The diamine residue in the main chain of the polyimide 2 contains an aromatic diamine residue and / or an alicyclic diamine residue and, if necessary, other diamine residues. Specifically, (1) when there is only an aromatic diamine residue in the main chain of polyimide 2, the aromatic diamine residue when all the diamine residues in the main chain of polyimide 2 are 100 mol% The molar content of is 65 mol% or more and 100 mol% or less. (2) When there is only an alicyclic diamine residue in the main chain of polyimide 2, the molar content of the aromatic diamine residue when all the diamine residues in the main chain of polyimide 2 are 100 mol% Is a value of 0 mol%. (3) When there is an aromatic diamine residue and an alicyclic diamine residue in the main chain of polyimide 2, the aromatic diamine residue when all the diamine residues in the main chain of polyimide 2 are 100 mol% The molar content of the group and the alicyclic diamine residue is 10 mol% or more and 90 mol% or less. Furthermore, when there are an aromatic diamine residue and an alicyclic diamine residue in the main chain of polyimide 2, the molar content of the aromatic diamine residue is 35 mol% or less or 65 mol% or more. When the molar content of the aromatic diamine residue in polyimide 2 is greater than 35 mol% or less than 65 mol%, the refractive index difference between polyimide 1 and polyimide 2 is increased, and the range of refractive index adjustment by mixing is expanded. For the same reason, it is more preferable that the polyimide 2 has only one of an aromatic diamine residue and an alicyclic diamine residue.

  In addition, the aromatic diamine residue and the alicyclic diamine residue in the main chain of polyimide 2 are the same as the aromatic diamine residue and the alicyclic diamine residue in the main chain of polyimide 1. 1 is more preferable from the viewpoint of compatibility.

  The diamine residue in the polyimides 1 and 2 corresponds to the skeleton of the diamine or its derivative when the polyimide is synthesized.

  Examples of aromatic diamines used to introduce aromatic diamine residues in polyimides 1 and 2 are m-phenylenediamine, p-phenylenediamine, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane. 4,4′-diamino-3,3′-dimethyldiphenylmethane, o-tolidine, m-tolidine, 4,4′-diaminobenzophenone, 1,1-bis (4-aminophenyl) cyclohexane, 3,4′- Diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) benzophenone 2,2-bis [4- (4-aminophenoxy) phenyl] propane, , 4-bis [2- (4-aminophenyl) -2-propyl] benzene, 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene, 4,4′-bis (4- Aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, 4,4′-bis (3-aminophenoxy) biphenyl, bis [3- (4-aminophenoxy) phenyl] sulfone, 9,9 -Bis (4-aminophenyl) fluorene, 9,9-bis (4-amino-3-methylphenyl) fluorene, 9,9-bis (4-amino-3-fluorophenyl) fluorene, 2,2-bis ( 4-aminophenyl) hexafluoropropane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) fe L] hexafluoropropane, 2,2′-bis (trifluoromethyl) benzidine, 4,4′-bis (4-aminophenylthio) biphenyl, bis [4- (4-aminophenylthio) phenyl] sulfide, bis [4- (4-aminophenylthio) phenyl] sulfone, 1,4-bis (4-aminophenylthio) benzene, 4,4′-bis (4-aminophenylthio) benzophenone, and the like. From the viewpoint of increasing the heat resistance and refractive index of polyimide, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (4 -Aminophenoxy) phenyl] sulfone, 4,4′-bis (3-aminophenoxy) biphenyl, bis [3- (4-aminophenoxy) phenyl] sulfone, 9,9-bis (4-aminophenyl) fluorene, etc. More preferred as an aromatic diamine.

  The alicyclic diamine residue in polyimides 1 and 2 has a structure including an alicyclic structure such as a cyclopentyl group, a cyclohexyl group, a bicyclopentyl group, and a bicyclooctyl group. From the viewpoint of the heat resistance of polyimide and the solubility in a solvent, the alicyclic diamine residue in the main chain of polyimide 1 and polyimide 2 more preferably has a structure represented by the following general formula (1).

(Wherein R1 to R8 each represents a hydrogen atom, Br, Cl, F, I, a phenyl group, or a linear or cyclic alkyl group having 1 to 6 carbon atoms, an alkenyl group, or an alkynyl group, provided that R1 to R8 may be the same or different.)

  Examples of the alicyclic diamine used for introducing the alicyclic diamine residue represented by the above general formula include 4,4′-methylenebis (aminocyclohexane), trans, trans-4,4′-methylenebis. (Aminocyclohexane), 4,4′-methylenebis (1-amino-2-methylcyclohexane), trans, trans-4,4′-methylenebis (1-amino-2-methylcyclohexane), 2,2-bis (4 -Aminocyclohexyl) propane.

  Examples of other alicyclic diamines include 1,4-cyclohexanediamine, trans-1,4-cyclohexanediamine, 1,4-bis (aminomethyl) cyclohexane, trans-1,4-bis (aminomethyl) cyclohexane. 4,4′-bicyclohexylamine, norbornanediamine, dicyclooctane bisaminomethane, adamantane diamine, adamantane bisaminomethane, and the like.

  As the diamine residue possessed by the polyimide, in addition to the aromatic diamine residue and the alicyclic diamine residue, it is more preferable to include a siloxane group-containing diamine residue as the other diamine residue. When the polyimide has a siloxane group-containing diamine residue, adhesion between the layer 2 containing polyimide as a main component and the substrate 1 or the layer 4 having an uneven structure can be improved. Furthermore, the molar content of the siloxane group-containing diamine residue when all diamine residues are 100 mol% is more preferably 3 mol% or more and 35 mol% or less. When the molar content of the siloxane group-containing diamine residue is less than 3 mol%, the effect of introducing the siloxane group is not observed. On the other hand, when it is larger than 35 mol%, film performance such as a decrease in Tg may be deteriorated. Examples of siloxane group-containing diamines used for introducing siloxane group-containing diamine residues into polyimide include 1,3-bis (3-aminopropyl) tetramethyldisiloxane and 1,4-bis (3-aminopropyl). Dimethylsilyl) benzene, dimethylsiloxane oligomer having amino groups at both ends, and the like.

  Examples of the acid dianhydride used for introducing the acid dianhydride residue of the polyimide 1 and the polyimide 2 include pyromellitic acid anhydride, 3,3′-biphthalic acid anhydride, 3,4′- Biphthalic anhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 4,4 ′-(hexafluoro Isopropylidene) diphthalic anhydride, aromatic dianhydrides such as 4,4′-oxydiphthalic dianhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, 1,2, 3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2.2 2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [ 2.2.1] Heptane-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid And aliphatic acid dianhydrides such as anhydride and 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride.

  From the viewpoint of improving the solubility, coatability and transparency of polyimide, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride , Meso-butane-1,2,3,4-tetracarboxylic dianhydride, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2 .1] heptane-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride is more preferred.

  The refractive index ni of the layer 2 mainly composed of the polyimide of the present invention is preferably nb ≧ ni ≧ ns with respect to the refractive index nb of the substrate 1 and ns of the low refractive index layer 3 refractive index. Polyimide 1 and polyimide 2 are mixed so as to satisfy such a refractive index range, and used as a layer 2 containing polyimide as a main component.

  Next, the manufacturing method of the optical member of this invention is demonstrated. The method for producing an optical member of the present invention is a method for producing an optical member in which a laminate for suppressing light reflection is formed on the surface of a substrate, and at least one layer of the laminate comprises a layer containing the polyimide. is there.

  A method for forming the layer 2 containing polyimide as a main component in the method for producing an optical member of the present invention will be described.

The method of forming the layer 2 mainly composed of the polyimide of the present invention is as follows:
1) At least an aromatic diamine, an alicyclic diamine and an acid dianhydride are added to a solvent, and a reaction is carried out in the order of polymerization and imidation, and the main chain has an aromatic diamine residue and an alicyclic diamine residue. A step of synthesizing polyimide 1,
2) At least aromatic diamine and / or alicyclic diamine and acid dianhydride are added to the solvent, the reaction is performed in the order of polymerization and imidization, and the aromatic diamine residue and / or alicyclic diamine is contained in the main chain. A step of synthesizing polyimide 2 having a residue and having a molar ratio of an aromatic diamine residue and an alicyclic diamine residue different from polyimide 1;
3) A step of dissolving the polyimide 1 and the polyimide 2 in a solvent to prepare a polyimide solution in which the polyimide 1 and the polyimide 2 are uniformly mixed;
4) The process of apply | coating the solution containing the polyimide 1 and the polyimide 2 on the base material or the thin film provided on the base material,
5) A step of drying and / or firing a thin film containing polyimide 1 and polyimide 2 at 23 ° C. or more and 250 ° C. or less under normal pressure or reduced pressure to form a layer mainly composed of polyimide,
Have

  Polyimide 1 and polyimide 2 are synthesized separately. For the synthesis of polyimide, a general synthesis method in which a polymerization (polyaddition) reaction and an imidization (dehydration condensation) reaction are sequentially performed in a solution can be used. The most common method is to react a diamine and acid dianhydride in a solvent to obtain a polyamic acid solution. The obtained polyamic acid is imidized in a solution to synthesize polyimide.

  The solvent used for the synthesis of the polyimide may be any solvent in which polyamic acid and polyimide are dissolved, and in general, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, etc. An aprotic polar solvent is used. In the process of obtaining a polyamic acid by reacting diamine and acid dianhydride, it is common to proceed the polymerization while removing the heat of reaction at 0 ° C. or higher and 30 ° C. or lower. However, when a alicyclic diamine is used and a salt is formed between the polyamic acid and the unreacted alicyclic diamine to form a precipitate, polymerization may be performed while heating at 80 ° C. or lower to dissolve the salt.

The imidation reaction is a method in which polyamic acid is dehydrated and closed to convert it into polyimide. The imidation includes a method of heating at 25 ° C. to 120 ° C. in the presence of a tertiary amine such as pyridine and triethylamine and acetic anhydride, and a method of azeotroping with xylene at 150 ° C. or more.
The imidation rate of polyimide is preferably 90% or more, and if it is less than that, the water absorption rate of polyimide increases and the film thickness and refractive index tend to fluctuate. More preferably, it is 93% or more and 99% or less.

  The solution containing polyimide 1 and polyimide 2 may be mixed directly with the solution after polyimide synthesis. Alternatively, the polyimide powder obtained by once reprecipitating the solution after the polyimide synthesis in a poor solvent may be used by dissolving it again in the solvent. When chemical imidization using a tertiary amine is performed, it is preferable to obtain a polyimide powder by reprecipitation in alcohol in order to remove various chemicals and unreacted monomers. Further, the polyimide powder is washed with alcohol, heated and vacuum dried, thereby enabling accurate weighing.

  The solution containing polyimide 1 and polyimide 2 may be prepared by sequentially adding each polyimide to the same solvent, or may be mixed after preparing each polyimide solution.

  Examples of the solvent used in the mixed solution of polyimide 1 and polyimide 2 include ketones such as 2-butanone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone. Esters such as ethyl acetate, n-butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl lactate, and γ-butyrolactone. Ethers such as tetrahydrofuran, dioxane, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, and diglyme. Various aromatic hydrocarbons such as toluene, xylene, and ethylbenzene. Chlorinated hydrocarbons such as chloroform, methylene chloride and tetrachloroethane. In addition, solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane and the like can be mentioned. Furthermore, alcohols such as 1-butanol, methyl cellosolve, and methoxypropanol can be used in combination.

  In order to form the layer 2 containing the polyimide of the present invention as a main component from the synthesized polyimide, first, a solution containing the polyimide 1 and the polyimide 2 is applied on a base material or a thin film provided on the base material.

  As a method for applying a solution containing polyimide, known application means such as a dipping method, a spin coating method, a spray method, a printing method, a flow coating method, and a combination thereof can be appropriately employed.

  Further, the solution containing the applied polyimide is dried and / or baked at 23 ° C. or higher and 250 ° C. or lower under normal pressure or reduced pressure. Drying and / or calcination of the polyimide-containing solution is mainly performed for removing the solvent, and the heating is preferably performed for about 5 minutes to 2 hours. As a heating method, it is necessary to appropriately select a hot air circulation oven, a muffle furnace, light such as infrared rays and microwaves, radiation or electromagnetic wave irradiation.

  The layer 2 containing polyimide as a main component can be mixed with components other than polyimide to such an extent that the optical properties, transparency, heat resistance and water resistance of the polyimide are not impaired. When mixing components other than polyimide, the components other than polyimide that can be mixed when the entire polyimide is 100 parts by weight are less than 20 parts by weight. When it mixes more, transparency, film | membrane intensity | strength, and the uniformity of a film thickness may be impaired.

Components mixed with components other than polyimide include silane coupling agents and phosphate esters for improving adhesion. In addition, for the purpose of improving the solvent resistance of the layer 2 containing polyimide as a main component, heat, a photocurable resin, or a crosslinking agent such as an epoxy resin, a melamine resin, or an acrylic resin can be mixed. In order to adjust the refractive index and increase the hardness of the film, a small amount of inorganic fine particles such as SiO ₂ , TiO ₂ , ZrO ₂ , SiO ₂ , ZnO, MgO, Al ₂ O ₃ can be mixed.

  The low refractive index layer 3 formed on the layer 2 mainly composed of the polyimide of the present invention may have a refractive index of 1.4 or less. Examples of the compound used include metal oxides, metal halides, and fluoropolymers. Is mentioned. More preferably, the low refractive index layer 3 is a porous film mainly composed of silicon oxide, magnesium fluoride or fluorinated acrylic polymer, or a layer having a fine uneven structure mainly composed of silicon oxide, aluminum oxide or transparent polymer. A higher antireflection effect can be obtained.

  FIG. 2 is a schematic schematic cross-sectional view showing the optical member according to this embodiment of the present invention.

  In FIG. 2, the optical member of the present invention has a layer 2 composed mainly of polyimide and a layer 4 composed of a fine concavo-convex structure sequentially laminated on the surface of a substrate 1. A fine concavo-convex structure 5 is formed on the outermost surface.

  The fine concavo-convex structure 5 forming the layer 4 composed of the fine concavo-convex structure which is one layer of the laminate is preferably a plate-like crystal of aluminum oxide. A plate-like crystal of aluminum oxide is formed by immersing a film mainly composed of aluminum oxide in warm water, so that the surface layer of the aluminum oxide film is subjected to peptization and the like, and is deposited and grown on the surface layer of the film Say that.

  The layer 4 having a fine concavo-convex structure is preferably a layer whose refractive index continuously increases from the surface layer side toward the substrate side, and the refractive index change with respect to the film thickness is as shown in FIG. Such a straight line or a curved line such as (b) and (c) can be expressed. Since the refractive index continuously increases from the surface layer side toward the base material side, the reflectance reduction effect is greater than when layers having a high refractive index are stacked in order from the surface layer side.

The layer 4 having a fine concavo-convex structure is formed of a plate-like crystal composed mainly of an oxide or hydroxide of aluminum or a hydrate thereof. A particularly preferred plate crystal is boehmite. In addition, by arranging these plate crystals, the end portions form fine concavo-convex structures 5, so the plate crystals are selectively used to increase the height of the fine concavo-convex and narrow the interval. It is arranged at a specific angle with respect to the surface of the substrate. In the present invention, an oxide or hydroxide of aluminum or a hydrate thereof is referred to as aluminum oxide. In addition, aluminum oxide alone or one or more oxide layers containing any of ZrO ₂ , SiO ₂ , TiO ₂ , ZnO, and MgO and containing 70 mol% or more of aluminum oxide are mainly composed of aluminum oxide. It shall be called a layer.

  The case where the surface of the base material 1 is a flat surface such as a flat plate, a film or a sheet is shown in FIG. The plate-like crystal has an average angle of an angle θ1 of 45 ° or more and 90 ° or less, preferably 60 ° or more and 90 ° or less with respect to the surface of the substrate, that is, the inclination direction 6 of the plate crystal and the substrate surface. It is desirable to arrange so that.

  Moreover, the case where the surface of the base material 1 has a two-dimensional or three-dimensional curved surface is shown in FIG. The plate-like crystal has an average angle θ2 of 45 ° or more and 90 ° or less, preferably 60 ° or more and 90 ° with respect to the surface of the substrate, that is, between the inclination direction 7 of the plate crystal and the tangent 8 of the substrate surface. It is desirable to arrange it so that it is below °. Note that the values of the angles θ1 and θ2 may exceed 90 ° depending on the inclination of the plate-like crystal. In this case, the values are measured to be 90 ° or less.

  The layer thickness of the layer 4 having a fine concavo-convex structure is preferably 20 nm or more and 1000 nm or less, and more preferably 50 nm or more and 1000 nm or less. When the layer thickness for forming the unevenness is 20 nm or more and 1000 nm or less, the antireflection performance by the fine uneven structure is effective, and the mechanical strength of the uneven structure is eliminated, and the manufacturing cost of the fine uneven structure is advantageous. Become. In addition, when the layer thickness is 50 nm or more and 1000 nm or less, the antireflection performance is further improved, which is more preferable.

  The surface density of the fine irregularities of the present invention is also important, and the average surface roughness Ra ′ value obtained by expanding the corresponding centerline average roughness is 5 nm or more, more preferably 10 nm or more, and further preferably 15 nm or more and 100 nm or less. is there. Further, the surface area ratio Sr is 1.1 or more, more preferably 1.15 or more, and further preferably 1.2 or more and 3.5 or less.

  One of the evaluation methods of the obtained fine concavo-convex structure is observation of the surface of the fine concavo-convex structure with a scanning probe microscope, and the average surface roughness Ra ′ obtained by extending the center line average roughness Ra of the film by the observation. The value and the surface area ratio Sr are determined. That is, the average surface roughness Ra ′ value (nm) is obtained by applying the centerline average roughness Ra defined in JIS B 0601 to the measurement surface and extending it three-dimensionally. The absolute value of the deviation up to the average value ”is expressed by the following equation (1).

Ra ′: average surface roughness value (nm),
S ₀ : Area when the measurement surface is ideally flat, | X _R −X _L | × | Y _T −Y _B |, F (X, Y): High at the measurement point (X, Y) X is the X coordinate, Y is the Y coordinate,
X _L to X _R : X coordinate range of the measurement surface,
Y _B to Y _T : Y coordinate range of the measurement surface,
Z ₀ : Average height in the measurement plane.

The surface area ratio Sr is Sr = S / S ₀ [S ₀ : Area when the measurement surface is ideally flat. S: Surface area of the actual measurement surface. ]. The actual surface area of the measurement surface is obtained as follows. First, it is divided into minute triangles composed of the three closest data points (A, B, C), and then the area ΔS of each minute triangle is obtained using a vector product. ΔS (ΔABC) = [s (s−AB) (s−BC) (s−AC)] 0.5 [where AB, BC, and AC are the lengths of each side, and s≡0.5 ( AB + BC + AC)], and the sum of ΔS is the surface area S to be obtained. When the surface density of the fine irregularities is Ra ′ is 5 nm or more and Sr is 1.1 or more, antireflection by the irregular structure can be expressed. If Ra ′ is 10 nm or more and Sr is 1.15 or more, the antireflection effect is higher than that of the former. When Ra ′ is 15 nm or more and Sr is 1.2 or more, the performance can withstand actual use. However, when Ra ′ is 100 nm or more and Sr is 3.5 or more, the effect of scattering by the concavo-convex structure is superior to the antireflection effect, and sufficient antireflection performance cannot be obtained.

In this invention, it has the following each process for forming the layer which has an uneven structure in the outermost surface of a laminated body.
6) A step of applying an aluminum oxide precursor sol to the outermost surface of the laminate,
7) A step of drying and / or baking the applied aluminum oxide precursor sol film to form an aluminum oxide film,
8) A step of immersing the aluminum oxide film in warm water to form a concavo-convex structure made of plate crystals mainly composed of aluminum oxide.

  In the present invention, when the layer 4 having a fine concavo-convex structure contains aluminum oxide as a main component, the layer 2 containing polyimide as a main component includes either a film of metal Al alone or metal Al and metal Zn or metal Mg. A metal film is formed. Then, it is formed by being immersed in warm water of 50 ° C. or higher and / or exposed to water vapor. At this time, the concavo-convex structure 5 is formed on the metal surface by hydration, dissolution, and reprecipitation. On the other hand, a layer mainly composed of aluminum oxide is formed on the layer 2 mainly composed of polyimide, and the fine concavo-convex structure 5 can be deposited on the surface by being immersed in warm water or exposed to water vapor in the same manner as described above. it can. The layer containing aluminum oxide as a main component can be formed by known CVD, PVD vapor phase method, liquid phase method such as sol-gel method, hydrothermal synthesis using an inorganic salt, or the like. In such a method of providing a plate-like crystal of aluminum oxide, an amorphous aluminum oxide layer may remain below the uneven structure 5 in the layer 4 having a fine uneven structure.

  From the point that a uniform antireflection layer can be formed on a large area or non-planar substrate, a gel film formed by applying an aluminum oxide precursor sol containing aluminum oxide is treated with warm water to produce an alumina plate crystal The method of growing is preferable.

As the raw material for the gel film obtained from the aluminum oxide precursor sol, an Al compound is used and / or at least one compound selected from the group consisting of Zr, Si, Ti, Zn, and Mg together with the Al compound. As raw materials for Al ₂ O ₃ , ZrO ₂ , SiO ₂ , TiO ₂ , ZnO, and MgO, each metal alkoxide, salt compound such as chloride and nitrate can be used. From the viewpoint of film forming properties, it is particularly preferable to use a metal alkoxide as a ZrO ₂ , SiO ₂ , or TiO ₂ raw material.

  Examples of the aluminum compound include aluminum ethoxide, aluminum isopropoxide, aluminum-n-butoxide, aluminum-sec-butoxide, aluminum-tert-butoxide, and aluminum acetylacetonate. Moreover, these oligomers, aluminum nitrate, aluminum chloride, aluminum acetate, aluminum phosphate, aluminum sulfate, aluminum hydroxide, etc. are mentioned.

  Specific examples of the zirconium alkoxide include the following. Zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetra n-propoxide, zirconium tetraisopropoxide, zirconium tetra n-butoxide, zirconium tetra t-butoxide and the like can be mentioned.

As the silicon alkoxide, various compounds represented by the general formula Si (OR) ₄ can be used. R may be the same or different lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and isobutyl group.

  Examples of the titanium alkoxide include tetramethoxy titanium, tetraethoxy titanium, tetra n-propoxy titanium, tetraisopropoxy titanium, tetra n-butoxy titanium, and tetraisobutoxy titanium.

  Examples of the zinc compound include zinc acetate, zinc chloride, zinc nitrate, zinc stearate, zinc oleate, and zinc salicylate, with zinc acetate and zinc chloride being particularly preferred.

  Examples of the magnesium compound include magnesium alkoxides such as dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium and dibutoxy magnesium, magnesium acetylacetonate, magnesium chloride and the like.

  Any organic solvent may be used as long as it does not cause the alkoxide or the like to gel. For example, alcohols such as methanol, ethanol, 2-propanol, butanol, pentanol, ethylene glycol, or ethylene glycol mono-n-propyl ether. Various aliphatic or alicyclic hydrocarbons such as n-hexane, n-octane, cyclohexane, cyclopentane, and cyclooctane. Various aromatic hydrocarbons such as toluene, xylene, and ethylbenzene. Various esters such as ethyl formate, ethyl acetate, n-butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate. Various ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Various ethers such as dimethoxyethane, tetrahydrofuran, dioxane, diisopropyl ether. Various chlorinated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, tetrachloroethane. Examples include aprotic polar solvents such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, and ethylene carbonate. From the viewpoint of the stability of the solution, it is preferable to use alcohols among the various solvents described above.

  In the case of using an alkoxide raw material, aluminum, zirconium, and titanium alkoxides are particularly highly reactive with water, and are rapidly hydrolyzed by the addition of moisture and water in the air, resulting in cloudiness and precipitation of the solution. In addition, aluminum salt compounds, zinc salt compounds, and magnesium salt compounds are difficult to dissolve with only an organic solvent, and the stability of the solution is low. In order to prevent these, it is preferable to add a stabilizer to stabilize the solution.

  Examples of the stabilizer include acetylacetone, dipyrobaylmethane, trifluoroacetylacetone, hexafluoroacetylacetone, benzoylacetone, dibenzoylmethane, 3-methyl-2,4-pentanedione, 3-ethyl-2,4-pentane. Β-diketone compounds such as dione. Methyl acetoacetate, ethyl acetoacetate, allyl acetoacetate, benzyl acetoacetate, acetoacetate-iso-propyl, acetoacetate-tert-butyl, acetoacetate-iso-butyl, acetoacetate-2-methoxyethyl, 3-keto-n Β-ketoester compounds such as methyl valeric acid. Furthermore, alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine can be exemplified. The addition amount of the stabilizer is preferably about 1 in terms of molar ratio to the alkoxide or salt compound. Further, after the addition of the stabilizer, it is preferable to add a catalyst for the purpose of promoting a part of the reaction in order to form an appropriate precursor. Examples of the catalyst include nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, ammonia and the like.

  The aluminum oxide precursor sol can be applied to the outermost surface of the laminate on the layer 2 containing polyimide as a main component or above the layer 2 containing polyimide as a main component. As a coating method, known coating means such as a dipping method, a spin coating method, a spray method, a printing method, a flow coating method, and a combination thereof can be appropriately employed.

  The applied aluminum oxide precursor sol film can be dried and / or baked at 60 ° C. or higher and 250 ° C. or lower to form an aluminum oxide film. The higher the heat treatment temperature, the more easily the film becomes denser. However, when the heat treatment temperature exceeds 250 ° C., the substrate is damaged such as deformation. More preferably, it is 100 degreeC or more and 200 degrees C or less. The heating time depends on the heating temperature, but is preferably 10 minutes or longer.

  The aluminum oxide film is immersed in warm water to form a concavo-convex structure formed from a plate crystal mainly composed of aluminum oxide. By soaking in warm water, the surface layer of the gel film containing aluminum oxide is subjected to peptization and the like, and some components are eluted. Due to the difference in solubility of various hydroxides in warm water, plate crystals mainly composed of aluminum oxide are precipitated and grown on the surface layer of the gel film. In addition, it is preferable that the temperature of warm water shall be 40 to 100 degreeC. The hot water treatment time is about 5 minutes to 24 hours.

In hot water treatment of a gel film in which an oxide such as TiO ₂ , ZrO ₂ , SiO ₂ , ZnO, or MgO is added as a different component to a film containing aluminum oxide as a main component, the difference in solubility of each component in hot water is used to crystallize the film. Is going on. Therefore, unlike the hot water treatment of an aluminum oxide single component film, the size of the plate crystal can be controlled over a wide range by changing the composition of the inorganic component. As a result, it is possible to control the concavo-convex shape formed by the plate crystal over the wide range. Further, when ZnO is used as a subcomponent, it can be co-deposited with aluminum oxide, so that the refractive index can be controlled over a wider range, and excellent antireflection performance can be realized.

  Examples of the substrate 1 used in the present invention include glass, resin, glass mirror, resin mirror, and the like. The following are mentioned as a typical thing of a resin base material. Films of thermoplastic resins such as polyester, triacetyl cellulose, cellulose acetate, polyethylene terephthalate, polypropylene, polystyrene, polycarbonate, polysulfone, polyacrylate, polymethacrylate, ABS resin, polyphenylene oxide, polyurethane, polyethylene, polycycloolefin, polyvinyl chloride And molded products. Moreover, the crosslinked film obtained from various thermosetting resins, such as unsaturated polyester resin, a phenol resin, bridge | crosslinking-type polyurethane, a bridge | crosslinking-type acrylic resin, a bridge | crosslinking-type saturated polyester resin, the bridge | crosslinking molded article, etc. are mentioned. Specific examples of the glass include alkali-free glass and alumina silicate glass. The substrate used in the present invention may be any substrate that can be finally shaped according to the purpose of use, such as a flat plate, film or sheet, and having a two-dimensional or three-dimensional curved surface. Also good. The thickness can be appropriately determined and is generally 5 mm or less, but is not limited thereto.

  In addition to the layers described above, the transparent optical member of the present invention can further be provided with layers for imparting various functions. For example, in order to improve film hardness, a hard coat layer is provided on a layer having a fine concavo-convex structure, or a water-repellent film layer such as fluoroalkylsilane or alkylsilane is provided for the purpose of preventing adhesion of dirt. Can be. On the other hand, an adhesive layer or a primer layer can be provided in order to improve the adhesion between the substrate and the layer containing polyimide as a main component.

  Hereinafter, the present invention will be described specifically by way of examples. However, the present invention is not limited to such examples. The optical film having fine irregularities on the surface obtained in each example and comparative example was evaluated by the following method.

(1) Purification of cycloaliphatic diamine 4,4'-methylenebis (aminocyclohexane) 4,4'-methylenebis (aminocyclohexane) (hereinafter abbreviated as DADCM; manufactured by Tokyo Chemical Industry) It was completely dissolved. After stopping the heating and allowing to stand at room temperature for several days, the precipitate was filtered off and dried under reduced pressure. 61 g of purified DADCM in the form of a white solid was obtained. From the gas chromatography analysis, the content of trans, trans-isomer was 94%.
¹ H-NMR (DMSO-d ₆ ); δ 0.83 (2H, m), δ 0.97 (2H, q), δ 1.18 (2H, m), δ 1.60 (2H, d), δ 1.69 (2H, d), δ 2.05 (2H, s), δ 2.42 (2H, m), δ 3.30 (4H, b)

(2) Synthesis of h from polyimide a to alicyclic diamine DADCM and aromatic diamine 4,4′-bis (4-aminophenoxy) biphenyl purified in (1) so that the total amount becomes 12 mmol (product name BAPB: Wakayama) Seiki Kogyo) and siloxane-containing diamine 1,3-bis (3-aminopropyl) tetramethyldisiloxane (product name PAM-E: Shin-Etsu Chemical Co., Ltd.) , Abbreviated as DMAc).

  About 12 mmol of acid dianhydride was added to the diamine solution while cooling with water. Acid dianhydride is 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (product name TDA-100: Shin Nippon Rika) Or 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (product name B-4400: manufactured by DIC) was used. The amount of DMAc was adjusted so that the total mass of diamine and acid dianhydride was 20% by weight.

This solution was stirred at room temperature for 15 hours to conduct a polymerization reaction. Furthermore, after adjusting to 8 wt% by dilution with DMAc, 7.4 ml of pyridine and 3.8 ml of acetic anhydride were added and stirred at room temperature for 1 hour. Furthermore, it stirred for 4 hours, heating at 60-70 degreeC with an oil bath. The polymerization solution was reprecipitated in methanol or methanol to remove the polymer, and then washed several times in methanol. After vacuum drying at 100 ° C., a white to pale yellow powdery polyimide was obtained. ^The residual amount of carboxyl groups was measured from the ¹ H-NMR spectrum, and the imidization rate was determined. The polymerization compositions of polyimides a to h are shown in Table 1.

(note)
TDA-100: 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride B-4400: 5- (2,5- Dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride DADCM: 4,4′-methylenebis (aminocyclohexane) (hexane recrystallized product)
BAPB: 4,4′-bis (4-aminophenoxy) biphenyl PAM-E: 1,3-bis (3-aminopropyl) tetramethyldisiloxane

(3) Preparation of aluminum oxide precursor sol 14.8 g of aluminum-sec-butoxide (ASBD, manufactured by Kawaken Fine Chemical), 3.42 g of 3-methyl-2,4-pentanedione, and 14 g of 2-ethyl The butanol was mixed and stirred until uniform. 1.62 g of 0.01 M dilute hydrochloric acid was dissolved in a mixed solvent of 2-ethylbutanol / 1-ethoxy-2-propanol, and then slowly added to the aluminum-sec-butoxide solution, followed by stirring for a while. The solvent was finally prepared so that the mixed solvent in which the mixing weight ratio of 2-ethylbutanol and 1-ethoxy-2-propanol was 7/3 was 59.3 g. Furthermore, the aluminum oxide precursor sol was prepared by stirring in an oil bath at 120 ° C. for 2 to 3 hours or more.

(4) Cleaning of substrate Various glass substrates having a size of about φ30 mm and a thickness of about 2 mm polished on both surfaces were ultrasonically cleaned with an alkaline detergent and IPA and then dried in an oven.

(5) Reflectance measurement Using an absolute reflectance measurement device (USPM-RU, Olympus), reflectance measurement was performed at an incident angle of 0 ° in the wavelength range of 400 nm to 700 nm.

(6) Measurement of film thickness and refractive index Using a spectroscopic ellipsometer (VASE, manufactured by JA Woollam Japan), the wavelength was measured from 380 nm to 800 nm.

(7) Surface observation of substrate The substrate surface was subjected to Pd / Pt treatment, and surface observation was performed at an acceleration voltage of 2 kV using FE-SEM (S-4800, manufactured by Hitachi High-Tech).

Example 1
Polyimide 1 as polyimide 1 (40 mol% aromatic diamine residue, 40 mol% alicyclic diamine residue) and polyimide b as polyimide 2 (15 mol% aromatic diamine residue, alicyclic diamine residue) 60 mol%) was dissolved in 49 g of a cyclohexanone / cyclopentanone mixed solvent so that the total amount was 1 g, and 0.02 g of triethoxysilyl 3-isocyanate and several drops of ion-exchanged water were added. Polyimide a and polyimide b were used alone or in combination to prepare four types of polyimide solutions.

  The combinations of polyimide 1 and polyimide 2 used in Examples 1 to 8 are shown in Table 2. However, the molar content of the aromatic diamine residue and the alicyclic diamine residue in polyimide 1 and polyimide 2 was calculated assuming that all diamine residues including the siloxane-containing diamine were 100 mol%.

An appropriate amount of each polyimide solution was dropped onto the polished surface of glass A having nd = 1.77 and νd = 50 containing La ₂ O ₅ as a main component. Further, spin coating was performed at 3000 to 4000 rpm for 20 seconds, and the substrate was dried at 140 ° C. for 30 minutes to produce a polyimide film having a film thickness of about 45 to 50 nm. The polyimide film is a film of only polyimide a, a film having a weight ratio (a / b) of polyimides a and b of 0.65 / 0.35 or 0.35 / 0.65, and four kinds of uniform films of only polyimide b. Was made. The refractive index of polyimide was measured using ellipsometry, and the relationship between the content (wt%) of polyimide a in the polyimide film and the refractive index was plotted (FIG. 6). As a result, it was found that the refractive index plot of the mixed film of polyimides a and b was placed on a straight line connecting the refractive index of 1.618 of polyimide a alone to the refractive index of 1.580 of polyimide b.

Example 2
The same operation as in Example 1 was performed except that polyimide b was changed to polyimide c (65 mol% aromatic diamine residue and 20 mol% alicyclic diamine residue) as polyimide 2. The obtained polyimide film has a film thickness of about 45 to 50 nm, a film made only of polyimide a, and a weight ratio (a / c) of polyimides a and c of 0.65 / 0.35 or 0.35 / 0.65. The film was a uniform film of four types of only polyimide c. The relationship between the content of polyimide a in the polyimide film (wt%) and the refractive index was plotted (FIG. 6). As a result, it was found that the refractive index plot of the mixed film of polyimides a and c was placed on a straight line connecting the refractive index 1.618 of polyimide a alone to the refractive index 1.661 of polyimide c.

Example 3
The same operation as in Example 1 was performed except that polyimide b was changed to polyimide d as polyimide 2 (there was no aromatic diamine residue and the alicyclic diamine residue was 40 mol%). The obtained polyimide film has a film thickness of about 45 to 50 nm, a film made only of polyimide a, and the weight ratio (a / d) of polyimides a and d is 0.87 / 0.13, 0.7 / 0.3, Alternatively, the film was a 0.37 / 0.63 film and five uniform films of polyimide d alone. The relationship between the content (wt%) of polyimide a in the polyimide film and the refractive index was plotted (FIG. 7). As a result, it was found that the refractive index plot of the mixed film of polyimides a and d was placed on a straight line connecting the refractive index 1.618 of polyimide a alone to the refractive index 1.558 of polyimide d.

Example 4
The same operation as in Example 1 was performed except that the polyimide b was changed to polyimide e (90 mol% aromatic diamine residue, no alicyclic diamine residue) as polyimide 2. The obtained polyimide film has a film thickness of about 45 to 50 nm, a film made only of polyimide a, and the weight ratio (a / e) of polyimides a and e is 0.8 / 0.2, 0.5 / 0.5, Alternatively, the film was a 0.35 / 0.65 film and five uniform films of polyimide e alone. The relationship between the content (wt%) of polyimide a in the polyimide film and the refractive index was plotted (FIG. 7). As a result, it was found that the refractive index plot of the mixed film of polyimide a and e was placed on a straight line connecting the refractive index 1.618 of polyimide a alone to the refractive index 1.680 of polyimide e.

Example 5
Polyimide a as polyimide 1 is changed to polyimide f (aromatic diamine residue is 40 mol%, alicyclic diamine residue is 40 mol%), and polyimide b is changed to polyimide g (aromatic diamine residue: fatty acid as polyimide 2). The same operation as in Example 1 was performed except that the molar ratio of the cyclic diamine residue was changed to 0: 1). The obtained polyimide film has a film thickness of about 45 to 50 nm, a film of polyimide f only, and a weight ratio (f / g) of polyimide f to g of 0.68 / 0.32 or 0.22 / 0.78. The film was a uniform film of four types consisting only of polyimide g. The relationship between the content (wt%) of polyimide f in the polyimide film and the refractive index was plotted (FIG. 8). As a result, it was found that the refractive index plot of the mixed film of polyimide f and g was placed on a straight line connecting the refractive index 1.600 of polyimide f alone to the refractive index 1.537 of polyimide g.

Example 6
The same as Example 1 except that polyimide a was changed to polyimide f as polyimide 1 and polyimide b was changed to polyimide h (90 mol% aromatic diamine residue, no alicyclic diamine residue) as polyimide 2. The operation was performed. The obtained polyimide film has a film thickness of about 45 to 50 nm, a film of only polyimide f, and a weight ratio (f / h) of polyimide f to h of 0.67 / 0.33 or 0.33 / 0.67. There were four types of uniform films consisting of only the film and polyimide h. The relationship between the content (wt%) of polyimide f in the polyimide film and the refractive index was plotted (FIG. 8). As a result, it was found that the refractive index plot of the mixed film of polyimide f and h was placed on a straight line connecting the refractive index 1.600 of polyimide f alone to the refractive index 1.663 of polyimide h.

Example 7
The same operation as in Example 1 was performed except that polyimide b was changed to polyimide g as polyimide 2. The obtained polyimide film has a film thickness of about 45 to 50 nm, a film of only polyimide a, a film having a weight ratio (a / g) of polyimides a and g of 0.5 / 0.5, and three kinds of polyimide g only. It was a uniform film. The relationship between the content (wt%) of polyimide a in the polyimide film and the refractive index was plotted (FIG. 9). As a result, it was found that the refractive index plot of the mixed film of polyimide a and g was placed on a straight line connecting the refractive index 1.618 of polyimide a alone to the refractive index 1.537 of polyimide g.

Example 8
The same operation as in Example 1 was performed except that polyimide b was changed to polyimide h as polyimide 2. The obtained polyimide film has a film thickness of about 45 to 50 nm, a film only of polyimide a, a film having a weight ratio (a / h) of polyimides a and h of 0.5 / 0.5, and only three types of polyimide h. It was a uniform film. The relationship between the content (wt%) of polyimide a in the polyimide film and the refractive index was plotted (FIG. 9). As a result, it was found that the refractive index plot of the mixed film of polyimide a and h was placed on a straight line connecting the refractive index 1.618 of polyimide a alone to the refractive index 1.663 of polyimide h.

Comparative Example 1
Both polyimide d (no aromatic diamine residue, alicyclic diamine residue is 70 mol%) and polyimide e (90 mol% aromatic diamine residue, no alicyclic diamine residue) are both polyimides 2. The same operation as Example 1 was performed except having changed to the polyimide. Table 2 shows the combinations of polyimides used in Comparative Example 1.

  The obtained polyimide film has a film thickness of about 45 to 50 nm, a film made only of polyimide d, and the weight ratio (d / e) of polyimides d and e is 0.8 / 0.2, 0.6 / 0.4, Seven films of 0.45 / 0.55, 0.3 / 0.7, or 0.15 / 0.85 and polyimide e alone were obtained. The mixed film of polyimides d and e was non-uniform and spiders were generated. When the relationship between the content (wt%) of polyimide d in the polyimide film and the refractive index is plotted (FIG. 10), it is on a straight line connecting the refractive index 1.558 of only polyimide d to the refractive index 1.680 of polyimide e. The refractive index plot of the mixed film of polyimides d and e was not included.

Example 9
Polyimide a / polyimide d (weight ratio) prepared in Examples 3, 5, and 7 on the polished surface of glass A having nd = 1.77 and νd = 50 containing La ₂ O ₅ as a main component = 0.37 / 0.63 (refractive index 1.578), polyimide f / polyimide g (weight ratio) = 0.68 / 0.32 (refractive index 1.580), polyimide a / polyimide g (weight ratio) = 0.5 / Mixed films of 0.5 (refractive index of 1.577) were prepared. An appropriate amount of an aluminum oxide precursor sol is dropped on each polyimide mixed film, spin-coated at 4000 rpm for 20 seconds, and then baked in a hot air circulating oven at 140 ° C. for 60 minutes to form amorphous aluminum oxide on the polyimide 1 film. The membrane was coated.

  Next, after being immersed in warm water of 80 ° C. for 20 minutes, it was dried at 60 ° C. for 15 minutes.

  When the FE-SEM observation of the obtained film surface was performed, a fine concavo-convex structure in which plate crystals mainly composed of aluminum oxide were randomly and intricately complicated was observed.

  Next, the absolute reflectance of the optical film on the glass A was measured, and three types of glass substrates with an antireflection film having an absolute reflectance of 450 to 650 nm of 0.1% or less were obtained (FIG. 11). There was no difference in the antireflection performance on the polyimide mixed film having the same refractive index. In addition, there was no variation in reflectance within each substrate, and no spiders were generated due to scattering.

Example 10
Polyimide a / polyimide e (weight ratio) = 0.65 / manufactured in Examples 4, 6, and 8 on the polished surface of glass B having nd = 1.83 and νd = 43 containing La ₂ O ₅ as a main component. 0.35 (refractive index 1.641), polyimide f / polyimide h (weight ratio) = 0.33 / 0.67 (refractive index 1.643), polyimide a / polyimide h (weight ratio) = 0.5 / Mixed films of 0.5 (refractive index of 1.641) were respectively produced. Thereafter, the same operation as in Example 9 was performed to produce an antireflection film on the glass B. The absolute reflectance of the optical film on the glass A was measured, and three types of glass substrates with an antireflection film having an absolute reflectance of 450 to 650 nm of 0.1% or less were obtained (FIG. 12). There was no difference in the antireflection performance on the polyimide mixed film having the same refractive index. In addition, there was no variation in reflectance within each substrate, and no spiders were generated due to scattering.

Comparative Example 2
Polyimide d / polyimide e (weight ratio) prepared in Comparative Example 1 on the polished surface of glass A having nd = 1.77 and νd = 50 containing La ₂ O ₅ as a main component = 0.8 / 0.2 ( A mixed film having a refractive index of 1.581) was produced. Thereafter, the same operation as in Example 9 was performed to produce an antireflection film on the glass A. The absolute reflectance of the optical film on the glass A was measured, and the absolute reflectance from 450 to 650 nm was 0.2% or less. However, a variation in reflectance of about 0.1% was observed in the substrate, and generation of spiders due to scattering was also confirmed. When FE-SEM observation of the cross section of the substrate was performed, it was confirmed that one polyimide phase-separated into islands at intervals of several μm in the polyimide film.

Comparative Example 3
Polyimide d / polyimide e (weight ratio) prepared in Comparative Example 1 on the polished surface of glass B with nd = 1.83 and νd = 43 containing La ₂ O ₅ as the main component = 0.3 / 0.7 ( A mixed film having a refractive index of 1.645) was produced. Thereafter, the same operation as in Example 9 was performed to produce an antireflection film on the glass B. The absolute reflectance of the optical film on the glass A was measured, and the absolute reflectance from 450 to 650 nm was 0.2% or less. However, a variation in reflectance of about 0.1% was observed in the substrate, and generation of spiders due to scattering was also confirmed. Moreover, when FE-SEM observation of the cross section of the substrate was performed, it was confirmed that one polyimide in the polyimide film was phase-separated into islands at intervals of several μm.

  The optical member of the present invention can correspond to a transparent substrate having an arbitrary refractive index, and exhibits an excellent antireflection effect for visible light. Various displays such as word processors, computers, televisions, and plasma display panels. Optical members such as polarizing plates used in liquid crystal display devices, sunglasses lenses made of various optical glass materials and transparent plastics, prescription eyeglass lenses, camera finder lenses, prisms, fly-eye lenses, toric lenses, various optical filters, sensors, and the like. Furthermore, a photographing optical system using them, an observation optical system such as binoculars, and a projection optical system used for a liquid crystal projector or the like. Various optical lenses such as scanning optical systems used in laser beam printers. It can be used for optical members such as covers of various instruments, window glass of automobiles, trains and the like.

DESCRIPTION OF SYMBOLS 1 Base material 2 Layer which has polyimide as a main component 3 Low refractive index layer which has the space | gap by porous or uneven structure 4 Layer which consists of fine uneven structure 5 Fine uneven structure 6 Inclination direction of plate crystal 7 Inclination direction of plate crystal 8 Tangent of substrate surface

Claims (11)

In the optical member in which a laminate for suppressing light reflection is formed on the surface of the base material, the outermost surface of the laminate is a layer having a porous or uneven structure, and at least one layer of the laminate is A layer mainly composed of polyimide, and the layer mainly composed of polyimide has 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 4,4 ′-( Hexafluoroisopropylidene) diphthalic anhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid Dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene- 1,2-Zika Boronic acid anhydride or acid dianhydride residue derived from 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride , Aromatic diamine residue, and polyimide 1 having an alicyclic diamine residue, and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 4,4 ′-( Hexafluoroisopropylidene) diphthalic anhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid Dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene- 1,2-di Carboxylic acid anhydrides, or 4- (2,5-di-oxo-tetrahydrofuran-3-yl) -1,2,3,4-dianhydride residue is derived from a tetrahydronaphthalene-1,2-dicarboxylic acid anhydride has a contact and aromatic diamine residue, and the content of the aromatic diamine residue containing different polyimides 2 polyimide 1, imidization ratio of the polyimide 1 and the polyimide 2 is 90% or more An optical member. Claim 1 Symbol placement of the optical member, wherein the aromatic diamine residue, wherein the polyimide 2 and the polyimide 1 has is the same. In the optical member in which a laminate for suppressing light reflection is formed on the surface of the base material, the outermost surface of the laminate is a layer having a porous or uneven structure, and at least one layer of the laminate is A layer mainly composed of polyimide, and the layer mainly composed of polyimide has 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 4,4 ′-( Hexafluoroisopropylidene) diphthalic anhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid Dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene- 1,2- Carboxylic anhydride or acid dianhydride residue derived from 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride , Aromatic diamine residue, and polyimide 1 having an alicyclic diamine residue, and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 4,4 ′-( Hexafluoroisopropylidene) diphthalic anhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid Dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene- 1 2-dicarboxylic anhydride or acid dianhydride derived from 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride It contains polyimide 2 having a residue and an alicyclic diamine residue and not containing an aromatic diamine residue, and the imidization ratio of the polyimide 1 and the polyimide 2 is 90% or more, Optical member to be used. The optical member according to claim 3, wherein the polyimide 2 and the polyimide 1 have the same alicyclic diamine residue. The optical member according to claim 3 or 4 , wherein the alicyclic diamine residue in the main chain of the polyimide 1 and the polyimide 2 has a structure represented by the following general formula (1).

(Wherein R1 to R8 each represents a hydrogen atom, Br, Cl, F, I, a phenyl group, or a linear or cyclic alkyl group having 1 to 6 carbon atoms, an alkenyl group, or an alkynyl group, provided that R1 to R8 may be the same or different.) The optical member according to any one of claims 1 to 5 , wherein the polyimide 1 and / or the polyimide 2 have a siloxane-containing diamine residue. The optical member according to any one of claims 1 to 6 refractive index difference of the polyimide 1 and the polyimide 2, characterized in that at least 0.01. The optical member according to any one of claims 1 to 7 , wherein the concavo-convex structure is formed of a plate crystal mainly composed of aluminum oxide. A laminate for suppressing light reflection is formed on a substrate surface, and at least one layer of the laminate is a method for producing an optical member comprising a layer mainly composed of polyimide,
1) At least aromatic diamine, alicyclic diamine, and acid dianhydride are reacted in a solvent, and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride in the main chain, 4 '-(hexafluoroisopropylidene) diphthalic anhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, bicyclo [2.2.2] octane-2,3,5,6 -Tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl- Derived from 3-cyclohexene-1,2-dicarboxylic anhydride or 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride Is acid two Anhydride residue, an aromatic diamine residue, and having an alicyclic diamine residue, a step of imidization to synthesize polyimide 1 90% or more,
2) at least aromatic diamines Contact and acid dianhydride was reacted in a solvent, in the main chain, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 4,4'- (Hexafluoroisopropylidene) diphthalic anhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic Acid dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene An acid derived from -1,2-dicarboxylic anhydride or 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride dianhydride residue, Oyo Have aromatic diamine residue, a is the imidization of 90% or more, and the step of the content of the aromatic diamine residue to synthesize different polyimide 2 polyimide 1,
3) A step of preparing a polyimide solution by dissolving the polyimide 1 and the polyimide 2 in a solvent,
4) A step of applying the polyimide solution on a substrate or a thin film provided on the substrate,
5) A step of drying and / or firing the applied polyimide solution to form a layer mainly composed of polyimide,
The manufacturing method of the member for optics characterized by having. A laminate for suppressing light reflection is formed on a substrate surface, and at least one layer of the laminate is a method for producing an optical member comprising a layer mainly composed of polyimide,
1) At least aromatic diamine, alicyclic diamine, and acid dianhydride are reacted in a solvent, and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride in the main chain, 4 '-(hexafluoroisopropylidene) diphthalic anhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, bicyclo [2.2.2] octane-2,3,5,6 -Tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl- Derived from 3-cyclohexene-1,2-dicarboxylic anhydride or 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride Is Dianhydride residue, an aromatic diamine residue, and having an alicyclic diamine residue, a step of imidization to synthesize polyimide 1 90% or more,
2) At least alicyclic diamine and acid dianhydride are reacted in a solvent, and 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 4,4 ′-( Hexafluoroisopropylidene) diphthalic anhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid Dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene- 1,2-dicarboxylic anhydride, or 2- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride Anhydride residues, And has a cycloaliphatic diamine residue, and free of aromatic diamines, process for imidation ratio to synthesize a polyimide 2 is 90% or more,
3) A step of preparing a polyimide solution by dissolving the polyimide 1 and the polyimide 2 in a solvent,
4) A step of applying the polyimide solution on a substrate or a thin film provided on the substrate,
5) A step of drying and / or firing the applied polyimide solution to form a layer mainly composed of polyimide,
The manufacturing method of the member for optics characterized by having. The method for producing an optical member according to claim 9 or 10 , further comprising the following steps for forming a layer having an uneven structure on the outermost surface of the laminate.
6) A step of applying an aluminum oxide precursor sol to the outermost surface of the laminate,
7) A step of drying and / or baking the applied aluminum oxide precursor sol film to form an aluminum oxide film,
8) A step of immersing the aluminum oxide film in warm water to form a concavo-convex structure made of plate crystals mainly composed of aluminum oxide.

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