Molded optical body

Abstract

Provided is an optical molded article having high shape stability and optical performance stability even after being stored in a high-temperature, high-humidity environment. This optical molded body comprises a resin substrate, a moisture-proof layer, and an optical functional layer in this order, and is characterized in that the moisture-proof layer is an amorphous film containing aluminum, silicon, oxygen, and carbon, and the optical functional layer is an antireflection layer and / or a partially reflective film.

Description

TECHNICAL FIELD

[0001] The present application relates to an optical shaped body. BACKGROUND

[0002] In the past, glass has been used in optical shaped bodies such as lenses and prisms, but in recent years, resin materials have been gradually used in the background of the degree of freedom in design such as lightness, miniaturization, and asphericalization of lenses. In addition, in recent years, with the dramatic improvement in performance of optical products such as VR (Virtual Reality), AR (Augmented Reality), the precision of optical design inside the optical product has also been further improved. Therefore, regardless of whether it is glass or resin, not only at room temperature but also in a severe environment such as a high-temperature high-humidity environment, the stability of the shape stability, the optical performance such as the refractive index of the optical shaped body has become very strict.

[0003] However, resin materials have a problem that they cause changes in the shape, refractive index, and the like of the product due to moisture absorption. In order to solve this problem, attempts are being made to form a moisture-proof coating film on the surface of an optical shaped body composed of a resin base material. In Patent Literature 1, a technology for covering an optical shaped body with a moisture-proof coating film made of a polycrystal on an external air contact surface is disclosed.

[0004] PRIOR ART DOCUMENTS

[0005] PATENT LITERATURE

[0006] Patent Literature 1: Japanese Patent Application Laid-Open No. 2006-146025 SUMMARY

[0007] The results of the research by the present inventors have shown that the optical shaped body containing a moisture-proof coating film obtained by the method of the above-described prior art cannot obtain sufficient moisture resistance, and cannot suppress changes in performance caused by moisture absorption when stored in a high-temperature high-humidity environment.

[0008] Therefore, the present application is made in view of the above-described problems, and aims to provide an optical shaped body that has high shape stability and optical performance stability even after storage in a high-temperature high-humidity environment.

[0009] That is, the present application is as follows.

[0010] [1] An optical shaped body which is an optical shaped body containing a resin base material, a moisture-proof layer, and an optical functional layer in this order, characterized in that the moisture-proof layer is an amorphous film containing aluminum, silicon, oxygen, and carbon, and the optical functional layer is an antireflection film and / or a partial reflection film.

[0011] [2] The optical shaped body according to [1], wherein the moisture-proof layer further contains nitrogen.

[0012] [3] The molded body for optical use according to [1] or [2], wherein the moisture-proof layer contains an aluminum-based composition layer containing aluminum, oxygen, and carbon.

[0013] [4] The molded body for optical use according to [3], wherein, in the moisture-proof layer, the aluminum-based composition layer contains a layer in which the carbon content ratio is 0.1 to 10 atom%.

[0014] [5] The molded body for optical use according to [3] or [5], wherein, in the moisture-proof layer, the total of the contents of aluminum, oxygen, and carbon in the aluminum-based composition layer is 70 atom% or more.

[0015] [6] The molded body for optical use according to any one of [1] to [5], wherein the moisture-proof layer contains a silicon-based composition layer containing silicon, oxygen, and nitrogen.

[0016] [7] The molded body for optical use according to [6], wherein, in the moisture-proof layer, the silicon-based composition layer contains a layer in which the nitrogen content ratio is 0.1 to 10 atom%.

[0017] [8] The molded body for optical use according to [6] or [7], wherein, in the moisture-proof layer, the total of the contents of silicon, oxygen, and nitrogen in the silicon-based composition layer is 70 atom% or more.

[0018] [9] The molded body for optical use according to any one of [6] to [8], wherein the moisture-proof layer is composed of an alternating layered structure of the aluminum-based composition layer and the silicon-based composition layer.

[0019]

[10] The molded body for optical use according to [9], wherein, in the moisture-proof layer, the ratio of the total of the thicknesses of the aluminum-based composition layers to the total of the thicknesses of the silicon-based composition layers is 1:4 to 4:1 in terms of aluminum-based composition layer: silicon-based composition layer.

[0020]

[11] The molded body for optical use according to

[10] , wherein, in the alternating layered structure, the total number of layers is 6 or more.

[0021]

[12] The molded body for optical use according to

[11] , wherein the moisture-proof layer covers the entire molded product surface, and the film thickness distribution of the moisture-proof layer is within 10%.

[0022]

[13] The molded body for optical use according to any one of [1] to

[12] , wherein the resin-made substrate is formed of any one or more resins selected from the group consisting of a methacrylic resin, a polyester resin, a carbonate resin, a norbornene resin, and a modified norbornene resin.

[0023] According to the present application, it is possible to provide an optical molded body having sufficient moisture-proof properties, high shape stability and optical property stability even after storage in a high-temperature high-humidity environment. DETAILED DESCRIPTION

[0024] Hereinafter, a mode for carrying out the present application (hereinafter, referred to as "the present embodiment") will be described in detail, but the present application is not limited to the following description, and can be carried out in various modifications within the scope of the gist thereof.

[0025] <Optical molded body>

[0026] The optical molded body of the present embodiment successively includes a resin-made substrate, a moisture-proof layer, and an optical functional layer. Here, "successively" means the order of lamination (i.e., indicates "successive lamination"). The optical molded body of the present embodiment can further include a layer other than the above. As the layer to be further included, for example, a functional layer such as an anti-fouling layer, a water-repellent layer, an oil-repellent layer, a hard coat layer, and the like; a black coating layer for suppressing the incidence of light from the side, a pretreatment layer for improving the adhesion of each layer, a primer layer, and the like can be exemplified. The position where the layer to be further included is arranged can be any position between the resin-made substrate and the moisture-proof layer, between the moisture-proof layer and the optical functional layer, on the optical functional layer, and the like, within the range not impairing the effects of the present embodiment.

[0027] <Resin-made substrate>

[0028] The resin-made substrate of the present embodiment can be a resin molded body.

[0029] The shape of the resin-made substrate is not particularly limited, and as an example, various shapes such as a film, a sheet, a flat plate, a curved surface, a bowl, a lens, a block, a sphere, a rod, a cylinder, a cylinder, a tube, a fiber, and the like can be used. In addition to the above shapes, a shape in which fine processing is performed on the surface thereof, and the like can be exemplified. As a more specific example, the shape of the substrate of the present embodiment can also be a lens, a prism, a light guide, a diffraction grating shape.

[0030] The manufacturing method of the resin-made substrate is not particularly limited, and a publicly known method can be used. As an example, injection molding, extrusion molding, compression molding, injection compression molding, vacuum molding, pressure air molding, blow molding, cast polymerization, and the like can be exemplified. In addition, it can also be a molded body obtained by further performing grinding, turning processing on a molded body obtained by the manufacturing method.

[0031] The size of the above-mentioned resin-made substrate is not particularly limited. However, from the viewpoints of easiness of operation in the film-formation process and productivity, it is preferable to be φ 1 mm or more, more preferable to be φ 5 mm or more, further preferable to be φ 10 mm or more, still more preferable to be φ 20 mm or more, particularly preferable to be φ 30 mm or more, and it is preferable to be φ 300 mm or less, more preferable to be φ 200 mm or less, further preferable to be φ 150 mm or less, still more preferable to be φ 120 mm or less, and particularly preferable to be φ 100 mm or less.

[0032] Note that the above-mentioned size can be the size of one surface shape of the substrate. In addition, in the case of a substantially circular shape, it can be the diameter (for example, the length of the major axis in the case of an ellipse).

[0033] The thickness of the above-mentioned resin-made substrate is preferably 0.1 mm or more, more preferably 0.2 mm or more, further preferably 0.3 mm or more, particularly preferably 0.5 mm or more, and it is preferably 100 mm or less, more preferably 50 mm or less, further preferably 30 mm or less, and particularly preferably 25 mm or less. Here, the thickness means the distance between the main surface of the resin-made substrate and the opposite surface thereof. If the resin-made substrate is in the shape of a lens, the maximum distance in the optical axis direction between the light-incident surface and the opposite surface thereof can be used, if the resin-made substrate is in the shape of a prism, the maximum distance between the light-incident surface and the surface on the opposite side thereof (the farthest surface can be selected in the case where a plurality of surfaces on the opposite side exist) or the distance between the bottom surfaces of a polygonal prism, whichever is smaller, can be used, if the resin-made substrate is in the shape of a cylinder or an elliptic cylinder, the minimum outer diameter length or the distance between the bottom surfaces, whichever is smaller, can be used. In the case of a substrate from which light is incident in the lateral direction like a light guide plate, the maximum distance between the light-incident surface and the surface on the opposite side thereof is indicated.

[0034] In the case where the surface of the substrate is subjected to micro-embossing, the specific surface area of the above-mentioned resin-made substrate is preferably 0.1 mm -1 Further preferably 0.3 mm -1 Particularly preferably 0.5 mm -1 Further preferably 10 mm -1 Further preferably 8 mm -1 Particularly preferably 5 mm -1 Further preferably 3 mm -1 Further preferably 0.1 mm -1 Further preferably 0.3 mm -1 Particularly preferably 5 mm -1 Further preferably 4 mm -1 Particularly preferably 3 mm -1The specific surface area is preferably in the range of 0.1 to 100 m2 / g, more preferably 1 to 50 m2 / g, and even more preferably 5 to 30 m2 / g. When the specific surface area is in this range, it is preferable from the viewpoint of the balance between the surface functionality as an optical element and the shape change of the molded body accompanying the intrusion of moisture from the surface of the molded body. Here, the specific surface area refers to the surface area per unit volume of the base material.

[0035] The above resin base material can be a thermoplastic resin.

[0036] As the thermoplastic resin, for example, a methacrylic resin, a polycarbonate resin, a polyester resin, an aromatic polyamide resin, a polyolefin-based resin, a modified polyolefin-based resin, a modified norbornene-based resin, a norbornene-based resin, a cyclic block copolymer (CBC), triacetyl cellulose (TAC), polyphenylene sulfide (PPS), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyoxymethylene (POM), polyether ether ketone (PEEK), an ABS resin (acrylonitrile (A)-butadiene (B)-styrene (S)), a polyamide, a polyimide, or the like can be exemplified. Among these, from the aspect of optical use, a resin having excellent transparency is preferable, and thus a methacrylic resin, a polycarbonate resin, a polyester resin, a modified norbornene-based resin, TAC, PET, and more preferably any one selected from the group consisting of a methacrylic resin, a polyester resin, a carbonate-based resin, a modified norbornene-based resin, TAC, and PET, and even more preferably any one selected from the group consisting of a methacrylic resin, a polyester resin, a carbonate-based resin, and a modified norbornene-based resin, and even more particularly preferably a methacrylic resin are preferable from the viewpoint of low birefringence.

[0037] The above thermoplastic resin can be used singly or in combination of two or more. In addition, an additive can be optionally incorporated. The additive is not particularly limited as long as it can exert the effects of the present application, and can be appropriately selected depending on the purpose.

[0038] (Methacrylic Resin)

[0039] In the case where a methacrylic resin is used as the thermoplastic resin, a homopolymer of methyl methacrylate (MMA) can be used, or a copolymer of MMA and another monomer can be used. From the viewpoints of heat stability, heat resistance, and low birefringence, it is preferable to use a copolymer, and more preferably a random copolymer.

[0040] The composition of the methacrylic resin is not particularly limited, and can be set to a composition containing a methacrylic ester monomer unit (A): 50 to 100 wt%, a structural unit (B) having a ring structure in the main chain and / or side chain: 0 to 30 wt%, and another vinyl-based monomer unit (C) copolymerizable with the methacrylic ester monomer: 0 to 20 wt%.

[0041] As the methacrylic ester monomer unit (A), not limited to the following substances, for example, can be listed: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, cyclooctyl methacrylate, tricyclodecane methacrylate, isobornyl methacrylate, phenyl methacrylate, benzyl methacrylate, 1-phenylethyl methacrylate, 2-methoxyethyl methacrylate, 3-phenylpropyl methacrylate, 2,4,6-tribromophenyl methacrylate, and the like.

[0042] From the viewpoint of the heat resistance, optical properties, weather resistance of the obtained methacrylic resin, the methacrylic ester monomer is preferably methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, and from the viewpoint of easy availability and the like, is preferably methyl methacrylate, benzyl methacrylate.

[0043] The methacrylic ester monomer can be used alone only one, or can be used in combination of two or more.

[0044] By appropriately adjusting the ratio of the methacrylic ester monomer unit (A) of the methacrylic resin to the structural unit (B) having a ring structure in the main chain and / or side chain, and the other vinyl monomer unit (C) capable of copolymerization with the methacrylic ester monomer described later, the resin optical element of the present embodiment can be sufficiently endowed with heat stability, heat resistance, good color tone, low hygroscopicity, and reduced birefringence due to orientation and residual stress at the time of molding. From these viewpoints, as the content of the methacrylic ester monomer unit (A), relative to 100% by weight of the methacrylic resin, it is preferably 50% by weight or more, more preferably 55% by weight or more, and further preferably 60% by weight or more. In addition, it is preferably 100% by weight or less, more preferably 95% by weight or less, and further preferably 90% by weight or less.

[0045] As the structural unit (B) having a ring structure in the main chain and / or side chain, not limited to the following substances, for example, it is preferable to have at least one structural unit selected from the group consisting of a maleimide-based structural unit (B-1), a glutaric anhydride-based structural unit (B-2), a glutarimide-based structural unit (B-3), a lactone ring structural unit (B-4), an anhydride structural unit (B-5), an aromatic-based structural unit (B-6), and an alicyclic structural unit (B-7).

[0046] The structural unit (B) having a ring structure in the main chain and / or side chain can be used alone only one, or can be used in combination of two or more.

[0047] As the maleimide-based structural unit (B-1) constituting the methacrylic resin, a structural unit represented by the following general formula (1) can be preferably used.

[0048]

[0049] In the general formula (1), R 1 represents any one selected from the group consisting of a hydrogen atom, an alkyl group having a carbon atom number of 1 to 14, a cycloalkyl group having a carbon atom number of 3 to 14, an alkoxy group having a carbon atom number of 1 to 14, an aralkyl group having a carbon atom number of 7 to 14, and an aryl group having a carbon atom number of 6 to 14, the alkyl group, the cycloalkyl group, the alkoxy group, the aralkyl group, and the aryl group having or not having a substituent on a carbon atom.

[0050] As the monomer for forming the maleimide-based structural unit (B-1), not limited to the following substances, for example, the following can be listed: maleimide; N-methylmaleimide, N-ethylmaleimide, N-n-propylmaleimide, N-isopropylmaleimide, N-n-butylmaleimide, N-isobutylmaleimide, N-tert-butylmaleimide, N-n-pentylmaleimide, N-n-hexylmaleimide, N-n-heptylmaleimide, N-n-octylmaleimide, N-laurylmaleimide, and the like N-alkyl-substituted maleimides; N-cyclopentylmaleimide, N-cyclohexylmaleimide, 1-cyclohexyl-3-methyl-1H-pyrrole-2,5-dione, 1-cyclohexyl-3,4-dimethyl-1H-pyrrole-2,5-dione, 1-cyclohexyl-3-phenyl-1H-pyrrole-2,5-dione, 1-cyclohexyl-3,4-diphenyl-1H-pyrrole-2,5-dione, and the like N-cycloalkyl-substituted maleimides; N-phenylmaleimide, N-benzylmaleimide, N-(2-chlorophenyl)maleimide, N-(4-chlorophenyl)maleimide, N-(4-bromophenyl)maleimide, N-(2-methylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-(2-ethylphenyl)maleimide, N-(2-methoxyphenyl)maleimide, N-(2-nitrophenyl)maleimide, N-(2,4,6-trimethylphenyl)maleimide, N-(4-benzylphenyl)maleimide, N-(2,4,6-tribromophenyl)maleimide, N-naphthylmaleimide, N-anthrylmaleimide, 3-methyl-1-phenyl-1H-pyrrole-2,5-dione, 3,4-dimethyl-1-phenyl-1H-pyrrole-2,5-dione, 1,3-diphenyl-1H-pyrrole-2,5-dione, 1,3,4-triphenyl-1H-pyrrole-2,5-dione, and the like N-aryl-substituted maleimides.

[0051] The maleimide-based structural unit (B-1) described above can be used alone as only one kind, or two or more kinds in combination.

[0052] The content of the maleimide-based structural unit (B-1) is preferably 1 to 70% by mass, more preferably 3 to 60% by mass, and further preferably 5 to 40% by mass, when the methacrylic resin is set to 100% by mass. When the content of the maleimide-based structural unit (B-1) is within the range described above, a resin having good moldability, heat resistance, optical properties, low birefringence, and low water absorption can be obtained, and thus it is preferable.

[0053] The methacrylic resin containing the maleimide-based structural unit (B-1) can further contain, as needed, an aromatic vinyl monomer unit, an unsaturated nitrile monomer unit, or the like derived from other monomers copolymerizable with the methacrylic ester monomer unit (A) and the maleimide-based structural unit (B-1).

[0054] As the aromatic vinyl monomer, there is no particular limitation, and examples include styrene, α-methylstyrene, and the like, with styrene being preferred.

[0055] As the unsaturated nitrile monomer, there is no particular limitation, and examples include acrylonitrile, methacrylonitrile, ethyl acrylonitrile, and the like, with acrylonitrile being preferred.

[0056] As the glutaric anhydride-based structural unit (B-2) constituting the methacrylic resin, a structural unit represented by the following general formula (2) can be preferably used.

[0057]

[0058] In the general formula (2), R 1 and R 2 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, which can or can not be substituted with a hydroxyl group.

[0059] The method for forming the glutaric anhydride-based structural unit (B-2) described above is not particularly limited, and examples include a method in which a monomer having a structure represented by the following general formula (3) is copolymerized with a monomer forming the methacrylic ester monomer unit (A) described above, and then cyclized by heating with or without a catalyst.

[0060]

[0061] In the general formula (3), R 1 represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, which can or can not be substituted with a hydroxyl group.

[0062] R 2represents a hydrogen atom or a tert-butyl group.

[0063] In addition, as long as the monomer of the structure represented by General Formula (3) can exert the effects of the present application, the monomer can remain in the methacrylic resin in an unreacted state.

[0064] The glutarimide-based structural unit (B-3) constituting the methacrylic resin can be formed after polymerization of the resin.

[0065] As the (B-3) structural unit, a structural unit represented by the following General Formula (4) can be appropriately used.

[0066]

[0067] In the General Formula (4), R 1 and R 2 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, which can or can not be substituted with a hydroxyl group.

[0068] In addition, R 3 represents any one selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 6 to 14 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 18 carbon atoms.

[0069] Particularly preferably, R 1 , R 2 , and R 3 are each a methyl group.

[0070] The above glutarimide-based structural unit (B-3) can be used alone as only one kind, or two or more kinds in combination.

[0071] When the content of the glutarimide-based structural unit (B-3) is in the above range, a resin having good moldability, heat resistance, optical properties, and low birefringence can be obtained, and thus it is preferable. Note that the content of the glutarimide-based structural unit (B-3) can be calculated, for example, by the method described in

[0136] to

[0137] of International Publication No. 2015 / 098096.

[0072] The methacrylic resin containing the glutarimide-based structural unit (B-3) can further contain an aromatic vinyl monomer unit, as necessary.

[0073] As the aromatic vinyl monomer, there is no particular limitation, and examples include styrene, a-methylstyrene, and the like, with styrene being preferable.

[0074] The lactone ring structure unit (B-4) constituting the methacrylic resin can be formed after polymerization of the resin.

[0075] As the (B-4) structure unit, a structure unit represented by the following general formula (5) can be preferably used.

[0076]

[0077] In the general formula (5), R 1 , R 2 , and R 3 each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms. Note that the organic group can or can not contain an oxygen atom.

[0078] The above lactone ring structure unit (B-4) can be used alone as only one kind or in combination with two or more kinds.

[0079] The lactone ring structure unit can be formed, for example, by copolymerizing an acrylic monomer having a hydroxyl group with a methacrylic ester monomer such as methyl methacrylate to introduce a hydroxyl group and an ester group or a carboxyl group in a molecular chain, and then causing a de-alcoholization (esterification) or a dehydration condensation between these hydroxyl group and the ester group or the carboxyl group (hereinafter, also referred to as "cyclic condensation reaction").

[0080] As the acrylic monomer having a hydroxyl group used for polymerization, for example, 2-(hydroxymethyl)acrylic acid, 2-(hydroxyethyl)acrylic acid, 2-(hydroxymethyl)acrylic acid alkyl ester, 2-(hydroxyethyl)acrylic acid alkyl ester, and the like can be exemplified, and preferably, methyl 2-(hydroxymethyl)acrylate, ethyl 2-(hydroxymethyl)acrylate is used.

[0081] When the methacrylic resin is set to 100% by mass, the content of the lactone ring structure unit (B-4) is preferably 1 to 70% by mass, more preferably 3 to 60% by mass, and further preferably 5 to 40% by mass. When the content of the lactone ring structure unit (B-4) is in the above range, a resin having good moldability, heat resistance, optical properties, low birefringence, solvent resistance, and surface hardness can be obtained, and thus it is preferable.

[0082] The methacrylic resin containing the lactone ring structure unit (B-4) can further contain an aromatic vinyl monomer unit as needed.

[0083] As the aromatic vinyl monomer, there is no particular limitation, and styrene, a-methylstyrene, and the like can be exemplified, and preferably, styrene is used.

[0084] As the acid anhydride-based structural unit (B-5) constituting the methacrylic resin, for example, an acid anhydride such as maleic anhydride, a half ester of the acid anhydride with a linear or branched alcohol having 1 to 20 carbon atoms, an α, β-ethylenically unsaturated carboxylic acid, or the like can be used.

[0085] The content of the acid anhydride-based structural unit (B-5) is preferably 1 to 70% by mass, more preferably 3 to 60% by mass, and further preferably 5 to 40% by mass, when the methacrylic resin is set to 100% by mass. When the content of the acid anhydride-based structural unit (B-5) is in the above range, a resin having good moldability, heat resistance, optical properties, and low birefringence can be obtained, and thus it is preferable.

[0086] The methacrylic resin containing the acid anhydride-based structural unit (B-5) can further contain, as necessary, an aromatic vinyl monomer unit, an unsaturated nitrile monomer unit, or the like derived from other monomers copolymerizable with the methacrylic ester monomer unit (A) and the acid anhydride-based structural unit (B-5).

[0087] As the aromatic vinyl monomer, there is no particular limitation, and styrene, α-methylstyrene, or the like can be mentioned, with styrene being preferred.

[0088] As the unsaturated nitrile monomer, there is no particular limitation, and acrylonitrile, methacrylonitrile, ethyl acrylonitrile, or the like can be mentioned, with acrylonitrile being preferred.

[0089] As the aromatic-based structural unit (B-6) constituting the methacrylic resin, a structure represented by the following general formula (6) can be preferably used.

[0090]

[0091] In the general formula (6), R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, which may or may not be substituted with a hydroxyl group.

[0092] R 2 is any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 8 carbon atoms, and an aryloxy group having 6 to 8 carbon atoms, R 2 may all be the same group or different groups. In addition, R 2 may or may not form a ring structure with each other. In the general formula (6), n represents an integer of 0 to 5.

[0093] As specific examples of the monomer represented by the above general formula (6), there are no particular limitations, and examples that can be given include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene, p-t-butylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 1,1-diphenylethylene, isopropenylbenzene (a-methylstyrene), isopropenyltoluene, isopropenylethylbenzene, isopropenylpropylbenzene, isopropenylbutylbenzene, isopropenylpentylbenzene, isopropenylhexylbenzene, isopropenyl octylbenzene, and the like.

[0094] Among the above, styrene and a-methylstyrene are preferable from the viewpoint of imparting fluidity, reducing unreacted monomers by increasing the polymerization conversion rate, and the like, and styrene is more preferable.

[0095] The content of the aromatic structural unit (B-6) is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and further preferably 5 to 20% by mass, based on 100% by mass of the methacrylic resin. When the content of the aromatic structural unit (B-6) is within the above range, a resin having good moldability, heat resistance, optical properties, and low birefringence can be obtained, and thus it is preferable.

[0096] As the alicyclic structural unit (B-7) constituting the methacrylic resin, a saturated alicyclic hydrocarbon compound having a vinyl group can be preferably used.

[0097] From the viewpoint of mechanical strength, heat resistance, and moldability, the number of carbon atoms constituting the alicyclic structure is usually in the range of 4 to 30, preferably 5 to 20, more preferably 5 to 15, and most preferably 6.

[0098] As specific examples of such a monomer, for example, vinylcyclohexane, isopropenylcyclohexane, 4-methylisopropenylcyclohexane, 3-methylisopropenylcyclohexane, 4-methylvinylcyclohexane, 3-methylvinylcyclohexane, and the like can be given.

[0099] Such a structural unit can be formed, for example, by copolymerization of a vinylcycloalkane monomer and a methacrylate monomer such as methyl methacrylate. Alternatively, it can be formed by copolymerization of a vinylcycloalkene monomer, an aromatic vinyl monomer, and a methacrylate monomer such as methyl methacrylate, introducing an unsaturated alicyclic group and an aromatic ring into the molecular chain, and then hydrogenating them. In the hydrogenation reaction, it is preferable that all carbon-carbon unsaturated bonds including the aromatic ring be hydrogenated by 80% or more, more preferably 95% or more, and further preferably 99 to 100%.

[0100] As the vinylcycloalkene monomer used for polymerization, for example, 4-vinylcyclohexene, 4-isopropenylcyclohexene, 1-methyl-4-vinylcyclohexene, 2-methyl-4-vinylcyclohexene, 1-methyl-4-isopropenylcyclohexene, 2-methyl-4-isopropenylcyclohexene, and the like can be exemplified.

[0101] As the aromatic vinyl monomer used for polymerization, for example, styrene, α-methylstyrene, α-ethylstyrene, α-propylstyrene, α-isopropylstyrene, α-tert-butylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-tert-butylstyrene, 5-tert-butyl-2-methylstyrene, 4-monochlorostyrene, dichlorostyrene, 4-monofluorostyrene, 4-phenylstyrene, and the like can be exemplified.

[0102] The content of the alicyclic structural unit (B-7) is preferably 1 to 70% by mass, more preferably 3 to 60% by mass, and further preferably 5 to 40% by mass, when the methacrylic resin is set to 100% by mass. When the content of the alicyclic structural unit (B-7) is within the above range, a resin having good moldability, heat resistance, optical properties, and low birefringence can be obtained, and thus it is preferable.

[0103] As the other vinyl monomer unit (C) that can be copolymerized with the methacrylate monomer unit, an acrylic ester monomer unit (C-1), a cyano-containing vinyl monomer unit (C-2), and a monomer unit (C-3) other than these monomer units can be exemplified.

[0104] The other vinyl monomer unit (C) that can be copolymerized with the methacrylate monomer can be used alone as only one kind, or two or more kinds can be used in combination.

[0105] The (C) monomer unit can be appropriately selected depending on the properties required for the methacrylic resin according to the present embodiment, and in the case where heat stability, flowability, mechanical properties, chemical resistance, and the like are particularly required, at least one selected from the group consisting of the acrylic ester monomer unit (C-1) and the cyano-containing vinyl monomer unit (C-2) is preferably used.

[0106] As the acrylic ester structural unit (C-1) constituting the methacrylic resin, a structural unit represented by the following general formula (7) is preferably used.

[0107]

[0108] In the general formula (7), R 1 represents a hydrogen atom or an alkoxy group having 1 to 12 carbon atoms, R 2 represents an alkyl group having 1 to 18 carbon atoms.

[0109] As the monomer for forming the acrylate monomer unit (C-1), in the methacrylic resin of the present embodiment, from the viewpoint of improving weather resistance, heat resistance, flowability, and thermal stability, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, and the like are preferable, and methyl acrylate, ethyl acrylate, n-butyl acrylate are more preferable, and from the viewpoint of easy availability, methyl acrylate and ethyl acrylate are further preferable.

[0110] The above-described acrylate monomer unit (C-1) can be used alone as only one kind, or two or more kinds can be used in combination.

[0111] From the viewpoint of heat resistance and thermal stability, in the case where the total amount of the (A) monomer unit and the (B) structural unit is set to 100 mass%, the content in the case where the acrylate monomer unit (C-1) is used is preferably 5 mass% or less, and more preferably 3 mass% or less.

[0112] As the monomer for forming the cyano-containing vinyl-based monomer unit (C-2) constituting the methacrylic resin, there is no particular limitation, and for example, acrylonitrile, methacrylonitrile, and vinylidene cyanide can be exemplified, and from the viewpoint of easy availability and imparting chemical resistance, acrylonitrile is preferable.

[0113] The above-described cyano-containing vinyl-based monomer unit (C-2) can be used alone as only one kind, or two or more kinds can be used in combination.

[0114] From the viewpoint of maintaining solvent resistance and heat resistance, in the case where the total amount of the (A) monomer unit and the (B) structural unit is set to 100 mass%, the content in the case where the cyano-containing vinyl-based monomer unit (C-2) is used is preferably 15 mass% or less, more preferably 12 mass% or less, and further preferably 10 mass% or less.

[0115] As the monomer forming the monomer unit (C-3) other than (C-1) and (C-2) constituting the methacrylic resin, there is no particular limitation, and for example, amides such as acrylamide, methacrylamide, and the like; ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and the like, which are substances obtained by esterifying both terminal hydroxyl groups of ethylene glycol or an oligomer thereof with acrylic acid or methacrylic acid; neopentyl glycol di(meth)acrylate, di(meth)acrylate, and the like, which are substances obtained by esterifying the hydroxyl groups of two alcohols with acrylic acid or methacrylic acid; substances obtained by esterifying a polyol derivative such as trimethylolpropane, pentaerythritol, and the like with acrylic acid or methacrylic acid; polyfunctional monomers such as divinylbenzene, and the like can be exemplified.

[0116] From the viewpoint of improving the effect of imparting heat resistance by the (B) structural unit, the content of the other vinyl-based monomer unit (C) that can be copolymerized with the methacrylic monomer, when the methacrylic resin is set to 100% by mass, is preferably 0 to 20% by mass, 0 to 18% by mass, and more preferably 0 to 15% by mass.

[0117] In particular, in the case where a crosslinkable polyfunctional (meth)acrylate having a plurality of reactive double bonds is used as the (C) monomer unit, from the viewpoint of the flowability of the polymer, the content of the (C) monomer unit is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, and further preferably 0.2% by mass or less.

[0118] The stereoregularity of the methacrylic resin is not particularly limited to the syndiotacticity (rr) and the atacticity (mr) represented by a triad. The syndiotacticity (rr) is the proportion of the case where both of the two chains (diads) of a triad, which is a chain of three consecutive structural units, are racemic (rr). Similarly, the atacticity (mr) is the proportion of the case where the two chains (diads) of a triad are meso and racemo (mr). Note that, in the chain of the structural unit in the polymer molecule, the chain having the same stereo configuration is referred to as meso, and the chain having the opposite stereo configuration is referred to as racemo, and is respectively denoted as m and r.

[0119] The syndiotacticity (rr) ratio and the atacticity (mr) ratio represented by a triad can be measured by determining the 1H-NMR spectrum in deuterated chloroform at 30°C 1The meso-ratio (rr) and the racemo-ratio (mr) are obtained from the H-NMR spectrum. In the spectrum, when TMS (tetramethylsilane) is set to 0 ppm, a chemical shift corresponding to the meso-ratio (rr) is observed in the range of 0.6 to 0.95 ppm, and a chemical shift corresponding to the racemo-ratio (mr) is observed in the range of 0.95 to 1.10 ppm. The ratio of these peak areas to the area of the region of 0.6 to 1.35 ppm is the meso-ratio (rr) ratio and the racemo-ratio (mr) ratio.

[0120] (Other components)

[0121] In the case where a thermoplastic resin is used as a material constituting the resin substrate of the present embodiment, other resins known in the art can also be combined as long as the required properties of the resin substrate and the resin optical element of the present embodiment can be exhibited.

[0122] As the other resins, not limited to the following substances, for example, rubbery polymers such as acrylic rubbers, polyethylene-based resins, polypropylene-based resins, polystyrene-based resins, syndiotactic polystyrene-based resins, polycarbonate-based resins, ABS resins, acrylic resins, AS resins (acrylonitrile-styrene resins), BAAS resins (butadiene-acrylonitrile-butyl acrylate-styrene resins), MBS resins (methyl methacrylate-butadiene-styrene resins), AAS resins (acrylonitrile-butyl acrylate-styrene resins), biodegradable resins, polyurethane-based resins, alloys of polycarbonate-ABS resins, polyalkylene arylate-based resins (polybutylene terephthalate, polyethylene terephthalate, polypropylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, etc.), polyamide-based resins, polyphenylene ether-based resins, polyphenylene sulfide-based resins, phenol-based resins, and the like can be exemplified.

[0123] The various thermoplastic resins can be used alone as only one kind, or two or more kinds of resins can be used in combination.

[0124] In particular, in the case of being used in combination with a methacrylic resin, from the viewpoint of improving flowability, AS resins, BAAS resins are preferred, from the viewpoint of improving impact resistance, acrylic rubbery polymers, ABS resins, MBS resins are preferred, and from the viewpoint of improving chemical resistance, polyester resins are preferred. In the case where it is necessary to impart heat resistance, to impart impact resistance, to adjust optical properties, polycarbonate-based resins are preferred. Furthermore, in the case where the compatibility with the above-mentioned methacrylic resin is good, and the flowability, impact resistance, and the like are adjusted in a state where transparency is maintained, acrylic resins are preferred.

[0125] In the thermoplastic resin used in the present embodiment, in the case of combining the above thermoplastic resin with the other resin, it is only required to be within a range capable of exhibiting the effects of the present application, but in view of the effects of imparting properties, the blending ratio of the other resin is preferably set to 50% by mass or less, more preferably 45% by mass or less, further preferably 40% by mass or less, further more preferably 30% by mass or less, particularly preferably 20% by mass or less, relative to the total amount of 100% by mass of the above thermoplastic resin and the other resin.

[0126] In addition, in view of the effects of imparting properties when the other resin is blended, the lower limit value of the blending amount in the case of blending the other resin is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, further more preferably 3% by mass or more, particularly preferably 5% by mass or more.

[0127] The kind and content of the other resin can be appropriately selected depending on the effects expected when used in combination with the other resin.

[0128] (Additives)

[0129] In the case of using a thermoplastic resin in the present embodiment, an additive can be optionally blended. The additive is not particularly limited as long as it can exert the effects of the present application, and can be appropriately selected depending on the purpose.

[0130] As the additive, not limited to the following substances, for example, various stabilizers such as ultraviolet absorbers, heat stabilizers, light stabilizers, and the like; mold releasing agents, lubricants, plasticizers, flame retardants, flame retardant aids, curing agents, curing accelerators, antistatic agents, electric conductivity imparting agents, stress relaxing agents, crystallization accelerators, hydrolysis inhibitors, chain extenders, compatibilizers, nucleating agents, reinforcing materials such as fillers, impact imparting agents, flow adjusting agents, dyes, sensitizers, colorants, thickening agents, anti-settling agents, anti-sagging agents, filling materials, antifoaming agents, coupling agents, light diffusible particles, refractive index adjusting agents, heat ray absorbers, rust preventives, antibacterial and antifungal agents, antifouling agents, electrically conductive polymers, and the like can be exemplified.

[0131] The above resin-made substrate can be a thermosetting resin or a living energy-curable resin.

[0132] In the case of using the thermosetting resin and / or the active energy curing resin, for example, (meth)acrylate-based resins, epoxy-based resins, silicone-based resins, aliphatic allyl carbonate-based resins, aromatic allyl carbonate-based resins, polyurethane-based resins, polythiourethane-based resins, episulfide resins, polyurea-based resins, and the like can be exemplified. In addition, as needed, within a range not impairing the effects of the present application, an antioxidant, an ultraviolet absorber, a specific wavelength absorber, a release agent, a curing agent, a molecular weight adjusting agent, a photochromic agent, and the like can be added.

[0133] <Moisture-proof layer>

[0134] The moisture-proof layer of the present embodiment is an amorphous film containing aluminum, silicon, oxygen, and carbon. When the moisture-proof layer is a polycrystalline structure as in the technology disclosed in Patent Document 1, gas permeates along a continuous path constituted by grain boundaries of the polycrystalline, disorder in the vicinity of the grain boundaries, voids of the columnar structure, and the like, and thus a high moisture-proof effect for long-term storage under a high-temperature high-humidity environment cannot be obtained. By the moisture-proof layer being an amorphous film, the continuous path for gas permeation disappears, and thus the permeation speed of gas in the moisture-proof layer can be suppressed, a high moisture-proof effect for long-term storage under a high-temperature high-humidity environment can be obtained, and high shape stability and optical property stability can be imparted.

[0135] Note that the moisture-proof layer of the present embodiment can also have voids inside. In the case where voids exist inside the moisture-proof layer, the moisture-proof effect of the moisture-proof layer decreases, but the flexibility of the moisture-proof layer increases, and the shape stability and optical property stability under a high-temperature high-humidity environment improve. Thus, by appropriately determining the balance between the dispersion state of the voids and the thickness of the moisture-proof layer, the effects of the present embodiment can be exhibited. The number, size, and dispersion state of the voids are determined by the unreacted component amount of the raw gas in the moisture-proof film and the amount of gas generated from the resin-made base material or the like. Thus, the voids can be controlled by appropriately setting and implementing the film formation conditions of the moisture-proof film including the degree of vacuum of the chamber, the pretreatment (gas discharge) of the resin-made base material, and the like. When voids exist inside the moisture-proof layer, the number of the voids is preferably a moderate number that does not seriously impair the moisture-proof effect and optical properties of the moisture-proof layer. In addition, the size of the voids is smaller than the thickness of each layer constituting the moisture-proof layer, and is preferably a discontinuous structure. When the voids become a structure that penetrates the moisture-proof layer due to their size or by connection, flow is promoted due to the capillary phenomenon, and thus the moisture-proof effect is greatly impaired. Furthermore, in order to suppress light scattering in the voids, the size of the voids is preferably sufficiently smaller than the wavelength of use of the optical molded body.

[0136] The moisture-proof layer preferably further contains nitrogen. In addition, the moisture-proof layer preferably has an alternating layer structure of an aluminum-based composition layer and a silicon-based composition layer, the aluminum-based composition layer containing aluminum, oxygen, and carbon and the total content of aluminum, oxygen, and carbon being 70 atomic % or more; and the silicon-based composition layer containing silicon, oxygen, and nitrogen and the total content of silicon, oxygen, and nitrogen being 70 atomic % or more. The total content of aluminum, oxygen, and carbon in the aluminum-based composition layer is preferably 70 atomic % or more, more preferably 75 atomic % or more, further preferably 80 atomic % or more, and particularly preferably 85 atomic % or more. In addition, the total content of aluminum, oxygen, and carbon in the aluminum-based composition layer is preferably 99.5 atomic % or less, more preferably 99 atomic % or less, and further preferably 98.5 atomic % or less. By having the composition of the aluminum-based composition layer be 70 atomic % or more, excellent effects of shape stability and optical property stability in a high-temperature high-humidity environment are obtained. In addition, by having the composition of the aluminum-based composition layer be 99.5 atomic % or less, excellent effects of improving the flexibility of the moisture-proof layer and suppressing the generation of cracks in the moisture-proof layer and the optical functional layer in a high-temperature high-humidity environment are obtained. The total content of silicon, oxygen, and nitrogen in the silicon-based composition layer is preferably 70 atomic % or more, more preferably 75 atomic % or more, and further preferably 80 atomic % or more. In addition, the total content of silicon, oxygen, and nitrogen in the silicon-based composition layer is preferably 99.5 atomic % or less, more preferably 99 atomic % or less, further preferably 98 atomic % or less, further preferably 97 atomic % or less, and particularly preferably 96 atomic % or less. By having the composition of the silicon-based composition layer be 70 atomic % or more, excellent effects of shape stability and optical property stability in a high-temperature high-humidity environment are obtained. In addition, by having the composition of the silicon-based composition layer be 99.5 atomic % or less, excellent effects of improving the flexibility of the moisture-proof layer and suppressing the generation of cracks in the moisture-proof layer and the optical functional layer in a high-temperature high-humidity environment are obtained.

[0137] In the moisture-proof layer, the element present in the largest proportion in the aluminum-based composition layer is preferably oxygen, and the second largest element is preferably aluminum. In addition, the element present in the largest proportion in the silicon-based composition layer is preferably oxygen, and the second largest element is preferably silicon.

[0138] By having the moisture-proof layer have the above composition, each layer of the moisture-proof layer has sufficient moisture-proof performance, and the moisture-proof layer as a whole can exhibit high moisture-proof performance, and thus high shape stability and optical property stability are exhibited.

[0139] The ratio of the total thickness of the aluminum-based composition layer to the silicon-based composition layer (aluminum-based composition layer : silicon-based composition layer) is preferably 1 : 4 to 4 : 1, more preferably 1 : 3 to 3 : 1, and further preferably 1 : 2 to 2 : 1. A thin film formed of an inorganic compound generally has film stress. The aluminum-based composition layer has tensile stress, and the silicon-based composition layer has compressive stress. When the ratio of the total thickness of the aluminum-based composition layer to the silicon-based composition layer is within the above range, the film stress is moderately canceled, and the film stress of the moisture-proof layer as a whole becomes small, and thus is preferable. From the viewpoint of suppressing deformation of the substrate caused by forming the moisture-proof layer, and the viewpoint of good adhesion of the moisture-proof layer to the substrate layer, it is preferable that the film stress of the moisture-proof layer as a whole be small.

[0140] The total number of layers of the above-described alternating layered structure is preferably 6 or more. When the moisture-proof layer is a single-layer structure, in the case where the moisture-proof layer generates a crack due to failure to follow expansion of the resin substrate under a high-temperature high-humidity environment, the crack penetrates the entire moisture-proof layer. At this time, gas permeation occurs through a continuous path formed by the penetrated crack, and flow is promoted by capillary flow within the crack, and thus the moisture-proof effect of the moisture-proof layer greatly decreases. On the other hand, by the moisture-proof layer being a layered structure, even when a crack is generated in a part of the layered structure, the generation of the crack stops at the interface of the layered structure, and does not penetrate the entire moisture-proof layer. Thus, a continuous path formed by a crack is not generated, and the entire moisture-proof layer can maintain a high moisture-proof effect. Furthermore, in the present embodiment, an optical functional layer that is hard and has low flexibility is formed on the moisture-proof layer. The moisture-proof layer being an alternating layered structure itself also has the effect of effectively dispersing stress generated between a substrate that has a high expansion rate under a high-temperature high-humidity environment and an optical functional layer that is hard and has a low expansion rate. For such a stress dispersion effect and suppression of the generation of a penetrated crack, the more the number of layers, the higher the effect, and the total number of layers is more preferably 8 or more, further preferably 10 or more, particularly preferably 12 or more, and particularly more preferably 14 or more. In addition, from the viewpoint of productivity and uniformity of the film structure, the number of layers is preferably 100 or less, more preferably 80 or less, further preferably 60 or less, and particularly preferably 50 or less.

[0141] The above-described moisture-proof layer preferably covers the entire surface of the molded article. In addition, the film thickness distribution of the moisture-proof layer is preferably within 10%. In the case where the moisture-proof layer has a defect, or has a non-film-formed portion, or in the case where there is a portion where the moisture-proof effect is low due to the size of the thickness, moisture is unevenly taken up from the portion, and thus there is a case where the shape accuracy of the optical element as a whole decreases.

[0142] In the case where the moisture-proof layer is located on the outermost surface of the optical molded body, the outermost surface is preferably a silicon-based component layer. The silicon-based component layer has a relatively high surface hardness and low reactivity with components and moisture in the air, and thus can maintain a stable film for a long period of time. In order to protect the moisture-proof layer and the resin-made base material, the silicon-based component layer of the outermost surface is preferably set to a thickness of the silicon-based component layer inside the moisture-proof layer or more.

[0143] The moisture-proof layer described above can be formed by a publicly known method. From the viewpoint of obtaining an amorphous state having a uniform composition and the viewpoint of uniformly covering the entire surface of the molded product, formation by chemical vapor deposition is preferable, and formation by an atomic layer deposition method (ALD) is more preferable.

[0144] An apparatus for performing ALD can use a publicly known apparatus.

[0145] A raw material gas (precursor) used in ALD can use a publicly known compound.

[0146] As the raw material gas described above, an organometallic raw material can be listed, and more specifically, a raw material gas such as an organosilicon having a Si-O bond or a Si-C bond, a raw material gas containing a metal element-oxygen bond or a metal element-carbon bond, an organometallic complex, or a hydride of silicon or a metal can be listed. More specifically, as a reaction gas, silane (a general term for hydrides of silicon), TEOS (TetraEthyl OrthoSilicate), TMS (TriMethoxySilane), TES (TriEthoxySilane), TMA (TriMethyl Alminium), DMAI (DiMethylAluminum Isopropoxide), TDMAS (Tri(Dimethylamino)Silane), BDEAS (Bis(Diethylamino)Silane), BTBAS (Bis(Tert-Butylamino)Silane), or Orthrus (registered trademark, Air Liquide company) can be listed, or a substance using a heterogeneous complex containing a plurality of metal elements other than only one metal element can be listed.

[0147] As an oxidizing gas used in ALD, as an example, oxygen, water (water vapor), ozone, ammonia, nitrogen can be listed. In addition, the raw material gas and the oxidizing gas can be supplied into a reaction chamber of an ALD film formation apparatus using a carrier gas (N2, Ar, He, or the like), for example.

[0148] The moisture-proof layer described above can be formed by thermal ALD in which a chemical reaction is promoted by heat or PE-ALD (Plasma-Enhanced ALD) in which a chemical reaction is promoted by plasma. From the viewpoint of suppressing damage to the substrate during film formation, obtaining a moisture-proof layer having good adhesion, easily adjusting the composition to an appropriate range, less degradation of the moisture-proof performance in a high-temperature high-humidity environment, and obtaining an optical element having higher shape stability and performance stability, a layer formed by thermal ALD obtained by reacting an organic metal raw material as a raw material gas and an ozone gas as a reaction gas is preferably used.

[0149] The composition, structure, and film thickness uniformity obtained by ALD vary depending on various parameters such as the kind of raw material gas, the kind of oxidizing gas, the gas flow rate, the pulse time, the film formation temperature, the pressure, and the like. As an example, control can be performed by the following parameters. By appropriately setting these parameters, a moisture-proof film having the prescribed composition, structure, and film thickness uniformity in the present embodiment can be obtained.

[0150] Film formation temperature: The content ratio of aluminum, silicon, oxygen, carbon, and nitrogen varies with the film formation temperature, but the content increases or decreases depending on the adsorption state of the raw material gas during the raw material gas supply stage and the reactivity. In the case of focusing on the adsorption state of the raw material gas, for example, in the case where the raw material gas is physically adsorbed on the film formation surface to cause a condensation reaction, the higher the film formation temperature, the greater the kinetic energy of the raw material gas, and the lower the influence of physical adsorption, so unreacted components are less likely to remain, and the contents of aluminum, silicon, and oxygen increase. On the other hand, in the case where the adsorption of the raw material gas on the film surface is incomplete, when the film formation temperature is increased, the adsorption reaction easily proceeds, but depending on the composition of the raw material gas, a condensation reaction as described above can occur, and thus the contents of aluminum, silicon, and oxygen decrease. When the film formation temperature is made excessively high, the desorption of the adsorbed gas can be promoted, and the film thickness uniformity deteriorates. In the case of focusing on the reactivity of the raw material gas, in general, the higher the temperature, the higher the reactivity, so the contents of aluminum and silicon increase. From the composition viewpoint, since molecules formed at a high temperature easily move to a metastable position (lattice), an amorphous film is easily produced at a low film formation temperature, and a crystalline film is easily produced at a high temperature.

[0151] Selection of raw material gas: The higher the reactivity of the raw material gas, the less unreacted components are likely to remain, so the contents of aluminum, silicon, and oxygen increase.

[0152] Exhaust time of raw material gas: The shorter the exhaust time of the raw material gas, the greater the influence of the unreacted components remaining due to the influence of the physical adsorption of the raw material gas, and the contents of aluminum, silicon, and oxygen decrease.

[0153] Selection of oxidizing gas: By using an oxidizing gas with high reactivity, the progress of the reaction is promoted, and the contents of aluminum, silicon, and oxygen increase.

[0154] Concentration of oxidizing gas: By increasing the concentration of the oxidizing gas, the progress of the reaction is promoted, and the contents of aluminum, silicon, and oxygen increase. In addition, the film thickness uniformity is good.

[0155] Pulse time of oxidizing gas: The longer the oxidizing gas flows, the more the progress of the reaction is promoted, and the contents of aluminum, silicon, and oxygen increase. In addition, the film thickness uniformity is good.

[0156] Lifetime of oxidizing gas: In the case where a gas with a short lifetime (active species) is used as the oxidizing gas, since the oxidizing gas is deactivated before it reaches the entire surface of the molded product, unreacted raw material gas is easily left, and thus the contents of aluminum, silicon, and oxygen decrease. In addition, the film thickness uniformity decreases.

[0157] Degree of vacuum at the time of exhaust: When the degree of vacuum at the time of exhaust is low (the pressure is high), the discharge of the raw material gas and the oxidizing gas does not sufficiently proceed, the influence of the remaining unreacted components becomes large, and the contents of aluminum, silicon, and oxygen decrease.

[0158] In addition to these, the less the contents of aluminum, silicon, and oxygen contained in the obtained film, the more easily an amorphous film is produced.

[0159] The film formation temperature of ALD is preferably in a range in which the substrate does not deteriorate or deform, and is performed at a high temperature. Here, the film formation temperature refers to the temperature of the inner wall of the chamber into which the substrate is put at the time of film formation. The substrate is heated mainly by radiation heat from the inner wall of the chamber, and thus the substrate temperature is usually about 20°C lower than the inner wall of the chamber. For the film formation temperature, it is preferable to set the substrate temperature to be a temperature at which reliability tests are performed or more, and more preferably to set the substrate temperature to be a temperature at which reliability tests are performed or more. Specifically, as the film formation temperature, it is preferable to be 60°C or more, more preferable to be 70°C or more, further preferable to be 80°C or more, and particularly preferable to be 90°C or more. When the difference in expansion rate between the substrate and the moisture-proof layer is found, the reference temperature at which the strain generated between the two is 0 is near the substrate temperature at the time of film formation. Thus, by performing film formation at a film formation temperature of a temperature near the reliability test or more, not only does the difference in expansion rate between the substrate and the moisture-proof layer in the reliability test become small, but also the effect of the buffer layer as the moisture-proof layer is improved. Thus, the generation of cracks caused by the difference in expansion rate of the substrate, the moisture-proof layer, and the optical functional layer can be suppressed. On the other hand, from the viewpoint of suppressing the decomposition of the raw material gas, the deformation of the substrate caused by film stress, the generation of cracks in a low temperature region of -30°C or less caused by the difference in shrinkage rate of the substrate, the moisture-proof layer, and the optical functional layer, and the generation of a crystal phase, and the viewpoint of obtaining an amorphous film excellent in moisture-proof performance and flexibility, the film formation temperature is preferably 150°C or less, more preferably 140°C or less, further preferably 130°C or less, and particularly preferably 120°C or less.

[0160] The thickness of each layer of the moisture-proof layer is not particularly limited, and is preferably 1 nm or more, more preferably 2 nm or more, and further preferably 5 nm or more. In addition, the thickness of each layer of the moisture-proof layer is preferably 50 nm or less, more preferably 30 nm or less, further preferably 20 nm or less, further preferably 15 nm or less, and particularly more preferably 10 nm or less. When the thickness of each layer is in the above range, it is preferable from the viewpoint of suppression of film peeling / cracking caused by film stress, and transparency, flexibility, and productivity. The thickness of each layer can be the same or different for each layer.

[0161] Note that, from the viewpoint of suppressing chemical changes in the moisture-proof layer due to long-term exposure to a constant temperature and humidity environment, and maintaining good moisture-proof properties for a long period of time, the outermost layer (the layer farthest from the resin-made substrate) of the moisture-proof layer preferably uses a silicon-based composition layer. This silicon-based composition layer can be the same thickness as the silicon-based composition layer located more inward (the side closer to the resin-made substrate), or can be a different thickness, but is preferably set to a thickness equal to or greater than the silicon-based composition layer inward. In the case of being set to a different thickness, from the viewpoint of improving the protective properties of the moisture-proof film, it is preferably 5 nm or greater, more preferably 10 nm or greater, further preferably 15 nm or greater, and most preferably 20 nm or greater. On the other hand, from the viewpoints of suppressing cracks and productivity, it is preferably 100 nm or less, more preferably 50 nm or less, further preferably 30 nm or less.

[0162] In addition, from the viewpoint of the moisture-proof properties of the layer itself, the total thickness of the moisture-proof layer is preferably 20 nm or greater, more preferably 30 nm or greater, further preferably 50 nm or greater, and further preferably 60 nm or greater. In addition, from the viewpoint of productivity, maintaining the flexibility of the entire moisture-proof layer, and suppressing the generation of cracks, it is preferably 200 nm or less, more preferably 150 nm or less, further preferably 120 nm or less, and further preferably 100 nm or less.

[0163] <Aluminum-based composition layer>

[0164] From the viewpoints of the flexibility and crack resistance of the layer, the carbon content in the above-described aluminum-based composition layer is preferably 0.1 atom% or greater, more preferably 1 atom% or greater, further preferably 2 atom% or greater, and particularly preferably 3 atom% or greater. In addition, from the viewpoint of the moisture-proof properties of the layer, it is preferably 10 atom% or less, more preferably 9 atom% or less, and further preferably 8 atom% or less. When the carbon content is within this range, it is preferable from the viewpoint of the balance between the moisture-proof properties of the layer, the flexibility of the layer, and the crack resistance of the layer. In addition, when the carbon content is within this range, it is preferable from the viewpoint of easily obtaining an amorphous film in film formation under film formation temperature conditions below the heat resistance temperature of the resin-made substrate (about 150°C or lower).

[0165] In addition, the above-described aluminum-based composition layer can contain other atoms in addition to aluminum, oxygen, and carbon. As examples, nitrogen, silicon, and the like can be contained. In the case of containing other atoms, the content of each atom is preferably less than the content of aluminum atoms in the aluminum-based composition layer.

[0166] <Silicon-based composition layer>

[0167] From the viewpoint of the flexibility and the crack resistance of the layer, the nitrogen content in the above-described silicon-based composition layer is preferably 0.1 atomic% or more, more preferably 0.2 atomic% or more, and further preferably 0.4 atomic% or more. From the viewpoint of the moisture resistance of the layer, the nitrogen content is preferably 10 atomic% or less, more preferably 8 atomic% or less, further preferably 6 atomic% or less, and particularly preferably 4 atomic% or less. When the nitrogen content is within the range, it is preferable from the viewpoint of the balance between the moisture resistance of the layer, the flexibility of the layer, and the crack resistance of the layer. In addition, when the nitrogen content is within the range, it is preferable from the viewpoint that an amorphous film is easily obtained in film formation under a film formation temperature condition of 150°C or lower, which is the heat resistance temperature of the resin substrate.

[0168] In addition, the above-described silicon-based composition layer can contain other atoms in addition to silicon, oxygen, and nitrogen. As examples, carbon, aluminum, and the like can be contained. In the case where other atoms are contained, the content of each atom is preferably less than the content of silicon atoms in the silicon-based composition layer.

[0169] <Optical functional layer>

[0170] The optical functional layer of the present embodiment is an antireflection film and / or a partial reflection film.

[0171] The antireflection film is an optical functional layer having a function of reducing the surface reflectance of incident light. Typically, a layer having a spectral reflectance of less than 1% in the visible light wavelength range (400 to 700 nm) can be cited, and the wavelength range and the value of the spectral reflectance to be used can be appropriately set according to the use of the optical molded body.

[0172] The partial reflection film is an optical functional layer having a function of reflecting a part of incident light and transmitting a part. Typically, a half mirror having a spectral reflectance of 50% ± 5% in the visible light wavelength range (400 to 700 nm) can be cited, but the wavelength range and the value of the spectral reflectance to be used can be appropriately set according to the use of the optical molded body.

[0173] The optical functional layer of the present embodiment can be formed by a publicly known method. As examples, vacuum evaporation, sputtering, ion plating, dip coating, inkjet printing, and the like can be preferably used.

[0174] The optical functional layer of the present embodiment can have a layer structure of a dielectric single layer film, a dielectric multilayer film, a metal film, a thermosetting resin, a living energy ray-curable resin, and the like. In addition, a moth-eye structure in which the refractive index continuously changes from the side close to the moisture-proof layer to the air layer can also be used.

[0175] The optical functional layer can cover the entire surface of the optical molded body, or can cover only a portion of the light-transmitting surface. In addition, in the case of having a plurality of optically effective surfaces, the optical functional layer can be formed on any one surface, or can be formed on a plurality of surfaces.

[0176] In addition, the optical functional layer can have only an antireflection film and / or a partial reflection film, or can have other optical functional layers. As examples, high reflection characteristics (mirror) and characteristics such as bandpass filters, edge filters, dichroic filters, and notch filters can be given.

[0177] <Items using the optical molded body>

[0178] The optical molded body of the present embodiment can be used in combination with a housing as needed, or can be the housing itself. In addition, a film such as a protective film or an optical film can be attached and used.

[0179] The optical molded body of the present embodiment can be applied to optical components and the like for household appliances, OA equipment (office automation equipment), AV equipment (audio-visual equipment), battery electric components, lighting equipment, automobile components, and the like.

[0180] As an example of a preferred use, a lens for a head-mounted display (HMD) of VR (Virtual Reality) can be given. Since the head-mounted display is an image display device that is mounted on the head and used, it is required to be small and light and to have less discomfort at the time of mounting, and as a means for miniaturization, a method of combining a 1 / 4 wave plate and a reflective polarizing plate and the like on a lens, switching reflection and transmission by changing the polarization state of light after passing through the lens, and thereby making an image reciprocate once and a half in one piece of lens has been proposed (U.S. Patent No. 6563638, Japanese Patent Application Publication No. 2017-21321, and the like).

[0181] The above-described method is, for example, based on the following concept.

[0182] A 1 / 4 wave plate and a reflective polarizing plate are arranged on the back surface of a lens on which a partial reflection coating is performed on the front surface, and light incident from the front surface of the lens as circularly polarized light is converted into linearly polarized light by the 1 / 4 wave plate after passing through the lens. The linearly polarized light is reflected by the reflective polarizing plate, and is again converted into circularly polarized light opposite to the original by the 1 / 4 wave plate, and is incident from the back surface to the lens to reach the partial reflection coating portion on the front surface. The light emitted from the back surface of the lens by being reflected by the partial reflection coating portion becomes linearly polarized light whose direction is shifted by 90° from the original direction due to the 1 / 4 wave plate, and is incident to the eye as an image by the reflective polarizing plate. In this way, a high magnification and a wide field of view can be obtained in a thin optical module.

[0183] When the polarization state changes in the process of passing through the lens, for example, after the first pass through the lens, a part of the light transmits the reflective polarizer, the image with low magnification and the image with high magnification overlap, and it is difficult to obtain a clear image, and thus a lens with low birefringence is required. In addition, the influence on the imaging property accompanying the change in the shape of the lens caused by the change in humidity in use is also not preferable, and thus a lens with low hygroscopicity and high shape stability under a high-temperature high-humidity environment is required.

[0184] As other examples in which the optical member composed of the molded body of the present embodiment is suitably used, as optical members in household goods, OA equipment, AV equipment, battery electric parts, lighting equipment, and the like, for example, there can be cited: a light guide plate used in a display such as a smartphone, a palm computer (PDA), a tablet computer, a liquid crystal television, and the like, a display front panel, a touch panel; a lens used in a smartphone, a camera lens for a tablet computer, a lens used in a telephoto camera of a curved optical system, a long-distance camera (periscope camera), a prism, and the like; a VR (Virtual Reality) / AR (Augmented Reality) / MR (Mixed Reality) / XR (Cross Reality) head-mounted display, a liquid crystal projector, an optical member for a near-infrared sensor (LiDAR; Light Detection Ranging), and the like, such as a prism element, a waveguide, a free-form surface light guide member, a lens, particularly, an optical lens of a small size and a thin wall thickness with a non-uniform shape; an optical fiber, a cladding material for an optical fiber, a lens for optical communication, a prism, a lens, a Fresnel lens, a phase plate provided with a microlens array, an optical cover member, a base material constituting a polarizing light separating element, a polarizing mirror / phase difference film, a substrate to which a polarizing mirror / phase difference film is attached, a lens, and the like.

[0185] As the optical member in an automobile member and the like, there can be cited: a light guide plate for a vehicle-mounted display; a front panel of a vehicle-mounted instrument panel, an instrument cluster, a car navigation system, an information display, a display mounted on a rear seat, or an optical cover composed of a curved molded body; a lens, a prism, a light direction conversion element, a waveguide, a light guide body, a combiner, a dust-proof sheet, an optical cover member, and the like for a head-up display; a camera lens (particularly, a front lens) for a vehicle-mounted camera; a light guide rod, and the like.

[0186] As the optical member for an aerial display, for example, there can be cited: a retroreflective sheet, a base material of a partially transmissive mirror, an optical member in which a submillimeter shape is given for constituting an array of dihedral angle reflectors, a microlens array, a base material of a concave-convex mirror, a lens for enlarging or reducing an image and correcting an image surface, aberration, a light guide member, a direction conversion element, and the like.

[0187] In addition, the present application can be preferably used for a display device for a camera focus board or a digital signage for flowing and displaying information on a thin display connected to a network for the purpose of advertisement, promotion, or the like in an outdoor, a store front, a public institution, a vehicle, or the like.

[0188] [Examples]

[0189] Hereinafter, the content of the present application will be specifically described by citing examples and comparative examples. Note that the present application is not limited to the following examples.

[0190] The raw materials used in the production example are as follows.

[0191] [Monomer]

[0192] Methyl methacrylate (MMA): manufactured by Asahi Kasei Corporation.

[0193] N-phenylmaleimide (phMI): manufactured by Nippon Shokubai Co., Ltd.

[0194] N-cyclohexylmaleimide (chMI): manufactured by Nippon Shokubai Co., Ltd.

[0195] [Organic solvent]

[0196] M-xylene (mXy): manufactured by Mitsubishi Gas Chemical Company, Inc.

[0197] [Polymerization initiator]

[0198] 1,1-di(tert-butylperoxy)cyclohexane: manufactured by NOF Corporation, Perhexa C.

[0199] [Chain transfer agent]

[0200] n-octyl mercaptan: manufactured by Chevron Phillips Chemical Company.

[0201] (Production Example 1: methacrylic resin A)

[0202] Methyl methacrylate (hereinafter referred to as MMA) 358.6 kg, N-phenylmaleimide (hereinafter referred to as phMI) 29.4 kg, N-cyclohexylmaleimide (hereinafter referred to as chMI) 67.7 kg, n-octyl mercaptan as a chain transfer agent 0.77 kg, and m-xylene (hereinafter referred to as mXy) 224.3 kg were weighed and added to a 1.25 m 3 The reactor was stirred to obtain a mixed monomer solution.

[0203] Next, MMA 88.0 kg, phMI 6.3 kg, mXy 142.4 kg were weighed and added to the tank 1 and stirred, thereby obtaining a mixed monomer solution for additional addition.

[0204] For the content liquid of the reactor, bubbling with nitrogen was performed at a rate of 30 L / min for 1 hour, and for the tank 1, bubbling with nitrogen was performed at a rate of 10 L / min for 30 minutes, and dissolved oxygen was removed.

[0205] Then, the temperature of the solution in the reactor was raised to 115°C by blowing steam into the jacket, and a polymerization initiator solution obtained by dissolving 1,1-di(tert-butylperoxy)cyclohexane 0.470 kg in mXy 1.905 kg was added at a rate of 1.0 kg / hour while stirring at 50 rpm, thereby initiating polymerization.

[0206] Note that, in the polymerization, the temperature of the solution in the reactor was controlled at 115 ± 2°C by adjusting the temperature using the jacket. The rate of addition of the initiator solution was reduced to 0.5 kg / hour 30 minutes after initiation of the polymerization.

[0207] In addition, the mixed monomer solution for additional addition was added at a constant rate from the tank 1 for 4 hours from 1 hour after initiation of the polymerization.

[0208] Further, the rate of addition of the initiator solution was reduced to 0.25 kg / hour 3.5 hours after initiation of the polymerization, and the addition was stopped 5 hours after initiation of the polymerization.

[0209] After 12 hours from initiation of the polymerization, a polymer solution of a methacrylic resin having a ring structure in the main chain was obtained, and the polymerization was ended.

[0210] The polymer solution was supplied to a concentration device composed of a tubular heat exchanger and a vaporization tank, which was heated to 250°C in advance, and devolatilization was performed. The degree of vacuum of the vaporization tank was set to 10 to 15 Torr. The resin flowing from the vaporization tank was discharged with a gear pump, extruded from a strand die, and pelletized after water cooling, thereby obtaining a methacrylic resin A.

[0211] The composition of the obtained pellet-shaped polymer was confirmed, and as a result, the structural units derived from each of MMA, phMI, and chMI were 81.0 mass%, 6.6 mass%, and 12.4 mass%, respectively. In addition, the weight average molecular weight was 108000, Mw / Mn was 2.04, and the glass transition temperature was 134°C.

[0212] (Production Example 2: Methacrylic Resin B)

[0213] A glutarimide resin was produced using a methyl methacrylate-styrene copolymer (styrene content 8 mass%) having a molecular weight of 100,000 as a raw resin, monomethylamine as an imidization agent, and a 15-mm-diameter intermeshing co-rotating twin-screw extruder. The set temperature of each temperature control zone was set to 230 to 250°C, and the screw rotation speed was set to 150 rpm. The methyl methacrylate-styrene copolymer (hereinafter, also referred to as "MS resin") was supplied at 2 kg / hr, the resin was melted and filled with a kneading block, and then 8 parts by mass of monomethylamine was injected into the resin from a nozzle. A reverse helical blade was placed at the end of the reaction zone so as to fill the resin. The pressure of the exhaust port was reduced to -0.092 MPa, and the by-products after the reaction and excess monomethylamine were removed. The resin that came out in the form of a strand from a die provided at the outlet of the extruder was cooled in a water tank, and then pelletized with a pelletizer, thereby obtaining a glutarimide MS resin intermediate (1).

[0214] Next, the set temperature of each temperature control zone of a 15-mm-diameter intermeshing co-rotating twin-screw extruder was set to 230°C, and the screw rotation speed was set to 150 rpm. The obtained glutarimide MS resin intermediate (1) was supplied from a hopper at 1 kg / hr, the resin was melted and filled with a kneading block, and then a mixed solution of 0.8 parts by mass of dimethyl carbonate and 0.2 parts by mass of triethylamine was injected into the resin from a nozzle to reduce the carboxyl group in the resin. A reverse helical blade was placed at the end of the reaction zone so as to fill the resin. The pressure of the exhaust port was reduced to -0.092 MPa, and the by-products after the reaction and excess dimethyl carbonate were removed. The devolatilized imide resin that came out in the form of a strand from a die provided at the outlet of the extruder was cooled in a water tank, and then pelletized with a pelletizer, thereby obtaining a glutarimide MS resin intermediate (2).

[0215] Further, under conditions where the set temperature of each temperature control zone of the extruder was set to 230°C, the screw rotation speed was set to 150 rpm, and the supply amount was set to 1 kg / hr, the glutarimide MS resin intermediate (2) was fed into a 15-mm-diameter intermeshing co-rotating twin-screw extruder. The pressure of the exhaust port was reduced to -0.095 MPa, and the unreacted by-raw material and the like were removed. The devolatilized imide resin that came out in the form of a strand from a die provided at the outlet of the extruder was cooled in a water tank, and then pelletized with a pelletizer, thereby obtaining a methacrylic resin B (glutarimide MS resin).

[0216] The weight average molecular weight of the methacrylic resin B was 85,000, Mw / Mn was 1.8, the content of monomer units in the copolymer was 8 mass% for styrene units, 82 mass% for MMA units, and 10 mass% for glutarimide units, and the glass transition temperature was 128°C.

[0217] (Production Example 3: Methacrylic Resin C)

[0218] Into a reaction vessel equipped with a stirring device, a temperature sensor, a cooling tube, a nitrogen gas introduction tube, and a dropping pump, 5.40 parts by mass of methyl 2-(hydroxymethyl) acrylate (hereinafter, referred to as RHMA), 37.6 parts by mass of methyl methacrylate (hereinafter, referred to as MAA), 0.450 parts by mass of styrene (hereinafter, referred to as St), and 90.0 parts by mass of toluene were charged, and the temperature was raised to 105°C while nitrogen gas was introduced.

[0219] A solution composed of 3.63 parts by mass of toluene and 0.245 parts by mass of t-amyl peroxyisononanoate as an initial initiator was dropped for 9 minutes while solution polymerization was performed at 105°C to 110°C. Then, 11 minutes after the above operation, a solution composed of 4.42 parts by mass of toluene and 0.298 parts by mass of t-amyl peroxyisononanoate as a dropping initiator was dropped for 180 minutes. In addition, while dropping a solution composed of 6.6 parts by mass of RHMA, 45.9 parts by mass of MAA, and 4.05 parts by mass of St for 180 minutes, solution polymerization was performed at 105°C to 110°C, and further, aging was performed for 100 minutes.

[0220] A solution composed of 1.20 parts by mass of toluene and 0.0750 parts by mass of stearyl phosphate as a catalyst for ring-closing condensation reaction (ring-closing catalyst) was added to the obtained polymerization solution, and ring-closing condensation reaction for forming a lactone ring structure was performed at about 90°C to 110°C for 1.5 hours under reflux.

[0221] Next, the obtained polymerization solution was subjected to a cyclization condensation reaction by passing through a multi-tube heat exchanger maintained at 220°C, and then was introduced into a vent-type twin-screw-twin-screw extruder (L / D = 52) equipped with a vane-type polymer filter (filtering accuracy 5 μm) at the front end at a treatment speed of 90 parts by mass / hour in terms of the resin amount, to thereby perform devolatilization of the polymerization solution. The number of rear vent ports of the vent-type twin-screw-twin-screw extruder used was set to 1, the number of front vent ports was set to 4 (referred to as first, second, third, and fourth vent holes from the upstream side), the barrel temperature was set to 220°C, and the degree of reduced pressure was set to 13.3 to 400 hPa (10 to 300 mmHg). During the devolatilization, ion exchange water was introduced at a rate of 1.3 parts by mass / hour from behind the first, second, and third vent holes.

[0222] The weight average molecular weight of the obtained methacrylic resin C was 102,000, Mw / Mn was 2.3, the glass transition temperature was 125°C, and the proportions of the MMA units, the styrene units, the lactone ring structure, and the RHMA units in the copolymer were 76.8 mass%, 4.6 mass%, 16.9 mass%, and 1.7 mass%, respectively.

[0223] (Production Example 4: Methacrylic Resin D)

[0224] A monomer composition composed of 63.08 parts by mass of MMA, 38.54 parts by mass of styrene, and 0.46 parts by mass of t-amyl peroxy-2-ethylhexanoate as a polymerization initiator was continuously supplied at 1 kg / h to a 10 L complete mixing tank with a helical ribbon type stirring blade, and continuous polymerization was performed at an average residence time of 2.5 hours and a polymerization temperature of 150°C. The resin was continuously extracted from the bottom in a manner that the liquid surface of the polymerization tank was constant, and was supplied to a concentration device composed of a tubular heat exchanger and a vaporization tank to perform devolatilization. The degree of vacuum of the vaporization tank was set to 10 to 15 Torr. The resin flowing from the vaporization tank was discharged using a screw pump, was extruded from a strand die, was pelletized after water cooling, and was introduced into a desolventizing device, to thereby obtain a methyl methacrylate-styrene copolymer in the form of pellets.

[0225] The copolymer was dissolved in methyl isobutyrate to prepare a 10 mass% methyl isobutyrate solution. In a 1000 mL autoclave apparatus, 500 parts by mass of the 10 mass% methyl isobutyrate solution of the copolymer, 1 part by mass of 10 mass% Pd / C as a hydrogenation catalyst were charged, and the aromatic double bonds in the styrene sites of the copolymer were hydrogenated under a hydrogen pressure of 9 MPa at 200°C for 15 hours. The hydrogenation catalyst was removed with a filter, and 0.04 parts by mass of RIKEMAL H-100 was added to the polymer solution, which was then supplied to a concentration apparatus composed of a tubular heat exchanger and a vaporization tank and subjected to devolatilization. The degree of vacuum of the vaporization tank was set to 10 to 15 Torr. The resin flowing from the vaporization tank was discharged with a gear pump, extruded from a strand die, pelletized after water cooling, and thus the methacrylic resin D was obtained.

[0226] The composition of the obtained pellets was confirmed, and as a result of absorbance measurement at a wavelength of 260 nm, the hydrogenation rate of the aromatic double bonds in the styrene sites was 99%. In addition, as a result of NMR measurement, the structural units derived from each of MMA and vinylcyclohexane in the copolymer were 60.7 mass% and 39.3 mass%, respectively. The weight average molecular weight was 167,000, Mw / Mn was 1.9, and the glass transition temperature was 118°C.

[0227] (Production Example 5: Methacrylic Resin E)

[0228] The same operation as in Production Example 4 was performed except that 75.09 parts by mass of MMA and 26.04 parts by mass of styrene were used, and thus the methacrylic resin E was obtained.

[0229] The composition of the obtained pellets was confirmed, and as a result of absorbance measurement at a wavelength of 260 nm, the hydrogenation rate of the aromatic double bonds in the styrene sites was 99%. In addition, as a result of NMR measurement, the structural units derived from each of MMA and vinylcyclohexane in the copolymer were 73.2 mass% and 26.8 mass%, respectively. The weight average molecular weight was 148,000, Mw / Mn was 2.0, and the glass transition temperature was 118°C.

[0230] <Evaluation>

[0231] The evaluation of the resins produced in the production examples was performed as follows.

[0232] (1) Analysis of Structural Units

[0233] In each production example, unless otherwise specified, the structural units of the thermoplastic resin produced were identified by 1 H-NMR measurement and 13 C-NMR measurement, and the amounts thereof were calculated. 1H-NMR measurement and 13 The measurement conditions of C-NMR measurement are as follows.

[0234] Measurement device: ECZ400 manufactured by JEOL Ltd.

[0235] Measurement solvent: CDCl3or DMSO-d6.

[0236] Measurement temperature: 40°C.

[0237] (2) Measurement of molecular weight

[0238] The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the thermoplastic resin manufactured in the manufacturing example were measured under the following device and conditions.

[0239] Measurement device: gel permeation chromatograph (HLC-8320GPC) manufactured by Tosoh Corporation.

[0240] The measurement conditions are as follows.

[0241] Column: 1 TSKguardcolumn Super H-H, 2 TSKgel Super HM-M, and 1 TSKgel Super H2500 were connected in series and used.

[0242] Column temperature: 40°C.

[0243] Elution solvent: tetrahydrofuran, flow rate: 0.6 mL / minute, 2,6-di-tert-butyl-4-methylphenol (BHT) was added as an internal standard at 0.1 g / L.

[0244] Detector: RI (differential refractive) detector, detection sensitivity: 3.0 mV / minute.

[0245] Sample: 0.02 g of a tetrahydrofuran 20 mL solution of the thermoplastic resin. Injection amount: 10 μL.

[0246] Standard sample for calibration curve: 10 kinds of polymethyl methacrylate (manufactured by Polymer Laboratories; PMMA Calibration Kit M-M-10) having different molecular weights and known weight peak molecular weights were used.

[0247] The weight peak molecular weights (Mp) of the standard samples are as follows.

[0248] Standard sample 1: 1916000.

[0249] Standard sample 2: 625500.

[0250] Standard sample 3: 298900.

[0251] Standard sample 4: 138600.

[0252] Standard sample 5: 60150.

[0253] Standard sample 6: 27600.

[0254] Standard sample 7: 10290.

[0255] Standard sample 8: 5000.

[0256] Standard sample 9: 2810.

[0257] Standard sample 10: 850.

[0258] Under the above conditions, the RI detection intensity with respect to the elution time of the thermoplastic resin was measured.

[0259] The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the thermoplastic resin were calculated based on the calibration curve obtained by the measurement of the standard samples using the above calibration curve.

[0260] (3) Measurement of glass transition temperature

[0261] The glass transition temperature (Tg) (°C) of the thermoplastic resin was measured according to JIS-K7121.

[0262] First, about 10 mg of 4 points (4 places) were cut out from the test sample that had been conditioned (left to stand for 1 week at 23°C) under standard conditions (23°C, 50% RH) as test pieces.

[0263] Next, using a differential scanning calorimeter (manufactured by PerkinElmer Japan, Inc., Diamond DSC), under the conditions of a nitrogen flow rate of 25 mL / minute, the test sample was completely melted by raising the temperature from room temperature (23°C) to 200°C at a rate of 10°C / minute (1st temperature rise), and then lowering the temperature from 200°C to 40°C at a rate of 10°C / minute, and holding at 40°C for 5 minutes, and further, the glass transition temperature (Tg) (°C) was measured as the intersection point (midpoint glass transition temperature) of the stepwise change portion curve at the 2nd temperature rise and the straight line at equal distances from the respective baseline extensions in the vertical axis direction in the DSC curve plotted during the 2nd temperature rise under the above temperature raising conditions. Four points were measured for each test sample, and the arithmetic mean (rounded off to the 4th decimal place) of the 4 points was taken as the measured value.

[0264] [Example 1]

[0265] (Molding of lens)

[0266] Using the methacrylic resin A obtained in Production Example 1, injection molding of a biconvex lens having an optical axis thickness of 7.0 mm and an effective diameter of φ 41 mm was performed using an injection molding machine (manufactured by FANUC, S-2000i50B). As a finish, the single surface on the surface including the optical axis was a non-spherical shape having a curvature radius of R93.5 mm, a conic constant k = -1.12452, and no even constant was set. In addition, the other single surface on the surface including the optical axis was a spherical shape having an R67 mm.

[0267] The barrel temperature was set to Tg+135°C of the methacrylic resin A used, and the metal mold temperature was set to Tg-15°C of the methacrylic resin A used, and molding was performed. The holding pressure was set to 60 MPa for 4 seconds in the first stage, and then the holding pressure was set to 40 MPa for 3 seconds in the second stage in order to relax the stress and strain inside the molded product. In addition, the injection speed was set to 10 mm / s and molding was performed, and thus a lens molded product was obtained.

[0268] (Formation of moisture-proof layer)

[0269] Using an atomic layer deposition (ALD) device (manufactured by Meiden Nanoprocess Innovations, Inc., PO-ALD), an alternating layer stack film composed of aluminum-based composition layers and silicon-based composition layers was formed on the entire surface of the above lens. First, using DMAI gas as an organometallic raw material, using high-concentration ozone gas generated using a pure ozone generator (manufactured by Meiden Seizo Co., Ltd., MPOG-HM1A1) as an oxidizing agent, and using hot ALD with a film formation temperature of 110°C, film formation of an aluminum-based composition layer having a thickness of 10 nm was performed. Next, using Orthrus (registered trademark, Air Liquide company) as an organometallic raw material, using high-concentration ozone gas generated using a pure ozone generator (manufactured by Meiden Seizo Co., Ltd., MPOG-HM1A1) as a reaction agent, and using hot ALD with a film formation temperature of 110°C, film formation of a silicon-based composition layer having a thickness of 10 nm was performed. The same film formation was repeated four times under the same conditions, and the film formation was performed with an increased number of cycles so that the thickness of the silicon-based composition layer at the fourth time was 30 nm. Thus, a lens in which the entire surface was covered with an alternating layer stack film of an aluminum-based composition layer and a silicon-based composition layer having a total of 8 layers and a thickness of 100 nm was obtained. Here, the total thickness of the aluminum-based composition layers was 40 nm, and the total thickness of the silicon-based composition layers was 60 nm.

[0270] (Formation of optical function layer)

[0271] A lens was obtained by forming an antireflection film composed of an alternating layered film of titanium oxide and silicon oxide on the R67 mm spherical surface side of the lens by a vacuum evaporation method.

[0272] [Example 2]

[0273] In the film formation of the moisture-proof layer, the film formation of the aluminum-based component layer with a thickness of 10 nm and the film formation of the silicon-based component layer with a thickness of 10 nm were alternately repeated four times under the same conditions using hot ALD with a film formation temperature of 110°C, thereby obtaining a lens whose entire surface was covered with an alternating layered film with a thickness of 80 nm and a total of 8 layers having the composition shown in Table 1. Here, the total of the thicknesses of the aluminum-based component layers was 40 nm, and the total of the thicknesses of the silicon-based component layers was 40 nm.

[0274] Other than the above, a lens was obtained by the same operation as in Example 1.

[0275] [Example 3]

[0276] In the film formation of the moisture-proof layer, the film formation of the aluminum-based component layer with a thickness of 10 nm and the film formation of the silicon-based component layer with a thickness of 5 nm were alternately repeated four times under the same conditions using hot ALD with a film formation temperature of 100°C, thereby obtaining a lens whose entire surface was covered with an alternating layered film with a thickness of 60 nm and a total of 8 layers having the composition shown in Table 1. Here, the total of the thicknesses of the aluminum-based component layers was 40 nm, and the total of the thicknesses of the silicon-based component layers was 20 nm.

[0277] Other than the above, a lens was obtained by the same operation as in Example 1.

[0278] [Example 4]

[0279] In the film formation of the moisture-proof layer, the film formation of the aluminum-based component layer with a thickness of 5 nm and the film formation of the silicon-based component layer with a thickness of 5 nm were alternately repeated eight times under the same conditions using hot ALD with a film formation temperature of 100°C, and the film formation was performed with an increased number of cycles so that the thickness of the silicon-based component layer at the eighth time was 25 nm. An alternating layered film with a thickness of 100 nm and a total of 16 layers having the composition shown in Table 1 was formed. Here, the total of the thicknesses of the aluminum-based component layers was 40 nm, and the total of the thicknesses of the silicon-based component layers was 60 nm.

[0280] Other than the above, a lens was obtained by the same operation as in Example 1.

[0281] [Example 5]

[0282] In the film formation of the moisture-proof layer, the film formation of the aluminum-based component layer having a thickness of 10 nm and the film formation of the silicon-based component layer having a thickness of 5 nm were alternately repeated four times under the same conditions using hot ALD with a film formation temperature of 120°C, whereby a lens having an entire surface covered with an alternating layer stack film having a composition shown in Table 1 and a thickness of 60 nm in total of eight layers was obtained. Here, the total thickness of the aluminum-based component layers was 40 nm, and the total thickness of the silicon-based component layers was 20 nm.

[0283] In addition, in the production of the lens molded product, a partial reflection film (reflectance 50% ± 5%, wavelength range 450 to 650 nm) composed of an alternating layer stack film of titanium oxide and silicon oxide was formed on the R67 mm spherical surface side of the lens by a vacuum evaporation method.

[0284] In addition to the above, a lens was obtained by the same operation as in Example 1.

[0285] [Example 6]

[0286] In the production of the lens molded product, the methacrylic resin B obtained in Production Example 2 was used, and otherwise, a lens was obtained by the same operation as in Example 1.

[0287] [Example 7]

[0288] In the production of the lens molded product, the methacrylic resin C obtained in Production Example 3 was used, and otherwise, a lens was obtained by the same operation as in Example 1.

[0289] [Example 8]

[0290] In the production of the lens molded product, the methacrylic resin D obtained in Production Example 4 was used, and otherwise, a lens was obtained by the same operation as in Example 1.

[0291] [Example 9]

[0292] In the production of the lens molded product, the methacrylic resin E obtained in Production Example 5 was used, and otherwise, a lens was obtained by the same operation as in Example 1.

[0293] [Comparative Example 1]

[0294] In addition to the film formation of the moisture-proof layer not being performed in Example 1, a lens was obtained by the same operation as in Example 1.

[0295] [Comparative Example 2]

[0296] In addition to the film formation of the moisture-proof layer not being performed in Example 5, a lens was obtained by the same operation as in Example 5.

[0297] [Comparative Example 3]

[0298] In Example 1, in the film formation of the moisture-proof layer, the film formation was performed by alternately repeating the film formation of the aluminum-based composition layer having a thickness of 10 nm and the film formation of the silicon-based composition layer having a thickness of 10 nm four times under the same conditions, and the film formation time was extended to make the thickness of the silicon-based composition layer in the fourth time 30 nm. The film formation of the moisture-proof layer was performed on the aspheric side of the lens having an R of 93.5 mm, and then on the spherical side having an R of 67 mm. Thereby, a lens was obtained in which both surfaces of the lens were covered with an alternating layer stack having a composition shown in Table 1 and a thickness of 60 nm in total of 8 layers.

[0299] Other than this, a lens was obtained by the same operation as in Example 1.

[0300] [Comparative Example 4]

[0301] In Example 3, in the film formation of the moisture-proof layer, an aluminum-based composition layer having a thickness of 60 nm was formed as a single layer.

[0302] Other than this, a lens was obtained by the same operation as in Example 3.

[0303] <Evaluation>

[0304] The evaluation of the optical molded bodies produced in each of the examples and comparative examples was performed as follows. The evaluation results are shown in Table 1.

[0305] (1) Composition of the moisture-proof film

[0306] For the optical molded bodies produced in the examples and comparative examples, XPS measurement was performed from the air interface side of the moisture-proof layer under the following conditions, and the composition of the moisture-proof layer was confirmed. In determining the composition, the site having the largest concentration of aluminum or silicon was used.

[0307] <Analysis Conditions>

[0308] Apparatus used: VersaProbe II manufactured by ULVAC-PHI, INCORPORATED.

[0309] Excitation source: Monochromatic Al Kα.

[0310] Analysis size: About 200 μm φ.

[0311] Photoelectron take-off angle: 45°.

[0312] Pass Energy: 46.95 eV (narrow area scan).

[0313] <Ar + Sputtering Conditions>

[0314] Acceleration: 1 kV.

[0315] Raster Size: 2mm × 2mm, with azimuth rotation.

[0316] (2) Thickness and structure of the moisture-proof membrane

[0317] For the optical molded articles produced in the examples and comparative examples, cross-sectional observations were performed under the following conditions to confirm the uniformity of the moisture-proof layer thickness. Furthermore, the crystallinity of each layer of the moisture-proof layer was evaluated using electron diffraction patterns. In the absence of diffraction rings, it was confirmed whether each layer constituting the moisture-proof film was an amorphous structure, as it was considered an amorphous structure.

[0318] Equipment used (section machining): Hitachi High-Tech NX5000 and Japan FEI Company Helios 650.

[0319] Equipment used (cross-sectional observation / electron diffraction): Hitachi High-Tech HD2300.

[0320] The evaluation of film thickness uniformity is based on the following criteria.

[0321] A (Good): The difference between the film thickness at the location with the maximum film thickness and the film thickness at the location with the minimum film thickness is within 10% of the film thickness at the location with the maximum film thickness. However, if there are pinholes in the moisture-proof film, that location is excluded from the calculation. Additionally, if there are voids within the moisture-proof film, these voids are included in the film thickness calculation.

[0322] B (Poor): The value obtained by the above calculation method exceeds 10%.

[0323] (3) Reliability test under high temperature and high humidity environment

[0324] For the optical molded bodies manufactured in the examples and comparative examples, reliability tests were conducted under the following temperature and humidity conditions: 1 for 168 hours, 336 hours, and 504 hours, and 2 for 504 hours, to evaluate the reliability under high temperature and high humidity conditions. Optical components were placed in a constant temperature and humidity chamber (manufactured by ESPEC CORP., PL-2J) set to the specified temperature and humidity conditions and maintained for 168 hours, 336 hours, and 504 hours, and then removed for evaluation in steps (4) to (6).

[0325] Temperature and humidity conditions 1: 65℃, 90%RH.

[0326] Temperature and humidity condition 2: 85℃, 85%RH.

[0327] (4) Shape stability evaluation

[0328] The optical molded body before the reliability test under high-temperature high-humidity environment (i.e., 0 hours) and after the reliability test under high-temperature high-humidity environment for a prescribed time was subjected to non-contact shape accuracy measurement under the following conditions, and the shape stability was evaluated. Note that the shape accuracy measurement was performed on the aspheric side on which no optical functional layer was formed, because sufficient reflected light intensity was not obtained on the spherical side on which an antireflection film was formed, and it was difficult to perform measurement by the present measurement method.

[0329] Apparatus used: manufactured by Y-ECO Corporation, NH-3SPs.

[0330] Measurement surface: aspheric side.

[0331] Measurement site: through the optical center of the optical element and perpendicular to the direction of flow.

[0332] The evaluation was performed according to the following criteria.

[0333] A (Good): the absolute value of ΔPV was less than 2.0 μm.

[0334] B (Slightly Good): the absolute value of ΔPV was 2.0 μm or more and less than 5.0 μm.

[0335] C (Slightly Poor): the absolute value of ΔPV was 5.0 μm or more and less than 10.0 μm.

[0336] D (Poor): the absolute value of ΔPV was 10.0 μm or more.

[0337] Here, ΔPV is the amount of change in PV before and after the reliability test, and the value of the best fit R (Best Fit R) at 0 hours was commonly used in the calculation.

[0338] (5) Appearance Evaluation

[0339] The appearance of the optical molded body before the reliability test under high-temperature high-humidity environment (i.e., 0 hours) and after the reliability test under high-temperature high-humidity environment for a prescribed time was visually observed, and the presence or absence of cracks was confirmed. The evaluation was performed according to the following criteria.

[0340] A (Good): no generation of cracks was confirmed.

[0341] B (Slightly Good): a small amount (about 1 to 2) of cracks were generated.

[0342] C (Slightly Poor): a large amount (about several to several tens) of cracks were generated.

[0343] D (Poor): an innumerable amount of cracks were generated.

[0344] (6) Evaluation of optical properties

[0345] The optical function layer of the optical shaped body before the reliability test under high temperature and high humidity environment (i.e., 0 hours) and after the reliability test under high temperature and high humidity environment for a prescribed time is subjected to measurement of microspectral reflectance.

[0346] The value of the average reflectance in the range of wavelengths of 450 to 650 nm is confirmed to change how much before and after the reliability test.

[0347] In the case where the kind of the optical function layer is an antireflection film, the evaluation is performed in accordance with the following criteria.

[0348] A (good): the change amount is less than 0.1%.

[0349] B (slightly good): the change amount is 0.1% or more and less than 0.2%.

[0350] C (slightly poor): the change amount is 0.2% or more and less than 0.5%.

[0351] D (poor): the change amount is 0.5% or more.

[0352] In the case where the kind of the optical function layer is a partial reflection film, the evaluation is performed in accordance with the following criteria.

[0353] A (good): the change amount is less than 2.0%.

[0354] B (slightly good): the change amount is 2.0% or more and less than 2.5%.

[0355] C (slightly poor): the change amount is 2.5% or more and less than 3.0%.

[0356] D (poor): the change amount is 3.0% or more.

[0357]

[0358] The optical shaped body of the present embodiment has sufficient moisture-proof performance, and has high shape stability and optical property stability even under a high temperature and high humidity environment.

[0359] As examples of the optical molded body suitable for use in the present embodiment, as optical members in household articles, OA equipment, AV equipment, battery electric parts, lighting equipment, and the like, for example, there can be cited: light guide plates used in displays such as smartphones, PDAs, tablet computers, liquid crystal televisions, and the like; display front panels; touch panels; lenses used in cameras for smartphones, tablet computers, and the like; lenses, prisms, and the like used in long-range cameras (periscopic cameras) of the curved optical system; VR (Virtual Reality) / AR (Augmented Reality) / MR (Mixed Reality) / XR (Cross Reality) head-mounted displays; liquid crystal projectors; optical members such as prism elements, waveguides, free-form light guide members, lenses, particularly optical lenses of small and thin wall thickness uneven shapes, for near-infrared sensors (LiDAR; Light Detection Ranging), and the like; optical fibers; cladding materials for optical fibers; lenses, prisms, lenses, Fresnel lenses, phase plates provided with microlens arrays, optical cover members, substrates constituting polarizing light separating elements, polarizing mirrors, phase difference films, laminated polarizing mirrors, substrates for phase difference films, lenses, and the like.

[0360] As optical members in automobiles and the like, there can be cited: light guide plates for vehicle-mounted displays; front panels for vehicle-mounted instrument panels, instrument clusters, car navigation systems, information displays, displays mounted on rear seats, and the like; optical covers composed of curved molded bodies; lenses, prisms, light direction conversion elements, waveguides, light guide bodies, combiners, dustproof sheets, optical cover members, and the like for head-up displays; camera lenses (particularly front lenses) for vehicles; light guide rods; and the like.

[0361] As optical members for air displays, for example, there can also be cited: retroreflective sheets; substrates for partially transmissive mirrors; optical members shaped into submillimeter shapes for constituting arrays of dihedral angle reflectors; microlens arrays; passive optical elements; substrates for concave-convex mirrors; lenses for enlarging, reducing, and correcting images and aberrations; light guide members; direction conversion elements; and the like.

[0362] In addition, in addition to the above, it is also possible to be preferably used for display devices for digital signage for displaying information flowing on thin displays connected to a network for the purpose of publicity, advertising, and the like at outdoor places, store fronts, public institutions, vehicles, and the like.

Claims

1. An optical molded body which is an optical molded body comprising, in order, a resin substrate, a moisture-proof layer, and an optical functional layer, characterized in that, the moisture-proof layer is an amorphous film containing aluminum, silicon, oxygen, and carbon, the optical functional layer is an antireflection film and / or a partial reflection film.

2. The optical molded body according to claim 1, wherein, the moisture-proof layer further contains nitrogen.

3. The optical molded body according to claim 1, wherein, the moisture-proof layer comprises an aluminum-based composition layer containing aluminum, oxygen, and carbon.

4. The optical molded body according to claim 3, wherein, in the moisture-proof layer, the aluminum-based composition layer comprises a layer in which the carbon content ratio is 0.1 to 10 atomic %.

5. The optical molded body according to claim 3, wherein, in the moisture-proof layer, the total content of aluminum, oxygen, and carbon in the aluminum-based composition layer is 70 atomic % or more.

6. The optical molded body according to claim 2 or 3, wherein, the moisture-proof layer comprises a silicon-based composition layer containing silicon, oxygen, and nitrogen.

7. The optical molded body according to claim 6, wherein, in the moisture-proof layer, the silicon-based composition layer comprises a layer in which the nitrogen content ratio is 0.1 to 10 atomic %.

8. The optical molded body according to claim 6, wherein, in the moisture-proof layer, the total content of silicon, oxygen, and nitrogen in the silicon-based composition layer is 70 atomic % or more.

9. The optical molded body according to claim 6, wherein, the moisture-proof layer is composed of an alternating layered structure of the aluminum-based composition layer and the silicon-based composition layer.

10. The optical molded body according to claim 9, wherein, in the moisture-proof layer, the ratio of the total thickness of the aluminum-based composition layer to the total thickness of the silicon-based composition layer is 1:4 to 4:1 in terms of aluminum-based composition layer:silicon-based composition layer.

11. The optical molded body according to claim 10, wherein, in the alternating layered structure, the total number of layers is 6 or more.

12. The optical molded body according to claim 11, wherein, the moisture-proof layer covers the entirety of the molded product surface, and the film thickness distribution of the moisture-proof layer is within 10%.

13. The optical molded body according to claim 11, wherein, the resin substrate is formed of any one or more resins selected from the group consisting of a methacrylic resin, a polyester resin, a carbonate resin, a norbornene resin, and a modified norbornene resin.

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