JP2007009187A - Transparent resin molded body and eyeglass lens comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent resin molded body which has excellent optical properties, heat resistance and mechanical properties and various properties such as scratch resistance and durability in a good balance and to provide an eyeglass lens and the like comprising the same. <P>SOLUTION: The transparent resin molded body is covered with a cured transparent film composed of a composition containing an organic silicon compound and/or its hydrolyzate, a multifunctional epoxy resin having an aromatic ring and/or an aliphatic ring and inorganic fine particles which is coated on the surface of a transparent thermoplastic resin into which a sulfonic acid residue having a bicycloalkyl structure is introduced. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is excellent in optical characteristics such as high refractive index and low dispersion, and scratch resistance, abrasion resistance, impact resistance, chemical resistance, flexibility, heat resistance, flame resistance, light resistance and weather resistance. The present invention relates to a transparent resin molding suitable for optical applications such as a spectacle lens and a camera lens having excellent properties.

  In recent years, resin molded bodies have been proposed for various applications. In particular, various materials such as an optical lens, a functional optical film, and a disk substrate are applied to the resin molding according to various uses. In addition, with rapid development in the health care and electronics fields, the resin molded body is particularly desired to have higher functionality and higher performance required for the resin molded body itself. Among these uses, eyeglass lenses can be cited as a health care application of resin molded products suitable for optics. From the viewpoint of thinning, weight reduction, safety (impact resistance) and fashionability, etc. Material development is in progress. Currently, in the eyeglass lens field, 90% of the market is made up of resin lenses made of resin moldings in terms of safety and weight reduction superior to glass.

  Conventional resin for spectacle lenses includes resins such as CR-39, acrylic (halogen atom-containing bisphenol A-based and sulfur atom-containing systems), polyurethane, etc., but higher refractive index and lower dispersion. Many plastic lenses have been put to practical use.

  However, all of the above-mentioned resin lenses are thermosetting resins, and a cast polymerization method in which a monomer is cast into a glass mold is used as a method for manufacturing the resin lenses. However, this method has a problem in that the production cost is high, for example, a long polymerization process is required to obtain a uniform resin lens, and an annealing process is performed to alleviate stress strain. On the other hand, if a thermoplastic resin such as polycarbonate is applied to the lens, there is an advantage that the moldability is good and the manufacturing cost can be significantly reduced compared to the thermosetting resin, but polycarbonate has a low refractive index (d-line). The refractive index is 1.58.), And the performance as a vision correction glasses application is insufficient. Also, many thermoplastic resins having a refractive index higher than that of polycarbonate are known, but there are problems such as high dispersibility and coloring, and there are still problems in applying to optical lens applications.

  In recent years, plastic lens materials with a high refractive index have been developed, and the center thickness of the lens has been reduced and the lens periphery (edge thickness) has been reduced to reduce the wearing feeling. Lenses have the disadvantage of low impact resistance and easy cracking.

  In order to solve such drawbacks, a technique of providing a urethane resin primer layer composed of polyol and isocyanate between a thermosetting plastic lens and a hard coat layer (see Patent Document 1 and Patent Document 2), polyol and A technique using a primer layer of urethane resin composed of block type isocyanate (see Patent Document 3) and a technique using a primer composition composed of a polyisocyanate component and a polythiol component between an organic glass or inorganic glass and a hard coat layer (patent) Reference 4) has been proposed. However, since these proposals all use thermosetting plastic lenses, the impact resistance is insufficient, and the proposal of Patent Document 4 has problems such as insufficient weather resistance. There is.

  Further, when the thermoplastic lens is subjected to a surface treatment such as a hard coat function or an antireflection function, it has a disadvantage that the impact resistance is lowered as in the case of the thermosetting plastic lens. In order to solve such drawbacks, there has been proposed a technique of providing a hard coat made of urethane (meth) acrylate by UV curing on the surface of a plastic lens substrate made of polycarbonate resin (see Patent Document 5). In this proposal, the scratch resistance is insufficient.

In addition, among thermoplastic resins, a proposal has been made to perform surface treatment on a resin having a phosphonic acid ester group in the main chain, which has a particularly high refractive index and low dispersibility (see Patent Document 6 and Patent Document 7). )), It is possible to provide a plastic lens having a good balance of impact resistance, optical properties, thermal properties and scratch resistance, but it is said that the impact resistance and dispersibility, which are practical, are sufficient. It is difficult, and a plastic lens for spectacles for realizing further improvement in impact resistance and low dispersion has been desired.
JP-A 63-87223 JP 63-14001 A JP-A-3-109502 JP 11-193355 A JP 2000-9904 A JP 2003-206363 A JP 2003-268142 A

  The inventors of the present invention have made extensive studies in order to solve the above-described drawbacks, and improved the impact resistance and the scratch resistance of the surface while maintaining the original physical properties of the resin molded body, and have good adhesion and reflection interference fringes. The present inventors have found a transparent resin molded body coated with a cured transparent film that satisfies the above reduction, and have reached the present invention.

  The object of the present invention is coated with a cured transparent film excellent in impact resistance, high scratch resistance, excellent transparency, high refractive index, low dispersibility and mechanical properties, and an antireflection film. An object of the present invention is to provide a transparent resin molded article, particularly a transparent resin molded article suitable for optical spectacle lenses, and an optical article suitable for spectacle lenses made of the transparent resin molded article.

In order to solve the above problems, the present invention has the following configuration. That is,
(1) A phosphonic acid residue having at least a bicycloalkyl structure, and the following general formula (1)

[In General Formula (1), R ¹ and R ² are each independently an atom selected from the group consisting of a halogen atom, an aliphatic group having 1 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and a nitro group. Or a functional group, p and q are integers of p + q = 0 to 8, Y is a single bond, ether group, thioether group, alkylene group, alkylidene group, cycloalkylene group, cycloalkylidene group, phenylalkylidene group, carbonyl group, It represents a functional group selected from the group consisting of a sulfone group, an aliphatic phosphine oxide group, an aromatic phosphine oxide group, an alkylsilane group, a dialkylsilane group, and a fluorene group. General formula (1) may be further substituted. On the surface of a thermoplastic resin containing a dihydric phenol residue represented by the following general formula (2)

[In General Formula (2), R ³ represents a hydrocarbon group having an epoxy group or a glycidoxy group, R ⁴ represents a functional group selected from the group consisting of an alkyl group, an alkenyl group, and an allyl group, and Z represents A decomposable group, and r is 0 or 1; The organosilicon compound of the general formula (2) and / or a hydrolyzate thereof may be further substituted. And a hydrolyzate thereof, a polyfunctional epoxy resin having an aromatic ring and / or an aliphatic ring, and a transparent resin coated with a cured transparent film comprising a composition containing inorganic fine particles Molded body.

  (2) A phosphonic acid residue having a bicycloalkyl structure is represented by the following general formula (3):

[In general formula (3), l, m and n are each independently an integer of 1 to 4, X ¹ is an atom or electron pair selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom and an unshared electron pair. Represents. R ⁵ represents a functional group or an atom selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a halogen atom, and r is an integer of 0 to 4. The phosphonic acid residue of the general formula (3) may be further substituted. ] The transparent resin molding as described in said (1) characterized by the above-mentioned.

  (3) The thermoplastic resin further has the following general formula (4)

[In General Formula (4), R ⁶ represents an organic group, and X ² represents an atom or electron pair selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and an unshared electron pair. However, the phosphonic acid residue of the general formula (4) has a structure different from the phosphonic acid residue of the general formula (3) of the above (2). The molar fraction of the phosphonic acid residue represented by the general formula (3) of the above (2) and the phosphonic acid residue represented by the general formula (4) is represented by the following formula (I) )
1 ≧ (a) / {(a) + (b)} ≧ 0.01 (I)
[In the formula (I), (a) represents the number of moles of phosphonic acid residues having a bicycloalkyl group structure, and (b) represents the number of moles of phosphonic acid residues represented by the general formula (4). The transparent resin molded product according to (2) above, wherein

(4) The thermoplastic resin contains carbonate residues and / or divalent carboxylic acid residues, and the total number of moles of all phosphonic acid residues and the total number of moles of carbonate residues and divalent carboxylic acid residues is The following formula (II)
1 ≧ (c) / {(c) + (d)} ≧ 0.01 (II)
[In formula (II), (c) represents the total number of moles of phosphonic acid residues, and (d) represents the total number of moles of carbonate residues and divalent carboxylic acid residues. The transparent resin molded product according to (2) or (3), wherein

  (5) The transparent resin molded product according to any one of (1) to (4), wherein the Abbe number (νd) of the thermoplastic resin is 32 or more.

  (6) The transparent resin molded product according to any one of (1) to (5), wherein the thermoplastic resin has a d-line refractive index of 1.58 or more.

  (7) The cured transparent film whose difference from the d-line refractive index of the thermoplastic resin is 0.01 or less in absolute value is coated, according to any one of (1) to (6), Transparent resin molding.

  (8) The transparent resin molded product according to (7), wherein the inorganic fine particles include at least one fine particle selected from titanium dioxide, zirconium oxide, and antimony pentoxide.

  (9) The transparent resin molded article according to any one of (1) to (8), wherein a single-layer or multilayer antireflection film is formed on the surface of the cured transparent film.

  (10) An optical article comprising the transparent resin molded article according to any one of (1) to (9).

(11) A spectacle lens comprising the transparent resin molding according to any one of (1) to (10).
It is.

The transparent resin molded product obtained by the present invention has the following effects.
(1) The thermoplastic resin for the transparent resin molding can be injection-molded, and a mass-productive and inexpensive transparent resin molding can be obtained.
(2) It has a high refractive index, a high Abbe number, and a high glass transition temperature (Tg).
(3) It has a highly scratch-resistant surface and is excellent in heat resistance, chemical resistance and weather resistance.
(4) It is possible to obtain a spectacle lens having excellent impact resistance, a two-point frame spectacle, and a thin speckled spectacle lens.
(5) An optical article excellent in practicality in appearance can be obtained in which interference fringes and reflections on the lens surface are suppressed.

  The thermoplastic resin used in the present invention contains at least a phosphonic acid residue having a bicycloalkyl structure and a divalent phenol residue. Specifically, the thermoplastic resin used in the present invention has a structure having a pentavalent phosphorus atom, in particular, a phosphonic acid structure having a bicycloalkyl group introduced into the main chain of the polymer, is colorless and transparent, and has a high refractive index. An optically low-dispersion thermoplastic resin.

  Further, since the thermoplastic resin used in the present invention relates to optical use, the total light transmittance of a plate-like molded product having a width of 10 mm, a length of 25 mm, and a thickness of 3 mm obtained from this resin is 70% or more. It is preferable that it is 80% or more.

  The total light transmittance is defined below. Using a digital color computer (manufactured by Suga Test Instruments Co., Ltd .: SM-7CH), tristimulus values (X, Y, Z) were obtained by the transmission method, and the total light transmittance was defined as the Y value. The At that time, the total light transmittance can be converted into the total light transmittance of a plate-like molded product having a width of 10 mm, a length of 25 mm, and a thickness of 3 mm by applying Lambert-Beer's law.

Among optical properties, the refractive index depends on the intrinsic polarizability of the atomic group and the density of the atomic group, so that the bicycloalkyl structure having a high carbon density and containing a large amount of SP ³ carbon has a high refractive index. In addition, a high Abbe number can be expressed, which is extremely effective in practice.

As such a bicycloalkyl structure, a compact structure having 12 or less carbon atoms (bicyclododecane) forming a ring is preferable from the viewpoint of containing a large amount of SP ³ carbon per unit space, and more preferably carbon forming a ring. Those having a number of 9 (bicyclononane) or less are preferred.

As for the bond between the bicycloalkyl structure and the phosphorus atom, it is most preferable that the phosphorus atom is directly bonded to the bicycloalkyl skeleton in order to contain more SP ³ carbon in the space. You may couple | bond together via the alkylene group. From the viewpoint of optical properties, a more preferable phosphonic acid residue having a bicycloalkyl group is a phosphonic acid residue having a structure represented by the following general formula (3).

In general formula (3), l, m, and n each independently represent an integer of 1 to 4. By being in this range, a large amount of SP ³ carbon can be contained per unit space. l, m, and n are more preferably integers of 1 to 3. X ¹ represents an atom or an electron pair selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and an unshared electron pair. Moreover, general formula (3) may be further substituted.

The bonding position with the phosphorus atom on the bicycloalkyl structure is arbitrary, and may be either a bridge head or a bridge. The substituent R ⁵ is a functional group or atom selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a halogen atom, and r is an integer of 0 to 4. When r is an integer of 2 or more, two or more different substituents R ⁵ may be included on the same atom bicycloalkyl structure. Further, the thermoplastic resin may contain two or more phosphonic acid residues having different l, m, n, R ⁵ or X ¹ .

  Examples of suitable structures of such bicycloalkyl groups include bicyclo [2,2,1] -1-heptyl (1-norbornyl), bicyclo [2,2,1] -2-heptyl (2-norbornyl), bicyclo [ 2,2,1] -7-heptyl (7-norbornyl), bicyclo [2,2,2] -1-octyl, bicyclo [2,2,2] -2-octyl, bicyclo [3,2,1] -2-octyl, and bicyclo [3,2,2] -1-nonyl, bicyclo [4,2,2] -2-decanyl, and the like. These may be one kind or plural kinds.

The substituent R ⁵ on the bicycloalkyl structure may be introduced to such an extent that the optical properties are not impaired in order to control the mechanical properties and thermal properties, but the viewpoint of containing more SP ³ carbon per unit space. Therefore, the substituent R ⁵ is preferably a compact structure such as a methyl group, an ethyl group, or a halogen group. The substituent r is preferably 4 or less, more preferably 2 or less, from the same viewpoint.

  The thermoplastic resin used in the present invention is represented by the following general formula (4) in addition to the phosphonic acid residue represented by the general formula (3) in order to control thermal, chemical or mechanical properties. Phosphonic acid residues can be included.

In general formula (4), R ⁶ represents an organic group, and X ² represents an atom or electron pair selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and an unshared electron pair. The phosphonic acid residue has a structure different from that of the phosphonic acid residue of the general formula (3).

The following formula (II) is a formula representing the copolymerization fraction of the phosphonic acid residue represented by the general formula (3) to the phosphonic acid residue represented by the general formula (4).
1 ≧ (a) / {(a) + (b)} ≧ 0.01 (II)
That is, in formula (II), (a) is the number of moles of the phosphonic acid residue represented by the general formula (3), and (b) is the number of moles of the phosphonic acid residue represented by the general formula (4). However, when the value of the molar fraction [(a) / {(a) + (b)}] of the phosphonic acid residue represented by the general formula (3) is less than 0.01, the thermoplastic resin It is difficult to obtain the effects of the present invention such as a high Abbe number and a high refractive index. The value of [(a) / {(a) + (b)}] in the formula (II) which is the molar fraction is preferably in the range of 0.25 or more, more preferably 0.4 or more. Yes, more preferably 0.6 or more.

Specific examples of the substituent R ⁶ constituting the phosphonic acid residue represented by the general formula (4) include phenyl, halo-substituted phenyl, methoxyphenyl, ethoxyphenyl, ethyl, isopropyl, cyclohexyl, vinyl, allyl, Examples include benzyl, aminoalkyl, hydroxyalkyl, halo-substituted alkyl, and alkyl sulfide groups.

  Specific examples of the phosphonic acid unit constituting the phosphonic acid residue represented by the general formula (4) include methylphosphonic acid, ethylphosphonic acid, n-propylphosphonic acid, isopropylphosphonic acid, and n-butylphosphonic acid. Acid, isobutylphosphonic acid, t-butylphosphonic acid, n-pentylphosphonic acid, neopentylphosphonic acid, cyclohexylphosphonic acid, benzylphosphonic acid, chloromethylphosphonic acid, dichloromethylphosphonic acid, bromomethylphosphonic acid, dibromomethylphosphonic acid, 2-chloro Ethylphosphonic acid, 1,2-dichloroethylphosphonic acid, 2-bromoethylphosphonic acid, 1,2-dibromoethylphosphonic acid, 3-chloropropylphosphonic acid, 2,3-dichloropropylphosphonic acid, 3-bromopropylphosphonic acid 2,3-di Lomopropylphosphonic acid, 2-chloro-1-methylethylphosphonic acid, 1,2-dichloro-1-methylethylphosphonic acid, 2-bromo-1-methylethylphosphonic acid, 1,2-dibromo-1-methylethyl Phosphonic acid, 4-chlorobutylphosphonic acid, 3,4-dichlorobutylphosphonic acid, 4-bromobutylphosphonic acid, 3,4-dibromobutylphosphonic acid, 3-chloro-1-methylpropylphosphonic acid, 2,3- Dichloro-1-methylpropylphosphonic acid, 3-bromo-1methylpropylphosphonic acid, 2,3-dibromo-1-methylphosphonic acid, 1-chloromethylpropylphosphonic acid, 1-chloro-1-chloromethylpropylphosphonic acid, 1-bromomethylpropylphosphonic acid, 1-bromo-1-bromomethylpropylphosphonic acid, Lopentylphosphonic acid, 4,5-dichloropentylphosphonic acid, 5-bromopentylphosphonic acid, 4,5-dibromopentylphosphonic acid, 1-hydroxymethylphosphonic acid, 2-hydroxyethylphosphonic acid, 3-hydroxypropylphosphonic acid, 4-hydroxybutylphosphonic acid, 5-hydroxypentylphosphonic acid, 1-aminomethylphosphonic acid, 2-aminoethylphosphonic acid, 3-aminopropylphosphonic acid, 4-aminobutylphosphonic acid, 5-aminopentylphosphonic acid, methylthiomethylphosphone Acid, methylthioethylphosphonic acid, methylthiopropylphosphonic acid, methylthiobutylphosphonic acid, ethylthiomethylphosphonic acid, ethylthioethylphosphonic acid, ethylthiopropylphosphonic acid, propylthiomethylphosphonic acid, pro Pyrthioethylphosphonic acid, butylthiomethylphosphonic acid, phenylphosphonic acid, 4-chlorophenylphosphonic acid, 3,4-dichlorophenylphosphonic acid, 3,5-dichlorophenylphosphonic acid, 4-bromophenylphosphonic acid, 3,4-bromophenyl Phosphonic acid, 3,5-bromophenylphosphonic acid, 4-methoxyphenylphosphonic acid, 3,4-dimethoxyphenylphosphonic acid, 1-naphthylphosphonic acid, 2-naphthylphosphonic acid, 5,6,7,8-tetrahydro- 2-naphthylphosphonic acid, 5,6,7,8-tetrahydro-1-naphthylphosphonic acid, benzylphosphonic acid, 4-bromophenylmethylphosphonic acid, 3,4-dibromophenylmethylphosphonic acid, 3,5-dibromophenylmethylphosphonic acid , 2-Phenylethylphosphone 2- (4-bromophenyl) ethylphosphonic acid, 2- (3,4-dibromophenyl) ethylphosphonic acid, 2- (3,5-dibromophenyl) ethylphosphonic acid, 3-phenylpropylphosphonic acid, 3- (4-bromophenyl) propylphosphonic acid, 3- (3,4-dibromophenyl) propylphosphonic acid, 3- (3,5-dibromophenyl) propylphosphonic acid, 4-phenylbutylphosphonic acid, 4- (4- Bromophenyl) butylphosphonic acid, 4- (3,4-dibromophenyl) butylphosphonic acid, 4- (3,5-dibromophenyl) butylphosphonic acid, 2-pyridylphosphonic acid, 3-pyridylphosphonic acid, 4-pyridyl Phosphonic acid, 1-pyrrolidinomethylphosphonic acid, 1-pyrrolidinoethylphosphonic acid, 1-pyrrolidinopropylphosphine Acid, 1-pyrrolidinobutylphosphonic acid, pyrrole-1-phosphonic acid, pyrrole-2-phosphonic acid, pyrrole-3-phosphonic acid, thiophene-2-phosphonic acid, thiophene-3-phosphonic acid, dithian-2- Examples include phosphonic acid, trithian-2-phosphonic acid, furan-2-phosphonic acid, furan-3-phosphonic acid, vinylphosphonic acid, and allylphosphonic acid.

Further, X ² in the general formula (4) below as well Hosuhonausu acid residue is a thiophosphoric acid residue or unshared pair of electrons is a sulfur atom. These may be one type or a plurality of types.

  The thermoplastic resin used in the present invention can contain other acid residues in order to control thermal, chemical, mechanical properties, moldability, and the like. Examples of such other acid residues include heteroacid residues such as silicon acid, sulfuric acid and boric acid, carbonic acid residues, and divalent carboxylic acid residues. From the viewpoint of chemical stability and the like, a carbonic acid residue and a divalent carboxylic acid residue are preferable. These may be one kind or plural kinds.

Other acid residues such as a hetero acid residue, a carbonic acid residue and a divalent carboxylic acid residue are added to the thermoplastic resin used in the present invention within the range of the copolymerization fraction represented by the following formula (II). It is possible to control thermal, chemical, mechanical properties, moldability, and the like.
1 ≧ (c) / {(c) + (d)} ≧ 0.01 (II)
Formula (II) is a formula representing the copolymerization fraction of the total of the phosphonic acid residue represented by the general formula (3) and the phosphonic acid residue represented by the general formula (4) with respect to other acid residues. It is. That is, (c) in the formula (II) represents the total number of moles of phosphonic acid residues represented by the general formula (3) and the phosphonic acid residues represented by the general formula (4) (total phosphonic acid residues). (D) indicates the total number of moles of other acid residues. When the molar fraction of all phosphonic acid residues is less than 0.01, the high Abbe number of the resin does not appear, and it is difficult to obtain the effects of the present invention. Furthermore, the value of [(c) / {(c) + (d)}] in the above formula (II), which is the molar fraction of all phosphonic acid residues, is in the range of 0.25 or more from the above effect. Preferably, it is 0.5 or more, more preferably 0.75 or more.

  Examples of the divalent carboxylic acid constituting the divalent carboxylic acid residue among the carbonic acid residue and divalent carboxylic acid residue particularly preferably selected in the present invention include an aromatic dicarboxylic acid, a chain aliphatic dicarboxylic acid, and And cycloaliphatic dicarboxylic acids such as terephthalic acid, isophthalic acid, biphenyldicarboxylic acid, dicarboxydiphenylsulfone, malonic acid, succinic acid, adipic acid, cyclohexanedicarboxylic acid, dodecanedioic acid and sebacic acid. Is mentioned. These may contain one kind or plural kinds including carbonic acid residues.

  Among the divalent carboxylic acid residues, an aliphatic divalent carboxylic acid residue is particularly preferable, and a divalent carboxylic acid residue having 8 to 20 carbon atoms is particularly preferable from the viewpoint of the thermal characteristics and mechanical properties of the thermoplastic resin. It is. Specific examples of the thermoplastic resin containing these divalent carboxylic acid residues include cyclohexanedicarboxylic acid, dodecanedioic acid, and sebacic acid.

  As the divalent phenol residue contained in the thermoplastic transparent resin of the present invention, a structural unit using aromatic bisphenol as a raw material is preferable from the viewpoint of optical properties, heat resistance properties, mechanical properties, and the like. The dihydric phenol residue represented by 1) is particularly preferred.

In general formula (1), R ¹ and R ² are each independently an atom selected from the group consisting of a halogen atom, an aliphatic group having 1 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms and a nitro group. Or a functional group. p and q are integers of p + q = 0-8. Y is a single bond, ether group, thioether group, alkylene group, alkylidene group, cycloalkylene group, cycloalkylidene group, phenylalkylidene group, carbonyl group, sulfone group, aliphatic phosphine oxide group, aromatic phosphine oxide group, alkylsilane A functional group selected from the group consisting of a group, a dialkylsilane group and a fluorene group. The divalent phenol residue of the general formula (1) may be further substituted.

  Specific examples of the dihydric phenol constituting the dihydric phenol residue represented by the general formula (1) include 1,1-bis (4-hydroxyphenyl) methane and 1,1-bis (4-hydroxy). Phenyl) ethane, 1,1-bis (4-methyl-2-hydroxyphenyl) methane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) ) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cycloheptane, 1,1-bis (4-hydroxyphenyl) cyclooctane, 1, 1-bis (4-hydroxyphenyl) cyclodecane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 2,2-bis (4-hydroxypheny ) Propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -2-ethylhexane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 1,1-bis (3-methyl- 4-hydroxyphenyl) methane, 4,4′-biphenol, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -2-methylpropane, 1,1-bis ( 4-hydroxyphenyl) -1-phenylmethane, 2,2-bis (4-hydroxyphenyl) octane, 1,1-bis (3-methyl-4-hydroxyphenyl) Cyclohexane, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (3-tert-butyl-4- Hydroxyphenyl) propane, 2,2-bis (3-secbutyl-4-hydroxyphenyl) propane, bisphenol fluorene, 1,1-bis (2-methyl-4-hydroxy-5-tert-butylphenyl) -2- Methylpropane, 4,4 ′-[1,4-phenylene-bis (2-propylidene)]-bis (2-methylphenol), 1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane, 4, 4′-dihydroxyphenyl ether, 1,1-bis (2-hydroxyphenyl) methane, 2,4′-methylenebisph Enol, 1,1-bis (3-methyl-4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) propane, 1,1-bis (2-hydroxy-5-methylphenyl) ethane, , 1-bis (4-hydroxyphenyl) -3-methyl-butane, 1,1-bis (2-hydroxy-3,5-dimethylphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclopentane, 3,3-bis (4-hydroxyphenyl) pentane, 3,3-bis (3-methyl-4-hydroxyphenyl) pentane, 3, 3-bis (3,5-dimethyl-4-hydroxyphenyl) pentane, 2,2-bis (2-hydroxy-3,5-dimethylphenyl) propane, 2,2- (4-hydroxyphenyl) nonane, 1,1-bis (3-methyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 2 , 2-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (2-hydroxy-3-tert-butyl-5-methylphenyl) methane, 1-bis (4-hydroxyphenyl) diphenylmethane, terpene diphenol, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (2-methyl-4-hydroxy-5- tert-butylphenyl) -2-methylpropane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propa 1,1-bis (3,5-ditert-butyl-4-hydroxyphenyl) methane, 1,1-bis (3,5-disecbutyl-4-hydroxyphenyl) methane, 1,1-bis ( 3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (2-hydroxy-3,5-ditert-butylphenyl) ethane, 1,1-bis (3-nonyl-4-hydroxyphenyl) methane, 2,2-bis (3,5-ditert-butyl-4-hydroxyphenyl) propane, 1,1-bis (2-hydroxy-3,5-ditert-butyl-6-methylphenyl) methane, 1-bis (3-phenyl-4-hydroxyphenyl) -1-phenylethane, 4,4-bis (4-hydroxyphenyl) pentanoic acid, bis (4-hydroxyphenyl) ) Acetic acid butyl ester, 1,1-bis (3-fluoro-4-hydroxyphenyl) methane, 1,1-bis (2-hydroxy-5-fluorophenyl) methane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 1,1-bis (3-fluoro-4-hydroxyphenyl)- 1-phenylmethane, 1,1-bis (3-fluoro-4-hydroxyphenyl) -1- (p-fluorophenyl) methane, 1,1-bis (4-hydroxyphenyl) -1- (p-fluorophenyl) ) Methane, 2,2-bis (3-chloro-4-hydroxy-5-methylphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propa 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 1,1-bis (3,5-dibromo-4-hydroxyphenyl) methane, 2,2-bis (3,5-dibromo-4) -Hydroxyphenyl) propane, 2,2-bis (3-nitro-4-hydroxyphenyl) propane, 3,3'-dimethyl-4,4'-biphenol, 3,3 ', 5,5'-tetramethyl- 4,4′-biphenol, 3,3 ′, 5,5′-tetra tert-butyl-4,4′-biphenol, bis (4-hydroxyphenyl) ketone, 3,3′-difluoro-4,4′- Biphenol, 3,3 ′, 5,5′-tetrafluoro-4,4′-biphenol, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxyphenyl) sulfone, bis (3-me 4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (3,5-dibromo-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) thioether, bis ( 3-methyl-4-hydroxyphenyl) ether, bis (3-methyl-4-hydroxyphenyl) thioether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (3,5-dimethyl-4-hydroxy) Phenyl) thioether, 1,1-bis (2,3,5-trimethyl-4-hydroxyphenyl) -1-phenylmethane, 2,2-bis (4-hydroxyphenyl) dodecane, 2,2-bis (3- Methyl-4-hydroxyphenyl) dodecane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) Enyl) dodecane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3,5-ditert-butyl-4-hydroxyphenyl) -1- Phenylethane, 1,1-bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) -2-methylpropane, 1,1-bis (2-hydroxy-3,5-ditert-butylphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propanoic acid methyl ester, 2,2-bis (4-hydroxyphenyl) propanoic acid ethyl ester, isatin bisphenol, isatin biscresol, 2,2 ′, 3,3 ′ , 5,5'-Hexamethyl-4,4'-biphenol, bis (2-hydroxyphenyl) methane, 2,4'-methylenebisphenol 1,2-bis (4-hydroxyphenyl) ethane, 2- (4-hydroxyphenyl) -2- (2-hydroxyphenyl) propane, bis (2-hydroxy-3-allylphenyl) methane, 1,1- Bis (2-hydroxy-3,5-dimethylphenyl) -2-methylpropane, 1,1-bis (2-hydroxy-5-tert-butylphenyl) ethane, bis (2-hydroxy-5-phenylphenyl) methane 1,1-bis (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) methane, 2,2-bis (4-hydroxy) Phenyl) pentadecane, 2,2-bis (3-methyl-4-hydroxyphenyl) pentadecane, 2,2-bis (3,5-dimethyl) 4-hydroxyphenyl) pentadecane, 1,2-bis (3,5-ditert-butyl-4-hydroxyphenyl) ethane, bis (2-hydroxy-3,5-ditert-butylphenyl) methane, 2,2 -Bis (3-styryl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1- (p-nitrophenyl) ethane, bis (3,5-difluoro-4-hydroxyphenyl) methane Bis (3,5-difluoro-4-hydroxyphenyl) -1-phenylmethane, bis (3,5-difluoro-4-hydroxyphenyl) diphenylmethane, bis (3-fluoro-4-hydroxyphenyl) diphenylmethane, 2, 2-bis (3-chloro-4-hydroxyphenyl) propane, 3,3 ', 5,5'-tetrater t-butyl-2,2′-biphenol, 2,2′-diallyl-4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1 -Bis (4-hydroxyphenyl) -3,3,5,5-tetramethyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,4-trimethyl-cyclohexane, 1,1-bis ( 4-hydroxyphenyl) -3,3-dimethyl-5-ethyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethyl-cyclopentane, 1,1-bis (3,5 -Dimethyl-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis (3,5-diphenyl-4-hydroxyphenyl) -3,3,5-tri Til-cyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis (3-phenyl-4-hydroxyphenyl) -3,3 5-trimethyl-cyclohexane, 1,1-bis (3,5-dichloro-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9 -Bis (3,5-dimethyl-4-hydroxyphenyl) fluorene, 1,1-bis (3,5-dibromo-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, and α, α-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene and the like. These may be one kind or a plurality of kinds. These dihydric phenols can be used according to the performance of the obtained resin.

  Among the dihydric phenols, Y represented by the general formula (1) is a branched chain-containing alkylidene group, a cycloalkylidene group, a branched-chain-containing cycloalkylidene group, or a bicycloalkylidene in terms of optical properties, mechanical properties, and heat resistance. Particularly preferred are those selected from the group consisting of groups, particularly preferably 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclooctane, 1,1-bis. (4-hydroxyphenyl) cyclododecane, 1,1-bis (4-hydroxyphenyl) -4-methylcyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 2,2-bis (4 -Hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) -3, , 5-trimethyl cyclohexane, and 2,2-bis (4-hydroxyphenyl) norbornane.

  Moreover, dihydroxybenzene can be used in the range which does not impair the effect of this invention. Examples of these dihydroxybenzenes include resorcinol, hydroquinone and 1,2-dihydroxybenzene, and these can be used alone or in combination.

  Further, the thermoplastic resin used in the present invention is not necessarily linear, and polyhydric phenol can be copolymerized according to the performance of the obtained thermoplastic resin.

  Specific examples of such polyhydric phenols include tris (4-hydroxyphenyl) methane, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl]. Ethylidene] bisphenol, 2,3,4,4′-tetrahydroxybenzophenone, 4- [bis (4-hydroxyphenyl) methyl] -2-methoxyphenol, tris (3-methyl-4-hydroxyphenyl) methane, 4- [Bis (3-methyl-4-hydroxyphenyl) methyl] -2-methoxyphenol, 4- [bis (3,5-dimethyl-4-hydroxyphenyl) methyl] -2-methoxyphenol, 1,1,1- Tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3-methyl-4-hydroxyphenyl) ethane, 1,1,1 Tris (3,5-dimethyl-4-hydroxyphenyl) ethane, tris (3-methyl-4-hydroxyphenyl) methane, tris (3,5-dimethyl-4-hydroxyphenyl) methane, 2,6-bis [( 2-hydroxy-5-methylphenyl) methyl] -4-methylphenol, 4- [bis (3,5-dimethyl-4-hydroxyphenyl) methyl] -1,2-dihydroxybenzene, 2- [bis (2- Methyl-4-hydroxy-5-cyclohexylphenyl) methyl] -phenol, 4- [bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) methyl] -1,2-dihydroxybenzene, 4-methylphenyl-1 , 2,3-Trihydroxybenzene, 4-[(4-hydroxyphenyl) methyl] -1,2,3-trihydro Cybenzene, 4- [1- (4-hydroxyphenyl) -1-methyl-ethyl] -1,3-dihydroxybenzene, 4-[(3,5-dimethyl-4-hydroxyphenyl) methyl] -1,2, 3-trihydroxybenzene, 1,4-bis [1-bis (3,4-dihydroxyphenyl) -1-methyl-ethyl] benzene, 1,4-bis [1-bis (2,3,4-trihydroxy) Phenyl) -1-methyl-ethyl] benzene, 2,4-bis [(4-hydroxyphenyl) methyl] -1,3-dihydroxybenzene, 2- [bis (3-methyl-4-hydroxyfailyl) methyl] phenol 4- [bis (3-methyl-4-hydroxyfailyl) methyl] phenol, 2- [bis (2-methyl-4-hydroxyfailyl) methyl] phenol, 4- [ Bis (3-methyl-4-hydroxyphenyl) methyl] -1,2-dihydroxybenzene, 4- [bis (4-hydroxyphenyl) methyl] -2-ethoxyphenol, 2- [bis (2,3-dimethyl-) 4-hydroxyphenyl) methyl] phenol, 4- [bis (3,5-dimethyl-4-hydroxyphenyl) methyl] phenol, 3- [bis (3,5-dimethyl-4-hydroxyphenyl) methyl] phenol, 2 -[Bis (2-hydroxy-3,6-dimethylphenyl) methyl] phenol, 4- [bis (2-hydroxy-3,6-dimethylphenyl) methyl] phenol, 4- [bis (3,5-dimethyl-) 4-hydroxyphenyl) methyl] -2-methoxyphenol, 3,6- [bis (3,5-dimethyl-4-hydroxyphenyl) Methyl] -1,2-dihydroxybenzene, 4,6- [bis (3,5-dimethyl-4-hydroxyphenyl) methyl] -1,2,3-trihydroxybenzene, 2- [bis (2,3,3) 6-trimethyl-4-hydroxyphenyl) methyl] phenol, 2- [bis (2,3,5-trimethyl-4-hydroxyphenyl) methyl] phenol, 3- [bis (2,3,5-trimethyl-4-) Hydroxyphenyl) methyl] phenol, 4- [bis (2,3,5-trimethyl-4-hydroxyphenyl) methyl] phenol, 4- [bis (2,3,5-trimethyl-4-hydroxyphenyl) methyl]- 1,2-dihydroxybenzene, 3- [bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) methyl] phenol, 4- [bis ( -Methyl-4-hydroxy-5-cyclohexylphenyl) methyl] phenol, 4- [bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) methyl] -2-methoxyphenol, 2,4,6- [tris (4-hydroxyphenylmethyl) -1,3-dihydroxybenzene, 1,1,2,2-tetra (3-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetra (3,5- Dimethyl-4-hydroxyphenyl) ethane, 1,4-[[bis (4-hydroxyphenyl) methyl]] benzene, 1,4-di [bis (3-methyl-4-hydroxyphenyl) methyl] benzene, 1, 4-di [bis (3,5-dimethyl-4-hydroxyphenyl) methyl] benzene, 4- [1,1-bis (4-hydroxyphenyl) ethyl] Examples include aniline, (2,4-dihydroxyphenyl) (4-hydroxyphenyl) ketone, 2- [bis (4-hydroxyphenyl) methyl] phenol, and 1,3,3-tri (4-hydroxyphenyl) butane. It is done. These may be one kind or a plurality of kinds.

  The carbonate residue is a structural unit obtained using carbonate ester, carbonate halide or the like as a raw material. For example, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis Carbonic acid esters such as (diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, dicyclohexyl carbonate, and carbonate halides such as phosgene and triphosgene.

The Abbe number (νd) of the thermoplastic resin used in the present invention is preferably 32 or more. Here, the Abbe number is one of indices indicating the degree of light dispersion of the optical material, and is generally defined by the following formula (III).
Abbe number (νd) = (nd−1) / (nf−nc) (III)
(In formula (III), nd represents the refractive index of d-line (wavelength 587.6 nm), nf represents the refractive index of f-line (wavelength 486.1 nm), and nc represents the refractive index of c-line (wavelength 656.3 nm).)
The larger the Abbe number, the lower the dispersion. For example, in a resin used for a spectacle lens, the Abbe number is preferably 34 or more, and more preferably 35 or more.

  The refractive index at each wavelength is an eigenvalue for each substance. Therefore, the Abbe number is also an eigenvalue for each substance. That is, the value of the refractive index does not change depending on the measurement method, and a measurement method suitable for the shape of the molded body can be selected. A measurement method with higher accuracy is preferable, and for example, the minimum deviation method is suitable. Usually, there is a negative correlation between the Abbe number and the refractive index of the thermoplastic resin, and it is not easy to improve both properties. The resin of the present invention is a thermoplastic resin having a high Abbe number while maintaining a high refractive index equivalent to or higher than that of a conventional polycarbonate.

The thermoplastic resin used in the present invention preferably has a high refractive index in order to be used for optics, particularly for lenses. The refractive index (nd) is preferably 1.58 or more, more preferably 1.59 or more, as measured by d-line (wavelength 587.6 nm). However, as described above, the Abbe number and the refractive index have a negative correlation. Even if the refractive index is high, if the Abbe number is too low, the thermoplastic resin is not preferable when used in optical applications, particularly in lens applications. That is, there is a suitable range for each characteristic value. Regarding the Abbe number (νd) and the d-line refractive index (nd), it is particularly important in lens applications that the value represented by the following formula (IV) is 210.5 or more. Formula (IV) is a formula that indicates a region where both the Abbe number and the d-line refractive index are suitable. The value represented by the following formula (IV) is preferably higher and more preferably 211 or more.
(Νd) + 112 × (nd) (IV)
Next, the manufacturing method of the thermoplastic resin of the present invention and the molding method of the transparent resin molded body will be described.

  As a polymerization precursor for deriving a phosphonic acid residue having bicycloalkyl, a corresponding acid halide or ester can be used. As a synthesis method thereof, a method via a Diels-Alder reaction and a hydrogenation reaction between a phosphorus-containing vinyl derivative and various cyclic diene compounds (for example, see Phosphorus, Sulfur and Silicon and Related Elements 123P 35P (1997)). Are known, and those known methods can be used.

  That is, for example, in the case of a bicyclo [2,2,1] -2-heptylphosphonic acid derivative, cyclopentadiene and a vinylphosphonic acid derivative are converted into a bicyclo [2,2,2] -2-octylphosphonic acid derivative. Can be obtained by hydrogenating a Diels-Alder reaction between cyclohexadiene and a vinylphosphonic acid derivative.

  Examples of the method for producing the thermoplastic resin used in the present invention include a solution polymerization method in which an acid halide and a divalent phenol are reacted in an organic solvent (see, for example, Japanese Patent Publication No. 37-5599), or an acid halide. And dihydric phenol are heated in the presence of a catalyst such as magnesium chloride. Melt polymerization method in which divalent acid and divalent phenol are heated in the presence of diallyl carbonate (for example, Japanese Patent Publication No. 38-26299). And an interfacial polymerization method in which a divalent acid halide dissolved in an organic solvent incompatible with water and a divalent phenol dissolved in an alkaline aqueous solution are mixed (for example, Japanese Patent Publication No. 40-1959). For example, the solution polymerization method is preferably employed.

  An example of the solution polymerization method is as follows. A phosphonic acid derivative, which is a precursor molecule of a phosphonic acid residue, and a dihydric phenol are mixed and reacted in the presence of a base such as triethylamine, followed by a precursor molecule of a carbonate residue, For example, the resin of the present invention can be obtained by adding phosgene, triphosgene, a divalent carboxylic acid derivative, and the like and performing condensation polymerization. As the phosphonic acid derivative, carbonate derivative, and divalent carboxylic acid derivative, their halides, acid anhydrides, esters, and the like are used, but the type and the order of acting on the divalent phenol are not particularly limited.

  As a method for adjusting the molecular weight of the thermoplastic resin used in the present invention, a monofunctional substance can be added during polymerization. Examples of monofunctional substances used as molecular weight regulators here include monohydric phenols such as phenol, cresol, p-tert-butylphenol, monovalent acids such as benzoic acid chloride, methanesulfonyl chloride, and phenyl chloroformate. And chlorides.

  To the thermoplastic resin used in the present invention, various hindered phenol-based, hindered amine-based, thioether-based and phosphorus-based antioxidants can be added as long as the characteristics are not impaired.

  Furthermore, the thermoplastic resin used in the present invention can be blended with other resins and used as a molding material as long as the desired effects are not impaired. Examples of resins to be blended include polycarbonate, polyethylene, polypropylene, polystyrene, ABS resin, polymethyl methacrylate, polytrifluoroethylene, polytetrafluoroethylene, polyacetal, polyphenylene oxide, polybutylene terephthalate, polyethylene terephthalate, polyamide, polyimide, polyamide Examples thereof include imide, polyether imide, polysulfone, polyether sulfone, paraoxybenzoyl polyester, polyarylate, and polysulfide.

  In addition, the thermoplastic resin used in the present invention has high solubility in an organic solvent. Examples of such a solvent include methylene chloride, chloroform, 1,1,2,2-tetrachloroethane, 1 , 2-dichloroethane, tetrahydrofuran, 1,4-dioxane, toluene, xylene, γ-butyrolactone, benzyl alcohol, isophorone, chlorobenzene, dichlorobenzene, and hexafluoroisopropanol.

  Furthermore, although the thermoplastic resin used in the present invention is amorphous, whether it is amorphous or not is determined by a known method such as differential scanning calorimetry (DSC) or dynamic viscoelasticity measurement. You should check whether you are doing.

  As a method for analyzing the constituent components of the thermoplastic resin used in the present invention, a method using a nuclear magnetic resonance (NMR) spectrum is preferable. In particular, for a substituent on a phosphorus atom in a phosphonic acid residue, proton or phosphorus Nuclear magnetic resonance is preferred. Furthermore, when the accuracy of identification by the spectrum of the thermoplastic resin itself is not sufficient, the thermoplastic resin used in the present invention is hydrolyzed with alkalis and decomposed into monomer components, and then each component is quantified and qualitatively analyzed. can do. For example, by treating the thermoplastic resin used in the present invention with a strong base such as a large excess of alkali metal alcoholate in absolute alcohol, the dihydric phenol residue becomes a dihydric phenol and each acid residue becomes an alcoholate ion. Decomposes into the corresponding ester. Since these are all low molecular weight substances, they can be quantified and separated by high performance liquid chromatography and then subjected to detailed structural analysis by NMR spectrum or the like.

  The transparent resin molded product of the present invention has the following general formula (2) on the surface of the above-mentioned thermoplastic transparent resin.

[In General Formula (2), R ³ represents a hydrocarbon group having an epoxy group or a glycidoxy group, R ⁴ represents a functional group selected from the group consisting of an alkyl group, an alkenyl group, and an allyl group, and Z represents A decomposable group, and r is 0 or 1; The organosilicon compound of the general formula (2) and / or a hydrolyzate thereof may be further substituted. A cured transparent film comprising a composition containing an organosilicon compound and / or a hydrolyzate thereof, a polyfunctional epoxy resin having an aromatic ring and / or an aliphatic ring, and inorganic fine particles. is there.

  The main purpose of coating the cured transparent film is to supplement the surface hardness of the thermoplastic resin and improve the scratch resistance. Examples of organic polymers used as a film to supplement the surface hardness include polyvinyl alcohol, celluloses, melamine resins, epoxy resins, polysiloxane resins, acrylic resins, urethane resins, and polycarbonate resins. Particularly, scratch resistance is important. In such applications, a single or composite polymer such as acrylic resin, polysiloxane resin, epoxy resin, urethane resin, and melamine resin, which is a curable film, is preferably used. In consideration of various properties such as heat resistance, chemical resistance and optical properties in addition to scratch resistance, it is preferable to use a polysiloxane resin, and more preferably, an organosilicon represented by the general formula (2). A compound and / or a hydrolyzate thereof is used.

First, the organosilicon compound represented by the general formula (2) and / or a hydrolyzate thereof will be described. In the formula represented by the general formula (2), R ³ is selected from a hydrocarbon group having an epoxy group or a glycidoxy group, and R ⁴ is selected from the group consisting of an alkyl group, an alkenyl group and an allyl group. Z is a hydrolyzable group, and r is 0 or 1. The general formula (2) may be further substituted.

Therefore, specific examples of the substituent constituting R ⁴ include hydrocarbon groups such as methyl group, ethyl group, phenyl group and vinyl group, halogenated groups such as chloropropyl group and 3,3,3-trifluoropropyl group. Hydrocarbon groups, epoxy group-containing organic groups such as γ-glycidoxypropyl group and β- (3,4-epoxycyclohexyl) ethyl group, (meth) such as γ-methacryloxypropyl group and γ-acryloxypropyl group An acrylic group-containing organic group, and other examples include a mercapto group, a cyano group, and an amino group. Z is a hydrolyzable functional group and is not particularly limited as long as it generates a silanol group by hydrolysis reaction. Specific examples thereof include alkoxy groups such as a methoxy group, an ethoxy group, and a methoxyethoxy group. And an acyloxy group such as an acetoxy group, a halogen group such as a chloro group and a bromo group, and an aryloxy group such as a phenoxy group. Furthermore, r is 0 or 1, but from the viewpoint of improving scratch resistance, when r is 1, R ⁴ is a reactive group such as an epoxy group-containing organic group or a (meth) acryloxy group-containing organic group. It is preferable.

  Specific examples of these organosilicon compounds include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, Ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ -Chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane , Γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyl Triphenoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxy Silane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropylto Methoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltri Butoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyl Trimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyl Triethoxysilane, (3 , 4-Epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Triethoxysilane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxyethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxyethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3 , 4-epoxy Trialkoxysilanes such as cyclohexyl) propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ- (3,4-epoxycyclohexyl) butyltriethoxysilane, triacyloxysilane, or triphenoxysilane Or hydrolysates thereof and dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ -Methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopro Rumethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane , Α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyl Dimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane , Γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethylmethoxyethoxysilane, γ-glycid Xylpropylmethyldiphenoxysilane, γ-glycidoxypropylmethyldiacetoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ Dialkoxysilanes such as glycidoxypropyl vinyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, diphenoxysilane or diacyloxysilanes or Include the hydrolyzate.

  As the organosilicon compound represented by the general formula (2), it is preferable to use an organosilicon compound containing an epoxy group or a glycidoxy group particularly for the purpose of imparting dyeability. In order to reduce the refractive index, it is preferable to use an organosilicon compound containing a fluoroalkyl group or a methyl group. In order to further increase the refractive index, it is preferable to use an organosilicon compound containing a phenyl group or a styryl group.

  Furthermore, from the viewpoints of curing rate and ease of hydrolysis, Z is preferably an alkoxy group having 1 to 4 carbon atoms or an alkoxyalkoxy group. Among these organosilicon compounds, a hydrolyzate is preferable in order to lower the curing temperature and further promote the curing. Hydrolysis is produced by blending pure water or an acidic aqueous solution such as hydrochloric acid, acetic acid or sulfuric acid and stirring. It is also possible to easily control the degree of hydrolysis by adjusting the amount of pure water or acidic aqueous solution. At the time of hydrolysis, it is preferable to blend pure water or acidic aqueous solution in an amount equal to or more than 3 times and equal to or less than 3 times that of Z in the general formula (2) in terms of acceleration of curing. In the hydrolysis, alcohol or the like is produced, so that it can be hydrolyzed without a solvent. However, for the purpose of performing the hydrolysis more uniformly, the hydrolysis may be carried out after mixing the organosilicon compound and the solvent. Is possible. Depending on the purpose, the alcohol after hydrolysis can be used after removing an appropriate amount by heating and / or under reduced pressure, and an appropriate solvent can be added thereafter. Examples of these solvents include alcohols, esters, ethers, ketones, halogenated hydrocarbons, aromatic hydrocarbons such as toluene and xylene, and solvents such as N, N-dimethylformamide. These solvents can be used as a mixed solvent of two or more as required. In order to accelerate the hydrolysis reaction according to the purpose and further advance the reaction such as precondensation, it is possible to heat to room temperature or higher, and to reduce the precondensation, the hydrolysis temperature is lowered to room temperature or lower. It is also possible to do this.

  In the present invention, a polyfunctional epoxy resin having an aromatic ring and / or an aliphatic ring is included as a composition of the cured transparent film. The polyfunctional epoxy resin is used mainly for the purpose of improving the adhesion with the thermoplastic resin used in the present invention, and in particular, unless the purpose of coating the cured transparent film used in the present invention is impaired. Although it is not limited, for example, bisphenol A type epoxy resin and bisphenol F type epoxy resin are listed as specific examples.

  The compounding amount of the polyfunctional epoxy resin having an aromatic ring and / or an aliphatic ring in the present invention is 10 to 300 with respect to 100 parts by weight of the organosilicon compound represented by the general formula (2) and / or a hydrolyzate thereof. It is preferable that it is a weight part, More preferably, it is 50-100 weight part. When the blending amount is less than 10 parts by weight, there are problems such as generation of interference fringes, and when it exceeds 300 parts by weight, sufficient surface hardness cannot be obtained.

  Furthermore, in the present invention, there are inorganic fine particles as an essential component of the composition constituting the cured transparent film. The inorganic fine particles are used for the purpose of improving the scratch resistance of the coating, controlling the refractive index, and improving the heat resistance. Such inorganic fine particles are those that do not impair the transparency in the state of the coating film, and are not particularly limited as long as they achieve the purpose, but as a particularly preferable example from the viewpoint of providing workability and transparency, colloidal Dispersed sols can be mentioned. Specific examples include magnesium fluoride sol, silica sol, titanium oxide sol, cerium oxide sol, zirconia sol, antimony oxide sol, and alumina sol.

  In the present invention, since the d-line refractive index of the thermoplastic resin is particularly large, when the cured transparent film is applied, the difference between the d-line refractive index of the thermoplastic resin and the d-line refractive index of the cured transparent film. Therefore, reflection occurs at the interface between the two layers, and stripes due to interference of reflected light may be seen. In that case, the occurrence of interference fringes can be reduced by setting the refractive index of the cured transparent film to substantially the same value as the refractive index of the thermoplastic resin.

  As for the difference between the refractive index of the cured transparent film and the refractive index of the thermoplastic resin, it is preferable that the two differences are closer to 0 because there is an effect of reducing the generation of interference fringes, but the difference is within 0.01 in absolute value. More preferably.

  In the present invention, the most effective method for adjusting the refractive index of the cured transparent film is a method of changing the type and content of the inorganic fine particles to be contained. It can also be adjusted by changing the type and content of the organosilicon compound and / or its hydrolyzate, and the polyfunctional epoxy resin having an aromatic ring and / or an aliphatic ring, which are other contents of the cured transparent film. However, since the value of the change in refractive index due to the change in type is not large, it is necessary to greatly change the content to reach the target refractive index, such as scratch resistance, abrasion resistance, adhesion, etc. It is not preferable from the viewpoint of balance. On the other hand, with inorganic fine particles, the refractive index can be changed greatly with a small amount of change, and the balance with other physical properties such as scratch resistance, wear resistance, and adhesion due to the change of inorganic fine particles is lost. Therefore, the refractive index value can be adjusted efficiently.

  For high refractive index materials such as the thermoplastic resin of the present invention, interference fringe generation can be reduced by selecting high refractive index inorganic fine particles. Among inorganic fine particles, titanium dioxide, oxidation Zirconium and antimony pentoxide are preferably used.

  The blending amount of the inorganic fine particles is preferably 25 to 800 parts by weight, more preferably 100 to 400 parts by weight with respect to 100 parts by weight of the organosilicon compound represented by the general formula (2) and / or a hydrolyzate thereof. Part. When the blending amount of the inorganic fine particles is less than 25 parts by weight, a clear blending effect is not recognized. Conversely, when the blending amount is 800 parts by weight or more, there is a tendency that cracks occur in the coating.

  The particle diameter of the inorganic fine particles is preferably an average particle diameter of 1 to 200 nm, more preferably 5 to 100 nm. When the average particle diameter exceeds 200 nm, the transparency of the coating is lowered and the turbidity becomes large, so that it is difficult to increase the thickness. In addition, those having an average particle diameter of less than 1 nm have poor dispersion stability and poor reproducibility. Furthermore, there is no problem even if various surfactants and amines are blended in order to improve the dispersibility of the fine inorganic particles. Furthermore, there is no problem in using two or more kinds of fine inorganic particles in combination. The average particle diameter can be measured using a transmission electron microscope. Specifically, it can be calculated by selecting any 20 particles from the transmission electron micrograph image used for measurement of the average particle diameter and taking the average value of the respective particle diameters.

  In the composition for forming the above-mentioned cured transparent film, various surfactants can be used for the purpose of improving the flow at the time of coating, in particular, a block of dimethylpolysiloxane and alkylene oxide. Alternatively, a graft copolymer and a fluorine-based surfactant are effective. Furthermore, for the purpose of improving weather resistance and light resistance, it is also possible to add an antioxidant as a UV absorber or a method for improving heat deterioration. Further, in these compositions, inorganic compounds other than the fine inorganic particles can be blended within a range that does not significantly reduce the coating performance and transparency. The combined use of these blends can improve various properties such as adhesion to the transparent resin molding of the present invention, chemical resistance, scratch resistance, durability, and dyeability.

  As said inorganic material which can be mix | blended, the metal alkoxide represented by following General formula (5), a chelate compound, and / or its hydrolyzate are mentioned.

(In the general formula (5), R ⁷ is a functional group selected from the group consisting of an alkyl group, an acyl group and an alkoxyalkyl group, and m is the same value as the number of charges of the metal M. M is silicon, titanium. Zircon, antimony, tantalum, germanium and aluminum.)
In the case of forming a film having a hard coat property in the present invention, various curing agents can be used for the purpose of enabling curing acceleration or low-temperature curing. As the curing agent, various epoxy resin curing agents or various organosilicon resin curing agents are applied. Specific examples of these curing agents include various organic acids and acid anhydrides thereof, nitrogen-containing organic compounds, various metal complex compounds or metal alkoxides, and alkali metal organic carboxylates and carbonates. Examples include various salts, peroxides, and radical polymerization initiators such as azobisisobutyronitrile. These curing agents can be used in combination of two or more. Among these curing agents, for the purpose of the present invention, the following general formula (6) is particularly preferred from the viewpoint of the stability of the paint and the prevention of coloring of the coated film after coating.

(In General Formula (6), V is OL (L is an alkyl group having 1 to 4 carbon atoms), W is a general formula M ¹ COCH ₂ COM ² (M ¹ and M ² are all alkyls having 1 to 4 carbon atoms) Group) and a compound represented by the general formula M ³ COCH ₂ COOM ⁴ (wherein M ³ and M ⁴ each represent an alkyl group having 1 to 4 carbon atoms). An aluminum chelate compound represented by the following formula is useful: at least one selected from ligands, and n is 0, 1 or 2.

  Among the aluminum chelate compounds represented by the general formula (6), aluminum acetylacetonate, aluminum bisethylacetoacetate monoacetyl, from the viewpoint of solubility in the coating composition, stability and effect as a curing catalyst. Acetonate, aluminum di-n-butoxide-monoethyl acetoacetate, aluminum di-iso-propoxide-monomethyl acetoacetate and the like are preferred. There is no problem in using these curing agents in combination of two or more.

  As a coating method, a method used in a normal coating operation can be applied. For example, a dip coating method, a flow coating method, and a spin coating method are preferable. The coating composition applied in this manner is generally cured by heat drying. As a heating method, hot air or infrared rays can be used. The heating temperature should be determined according to the thermoplastic transparent resin to be applied and the coating composition to be used. Usually, the temperature is preferably from room temperature to 250 ° C, more preferably from 35 to 200 ° C. More preferably, a temperature of 70 ° C to 130 ° C is used. If the temperature is lower than this, curing or drying tends to be insufficient, and if the temperature is higher than this, thermal decomposition or cracking occurs, and further problems such as yellowing tend to occur.

  The thickness of the cured transparent film in the present invention is not particularly limited, but it is preferably used between 10 and 20,000 nm from the viewpoint of maintaining adhesion strength and scratch resistance. That is, if the film thickness is less than 10 nm, the coating effect is not recognized, and if it exceeds 20,000 nm, uneven coating tends to occur.

  In the present invention, antireflection properties can be preferably imparted. The antireflection property is, for example, preventing a spectacle lens from causing a reflection image called a ghost or a flare to cause discomfort to the eyes. For example, in a single-layer coating, a minimum reflectance, that is, a maximum transmittance can be obtained by selecting a coating having a refractive index lower than that of the substrate so that the optical film thickness is 1/4 or an odd multiple of the light wavelength. Is to give. Here, the optical film thickness is given by the product of the refractive index of the film and the film thickness of the film.

  Examples of a method for imparting antireflection properties include wet coating or dry coating such as vacuum deposition. Further, the film structure for imparting antireflection properties may be a single layer or a multilayer, and the refractive index and film of a film having a refractive index of a thermoplastic transparent resin, a shock-absorbing film and a hard-coating property. The optimum combination is determined depending on the thickness or the required antireflection performance. Regarding anti-reflection properties, many combinations have already been made (Optical Technology Contact, Vol. 9, No. 8.17-23. (1971), OPTICSOF THIN FILMS, 159-282. A. VASICICE (NORTH-HOLLAND PUBLISHING COMPANY). AMSTERDAM (1960) has been proposed, and there is no problem in using these combinations in the present invention.

  In addition, the above-described pretreatment and the like are effective as means for improving the adhesion between the layers. For example, a method for obtaining a molded body such as a lens from the resin according to the present invention can be manufactured by employing a known method, and is not particularly limited. Examples of the molding method include an injection molding method and a press. Examples thereof include a molding method, a compression molding method, a transfer molding method, a lamination molding method, and an extrusion molding method.

  Moreover, when shape | molding in a film form, a solution casting method, a melt-extrusion film forming method, etc. are mentioned, Especially a solution casting method is employ | adopted suitably. In the solution casting method, the organic solvent can be appropriately used, but it is preferable to mold using a halogen-containing solvent, particularly preferably methylene chloride.

  Since the resin used in the present invention is thermoplastic, it can be easily molded. Since the lens made of the transparent resin molding of the present invention has a high Abbe number and a high refractive index, it can provide an optically excellent lens with small chromatic aberration. In addition, the film using the transparent resin molding of the present invention has excellent optical properties (colorless and transparent and low light dispersion), and also has excellent surface processability because it has a good affinity for various solvents. In a highly functional film member required for a liquid crystal display or the like, an excellent functional film or base film can be provided.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited by these examples. Each measurement and evaluation was performed by the following method.

1. 1. Various properties of thermoplastic resin 1.1 Optical properties The thermoplastic resin was polished so that two surfaces perpendicular to each other had a mirror finish. A refractometer (manufactured by Kalnew Optical Industry Co., Ltd .: KPR-2) was used, and the d-line (wavelength: 587.6 nm) refractive index (nd) and Abbe number (νd) determined by the following formula were measured.
Abbe number (νd) = (nd−1) / (nf−nc)
(In the formula, nd: d-line refractive index (wavelength 587.6 nm), nt: f-line refractive index (wavelength 656.3 nm), nc: c-line refractive index (wavelength 486.1 nm)). It shows that the dispersion is low.

1.2 Glass Transition Temperature Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd .: SSC5200), the glass transition temperature (Tg) was measured under the following conditions. The measurement was performed twice for one sample without removing the sample from the measuring instrument, and the second measurement result was used. That is, immediately after the end of the first measurement operation, cooling and stabilization of the temperature after cooling were performed under the following conditions (a), and then the second measurement was performed immediately under the same conditions.
Sample container: Aluminum open-type sample container Sample amount: Approximately 5 mg
Atmosphere: Dry nitrogen flow (20 ml / min)
Measurement conditions: 0 to 250 ° C
Temperature rising rate: 10 ° C./min (a) Cooling, temperature stabilization conditions Cool to 0 ° C. at a cooling rate of 20 ° C./min in a dry nitrogen flow atmosphere of 20 ml / min, and hold in that state for 30 minutes. Stabilized.

2. Various performances of a transparent resin molded body formed by coating a cured transparent film and an antireflection film 2.1 Appearance was visually observed, and the sample was transparent and free from cracks.

2.2 Total Light Transmittance Using a digital SM color computer (manufactured by Suga Test Instruments Co., Ltd .: SM-7-CH), the total light transmittance (Tt%) and yellowness (ΔYI) were measured.

2.3 Haze A haze value (Hz%) was measured using a fully automatic direct-reading haze computer (manufactured by Suga Test Instruments Co., Ltd .: HGM-2DP).

2.4 Adhesiveness 100 grids reaching the 1 mm thermoplastic transparent resin are put on the coating surface with a rope knife from the top of the coating, and cellophane adhesive tape (trade name “Cello Tape” (registered trademark) Nichiban Co., Ltd.) ) Was attached and peeled rapidly in the 90-degree direction, and the film without peeling was marked as ◯.

2.5 Abrasion resistance The coated surface was rubbed with No. 0000 steel wool (manufactured by Nippon Steel Wool Co., Ltd .: trade name “Bonster”) to determine the degree of scratching. Judgment criteria are as follows.
○ ・ ・ ・ No scratches even when rubbed strongly.
Δ: Slightly scratched when rubbed strongly.
×: Scratches even with weak friction.

2.6 Impact resistance A 16.3 g steel ball was dropped from a height of 127 cm onto the center of a plastic molded body (minus lens: -2.00 D) produced to have a center thickness of 1.5 mm. Impact properties were judged. Judgment criteria are as follows.
○ ... No cracks or cracks.
X: Cracks, cracks and holes are generated.

2.7 Weather resistance Using a UV long life fade meter (manufactured by Suga Test Instruments Co., Ltd .: FAL-5B), irradiation for a predetermined time and yellowness (ΔYI) using the apparatus described in 2.2 above. It was measured.

2.8 Heat resistance The sample was allowed to stand in a drier set at a temperature of 120 ° C. for 8 hours, and the yellowness (ΔYI) was measured using the apparatus described in Section 2.2.

2.9 Interference fringes Light from a fluorescent lamp was reflected on the surface of a plastic molded body with a black background, and the generation of rainbow patterns due to light interference was observed with the naked eye. Judgment criteria are as follows.
○ ... Rainbow pattern is not recognized.
Δ: A faint rainbow pattern is observed.
X: A rainbow pattern is clearly observed.

(Examples 1-5, Comparative Examples 1-4)
[1] Synthesis of thermoplastic transparent resin According to the compositions shown in Tables 1 and 2, the thermoplastic resins of Examples 1 to 5 and Comparative Examples 1 to 4 were synthesized. The synthesis method will be described taking the composition of Example 4 as an example. Other Examples 1 to 3 and Comparative Examples 1 to 4 were carried out in the same manner as Example 4 except that the compositions were changed to the compositions shown in Tables 1 and 2.

  Under a nitrogen atmosphere, 80 mmol of raw material A (1,1-bis (4-hydroxyphenyl) cyclohexane) and 168 mmol of triethylamine were mixed in methylene chloride (40 ml) and stirred in an ice bath. A methylene chloride (5 mol / L) solution of the raw material B (2-norbornylphosphonic dichloride: 4 mmol) was added dropwise to the obtained solution over 15 minutes, and the mixture was stirred at room temperature for 60 minutes after the completion of the addition. Subsequently, a solution of raw material C (phenylphosphonic dichloride: 36 mmol) in methylene chloride (5 mol / L) was added dropwise over 15 minutes, and after completion of the addition, the mixture was stirred at room temperature for 60 minutes. Furthermore, a methylene chloride (5 mol / L) solution of raw material D (dodecanedioic acid dichloride: 12 mmol) was added dropwise over 15 minutes, and after completion of the addition, the mixture was stirred at room temperature for 60 minutes. Thereafter, a methylene chloride solution (0.6 mol / L) of triphosgene (28 mmol in terms of phosgene) was added dropwise over 15 minutes, and the mixture was stirred for 60 minutes after completion of the addition. Subsequently, the solid component was removed by filtering the reaction solution through a filter paper having a pore size of 0.5 μm, and the solution was washed several times with a mixture of 80 ml of 0.1N hydrochloric acid aqueous solution and 300 ml of pure water. Thereafter, the separated organic layer was put into 2000 ml of ethanol and reprecipitated, and the polymer was collected by filtration. The produced solid polymer was washed in the order of (1) 1000 ml of ethanol, (2) 1000 ml of water / ethanol = 1/1 mixed solution, and (3) 1000 ml of water, and dried to obtain the desired thermoplastic resin powder. Obtained at 95%.

  For other examples and comparative examples, thermoplastic resin powders were synthesized in the same manner except that the amount of raw material added was changed to the respective compositions shown in Table 1. A transparent resin molded body of a minus lens (−2.00 D) having a center thickness of 1.5 mm was produced from the obtained thermoplastic resin powder by an injection molding method, and the glass transition temperature, refractive index, and Abbe number were measured. The measured values in each example and comparative example are shown in Table 3.

[2] Preparation of Curable Film According to the coating compositions shown in Tables 1 and 2, the compositions for Examples 1 to 5 and Comparative Examples 1 to 4 were prepared, applied, and cured. Each method will be described by taking the composition of Example 4 as an example. Other Examples 1 to 3 and Comparative Examples 1 to 4 were carried out in the same manner as Example 4 except that the compositions were changed to the compositions shown in Tables 1 and 2.

2.1. Preparation of coating composition 2.1.1. Preparation of γ-glycidoxypropyltrimethoxysilane hydrolyzate A reactor equipped with a stirrer was charged with 53.6 g of γ-glycidoxypropyltrimethoxysilane, and the liquid temperature was kept at 10 ° C. 12.3 g of aqueous acetic acid solution was gradually added dropwise. After completion of the dropwise addition, the cooling was stopped to obtain a hydrolyzate of γ-glycidoxypropyltrimethoxysilane.

2.1.2. Preparation of coating composition To the γ-glycidoxypropyltrimethoxysilane hydrolyzate, 9.3 g of n-propyl alcohol, 9.7 g of benzyl alcohol, 40.5 g of dimethylformamide, silicon surfactant (Toray Dow Corning) Co., Ltd .: trade name: “SRX-298”) 0.8 g, and bisphenol A type epoxy resin (manufactured by Shell Chemical Co., Ltd .: trade name “Epicoat” (registered trademark) 827) 37.9 g Further, 252.7 g of water-dispersed antimony pentoxide sol (solid content concentration 30% by weight, average particle size 10 nm) and 7.6 g of aluminum acetylacetonate were blended and sufficiently stirred to obtain a coating composition.

2.2. Application and curing of curable coating On the transparent resin molding obtained in the above item 1, the coating composition is dip-coated at a pulling speed of 10 cm / min, and then pre-cured for 12 minutes at a temperature of 100 ° C. went. Then, it heated at 110 degreeC temperature for 4 hours, and obtained the transparent resin molding by which the cured transparent film was coated.

  For the other examples and comparative examples, the cured transparent film was coated in the same manner except that the amount of the raw material added was changed to the respective compositions after thermosetting shown in Table 1. About the obtained transparent resin molding, appearance, total light transmittance, yellowness, haze, adhesion, scratch resistance, impact resistance, light resistance (ΔYI value after 300 hours irradiation), and heat resistance (120 The ΔYI value after standing for 8 hours in a dryer at a temperature of 0 ° C. was measured.

[3] Formation of antireflection film The transparent resin molded body coated with the cured transparent film obtained in the above item 2 is subjected to plasma treatment (argon plasma 400 W × 60 seconds) and then from the substrate toward the atmosphere. In order, an antireflection multilayer film composed of five layers of SiO ₂ , ZrO ₂ , SiO ₂ , ZrO ₂ , and SiO ₂ was formed by a vacuum deposition method. The optical film thickness of each layer was formed so that the first SiO ₂ layer, the next ZrO ₂ and SiO ₂ equivalent film layer, the next ZrO ₂ layer, and the uppermost SiO ₂ layer were λ / 4. The design wavelength λ was 520 nm. The reflection interference color of the obtained film was green.

  The measured values in each example and comparative example are shown in Table 3.

(Note) Monomer name M1: 1,1-bis (4-hydroxyphenyl) cyclohexane M2: 2-norbornylphosphonic dichloride M3: 2-norbornylthiophosphonic dichloride M4: phenylphosphonic dichloride M5: dodecane Acid dichloride M6: triphosgene (copolymerization ratio is phosgene conversion)

(Note) Monomer name M7: γ-glycidoxypropyltrimethoxysilane M8: “Epicoat” (registered trademark) 827 (bisphenol A type epoxy resin)
(Note) Inorganic substance name M9: Water-dispersed antimony sol (solid content concentration 30% by weight, average particle size 10 nm)
M10: Methanol-dispersed silica sol (solid content concentration 30% by weight, average particle size 10 nm)

  In Comparative Examples 1 and 2, although the optical properties of the resin molded article show excellent values, Comparative Example 1 is inferior in scratch resistance and generation of interference fringes. In Comparative Example 2, appearance properties, adhesiveness and Due to the problem of impact resistance, the performance of the coated transparent transparent film is insufficient. As is clear from Comparative Examples 3 and 4, high refractive index thermoplastic resins such as conventional polyphosphonate resins or modified polycarbonate resins have an Abbe number of less than 32 and are used for optics, particularly for spectacle lenses. Is insufficient. Further, it can be seen that Comparative Example 3 using silica as the inorganic fine particles generates interference fringes and is not suitable for optical use.

  On the other hand, the transparent resin moldings of Examples 1 to 5 both have a high Abbe number and a refractive index, have a high scratch-resistant surface, and are excellent in impact resistance, heat resistance, durability, and the like. I understand.

  The transparent resin molded product of the present invention has a high refractive index, a high Abbe number, a high glass transition temperature (Tg), a high scratch-resistant surface, and is excellent in heat resistance, chemical resistance and weather resistance. In addition, it has excellent impact resistance and is suitable for two-point frame glasses and eyeglass lenses with a thin edge.

Claims (11)

A phosphonic acid residue having at least a bicycloalkyl structure, and the following general formula (1)

[In General Formula (1), R ¹ and R ² are each independently an atom selected from the group consisting of a halogen atom, an aliphatic group having 1 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and a nitro group. Or a functional group, p and q are integers of p + q = 0 to 8, Y is a single bond, ether group, thioether group, alkylene group, alkylidene group, cycloalkylene group, cycloalkylidene group, phenylalkylidene group, carbonyl group, It represents a functional group selected from the group consisting of a sulfone group, an aliphatic phosphine oxide group, an aromatic phosphine oxide group, an alkylsilane group, a dialkylsilane group, and a fluorene group. General formula (1) may be further substituted. On the surface of a thermoplastic resin containing a dihydric phenol residue represented by the following general formula (2)

[In General Formula (2), R ³ represents a hydrocarbon group having an epoxy group or a glycidoxy group, R ⁴ represents a functional group selected from the group consisting of an alkyl group, an alkenyl group, and an allyl group, and Z represents A decomposable group, and r is 0 or 1; The organosilicon compound of the general formula (2) and / or a hydrolyzate thereof may be further substituted. And a hydrolyzate thereof, a polyfunctional epoxy resin having an aromatic ring and / or an aliphatic ring, and a transparent resin coated with a cured transparent film comprising a composition containing inorganic fine particles Molded body. A phosphonic acid residue having a bicycloalkyl structure is represented by the following general formula (3):

[In general formula (3), l, m and n are each independently an integer of 1 to 4, X ¹ is an atom or electron pair selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom and an unshared electron pair. Represents. R ⁵ represents a functional group or an atom selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a halogen atom, and r is an integer of 0 to 4. The phosphonic acid residue of the general formula (3) may be further substituted. The transparent resin molded product according to claim 1, wherein the phosphonic acid residue is represented by the formula: The thermoplastic resin further has the following general formula (4):

[In General Formula (4), R ⁶ represents an organic group, and X ² represents an atom or electron pair selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and an unshared electron pair. However, the phosphonic acid residue of the general formula (4) has a structure different from that of the phosphonic acid residue of the general formula (3) of claim 2. The molar fraction of the phosphonic acid residue represented by the general formula (3) and the phosphonic acid residue represented by the general formula (4) is represented by the following formula (I )
1 ≧ (a) / {(a) + (b)} ≧ 0.01 (I)
[In the formula (I), (a) represents the number of moles of phosphonic acid residues having a bicycloalkyl group structure, and (b) represents the number of moles of phosphonic acid residues represented by the general formula (4). The transparent resin molded product according to claim 2, wherein: The thermoplastic resin contains carbonate residues and / or divalent carboxylic acid residues, and the total number of moles of all phosphonic acid residues and the total number of moles of carbonate residues and divalent carboxylic acid residues are represented by the following formula (II):
1 ≧ (c) / {(c) + (d)} ≧ 0.01 (II)
[In formula (II), (c) represents the total number of moles of phosphonic acid residues, and (d) represents the total number of moles of carbonate residues and divalent carboxylic acid residues. The transparent resin molded product according to claim 2 or 3, wherein:   The transparent resin molded product according to any one of claims 1 to 4, wherein the thermoplastic resin has an Abbe number (νd) of 32 or more.   The transparent resin molded product according to claim 1, wherein the thermoplastic resin has a d-line refractive index of 1.58 or more.   The transparent resin molding in any one of Claims 1-6 with which the cured transparent film whose difference with the d-line refractive index of a thermoplastic resin is 0.01 or less in an absolute value was coated.   The transparent resin molded product according to claim 7, wherein the inorganic fine particles include at least one fine particle selected from titanium dioxide, zirconium oxide, and antimony pentoxide.   The transparent resin molding in any one of Claims 1-8 in which the single-layer or the multilayer antireflection film was formed on the surface of the cured transparent film.   The optical article which consists of a transparent resin molding in any one of Claims 1-9.   A lens for spectacles comprising the transparent resin molded product according to claim 1.