JP2008056717A - Resin and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colorless transparent resin that exhibits excellent thermal stability and moldability and is excellent in impact resistance, heat resistance, crack resistance and hues, and a molded item and a film comprised of the same. <P>SOLUTION: The resin is constituted of a dihydric phenol residue and/or a dihydric alcohol residue, and a carbonate residue and/or a dibasic carboxylic acid residue and/or a dibasic heteroacid residue, and at least a part of polymer ends is represented by structural formula (1) below. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin having excellent thermal stability and moldability, and further being colorless and transparent and having high toughness, and a molded body containing the same.

  Various materials such as optical lenses, functional optical films or disk substrates have been applied to colorless and transparent materials, but in recent years, with the rapid development of healthcare and electronics, the materials themselves The functions and performance required for the products are becoming increasingly precise and superior.

  Eyeglass lenses can be cited as a typical healthcare application of optical materials, but these eyeglass lenses are being actively developed from the viewpoint of thinning, weight reduction, fashionability, etc., and now they are impact resistant. Due to the advantages such as light weight, resin lenses account for 90% of the market.

  Conventional glasses lens resins are roughly classified into three resins, CR39 (Colombian resin 39), acrylic and urethane, and many resins have been developed and put into practical use with the aim of low dispersion and high refraction. Since all of these resins are thermosetting, cast polymerization is used for molding into optical lenses, but this method has a problem that the polymerization time is long and the manufacturing cost is high, such as the subsequent annealing process. .

  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 lens manufacturing cost can be significantly reduced compared to the thermosetting resin, but the refractive index is as low as 1.58. 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 colorability, and there are problems in applying them to optical lens applications.

  As a result of intensive studies to find a thermoplastic resin having a high refractive index and a low dispersion, the present inventors have introduced a structure having a pentavalent phosphorus atom, in particular, a phosphonic acid structure into the main chain of the polymer, thereby providing colorless. It has been found that a thermoplastic resin that is transparent, highly refractive, and low in dispersion can be obtained (see Patent Document 1).

  Various resins containing a phosphorus functional group are known. Particularly, a resin containing a phosphonate group in the main chain is called a polyphosphonate (KS Kim, J. Appl. Polym. Sci., 28, 1119 ( 1983), Y. Imai et al, Makromol. Chem., Rapid Commun., 1, 419 (1980), U.S. Pat. No. 3,719,727), and vigorous research has been conducted aiming at a flame-retardant function. Since many of these known polyphosphonate resins did not have detailed knowledge about various physical properties such as optical properties and mechanical properties, the present inventors synthesized them and evaluated the physical properties. As a result, these known polyphosphonate resins have low molecular weight, so that their mechanical properties are insufficient, and their refractive index and light dispersion properties are insufficient. In addition, WO01 / 34683 describes optical use of polyphosphonate. However, it is difficult to say that it has a low molecular weight and sufficient mechanical properties. Furthermore, the known literature does not have a detailed description of light dispersion properties (Abbe number). The present inventors have confirmed that sufficient light dispersion characteristics cannot be obtained.

  As a general method for producing a polyphosphonate polymer, for example, a solution polymerization method in which an acid halide and a divalent phenol are reacted in an organic solvent (A. Conix, Ind. Eng. Chem., 51, 147 (1959) No. 37-5599), a melt polymerization method in which an acid halide and a divalent phenol are heated in the presence of a catalyst such as magnesium chloride, and a divalent acid and a divalent phenol are heated in the presence of diallyl carbonate. Melt polymerization method (Japanese Patent Publication No. 38-26299), 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 (WM Eareckson) , J. Poly. Sci., XL 399 (1959), and Japanese Patent Publication No. 40-1959).

  As for polyphosphonate-carbonate copolymers, polymers using interfacial polycondensation are known (see Patent Document 2 and Patent Document 3). In any of these, a phosphonate oligomer is formed, and then the polymer main chain is extended with phosgene or the like. However, the present inventors have confirmed that interfacial polycondensation easily breaks the phosphonate bond, which makes it difficult to accurately control the ratio of carbonate to phosphonate, and it is difficult to improve the molecular weight. Yes. In fact, according to the method described in Patent Document 2, it is shown that when the phosphonate content is higher than that of carbonate, the mechanical properties become insufficient. Further, phosgene is used as a raw material for the carbonate residue, and it is difficult to say that it is an environmentally and technically sufficient polymerization method. Therefore, as a result of intensive studies to find out a method for producing a polyphosphonate-carbonate copolymer that does not use a toxic raw material such as phosgene, the present inventors have used a carbonate polymer or oligomer of a dihydric phenol as a raw material for a carbonate residue. Has been found that the cracking of the bond easily proceeds with a dihydric phenol monomer in the presence of a base such as triethylamine, and further, the phosphonic acid halide, which is a phosphonic acid residue raw material, is allowed to act at a high concentration following the cracking reaction. It has been found that the main chain can be extended with a phosphonic acid residue raw material, that is, a very high molecular weight phosphonate-carbonate random copolymer can be obtained without using phosgene. (See Patent Document 4).

However, the phosphonate-carbonate random copolymer, which has a main chain extended with a phosphonic acid residue raw material, is remarkably deteriorated in molecular weight and physical properties due to thermal decomposition during molding. There arises a problem that it is significantly inferior to a phosphonate-carbonate random copolymer of the same composition in which the main chain is extended from the residue raw material, and there is a high demand for improvement thereof, that is, improvement of the thermal stability of the polymer.
JP 2002-167440 A JP-A-61-285225 Japanese Patent Laid-Open No. 61-238826 JP 2002-78588 A

  An object of the present invention is to provide a resin having excellent thermal stability and moldability, and further being colorless and transparent and having high toughness, and a molded product containing the same.

  As a result of intensive studies to solve the above problems, the present inventors have suppressed the molecular weight reduction and physical property degradation due to thermal decomposition of the polymer by setting at least one polymer terminal to the following structural formula (1). The present inventors have found that this can be done and have completed the present invention.

  That is, the present invention is composed of a dihydric phenol residue and / or a dihydric alcohol residue, and a carbonate residue and / or a divalent carboxylic acid residue and / or a divalent heteroacid residue, and at least 1 The polymer terminal of a part is following structural formula (1), Resin characterized by the above-mentioned.

[In Structural Formula (1), R ¹ R ² is selected from organic groups, and Structural Formula (1) may be further substituted. ]

  According to the present invention, a resin having excellent thermal stability and moldability, and further being colorless and transparent and having high toughness can be obtained. In addition to being able to be used in various fields such as general-purpose molded articles or film applications, particularly in lenses or optical films, the use of this resin further exhibits excellent effects.

  Among the resins composed of a dihydric phenol residue and / or a dihydric alcohol residue, and a carbonate residue and / or a divalent carboxylic acid residue and / or a divalent heteroacid residue, particularly a phosphonic acid residue raw material The phosphonate-carbonate random copolymer that has undergone main chain extension in Fig. 1 has a remarkable decrease in molecular weight and physical properties due to thermal decomposition during molding, and the moldability, optical properties, mechanical properties, etc. It was significantly inferior compared to the phosphonate-carbonate random copolymer of the same composition which was extended. As a result of intensive investigation and investigation of the cause, it has been found that a resin having a specific structure at the polymer terminal is excellent in the thermal stability of the polymer itself and can suppress a decrease in molecular weight and physical properties due to thermal decomposition. It came to complete.

  That is, the present invention is composed of a dihydric phenol residue and / or a dihydric alcohol residue, and a carbonate residue and / or a divalent carboxylic acid residue and / or a divalent heteroacid residue, and at least 1 The polymer terminal of a part is related with resin characterized by following Structural formula (1).

[In Structural Formula (1), R ¹ R ² is selected from organic groups, and Structural Formula (1) may be further substituted. ]
Hereinafter, the resin of the present invention will be specifically described.

  In the resin of the present invention, the resin is composed of a dihydric phenol residue and / or a dihydric alcohol residue, and a carbonate residue and / or a divalent carboxylic acid residue and / or a divalent heteroacid residue, and at least Although it is essential that one part of the polymer terminal is the above structural formula (1), the higher the content of the structural formula (1), the better the thermal stability, and 50% or more of the entire polymer terminal is 100%. % Is preferable, more preferably 70% or more and less than 100%, still more preferably 80% or more and less than 100%.

The substituent R ¹ R ² on the phosphorus atom of the compound represented by the structural formula (1) is selected from organic groups, and specific examples include C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, phenyl , Chlorophenyl, p-tolyl, benzyl, biphenyl, or cyclohexyl.

  Here, 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 preferred, and in particular, a thiophosphonic acid residue or a phosphorus atom in a phosphonic acid residue. For these substituents, 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 resin of the present invention preferably contains a thiophosphonic acid residue represented by the following structural formula (2).

In the structural formula (2), R ³ represents an organic group, and the structural formula (2) may be further substituted. Specific examples of the substituent R ³ include phenyl, halo-substituted phenyl, methoxyphenyl, ethoxyphenyl, ethyl, isopropyl, cyclohexyl, vinyl, allyl, benzyl, aminoalkyl, hydroxyalkyl, halo-substituted alkyl and alkyl sulfide groups, bicyclo Alkyl groups are preferred. Examples of suitable structures of the bicycloalkyl group 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, bicyclo [3,2,2] -1-nonyl, bicyclo [4,2,2] -2-decanyl and the like can be mentioned.

  Here, in the structural formula (2), a thiophosphinic acid residue having two organic groups in the form of a phosphorus atom, a thiophosphinic acid residue, a phosphonite residue that is a trivalent phosphorus functional group, partially substituted, Contains thiophosphonic acid residues.

  Moreover, it is preferable that the molar fraction of a thiophosphonic acid residue, a dihydric phenol residue, and a dihydric alcohol residue satisfies Formula (I).

1 ≧ (a) / (b) ≧ 0.0005 (I)
Formula (I) is a formula representing the mole fraction of thiophosphonic acid residues and dihydric phenol residues and / or dihydric alcohol residues, that is, (a) is the number of moles of thiophosphonic acid residues, and (b) is The number of moles of the dihydric phenol residue and / or dihydric alcohol residue is shown, and the value of the molar fraction (a) / (b) of the thiophosphonic acid residue is preferably 0.1 in order to improve the thermal stability. It is 0005 or more, More preferably, it is 0.01 or more, More preferably, it is 0.1 or more, More preferably, it is 0.25 or more.

  In order to control the thermal, chemical or mechanical properties, the resin used in the present invention is not limited to the thiophosphonic acid residue represented by the above structural formula (2), but the phosphone represented by the following structural formula (3). Acid residues can be included.

In Structural Formula (3), R ⁴ represents an organic group, X represents oxygen, selenium, or a lone pair. Moreover, the phosphonaus acid residue whose X in said Structural formula (3) is a lone pair is also mentioned similarly. These may be one kind or plural kinds.

  It is preferable that the total number of moles of these phosphonic acid residues and the total number of carbonate residues satisfy the formula (II).

1 ≧ (c) / {(c) + (d)} ≧ 0.01 (II)
Formula (II) is a copolymer of the total thiophosphonic acid residue represented by the structural formula (2) and the phosphonic acid residue represented by the structural formula (3) with respect to all acid residues including carbonate residues. It is a formula showing a fraction. That is, (c) in the formula (II) represents the total number of moles of thiophosphonic acid residues represented by the structural formula (2) and the phosphonic acid residues represented by the structural formula (3) (total phosphonic acid residues). (D) indicates the number of moles of carbonate residues. When the molar fraction of all phosphonic acid residues is less than 0.01, the characteristics as a resin for an optical lens are hardly exhibited. 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 0.05 or more from the viewpoint of the above effect. It is preferable that it is 0.25 or more.

  Here, the carbonate residue is a structural unit obtained using carbonate ester, carbonate halide or the like as a raw material. Examples of the raw material include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, Examples thereof include carbonates such as dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate and dicyclohexyl carbonate, and carbonate halides such as phosgene and triphosgene.

  The molecular weight of the obtained resin is preferably 10,000 or more in terms of mechanical properties, more preferably 20,000 or more, still more preferably 30,000 or more, and a linear oligomer having a molecular weight of 5,000 or less contained in the resin. The content of the component is preferably 0% by weight to 5% by weight, more preferably 0% by weight to 4% by weight, and still more preferably 0% by weight to 1% by weight.

  Examples of the method for producing the resin of 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), an acid halide and a divalent phenol. Melt polymerization method in which phenol is heated in the presence of a catalyst such as magnesium chloride, and melt polymerization method in which divalent acid and divalent phenol are heated in the presence of diallyl carbonate (see, 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 (see, for example, Japanese Patent Publication No. 40-1959). In particular, the solution polymerization method is preferably employed.

    An example of the solution polymerization method will be described. In the presence of a base such as triethylamine in a solvent, a divalent phenol and / or dihydric alcohol, and a phosphonic acid derivative that is a precursor molecule of a phosphonic acid residue, and a precursor of a carbonate residue. Phosgene derivatives such as phosgene and triphosgene, which are body molecules, are allowed to act until the reaction rate of dihydric phenol and / or dihydric alcohol is 0% or more and 99.95% or less. The resin of the present invention can be obtained by extending the main chain of the polymer with a certain thiophosphonsan derivative. As phosphonic acid derivatives and carbonate derivatives, their halides, acid anhydrides, esters, and the like are used, but the type and order of acting on the dihydric phenol are not particularly limited, but the main chain extension uses a thiophosphonic acid derivative. Therefore, heat resistance can be improved.

  Here, when introducing a carbonate group as a copolymerization component, it is common to use a phosgene derivative such as phosgene or triphosgene as described above. However, phosgene and phosgene derivatives are unstable in the atmosphere, so they are easy to handle. is not. Further, since these compounds are unstable compounds, they may be decomposed to generate impurities, which may cause the resin to be colored or hinder the high molecular weight of the resin.

  Therefore, it is preferable to use a carbonate polymer of a dihydric phenol or a carbonate oligomer of a dihydric phenol without using phosgene or a phosgene derivative for introduction of a carbonate group, so that there is no impurity of the phosgene derivative. The resin having a high rate and low yellowness can be obtained.

  The concentration of the dihydric phenol residue when the monomer that gives the thiophosphonic acid residue is allowed to act on a carbonate polymer of a dihydric phenol or a mixture containing a carbonate oligomer of a dihydric phenol is high. Is advantageous in promoting the ring-opening reaction of the cyclic oligomer, and is preferably 1.0 mol / L or more. The concentration is more preferably 1.5 mol / L or more, and still more preferably 2.0 mol / L or more.

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

  The resin of the present invention has a toughness value of preferably 3 N / mm or more, more preferably 5 N / mm or more when molded as a plate-like molded body (width 10 mm, length 25 mm, thickness 3 mm). .

  Here, the toughness value is defined as follows. The sample was subjected to a bending test using Tensilon manufactured by Orientec Co., Ltd. at a distance between fulcrums of 22 mm and a bending speed of 1.5 mm / min to obtain bending stress and broken displacement. The evaluation parameter was calculated by a toughness value that is an index of brittleness.

Toughness value (N / mm) = bending stress × breaking displacement Further, when the resin obtained in the present invention is used as an optical resin, a plate-like plate having a width of 10 mm, a length of 25 mm, and a thickness of 3 mm obtained from the resin. The total light transmittance of the molded body is preferably 70% or more and the yellowness is about 30 or less, more preferably the total light transmittance is 80% or more and the yellowness is 30 or less, more preferably 10 or less.

The total light transmittance and yellowness are defined below. Tristimulus values (X, Y, Z) of the sample were determined by the transmission method using a digital color computer (manufactured by Suga Test Instruments Co., Ltd .: SM-7CH). The total light transmittance is defined as a value of Y. The yellowness (ΔYI) is obtained by attaching the sample to obtain (X, Y, Z), obtaining the YI value (YI ₂ ) by the following formula (II), and then removing the sample in the same manner as X, Y and Z were obtained, similarly, a reference value YI ₁ was obtained and calculated from the following formula (III).

YI = 100 × (1.28X−1.06Z) / Y Formula (II)
X, Y, Z: Tristimulus value of sample in standard light C ΔYI = YI ₂ −YI ₁ Formula (III)
ΔYI: yellowness, YI ₁ : reference value, YI ₂ : measured value of sample.

  The total light transmittance can be converted to the total light transmittance of a plate-shaped molded article having a width of 10 mm, a length of 25 mm, and a thickness of 3 mm by applying the Lambert-Beer law.

  Further, the impact strength described in the present invention is measured by an Izod impact test (ISO 180). The Izod impact test refers to the energy consumed for breaking per unit test piece width by hitting and breaking the test piece with a pendulum hitting rod having specific energy and linear velocity. In addition, it is most preferable to use a test piece shape that has been processed according to ISO 180 / 4A, and to test a test piece that has been stored for 50 hours at a room temperature of 23 ° C. and a humidity of 50% after processing.

  Further, the present inventors have found that the gut, plate or film-shaped molded article containing the resin of the present invention also has excellent flame retardancy.

Furthermore, when the present resin is molded into an optical anisotropic body, the present inventors have excellent birefringence / wavelength in the use of a retardation film (also known as a retardation plate, a λ / 4 plate, or a circularly polarizing plate). It has been found that it exhibits dispersion characteristics. When light is transmitted through a general optical anisotropic body of resin, for example, a uniaxially stretched film, the birefringence increases as the wavelength of the light is shorter, and the degree tends to increase as the wavelength is shorter. . In the retardation film application, it is optically ideal that the following condition is satisfied with respect to the relationship between the birefringence and the wavelength. That is,
(A) having a sufficiently large birefringence in a film of 100 microns or less,
(B) At this time, the change of the birefringence with the wavelength is constant, that is, the relationship between the birefringence and the wavelength is a proportional relationship (primary relationship),
It is.

  An ideal retardation film can be prepared by combining two optical anisotropic films satisfying these conditions and having different birefringence / wavelength dispersion characteristics. When the present inventors made an optical anisotropic body by stretching a film obtained by forming the resin of the present invention, the relationship between birefringence and wavelength is closer to the primary relationship than conventional resins. In addition, it has been found that a retardation film having excellent wavelength dispersion characteristics can be obtained by combining the stretched film of the present invention and a conventional optically anisotropic film of a polyalkane resin. Furthermore, the high molecular weight of the polymer is important not only for the mechanical properties of the film but also for the optical properties. That is, the higher the molecular weight of the polymer, the stronger the orientation of the polymer main chain during uniaxial stretching, and the higher the birefringence, so that the function can be expressed with a thinner film. The present inventors have found that when the resin of the present invention is applied to the application, further thinning can be achieved.

Specific examples of the substituent R ⁴ on the phosphorus atom of the compound represented by the structural formula (3) used in the present invention include phenyl, halo-substituted phenyl, methoxyphenyl, ethoxyphenyl, ethyl, isopropyl, cycloalkyl, Examples include vinyl, allyl, benzyl, aminoalkyl, hydroxyalkyl, halo-substituted alkyl and alkyl sulfide groups.

  Specific examples of the phosphonic acid constituting such a phosphonic acid residue include methylphosphonic acid, ethylphosphonic acid, n-propylphosphonic acid, isopropylphosphonic acid, n-butylphosphonic acid, isobutylphosphonic acid, and t-butylphosphonic acid. Acid, n-pentylphosphonic acid, neopentylphosphonic acid, cyclohexylphosphonic acid, benzylphosphonic acid, chloromethylphosphonic acid, dichloromethylphosphonic acid, bromomethylphosphonic acid, dibromomethylphosphonic acid, 2-chloroethylphosphonic acid, 1,2-dichloroethyl Phosphonic acid, 2-bromoethylphosphonic acid, 1,2-dibromoethylphosphonic acid, 3-chloropropylphosphonic acid, 2,3-dichloropropylphosphonic acid 3-bromopropylphosphonic acid, 2,3-dibromopropylphosphonic acid, 2 Chloro-1-methylethylphosphonic acid, 1,2-dichloro-1-methylethylphosphonic acid, 2-bromo-1-methylethylphosphonic acid, 1,2-dibromo-1-methylethylphosphonic 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 -1-methylpropylphosphonic acid, 2,3-dibromo-1-methylphosphonic acid, 1-chloromethylpropylphosphonic acid, 1-chloro-1-chloromethylpropylphosphonic acid, 1-bromomethylpropylphosphonic acid, 1-bromo-1 -Bromomethylpropylphosphonic acid, 5-chloropentylphosphonic acid, 4, -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, methylthiomethylphosphonic acid, methylthioethylphosphonic acid, methylthio Propylphosphonic acid, methylthiobutylphosphonic acid, ethylthiomethylphosphonic acid, ethylthioethylphosphonic acid, ethylthiopropylphosphonic acid, propylthiomethylphosphonic acid, propylthioethylphosphonic acid, Tylthiomethylphosphonic acid, phenylphosphonic acid, 4-chlorophenylphosphonic acid, 3,4-dichlorophenylphosphonic acid, 3,5-dichlorophenylphosphonic acid, 4-bromophenylphosphonic acid, 3,4-bromophenylphosphonic 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-phenylethylphosphonic Acid, 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-pyridylphosphonic acid, 1-pyrrolidinomethylphosphonic acid 1-pyrrolidinoethylphosphonic acid, 1-pyrrolidinopropylphosphonic acid, 1-pyrrolidinobutyl Sulfonic acid, pyrrole-1-phosphonic acid, pyrrole-2-phosphonic acid, pyrrole-3-phosphonic acid, thiophene-2-phosphonic acid, thiophene-3-phosphonic acid, dithian-2-phosphonic acid, trithian-2-phosphone Examples include acids, furan-2-phosphonic acid, furan-3-phosphonic acid, vinylphosphonic acid, allylphosphonic acid, 2-norbornylphosphonic acid, and bicyclo [2,2,2] octylphosphonic acid. These may be one kind or plural kinds. These phosphonic acids may be phosphonic acid derivatives such as acid chlorides, esters and amides thereof.

  In the structural formula (3), a phosphonic acid residue includes a phosphinic acid residue having two organic groups in the form of phosphorus atoms and a phosphoric acid residue.

  In addition, these phosphonic acid residues may be partially replaced with phosphonite residues that are the corresponding trivalent phosphorus functional groups (X = unshared electron pair). Thereby, the oxidation resistance of resin can be provided.

  Specific examples of dihydric phenols include 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) 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-hydroxy) Phenyl) 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-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydride) Xylphenyl) 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- Droxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3- sec butyl-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′-methylenebisphenol, 1,1-bis (3-methyl-4-hydroxy) Cyphenyl) methane, 1,1-bis (4-hydroxyphenyl) propane, 1,1-bis (2-hydroxy-5-methylphenyl) ethane, 1,1-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-bis (4-hydroxyphenyl) nonane, 1,1-bi (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, 1,1-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) propane, 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-hydroxy) Phenyl) propane, 1,1-bis (2-hydroxy-3,5-ditert-butyl-6-methylphenyl) methane, 1,1-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-hexa Fluoropropane, 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) propane, 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-methyl-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-hydroxyphenyl) 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) dodecane, 1,1-bis (3-tert-butyl) Til-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, methyl 2,2-bis (4-hydroxyphenyl) propanoate 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-hydroxyphenyl) pentadecane, 2,2-bis (3-methyl- 4-hydroxyphenyl) pentadecane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) pentadecane, 1,2- (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-hydroxy) Phenyl) propane, 3,3 ′, 5,5′-tetra-tert-butyl-2,2′-biphenol, 2,2′-di Allyl-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-trimethyl-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, α, α-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene, etc. These may be used alone or in combination of two or more. These dihydric phenols can be used according to the performance of the obtained polymer.

  Among these dihydric phenols, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-methylcyclohexane, 1,1-bis are optically and mechanically characteristic. (4-Hydroxyphenyl) -4-isopropylcyclohexane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane and 1,1-bis (4-hydroxyl) cyclododecane are particularly suitable.

  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.

  The resin of the present invention preferably contains a trivalent phenol residue represented by the following structural formula (4). Specific examples of the trivalent phenol constituting the trivalent phenol residue include the following.

  4,4 '-[1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) -phenyl) -ethylidene] bisphenol, 4,4'-[1- (4- (1- (4 -Hydroxyphenyl) -1-methyl) -phenyl) -methylidene] bisphenol, 4,4 '-[1- (4- (1- (4-hydroxyphenyl) -1-ethyl) -phenyl) -methylidene] bisphenol, 4,4 '-[1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) -phenyl) -methylidene] bisphenol, 4,4'-[1- (4- (1- (4 -Hydroxyphenyl) -1-methylpropyl) -phenyl) -ethylidene] bisphenol, 4,4 '-[1- (4- (1- (4-hydroxyphenyl) -1-ethylethyl) -phenyl) -ethylide ] Bisphenol, 4,4 '-[1- (4- (1- (4-hydroxyphenyl) -1-ethylpropyl) -phenyl) -ethylidene] bisphenol, 4,4'-[1- (4- (1 -(4-Hydroxyphenyl) -1-propylpropyl) -phenyl) -ethylidene] bisphenol, 4,4 '-[1- (4- (1- (4-hydroxyphenyl) -1-methylbutyl) -phenyl)- Ethylidene] bisphenol, 4,4 ′-[1- (4- (1- (4-hydroxyphenyl) -1-methylpentyl) -phenyl) -ethylidene] bisphenol, 4,4 ′-[1- (4- ( 1- (4-hydroxyphenyl) -1-methylhexyl) -phenyl) -ethylidene] bisphenol, 4,4 ′-[1- (4- (1- (4-hydroxyphenyl)- -Methylheptyl) -phenyl) -ethylidene] bisphenol, 4,4 '-[1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) -phenyl) -propylidene] bisphenol, 4,4' -[1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) -phenyl) -butylidene] bisphenol, 4,4 '-[1- (4- (1- (4-hydroxyphenyl)] -1-methylethyl) -phenyl) -pentylidene] bisphenol, 4,4 ′-[1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) -phenyl) -hexylidene] bisphenol, 4, 4 '-[1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) -phenyl) -heptylidene] bisphenol, 4,4'-[1- ( 4- (1- (4-hydroxyphenyl) -1-phenylethyl) -phenyl) -ethylidene] bisphenol, 4,4 ′-[1- (4- (1- (4-hydroxyphenyl) -1,1- Diphenylmethyl) -phenyl) -ethylidene] bisphenol, 4,4 '-[1- (4- (1- (4-hydroxyphenyl) -1-naphthylethyl) -phenyl) -ethylidene] bisphenol, 4,4'- [1- (4- (1- (4-hydroxyphenyl) -1,1-dinaphthylmethyl) -phenyl) -ethylidene] bisphenol, 4,4 ′-[1- (4- (1- (4-hydroxy Phenyl) -1-trifluoromethylethyl) -phenyl) -ethylidene] bisphenol, 4,4 '-[1- (4- (1- (4-hydroxyphenyl) -1,1-ditrifluoro) Methylmethyl) -phenyl) -ethylidene] bisphenol, 4,4 ′-[1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) -phenyl) -ethylidene] -3-methylbisphenol, 4 , 4 '-[1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) -phenyl) -ethylidene] -3,5-dimethylbisphenol, 4,4'-[1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) -phenyl) -ethylidene] -3- (1-methylethyl) bisphenol, 4,4 '-[1- (4- (1- (4-hydroxy) Phenyl) -1-methylethyl) -phenyl) -ethylidene] -3,5-di (1-methylethyl) bisphenol, 4,4 ′-[1- (4- (1- (4-hydroxyphenyl)- -Methylethyl) -phenyl) -ethylidene] -3-cyclohexylbisphenol, 4,4 '-[1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) -phenyl) -ethylidene] -3 , 5-dicyclohexylbisphenol, 4,4 '-[1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) -phenyl) -ethylidene] -3-phenylbisphenol, 4,4'-[ 1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) -phenyl) -ethylidene] -3,5-diphenylbisphenol, 4,4 '-[1- (4- (1- (4 -Hydroxyphenyl) -1-methylethyl) -phenyl) -ethylidene] -3-naphthylbisphenol, 4,4 '-[1- (4- (1- (4-hydroxypheny) L) -1-methylethyl) -phenyl) -ethylidene] -3,5-dinaphthylbisphenol, 4,4 '-[1- (4- (1- (4-hydroxyphenyl) -1-methylethyl)- Phenyl) -ethylidene] -3-fluorobisphenol, 4,4 '-[1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) -phenyl) -ethylidene] -3,5-difluoro Bisphenol, 4,4 '-[1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) -phenyl) -ethylidene] -3-bromobisphenol, 4,4'-[(1- ( 4- (1- (4-hydroxyphenyl) -1-methylethyl) -phenyl) -ethylidene)))-3,5-dibromobisphenol, 4,4 '-[1- (4- (1- (4- Hydroxypheny ) -1-Methylethyl) -phenyl) -ethylidene] -3-chlorobisphenol, 4,4 '-[1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) -phenyl) -ethylidene ] -3,5-dichlorobisphenol and the like. Among the above trivalent phenol derivatives, 4,4 ′-[1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) -phenyl) -ethylidene] bisphenol is particularly easy to produce. It is more preferable because it has good water solubility and can easily control the interaction of the phosphonate carbonate copolymer.

  In addition, the polymer of the present invention does not necessarily need to be linear, and a polyhydric phenol can be copolymerized according to the performance of the obtained polymer. 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, 1,3,3-tri (4-hydroxyphenyl) butane, and the like. These can be used alone or in combination.

  To the resin of 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.

Further, the type of the nitrogen-containing basic compound is not limited as long as it has an electron donating property. Specific examples of the nitrogen-containing basic compound include tetramethylammonium hydroxide (Me ₄ NOH), tetraethylammonium hydroxide (Et ₄ NOH), tetrabutylammonium hydroxide (Bu ₄ NOH), and trimethylbenzylammonium hydroxide. (Phenyl-CH ₂ (Me) ₃ NOH) and other ammonium hydroxides having alkyl, aryl, alkylaryl groups, etc., trimethylamine, triethylamine, dimethylbenzylamine, tertiary amines such as triphenylamine, R ₂ NH ( Wherein R is an alkyl group such as methyl or ethyl, or an aryl group such as phenyl or toluyl), a primary amine represented by RNH ₂ (wherein R is as defined above), 2-methylimidazole, 2 -Imidazoles such as phenylimidazole, ammonium carboxylates such as tetramethylammonium acetate (Me ₄ NOCOCH ₃ ), tetramethylammonium borohydride (Me ₄ NBH ₄ ), tetrabutylammonium tetraphenylborate (Bu ₄ NBPh ₄ ) And basic salts such as tetramethylammonium tetraphenylborate (Me ₄ NBPh ₄ ). These nitrogen-containing basic compounds can be used alone or in admixture of two or more.

  Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium acetate, potassium acetate, lithium acetate, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, Sodium acetate, potassium acetate, lithium acetate, sodium stearate, potassium stearate, lithium stearate, sodium borate, potassium borate, lithium borate, sodium borohydride, potassium borohydride, lithium borohydride, phenylation Lithium boron, sodium benzoate, potassium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, bisphenol A and the like are sodium salts, dipotassium salts, dirichtes Arm salts, the sodium salt of phenol, dipotassium salt, dilithium salt, and the like.

  Alkaline earth metal compounds include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate. Strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, magnesium borate and the like. These alkali metal compounds and / or alkaline earth metals can be used alone or in admixture of two or more.

  Moreover, the resin of this invention can use an organic solvent according to the solubility of the monomer to be used. Solvents include methylene chloride, chloroform, 1,1,2,2-tetrachloroethane, 1,2-dichloroethane, tetrahydrofuran, 1,4-dioxane, toluene, xylene, γ-butyrolactone, benzyl alcohol, isophorone, chlorobenzene and di- And chlorobenzene.

  For example, a method for obtaining a molded body such as a lens using the resin of the present invention can be a known method, and is not particularly limited. For example, an injection molding method, a press molding method, a compression molding method, a transfer method, a transfer method, and the like. Examples include formation molding, lamination molding, and extrusion molding.

  Moreover, as a method of shape | molding resin obtained by this invention in a film form, a solution casting method, a melt extrusion film forming method, etc. are mentioned, Especially solution casting is employ | adopted suitably. In the solution casting method, the organic solvent can be appropriately used, but is preferably a halogen-containing solvent, and particularly preferably methylene chloride.

  Specific embodiments of the present invention will be described below with reference to examples, but the present invention is not limited thereto. The resin was evaluated by the following method.

(Molecular weight measurement)
A 0.2 wt% chloroform solution of the resin was measured by GPC (Gel Permeation Chromatography) [GPC8020, manufactured by Tosoh Corporation], and the number average molecular weight calibrated with standard polystyrene was defined as Mn1.

(Evaluation of thermal decomposition)
Mn2 is obtained by sealing 1 g of resin in a test tube and measuring the number average molecular weight after heating for 30 minutes with GLASS TUBE OVEN (SIBATA GTO-350RD) at 300 ° C. under an argon atmosphere (50 ml / min). The value obtained by dividing the difference between the number average molecular weight Mn1 and Mn2 before heating by Mn1 was obtained. A value of 0.06 or less and less than 0.08 is good, a value of 0.08 or more and less than 0.1 is acceptable, and a value of 0.1 or more is regarded as defective.

(Mechanical properties)
The resin was hot press-molded into a plate shape having a width of 10 mm, a length of 25 mm, and a thickness of 3 mm, and using a Tensilon (Model RTM-100) manufactured by Orientec Co., Ltd., a distance between fulcrums of 22 mm, a bending speed of 1.5 mm / A bending test was performed in minutes. The evaluation parameter was a toughness value (bending stress × breaking displacement) that is an index of brittleness.

(Measurement of impact strength)
Method of ISO 180 after cutting an injection molded article to prepare a test piece of 12.7 × 63.5 × 3.2 mm (ISO 180 / 4A) and leaving it at room temperature 23 ° C. and humidity 50% for 50 hours. The Izod impact strength was measured according to

[Crack resistance]
After bending both ends of an injection-molded strip-shaped test piece of 13 mm × 128 mm and a thickness of 1.5 mm with a test jig so that the length of the string becomes 110 mm, the center surface of the test piece Salad oil (billion-year-old canola oil) was applied to the sample and evaluated by a constant strain method in which the time until the test piece broke at 23 ° C. was measured.

[Measurement of degree of polymerization of carbonate oligomer]
Using a nuclear magnetic resonance apparatus (JEOL Ltd .: EX270 type) in deuterated chloroform, the average value was calculated from the integral ratio of the spectrum indicating the terminal and the spectrum indicating the polymer unit. The ratio of the chain oligomer was the ratio of the intensity of the nuclear magnetic resonance spectrum (NMR) peak indicating the end to the peak intensity estimated when all were assumed to be chain oligomers.

(Polymer end analysis)
Using a nuclear magnetic resonance apparatus (JEOL Ltd .: EX270 type) in deuterated chloroform, the structural formula (1) for the entire polymer terminal from the integral ratio of the spectrum indicating the terminal of the structural formula (1) and the spectrum indicating the polymer unit. ) Terminal amount was calculated.

(Measurement of optical properties)
The resin molded product is polished with sandpaper and buff so that two surfaces that are perpendicular to each other are mirror-finished, and evaluated with a refractometer (Kalnew Optical Co., Ltd .: KPR-2). Wavelength: 587.6 nm) Refractive index (nd), Abbe number (νd) obtained from equation (4) was measured.

[Measurement of retardation]
Retardation of the resin of the present invention formed into a film and uniaxially stretched was measured using RETS-1100 (cell gap measuring device) manufactured by Otsuka Electronics.

[Measurement of glass transition temperature (Tg)]
A DSC (SSC 5200) system manufactured by Seiko Denshi Kogyo was used. Tg is observed when the temperature is raised to 250 ° C. at 10 ° C./min and held for 3 minutes, then cooled to 0 ° C. at −50 ° C./min and held for 3 minutes, and then heated again at 10 ° C./min. This is a value calculated from the peak top of Tg. The measurement was carried out using a sample dried under vacuum at 80 ° C. for 8 hours.

[Example 1]
[Preparation of carbonate oligomer raw material: Melting method]
1,1-bis (4-hydroxyphenyl) cyclohexane (0.67 mol: 180 g), diphenyl carbonate (120 g), and sodium phenolate (1 g) were weighed in a glass eggplant flask (1 L). After purging with nitrogen, the contents were heated to 220 ° C., the contents were melted, and the pressure was reduced to about 60 mmHg over 1 hour while maintaining the temperature at 220 ° C. Further, the pressure was reduced to about 0.4 mmHg and the mixture was heated as it was for 2 hours. After cooling, it was purged with nitrogen to obtain an oligomer at a DPC conversion rate of 93%. The obtained carbonate oligomer was an average oligomer of bisphenol / carbonate = 4/3 by NMR.

[Polymer polymerization]
1,1-bis (4-hydroxyphenyl) cyclohexane (16.9 g: 63 mmol), 4,4 ′-[1- (4- (1- (4-hydroxy) in methylene chloride (30 ml) under nitrogen atmosphere. Phenyl) -1-methylethyl) -phenyl) -ethylidene] bisphenol (0.04 g: 0.09 mmol), 1,1-bis (4-hydroxyphenyl) cyclohexane carbonate oligomer (tetramer) (9 g) and triethylamine ( 20.1 ml: 144 mmol) were mixed and stirred at 20 ° C. To this solution, a solution of phenylthiophosphonic acid dichloride (9.6 ml: 63.7 mmol) in 20 ml of methylene chloride was added dropwise over 30 minutes and the mixture was stirred at 20 ° C. for 3 hours. To this solution, phenylthiophosphonic acid dichloride (1 0.1 ml: 7.1 mmol) in 4 ml of methylene chloride was added dropwise over 10 minutes, and the mixture was stirred at 20 ° C. for 60 minutes after the completion of the addition. Thereafter, 50 ml of methylene chloride was poured into the reaction solution, 0.1N HCl aqueous solution and distilled water were poured, and the pH of the aqueous solution layer was adjusted to around 6.5 to separate and wash the organic layer. The separated organic layer was then filtered through a 0.5 μm membrane filter, poured into 2000 ml of ethanol and reprecipitated, and the polymer was collected by filtration and dried at 100 ° C. for 20 hours to obtain the desired resin powder in a total yield of 90%. Got in. The molecular weight, thermal decomposition degree, polymer terminal, mechanical properties, impact strength, crack resistance, optical properties, and glass transition temperature of the obtained resin powder were evaluated as described above.

[Example 2]
1,1-bis (4-hydroxyphenyl) cyclohexane (16.9 g: 63 mmol), 4,4 ′-[1- (4- (1- (4-hydroxy) in methylene chloride (30 ml) under nitrogen atmosphere. Phenyl) -1-methylethyl) -phenyl) -ethylidene] bisphenol (0.04 g: 0.09 mmol) and triethylamine (18.4 ml: 133 mmol) were mixed and stirred at 20 ° C. To this solution, a solution of norbornylphosphonic dichloride (1 ml: 6.3 mmol) in 2 ml of methylene chloride was added dropwise over 5 minutes under ice-cooling, and the mixture was stirred at 20 ° C. for 3 hours. / L of triphosgene in methylene chloride (23.57 ml) was added dropwise over 20 minutes, and the mixture was stirred at 20 ° C. for 60 minutes after completion of the addition. Subsequently, a solution of phenylthiophosphonic acid dichloride (2.4 ml: 15.8 mmol) in 4 ml of methylene chloride was added dropwise to the solution over 10 minutes, and the mixture was stirred at 20 ° C. for 1 hour. After completion of the addition, the solution was stirred at 20 ° C. for 60 minutes. Thereafter, it was post-treated in the same manner as in Example 1 to obtain a polymer with a yield of 92%, and molded and evaluated.

[Example 3]
1,1-bis (4-hydroxyphenyl) cyclohexane (16.9 g: 63 mmol), 4,4 ′-[1- (4- (1- (4-hydroxy) in methylene chloride (30 ml) under nitrogen atmosphere. Phenyl) -1-methylethyl) -phenyl) -ethylidene] bisphenol (0.04 g: 0.09 mmol), 1,1-bis (4-hydroxyphenyl) cyclohexane carbonate oligomer (tetramer) (9 g) and triethylamine ( 20.1 ml: 144 mmol) were mixed and stirred at 20 ° C. To this solution was added dropwise a solution of phenylphosphonic dichloride (8.9 ml: 63.7 mmol) in 20 ml of methylene chloride over 30 minutes under ice-cooling, and the mixture was stirred at 20 ° C. for 3 hours. To this solution, phenylthiophosphonic dichloride (1. 1 ml: 7.1 mmol) in 4 ml of methylene chloride was added dropwise over 10 minutes, and the mixture was stirred at 20 ° C. for 60 minutes after completion of the addition. Thereafter, it was post-treated in the same manner as in Example 1 to obtain a polymer with a yield of 92%, and molded and evaluated.

[Example 4]
1,1-bis (4-hydroxyphenyl) cyclohexane (16.9 g: 63 mmol), 4,4 ′-[1- (4- (1- (4-hydroxy) in methylene chloride (30 ml) under nitrogen atmosphere. Phenyl) -1-methylethyl) -phenyl) -ethylidene] bisphenol (0.04 g: 0.09 mmol), 1,1-bis (4-hydroxyphenyl) cyclohexane carbonate oligomer (tetramer) (9 g) and triethylamine ( 20.1 ml: 144 mmol) were mixed and stirred at 20 ° C. Under ice cooling, a solution of norbornylphosphonic dichloride (10.1 ml: 63.7 mmol) in 20 ml of methylene chloride was added dropwise over 30 minutes and stirred at 20 ° C. for 3 hours. To this solution, phenylthiophosphonic dichloride ( 1.1 ml: 7.1 mmol) in 4 ml of methylene chloride was added dropwise over 10 minutes. After completion of the addition, the solution was stirred at 20 ° C. for 60 minutes. Thereafter, it was post-treated in the same manner as in Example 1 to obtain a polymer in a yield of 92%, and molded and evaluated. [Example 5]
Polymerization was performed in the same manner as in Example 1 except that norbornylthiophosphonic acid dichloride was used instead of phenylthiophosphonic acid dichloride, to obtain a polymer in a total yield of 94%. The obtained resin was evaluated in the same manner as in Example 1.

[Example 6]
A polymer was obtained in a total yield of 94% by polymerizing in the same manner as in Example 2 except that norbornylthiophosphonic acid dichloride was used instead of phenylthiophosphonic acid dichloride. The obtained resin was evaluated in the same manner as in Example 1.

[Example 7]
The resin obtained in Example 1 was further pelletized by heating and extrusion at 270 ° C., and a film having a width of 200 mm and a thickness of 25 μm was prepared from this pellet by a solution casting method (methylene chloride solution). The film was stretched 1.3 times at a stretching temperature of 165 ° C. and a stretching speed of 100 mm / min. The film thickness after stretching was 20 μm.

  The film obtained under the above conditions showed a retardation at a wavelength of 550 nm of 143.6 nm, a wavelength of 450 nm of 157.3 nm, and a wavelength of 650 nm of 135.7 nm.

[Comparative Example 1]
1,1-bis (4-hydroxyphenyl) cyclohexane (16.9 g: 63 mmol), 4,4 ′-[1- (4- (1- (4-hydroxy) in methylene chloride (30 ml) under nitrogen atmosphere. Phenyl) -1-methylethyl) -phenyl) -ethylidene] bisphenol (0.04 g: 0.09 mmol), 1,1-bis (4-hydroxyphenyl) cyclohexane carbonate oligomer (tetramer) (9 g) and triethylamine ( 20.1 ml: 144 mmol) were mixed and stirred at 20 ° C. To this solution was added dropwise a solution of phenylphosphonic dichloride (8.9 ml: 63.7 mmol) in 20 ml of methylene chloride over 30 minutes under ice cooling, and the mixture was stirred at 20 ° C. for 3 hours. To this solution, phenylphosphonic dichloride (1.1 ml) was added. : 7.1 mmol) in 4 ml of methylene chloride was added dropwise over 10 minutes. After completion of the addition, the solution was stirred at 20 ° C. for 60 minutes. Thereafter, the polymer was post-treated in the same manner as in Example 1 to obtain a polymer with a yield of 93%. The obtained resin was evaluated in the same manner as in Example 1.

[Comparative Example 2]
1,1-bis (4-hydroxyphenyl) cyclohexane (16.9 g: 63 mmol), 4,4 ′-[1- (4- (1- (4-hydroxy) in methylene chloride (30 ml) under nitrogen atmosphere. Phenyl) -1-methylethyl) -phenyl) -ethylidene] bisphenol (0.04 g: 0.09 mmol) and triethylamine (18.4 ml: 133 mmol) were mixed and stirred at 20 ° C. To this solution, a solution of norbornylphosphonic dichloride (1 ml: 6.3 mmol) in 2 ml of methylene chloride was added dropwise over 5 minutes under ice-cooling, and the mixture was stirred at 20 ° C. for 3 hours. / L of triphosgene in methylene chloride (23.57 ml) was added dropwise over 20 minutes, and the mixture was stirred at 20 ° C. for 60 minutes after completion of the addition. Subsequently, a solution of phenylphosphonic dichloride (2.2 ml: 15.8 mmol) in 4 ml of methylene chloride was added dropwise to the solution over 10 minutes, and the mixture was stirred at 20 ° C. for 1 hour. After completion of the addition, the solution was stirred at 20 ° C. for 60 minutes. Thereafter, it was post-treated in the same manner as in Example 1 to obtain a polymer with a yield of 92%, and molded and evaluated.

[Comparative Example 3]
1,1-bis (4-hydroxyphenyl) cyclohexane (16.9 g: 63 mmol), 4,4 ′-[1- (4- (1- (4-hydroxyphenyl) in methylene chloride (30 ml) under nitrogen atmosphere. ) -1-Methylethyl) -phenyl) -ethylidene] bisphenol (0.04 g: 0.09 mmol) and triethylamine (18.4 ml: 133 mmol) were mixed and stirred at 20 ° C. To this solution, a solution of norbornylphosphonic dichloride (1 ml: 6.3 mmol) in 2 ml of methylene chloride was added dropwise over 5 minutes under ice-cooling and stirred at 20 ° C. for 3 hours. Phenylphosphonic dichloride (2.2 ml) was added to this solution. : 15.8 mmol) in 4 ml of methylene chloride was added dropwise over 10 minutes and the mixture was stirred at 20 ° C. for 1 hour, and then this solution was added to a methylene chloride solution of triphosgene having a concentration of 0.581 mol / l in an ice bath (23.23). 57 ml) was added dropwise over 20 minutes, and after completion of the dropwise addition, the mixture was stirred at 20 ° C. for 60 minutes. Thereafter, the polymer was post-treated in the same manner as in Example 1 to obtain a polymer with a yield of 90%. The obtained resin was evaluated in the same manner as in Example 1.

[Comparative Example 4]
From the resin obtained in Comparative Example 1, a film having a width of 200 mm and a thickness of 25 μm was prepared by a solution casting method (methylene chloride solution). The film was stretched 1.3 times at a stretching temperature of 150 ° C. and a stretching speed of 180 mm / min. The film thickness after stretching was 20 μm.

  The film obtained under the above conditions showed retardation of 47.6 nm at a wavelength of 550 nm, 51.9 nm at a wavelength of 450 nm, and 44.9 nm at a wavelength of 650 nm.

  Table 1 shows the evaluation results of the resins prepared in Examples 1 to 6 and Comparative Examples 1 to 3.

  It can be seen from Comparative Example 1 that the resin produced by the conventional method has a high degree of thermal decomposition and insufficient impact strength and crack resistance.

  On the other hand, it can be seen that the resins of the present invention obtained in Examples 1 to 6 have a low degree of thermal decomposition, excellent impact strength and crack resistance, and excellent moldability. In addition, as a retardation film application, since the resin of the present invention maintains high mechanical properties, it is strongly oriented during uniaxial stretching, resulting in a larger birefringence, which is effective for thinning a retardation film. I understand that.

A resin having high heat resistance, toughness, crack resistance and impact resistance, and also having excellent optical properties such as colorless and transparent, high refraction and low dispersion is used as an optical resin or film.

Claims (11)

It is composed of a dihydric phenol residue and / or a dihydric alcohol residue, and a carbonate residue and / or a divalent carboxylic acid residue and / or a divalent heteroacid residue. A resin characterized by the structural formula (1).

[In Structural Formula (1), R ¹ R ² is selected from organic groups, and Structural Formula (1) may be further substituted. ] The thiophosphonic acid residue represented by the following structural formula (2) is included, and the molar fraction of the thiophosphonic acid residue, the dihydric phenol residue, and the dihydric alcohol residue satisfies the formula (I). resin.

[In Structural Formula (2), R ³ represents an organic group, and Structural Formula (2) may be further substituted. ]
1 ≧ (a) / (b) ≧ 0.0005 (I)
[In Formula (I), (a) shows the number of moles of thiophosphonic acid residue, and (b) shows the number of moles of dihydric phenol residue and dihydric alcohol residue. ] A carbonate residue and / or a phosphonic acid residue represented by the following structural formula (3) is included, and the total number of moles of all phosphonic acid residues and the total number of carbonate residues satisfies the formula (II): Or resin of 2.

[In Structural Formula (3), R ⁴ represents an organic group, X represents oxygen, selenium, or a lone pair of electrons. Structural formula (3) may be further substituted. ]
1 ≧ (c) / {(c) + (d)} ≧ 0.01 (II)
[In Formula (II), (c) represents the number of moles of all phosphonic acid residues, and (d) represents the number of moles of carbonate residues. ] The resin according to any one of claims 1 to 3, wherein a phosphonite residue is contained. The resin in any one of Claims 1-4 in which the trihydric phenol residue shown by following Structural formula (4) is contained.

[In Structural Formula (4), R ⁵¹ , R ⁵² , and R ⁵³ are each independently a hydrogen atom, an aliphatic hydrocarbon having 1 to 20 carbon atoms, an aromatic hydrocarbon having 1 to 20 carbon atoms, a halogen atom, or a nitro group. R, s, and t are each independently an integer of 0 to 4. Z is a phenyl group, an alkylidine group, a branched chain-containing alkylidyne group, a cycloalkylidine group, a branched chain-containing cycloalkylidine group, a phenylalkylzine group, an aliphatic phosphine oxide group, an aromatic phosphine oxide group, an alkylsilane group, a fluorene Selected from the group. Structural formula (4) may be further substituted. ] The trivalent phenol residue represented by the structural formula (4) is 4,4 ′-[1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) -phenyl) -ethylidene] bisphenol. The resin according to claim 5. The number average molecular weight is 10,000 or more, The resin according to any one of claims 1 to 6. Reaction rate of dihydric phenol and / or dihydric alcohol with dihydric phenol and / or dihydric alcohol, and carbonate derivative and / or divalent carboxylic acid derivative and / or divalent hetero acid derivative in the presence of a base in a solvent. 2. The method for producing a resin according to claim 1, wherein the polymer main chain is extended with a thiophosphonic acid derivative after the reaction is allowed to reach 0 to 99.95%. A process comprising reacting a divalent phenol carbonate polymer or a divalent phenol carbonate oligomer with a divalent phenol monomer in the presence of a base in a solvent, and then reacting with a thiophosphonic acid derivative. Item 9. A method for producing a resin according to Item 8. 10. The method for producing a resin according to claim 9, wherein at least a part of the thiophosphonic acid derivative is reacted at a concentration of 1.0 mol / L or more as a concentration of the dihydric phenol residue in the solution. The molded object formed by containing the resin in any one of Claims 1-7.