JP2018002894A - Thermoplastic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin having high refractive index, low birefringence and high thermostability, the thermoplastic resin particularly excellent in optical properties.SOLUTION: A thermoplastic resin contains a repeating unit represented by general formula (1) of 70 mol% or more in all the units (Rand R, and Rand Rindependently represent a C1-10 aromatic group that may contain a hydrocarbon group; n and m, and o and p independently represent an integer of 0 or more; R-R, and R-Rindependently represent H, a halogen element, or a C1-12 aromatic group that may contain a hydrocarbon group).SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic resin and an optical lens. More specifically, the present invention relates to a thermoplastic resin having a specific ester structure having high refractive index, low birefringence, and high heat resistance, and an optical lens comprising the same.

  Optical glass or optical transparent resin is used as a material for optical lenses used in optical systems of various cameras such as cameras, film-integrated cameras, and video cameras. Optical glass is excellent in heat resistance, transparency, dimensional stability, chemical resistance, and the like, but has problems of high material cost, poor moldability, and low productivity.

  On the other hand, an optical lens made of an optical resin has an advantage that it can be mass-produced by injection molding, and polycarbonate, polyester carbonate, polyester resin, etc. are used as a high refractive index material for a camera lens. However, in recent years, development of a resin having a high refractive index has been demanded due to the lighter, thinner and smaller products. In general, when the refractive index of an optical material is high, a lens element having the same refractive index can be realized on a surface with a smaller curvature. Therefore, the amount of aberration generated on this surface can be reduced, the number of lenses can be reduced, It becomes possible to reduce the polarization sensitivity and reduce the thickness by reducing the lens thickness.

  When an optical resin is used as an optical lens, heat resistance, transparency, low water absorption, chemical resistance, low birefringence, and wet heat resistance are required in addition to the refractive index and Abbe number. Therefore, there exists a weak point that a use location is limited by the characteristic balance of resin. In particular, in recent years, a camera lens having higher imaging performance and lower birefringence has been demanded as the resolution is increased by increasing the number of pixels. In general, as a method of reducing the birefringence, there is a method of canceling each other's birefringence between compositions having positive and negative birefringences having different signs. For this reason, the composition ratio of materials having birefringence with different signs is very important.

  Patent Document 1 includes, as a monomer component, a biaryl compound that is bonded with a bond axis that can impart internal rotational isomerism, and at least one aryl group has 4n + 6 (n is a natural number) with respect to the bond axis. A resin composition is disclosed, having excellent properties such as excellent transparency, low optical anisotropy, and high refractive index, but for optical lenses having higher refractive index and lower birefringence. The material has not been obtained yet.

JP 2001-72872 A

Accordingly, a first object of the present invention is to provide a thermoplastic resin having a high refractive index, a low birefringence and a high heat resistance, and particularly excellent in optical properties.
A second object of the present invention is to provide a thermoplastic resin having a particularly high refractive index and excellent optical properties in addition to the first object.

  As a result of intensive studies aimed at achieving this object, the present inventors have found that the above problems can be solved by the thermoplastic resin represented by the following general formula (1), and have reached the present invention.

（式（１）において、Ｒ^１およびＲ^２は夫々独立して、炭素原子数１〜１０の芳香族基を含んでもよい炭化水素基を示し、ｎおよびｍは夫々独立して０以上の整数を示す。Ｒ^３〜Ｒ^１０は夫々独立して、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素数１〜１２の芳香族基を含んでいても良い炭化水素基を示す。Ｒ^１1およびＲ¹²は夫々独立して、炭素原子数１〜１０の芳香族基を含んでもよい炭化水素基を示し、oおよびpは夫々独立して０以上の整数を示す。Ｒ^１３〜Ｒ^2０は夫々独立して、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素数１〜１２の芳香族基を含んでいても良い炭化水素基を示す。） That is, the present invention
1. The thermoplastic resin which the repeating unit represented by following General formula (1) contains 70 mol% or more in all units.

(In Formula (1), R ¹ and R ² each independently represent a hydrocarbon group that may contain an aromatic group having 1 to 10 carbon atoms, and n and m each independently represent an integer of 0 or more. R ^{3 to} R ¹⁰ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms. R ¹¹ and R ¹² are each independently represents a hydrocarbon group which may include an aromatic group having 1 to 10 carbon atoms, o and p is an each independently an integer of 0 or more .R ¹³ to R ²⁰ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms.)

2. In the general formula (1), R ¹ and R ² are each a hydrocarbon group having 1 to 3 carbon atoms, n and m are each 0 or 1, and R ^{3 to} R ¹⁰ are each hydrogen. 2. The thermoplastic resin as described in 1 above, which is a hydrocarbon group which may contain an atom or an aromatic group having 1 to 12 carbon atoms.
3. ^{3. The} thermoplastic resin as described in 2 above, wherein, in the general formula (1), R ¹ and R ² are each a methylene group, n and m are each 1, and R ^{3 to} R ¹⁰ are hydrogen atoms.
4). In the general formula (1), R ¹¹ and R ¹² are each a hydrocarbon group having 1 to 4 carbon atoms, o and p are each 0 or 1, and R ^{13 to} R ²⁰ are each hydrogen. 2. The thermoplastic resin as described in 1 above, which is a hydrocarbon group which may contain an atom or an aromatic group having 1 to 12 carbon atoms.
5. 5. The thermoplastic resin as described in 4 above, wherein in the general formula (1), R ¹¹ and R ¹² are each an ethylene group, o and p are each 1, and R ^{13 to} R ²⁰ are hydrogen atoms.
6). The thermoplastic resin according to any one of 1 to 5 above, which has a refractive index of 1.650 to 1.700.
7). The thermoplastic resin according to any one of 1 to 6, which has a specific viscosity of 0.12 to 0.40.
8). The thermoplastic resin according to any one of 1 to 7 above, which has a glass transition temperature of 128 to 160 ° C.
9. The thermoplastic resin according to any one of 1 to 8, wherein the orientation birefringence is 0 to 4 × 10 ⁻³ .
10. The thermoplastic resin according to any one of 1 to 9, wherein the thermoplastic resin is polyester or polyester carbonate resin.
11. The optical member which consists of a thermoplastic resin in any one of said 1-10.
12 An optical lens made of the thermoplastic resin according to any one of 1 to 10 above.

  Since the thermoplastic resin of the present invention has a high refractive index, a low birefringence, and a high heat resistance, its industrial effects are exceptional.

2 is a proton NMR of the polyester resin obtained in Example 1.

The present invention will be described in more detail.
The thermoplastic resin of the present invention needs to contain 70 mol% or more of the repeating unit represented by the general formula (1), and the specific thermoplastic resin is preferably a polyester resin or a polyester carbonate resin. In particular, a polyester resin is preferable from the viewpoint of the effect of the present invention.

In the general formula (1), R ¹ and R ² each independently represent a hydrocarbon group that may contain an aromatic group having 1 to 10 carbon atoms, and n and m each independently represent 0 or more. Indicates an integer. R ^{3 to} R ¹⁰ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms. R ¹¹ and R ¹² each independently represent a hydrocarbon group that may contain an aromatic group having 1 to 10 carbon atoms, and o and p each independently represent an integer of 0 or more. R ^{13 to} R ²⁰ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms.

R ¹ and R ² are preferably each independently a hydrocarbon group having 1 to 3 carbon atoms, and n and m are preferably each independently an integer of 0 or 1. R ^{3 to} R ¹⁰ are preferably each independently a hydrogen atom or a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms. R ¹¹ and R ¹² are preferably each independently a hydrocarbon group having 1 to 4 carbon atoms, and o and p are preferably each independently an integer of 0 or 1. R ^{13 to} R ²⁰ are preferably each independently a hydrogen atom or a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms. Particularly preferably, R ¹ and R ² represent a methylene group, n and m represent 1, R ^{3 to} R ¹⁰ represent a hydrogen atom, R ¹¹ and R ¹² represent an ethylene group, o and p Represents 1 and R ^{13 to} R ²⁰ represent a hydrogen atom.

Furthermore, R ¹ and R ² may be the same or different, n and m may be the same or different, and R ^{3 to} R ¹⁰ may be the same or different. R ¹¹ and R ¹² may be the same or different, o and p may be the same or different, and R ^{13 to} R ²⁰ may be the same or different. May be.

  The repeating unit represented by the general formula (1) is 70 mol% or more of the whole, preferably 75 mol% or more, more preferably 80 mol% or more. Within this range, the balance between heat resistance and moldability is excellent.

  In the general formula (1), the 1,1′-binaphthyl skeleton has a conformation that improves the heat resistance and refractive index of the thermoplastic resin and is orthogonal to the bond axis connecting two naphthalene rings. Therefore, there is an effect of reducing birefringence.

The 1,1′-binaphthyl skeleton may be substituted with a substituent or may be condensed with each other. Various substituents are exemplified and are not particularly limited, but typically, alkyl, aryl and the like can be mentioned. As said alkyl group, a C1-C12 thing is preferable and may be linear or branched. Examples of the aryl group include a phenyl group, a naphthyl group, and a biphenyl group.
Further, the binaphthyl skeleton may be any of R, S and racemates, and preferably a racemate. Racemates that do not require optical resolution have a cost advantage.

The first object of the present invention is to provide a high refractive index and high heat resistance, and the refractive index at a measurement wavelength of 589 nm (hereinafter sometimes abbreviated as nD) at 25 ° C. is 1.650 to 1.700. It is preferable that it is, It is more preferable in it being 1.655-1.695, It is still more preferable in it being 1.657-1.686.
. The glass transition point (hereinafter sometimes abbreviated as Tg) is preferably 128 to 160 ° C, and more preferably 130 to 158 ° C.
The relational expression between nD and Tg calculated from the result of this implementation is
Tg> −850 nD + 1555 (1)
It is preferable that the relationship is satisfied.

  The second object of the present invention is to provide a particularly high refractive index in addition to the first object, more preferably nD is 1.675 to 1.690, and Tg is More preferably, it is 130-143 degreeC, Furthermore, it is most preferable that nD is 1.679-1.682, and Tg is 130-137 degreeC.

The refractive index is measured at 25 ° C. and wavelength 589 nm. When the refractive index is 1.650 or more, the spherical aberration of the lens can be reduced, and the focal length of the lens can be shortened.
The Abbe number (ν) of the thermoplastic resin of the present invention is preferably 17 to 25, and more preferably 17 to 23. The Abbe number is calculated from the refractive indices at wavelengths of 486 nm, 589 nm, and 656 nm measured at 25 ° C. using the following formula.
v = (nD-1) / (nF-nC)
In the present invention,
nD: refractive index at a wavelength of 589 nm,
nC: refractive index at a wavelength of 656 nm,
nF: Refractive index at a wavelength of 486 nm.

The thermoplastic resin of the present invention is calculated by the following formula, and the absolute value of orientation birefringence (Δn) is preferably 0 to 4 × 10 ⁻³ , more preferably 0 to 2 × 10 ⁻³ . is there. The orientation birefringence (Δn) is measured at a wavelength of 589 nm when a 100 μm-thick cast film obtained from the thermoplastic resin of the present invention is stretched twice at Tg + 10 ° C. It is preferable that the orientation birefringence is within the above range because the optical distortion of the lens becomes small.
Δn = Re / d
Δn: orientation birefringence
Re: Phase difference (nm)
d: Thickness (nm)
The repeating unit of the general formula (1) can be produced by reacting a diol component described later and a dicarboxylic acid component.

Specific raw materials will be described below.
<Dicarboxylic acid component of general formula (1)>
As the dicarboxylic acid component, a compound represented by the following formula (a) or an ester-forming derivative thereof is mainly preferably used.

In the above general formula (a) of the dicarboxylic acid used as a raw material of the general formula (1) of the present invention, R ¹ and R ² each independently represents a hydrocarbon having 1 to 10 carbon atoms. And n and m each independently represent an integer of 0 or more. R ^{3 to} R ¹⁰ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms. R ¹ and R ² are preferably each independently a hydrocarbon group having 1 to 3 carbon atoms, and n and m are preferably each independently an integer of 0 or 1. R ^{3 to} R ¹⁰ are preferably each independently a hydrogen atom or a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms. Particularly preferably, R ¹ and R ² represent a methylene group, n and m represent 1, and R ^{3 to} R ¹⁰ represent a hydrogen atom. Furthermore, R ¹ and R ² may be the same or different, n and m may be the same or different, and R ^{3 to} R ¹⁰ may be the same or different. Also good.

Hereinafter, typical specific examples of the dicarboxylic acid represented by the general formula (a) or an ester-forming derivative thereof are shown, but the raw materials used in the general formula (1) of the present invention are not limited thereto. Absent.
2,2′-dicarboxy-1,1′-binaphthyl, 2,2′-bis (carboxymethoxy) -1,1′-binaphthyl, 2,2′-bis (2-carboxyethoxy) -1,1 ′ -Binaphthyl, 2,2'-bis (3-carboxypropoxy) -1,1'-binaphthyl, 2,2'-dimethoxycarbonyl-1,1'-binaphthyl, 2,2'-bis (methoxycarbonylmethoxy)- 1,1′-binaphthyl, 2,2′-bis (2-methoxycarbonylethoxy) -1,1′-binaphthyl, 2,2′-bis (3-methoxycarbonylpropoxy) -1,1′-binaphthyl, 2 , 2′-diethoxycarbonyl-1,1′-binaphthyl, 2,2′-bis (ethoxycarbonylmethoxy) -1,1′-binaphthyl, 2,2′-bis (2-ethoxycarbonylethoxy) -1, 1'-Binafuchi 2,2'-bis (3-ethoxycarbonylpropoxy) -1,1'-binaphthyl, 2,2'-diphenoxycarbonyl-1,1'-binaphthyl, 2,2'-bis (phenoxycarbonylmethoxy)- 1,1′-binaphthyl, 2,2′-bis (2-phenoxycarbonylethoxy) -1,1′-binaphthyl, 2,2′-bis (3-phenoxycarbonylpropoxy) -1,1′-binaphthyl, 2 , 2′-ditert-butoxycarbonyl-1,1′-binaphthyl, 2,2′-bis (tert-butoxycarbonylmethoxy) -1,1′-binaphthyl, 2,2′-bis (2-tert-butoxy) Carbonylethoxy) -1,1′-binaphthyl, 2,2′-bis (3-tert-butoxycarbonylpropoxy) -1,1′-binaphthyl and the like. Among these, 2,2′-bis (carboxymethoxy), in which R ¹ and R ² in the general formula (a) are methylene groups, o and p are 1, and R ^{3 to} R ¹⁰ are hydrogen atoms Most preferred is -1,1′-binaphthyl (hereinafter sometimes abbreviated as BCMB) or an ester-forming derivative thereof.

<Diol component of general formula (1)>
As the diol component, a compound represented mainly by the general formula (b) is preferably used.

In the general formula (b) of the diol component that is a raw material of the general formula (1), R ¹¹ and R ¹² each independently represents a hydrocarbon group that may contain an aromatic group having 1 to 10 carbon atoms. O and p each independently represent an integer of 0 or more. R ^{13 to} R ²⁰ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms. R ¹¹ and R ¹² are each preferably a hydrocarbon group having 1 to 4 carbon atoms, and o and p are each preferably an integer of 0 or 1. R ^{13 to} R ²⁰ are preferably each independently a hydrogen atom or a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms. Particularly preferably, R ¹¹ and R ¹² represent an ethylene group, o and p represent 1, and R ^{13 to} R ²⁰ represent a hydrogen atom. Furthermore, R ¹¹ and R ¹² may be the same or different, o and p may be the same or different, and R ^{13 to} R ²⁰ may be the same or different. Also good.

Specifically, in the general formula (b), R ¹¹ and R ¹² are ethylene groups, o and p are 1, and R ^{13 to} R ²⁰ are hydrogen atoms, 2,2′-bis (2- 1,1′-bi-2-naphthol in which hydroxyethoxy) -1,1′-binaphthyl (hereinafter sometimes abbreviated as BHEB) or o and p are 0, and R ^{13 to} R ²⁰ are hydrogen atoms More preferably.

<Copolymerization component other than general formula (1)>
The thermoplastic resin in the present invention has a repeating unit represented by the general formula (1), but may contain a copolymer component separately. Examples of the copolymer component include dicarboxylic acid components other than those represented by the general formula (a), diol components other than the compounds represented by the general formula (b), and repeating units having a carbonate bond.

  Specific examples of the dicarboxylic acid component as a copolymerization component include aliphatic dicarboxylic acid components such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, methylmalonic acid, and ethylmalonic acid, Monocyclic aromatic dicarboxylic acid components such as phthalic acid, isophthalic acid, terephthalic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid , Polycyclic aromatic dicarboxylic acid components such as anthracene dicarboxylic acid and phenanthrene dicarboxylic acid, biphenyl dicarboxylic acid components such as 2,2′-biphenyldicarboxylic acid, 1,4-cyclodicarboxylic acid, 2,6-decalin dicarboxylic acid and the like Of the alicyclic dicarboxylic acid component. You may use these individually or in combination of 2 or more types. In addition, acid chlorides and esters may be used as these derivatives. Among these, a monocyclic aromatic dicarboxylic acid component, a polycyclic aromatic dicarboxylic acid component, and a biphenyl dicarboxylic acid component are preferable because the heat resistance and the refractive index are easily increased.

  Specific examples of the diol component as the copolymer component include aliphatic diol components such as ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, and nonanediol, and tricyclo [5.2. 1.02,6] decane dimethanol, cyclohexane-1,4-dimethanol, decalin-2,6-dimethanol, norbornane dimethanol, pentacyclopentadecane dimethanol, cyclopentane-1,3-dimethanol, spiro Alicyclic diol components such as glycol and isosorbide, hydroquinone, resorcinol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyph Enyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 1,3-bis (2- (4-hydroxyphenyl) -2-propyl) benzene, bis (4-hydroxyphenyl) sulfone, bis (4 -(2-hydroxyethoxy) phenyl) sulfone, bis (4-hydroxyphenyl) sulfide, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxy) Phenyl) cyclohexane, biphenol, bisphenolfluorene, biscresol fluorene, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl ] Fluorene, dihydroxynaphthalene, bis (2- Rokishietokishi) naphthalene, 10,10-bis (4-hydroxyphenyl) aromatic diol component such as anthrone like. You may use these individually or in combination of 2 or more types. Among these, ethylene glycol, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, and 9,9-bis [4- are easy to suppress the decrease in heat resistance and refractive index while improving moldability. (2-Hydroxyethoxy) -3-phenylphenyl] fluorene and biscresol fluorene are preferred.

  In addition, examples of the repeating unit having a carbonate bond as a specific copolymer component include those obtained by carbonate-bonding the diol component exemplified in the general formula (b) and the diol component exemplified as the copolymer component described above. Among these, the diol component exemplified in the general formula (b) and 9,9-bis [4- (2-hydroxyethoxy) phenyl are easy to suppress the decrease in heat resistance and refractive index while improving the moldability. It is preferable to use fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene, or biscresol fluorene.

  The thermoplastic resin of the present invention is obtained by subjecting the raw materials represented by the general formulas (a) and (b) to an esterification reaction or a transesterification reaction, and subjecting the obtained reaction product to a polycondensation reaction. A molecular weight body may be used.

  Specifically, for example, in the presence of an inert gas, a diol component and a dicarboxylic acid component or a diester thereof are mixed, and the reaction is usually performed at 120 to 350 ° C., preferably 150 to 300 ° C. under reduced pressure. . The degree of vacuum is changed stepwise, and finally, water or alcohol produced at 0.13 kPa or less is distilled out of the system, and the reaction time is usually about 1 to 10 hours.

  A polymerization catalyst known per se can be employed as the polymerization catalyst, and for example, an antimony compound, a titanium compound, a germanium compound, a tin compound, or an aluminum compound is preferable. Examples of such compounds include antimony, titanium, germanium, tin, aluminum oxides, acetates, carboxylates, hydrides, alcoholates, halides, carbonates, sulfates, and the like. These compounds can be used in combination of two or more. Among these, tin, titanium, and a germanium compound are preferable from the viewpoint of melt stability of the thermoplastic resin and hue.

  As the transesterification catalyst, a catalyst known per se can be employed. For example, a compound containing manganese, magnesium, titanium, zinc, aluminum, calcium, cobalt, sodium, lithium, or a lead element can be used. Specific examples include oxides, acetates, carboxylates, hydrides, alcoholates, halides, carbonates and sulfates containing these elements. Among these, compounds such as manganese, magnesium, zinc, titanium, cobalt oxides, acetates, alcoholates and the like are preferable from the viewpoints of melt stability of the thermoplastic resin, hue, and a small amount of polymer-insoluble foreign matter. Further, manganese, magnesium and titanium compounds are preferable. These compounds can be used in combination of two or more.

The amount of the catalyst used is, for example, about 0.01 × 10 ^{−4 to} 100 × 10 ⁻⁴ mol, preferably about 0.1 × 10 ⁻⁴ to 40 × 10 ⁻⁴ mol, relative to 1 mol of the dicarboxylic acid component. There may be.

  In addition, the thermoplastic resin of this invention may contain the copolymerization component other than forming the repeating unit of General formula (1) as above-mentioned. For example, when using it as a polyester carbonate resin, it can manufacture by making it react with dicarboxylic acid chloride and phosgene other than a diol component and a dicarboxylic acid component, or making a diol, dicarboxylic acid, and biaryl carbonate react.

Specific examples of the biaryl carbonate include carbonic acid diesters such as diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate. Of these, diphenyl carbonate is preferred.
The content of the dicarboxylic acid chloride, phosgene, or biaryl carbonate component is preferably less than 42 mol%, more preferably less than 30 mol%, and still more preferably less than 20 mol% with respect to 100 mol% of the dicarboxylic acid component.

<Additives>
The thermoplastic resin of the present invention is appropriately added with additives such as a heat stabilizer, an antioxidant, a mold release agent, a plasticizer, a filler, and an ultraviolet absorber as necessary to obtain a thermoplastic resin composition. Can be used.
As a mold release agent, that whose 90 weight% or more consists of ester of alcohol and a fatty acid is preferable. Specific examples of the ester of alcohol and fatty acid include monohydric alcohol and fatty acid ester and / or partial ester or total ester of polyhydric alcohol and fatty acid. The ester of the monohydric alcohol and the fatty acid is preferably an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. The partial ester or total ester of a polyhydric alcohol and a fatty acid is preferably a partial ester or a total ester of a polyhydric alcohol having 1 to 25 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Specific examples of the monohydric alcohol, saturated fatty acid and ester include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate and the like, and stearyl stearate is preferable.

Specific examples of partial esters or total esters of polyhydric alcohol and saturated fatty acid include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetra All esters or parts of dipentaerythritol, such as stearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate Examples include esters. Among these esters, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and a mixture of stearic acid triglyceride and stearyl stearate are preferably used.

The amount of the ester in the release agent is preferably 90% by weight or more, and more preferably 95% by weight or more when the release agent is 100% by weight.
The mold release agent to be blended in the thermoplastic resin composition is preferably in the range of 0.005 to 2.0 parts by weight, more preferably in the range of 0.01 to 0.6 parts by weight with respect to 100 parts by weight of the thermoplastic resin. The range of 0.02 to 0.5 parts by weight is more preferable.

Examples of the heat stabilizer include a phosphorus heat stabilizer, a sulfur heat stabilizer, and a hindered phenol heat stabilizer.
In the phosphorous heat stabilizer, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite is preferably used.
As content of the phosphorus-type heat stabilizer of a thermoplastic resin, 0.001-0.2 weight part is preferable with respect to 100 weight part of thermoplastic resins.
In the hindered phenol heat stabilizer, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is particularly preferably used.
As content of the hindered phenol type heat stabilizer in a thermoplastic resin, 0.001-0.3 weight part is preferable with respect to 100 weight part of thermoplastic resins.

  As the UV absorber, at least one UV absorber selected from the group consisting of benzotriazole UV absorbers, benzophenone UV absorbers, triazine UV absorbers, cyclic imino ester UV absorbers, and cyanoacrylates Is preferred.

In the benzotriazole ultraviolet absorber, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethyl) is more preferable. Butyl) -6- (2H-benzotriazol-2-yl) phenol].
Examples of the benzophenone ultraviolet absorber include 2-hydroxy-4-n-dodecyloxybenzophenone and 2-hydroxy-4-methoxy-2′-carboxybenzophenone.
Examples of the triazine ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- (4,6-bis ( And 2.4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-[(octyl) oxy] -phenol.
As the cyclic imino ester ultraviolet absorber, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one) is particularly suitable.

  The blending amount of the ultraviolet absorber is preferably 0.01 to 3.0 parts by weight with respect to 100 parts by weight of the thermoplastic resin. Sufficient weather resistance can be imparted.

<Optical lens>
The thermoplastic resin of the present invention is suitable for optical members, particularly optical lenses.
When the thermoplastic resin optical lens of the present invention is manufactured by injection molding, it is preferably molded under conditions of a cylinder temperature of 260 to 350 ° C. and a mold temperature of 90 to 170 ° C. More preferably, molding is preferably performed under conditions of a cylinder temperature of 270 to 320 ° C and a mold temperature of 100 to 160 ° C. When the cylinder temperature is higher than 350 ° C., the thermoplastic resin is decomposed and colored, and when it is lower than 260 ° C., the melt viscosity is high and molding tends to be difficult. When the mold temperature is higher than 170 ° C., it is difficult to take out a molded piece made of a thermoplastic resin from the mold. On the other hand, if the mold temperature is less than 90 ° C., the resin hardens too quickly in the mold during molding, making it difficult to control the shape of the molded piece, or sufficiently transferring the mold attached to the mold. Tends to be difficult.

  The optical lens of the present invention is preferably implemented using an aspherical lens shape as necessary. Since an aspheric lens can substantially eliminate spherical aberration with a single lens, it is not necessary to remove spherical aberration with a combination of a plurality of spherical lenses, thus reducing weight and reducing molding costs. It becomes possible. Therefore, the aspherical lens is particularly useful as a camera lens among optical lenses.

  Further, the optical lens of the present invention is particularly useful as a material for an optical lens having a thin and small size and a complicated shape because of high molding fluidity. As a specific lens size, the thickness of the central portion is 0.05 to 3.0 mm, more preferably 0.05 to 2.0 mm, and still more preferably 0.1 to 2.0 mm. Moreover, a diameter is 1.0 mm-20.0 mm, More preferably, it is 1.0-10.0 mm, More preferably, it is 3.0-10.0 mm. In addition, it is preferably a meniscus lens having a convex surface on one side and a concave surface on the other side.

  The lens made of the thermoplastic resin in the optical lens of the present invention is molded by an arbitrary method such as mold forming, cutting, polishing, laser processing, electric discharge processing, and etching. Among these, die molding is more preferable from the viewpoint of manufacturing cost.

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. The evaluation was performed by the following method.
(A) Film 3 g of the obtained thermoplastic resin was dissolved in 50 ml of methylene chloride and cast on a glass petri dish. After sufficiently drying at room temperature, it was dried at a temperature of 120 ° C. for 24 hours to prepare a cast film having a thickness of about 100 μm.

Evaluation was performed by the following method.
(1) Copolymerization ratio: The obtained thermoplastic resin was measured using proton NMR of JNM-AL400 manufactured by JEOL Ltd.
(2) Specific viscosity: The obtained thermoplastic resin was sufficiently dried, and the specific viscosity (η _sp ) at 20 ° C. of the solution was measured from a solution obtained by dissolving 0.7 g of the resin in 100 ml of methylene chloride.
(3) Glass transition point: The obtained thermoplastic resin was measured by DSC-60A manufactured by Shimadzu Corporation at a temperature rising rate of 20 ° C./min.
(4) Refractive index (nd): The refractive index (wavelength: 589 nm) at 25 ° C. was measured for the film prepared by the technique of (a) using an Abbe refractometer of DR-M2 manufactured by ATAGO.
(5) Oriented birefringence (Δn): A cast film having a thickness of 100 μm prepared by the method of (a) was stretched twice at Tg + 10 ° C., and the position at 589 nm was measured using an ellipsometer M-220 manufactured by JASCO Corporation. The phase difference (Re) was measured, and the orientation birefringence (Δn) was determined from the following formula.
Δn = Re / d
Δn: orientation birefringence
Re: Phase difference (nm)
d: Thickness (nm)
○: 0 or more, 2 × 10 ⁻³ or less Δ: 2 × 10 ^{−3 or} more, 4 × 10 ⁻³ or less ×: 4 × 10 ^{−3 or} more

Example 1
20.2 parts by weight of 2,2′-bis (carboxymethoxy) -1,1′-binaphthyl (BCMB), 2,2′-bis (2-hydroxyethoxy) -1,1′-binaphthyl (BHEB) 72 parts by weight and 17.0 × 10 ⁻³ parts by weight of tetrabutoxytitanium were placed in a reactor equipped with a stirrer and a distillation apparatus, heated to 180 ° C. under a nitrogen atmosphere and normal pressure, and stirred for 20 minutes. Thereafter, the temperature was gradually raised and reduced, and finally the temperature was raised and reduced to 260 ° C. and 0.13 kPa or less to conduct a transesterification reaction / polycondensation reaction. After reaching a predetermined stirring torque, the contents were taken out of the reactor to obtain polyester resin pellets. When the obtained pellets were analyzed by NMR, the dicarboxylic acid component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the diol component introduced into the polyester resin was It was 50 mol% with respect to all the monomer components (total dicarboxylic acid component + total diol component). Moreover, the specific viscosity of the obtained polyester resin was 0.28, the glass transition temperature Tg was 135 ° C., and the refractive index was 1.680.

Example 2
Polymerization was conducted in the same manner as in Example 1 except that BCMB was 20.12 parts by weight, BHEB was 14.98 parts by weight, and ethylene glycol (EG) was 6.83 parts by weight. When the obtained pellets were analyzed by NMR, the dicarboxylic acid component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the diol component introduced into the polyester resin was It was 50 mol% with respect to all monomer components (total dicarboxylic acid component + total diol component), 40 mol% was derived from BHEB, and 10 mol% was derived from EG. The obtained polyester resin had a specific viscosity of 0.27, a glass transition temperature Tg of 132 ° C., and a refractive index of 1.679.

Example 3
Polymerization was carried out in the same manner as in Example 1 except that 16.90 parts by weight of BCMB, 21.72 parts by weight of BHEB, and 3.64 parts by weight of diphenyl carbonate (DPC) were used. The obtained pellet was analyzed by NMR. As a result, the dicarboxylic acid component introduced into the polyester carbonate resin was 42 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the diol introduced into the polyester carbonate resin. The component was 58 mol% with respect to the total monomer component (total dicarboxylic acid component + total diol component). The obtained polyester carbonate resin had a specific viscosity of 0.27, a glass transition temperature Tg of 132 ° C., and a refractive index of 1.678.

Example 4
Polymerization was conducted in the same manner as in Example 1 except that 22.93 parts by weight of 2,2′-bis (ethoxycarbonylmethoxy) -1,1′-binaphthyl (BECMB) and 18.72 parts by weight of BHEB were used. The obtained pellets were analyzed by NMR. As a result, the diester component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total diester acid component + total diol component), and the diol component introduced into the polyester resin was all. It was 50 mol% with respect to the monomer component (total diester component + total diol component). Moreover, the specific viscosity of the obtained polyester resin was 0.28, the glass transition temperature Tg was 135 ° C., and the refractive index was 1.680.

Comparative Example 1
Polymerization was conducted in the same manner as in Example 1 except that BCMB was 20.12 parts by weight, BHEB was 11.23 parts by weight, and EG was 4.34 parts by weight. When the obtained pellets were analyzed by NMR, the dicarboxylic acid component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the diol component introduced into the polyester resin was It was 50 mol% with respect to all monomer components (total dicarboxylic acid component + total diol component), 30 mol% was derived from BHEB, and 20 mol% was derived from EG. The obtained polyester resin had a specific viscosity of 0.27, a glass transition temperature Tg of 128 ° C., and a refractive index of 1.777.

Comparative Example 2
Polymerization was conducted in the same manner as in Example 1 except that 9.71 parts by weight of dimethyl terephthalate (DMT), 18.72 parts by weight of BHEB, and 0 parts by weight of diphenyl carbonate (DPC) were used. The obtained pellets were analyzed by NMR. As a result, the diester acid component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total diester acid component + total diol component), and the diol component introduced into the polyester resin. It was 50 mol% with respect to all the monomer components (total diester acid component + total diol component). The obtained polyester resin had a specific viscosity of 0.25, a glass transition temperature Tg of 127 ° C., and a refractive index of 1.658.

Comparative Example 3
Polymerization was carried out in the same manner as in Example 1 except for 21.93 parts by weight of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (BPEF), 18.72 parts by weight of BHEB, and 21.85 parts by weight of DPC. When the obtained pellet was analyzed by NMR, 50 mol% was derived from BPEF and 50 mol% was derived from BHEB with respect to all monomer components introduced into the polycarbonate resin. The polycarbonate resin obtained had a specific viscosity of 0.23, a glass transition temperature Tg of 135 ° C., and a refractive index of 1.649.

Comparative Example 4
Polymerization was conducted in the same manner as in Example 1 except that 43.85 parts by weight of BPEF and 21.85 parts by weight of DPC were used. When the obtained pellet was analyzed by NMR, 100 mol% of the diol component introduced into the polycarbonate resin was derived from BPEF. The polycarbonate resin obtained had a specific viscosity of 0.24, a glass transition temperature Tg of 147 ° C., and a refractive index of 1.638.

Reference example 1
Polymerization was carried out in the same manner as in Example 1 except that 16.90 parts by weight of BCMB, 25.43 parts by weight of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene BPEF and 3.64 parts by weight of DPC were used. When the obtained pellet was analyzed by NMR, the dicarboxylic acid component introduced into the polyester carbonate resin was introduced into the polyester carbonate resin in an amount of 42 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component). The diol component was 58 mol% with respect to the total monomer component (total dicarboxylic acid component + total diol component). The polyester carbonate resin obtained had a specific viscosity of 0.24, a glass transition temperature Tg of 150 ° C., and a refractive index of 1.660.

  The value of the formula (1) in Table 1 is the ratio of the repeating unit represented by the formula (1) when the total of all repeating units is 100 mol%.

  The polyester or polyester carbonate resin obtained in Examples 1 to 3 in Table 1 is a resin having a high refractive index, low birefringence, and a good balance between heat resistance and moldability, and is excellent as an optical lens. On the other hand, the polymer of Comparative Example 1 has low heat resistance, and Comparative Example 2 does not sufficiently cancel out birefringence and has low heat resistance. The birefringence obtained from the polymer is large and the heat resistance is poor. Comparative Example 3 is a polycarbonate copolymer obtained by copolymerizing 1,1'-binaphthalene structure as a diol component BHEB with BPEF, but has a low refractive index.

  Since the thermoplastic resin of the present invention has high refractive index, low birefringence, and high heat resistance, it is an optical disk, transparent conductive substrate, optical card, sheet, film, optical fiber, lens, prism, optical film, substrate, optical It can be used for optical members such as filters and hard coat films, and is particularly useful for lenses.

Claims (12)

The thermoplastic resin which the repeating unit represented by following General formula (1) contains 70 mol% or more in all units.

(In Formula (1), R ¹ and R ² each independently represent a hydrocarbon group that may contain an aromatic group having 1 to 10 carbon atoms, and n and m each independently represent an integer of 0 or more. R ^{3 to} R ¹⁰ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms. R ¹¹ and R ¹² are each independently represents a hydrocarbon group which may include an aromatic group having 1 to 10 carbon atoms, o and p is an each independently an integer of 0 or more .R ¹³ to R ²⁰ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms.) In the general formula (1), R ¹ and R ² are each a hydrocarbon group having 1 to 3 carbon atoms, n and m are each 0 or 1, and R ^{3 to} R ¹⁰ are each hydrogen. The thermoplastic resin according to claim 1, which is a hydrocarbon group which may contain an atom or an aromatic group having 1 to 12 carbon atoms. The thermoplastic resin according to claim 2, wherein, in the general formula (1), R ¹ and R ² are each a methylene group, n and m are each 1, and R ^{3 to} R ¹⁰ are hydrogen atoms. . In the general formula (1), R ¹¹ and R ¹² are each a hydrocarbon group having 1 to 4 carbon atoms, o and p are each 0 or 1, and R ^{3 to} R ¹⁰ are each hydrogen. The thermoplastic resin according to claim 1, which is a hydrocarbon group which may contain an atom or an aromatic group having 1 to 12 carbon atoms. The thermoplastic resin according to claim 4, wherein, in the general formula (1), R ¹¹ and R ¹² are each an ethylene group, o and p are each 1, and R ^{13 to} R ²⁰ are hydrogen atoms. .   The thermoplastic resin according to any one of claims 1 to 5, which has a refractive index of 1.650 to 1.700.   The thermoplastic resin according to any one of claims 1 to 6, which has a specific viscosity of 0.12 to 0.40.   The thermoplastic resin according to any one of claims 1 to 7, which has a glass transition temperature of 128 to 160 ° C. The thermoplastic resin according to claim 1, wherein the orientation birefringence is 0 to 4 × 10 ⁻³ .   The thermoplastic resin according to any one of claims 1 to 9, wherein the thermoplastic resin is a polyester or a polyester carbonate resin.   The optical member which consists of a thermoplastic resin in any one of Claims 1-10. An optical lens made of the thermoplastic resin according to claim 1.

Images