JPH11255859A - Polyurethane, lens material for spectacles, material for contact lens, lens and preparation of polyurethane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a material of high transparency by reacting diisocyanate with a diol or dithiol having a fluorene frame or with a diol or dithiol having a fluorene frame and a polymer diol. SOLUTION: A diisocyanate is reacted with a diol or dithiol of formula I or with a compound of formula I and a polymer diol of formula II. The use of the polymer diol of formula II gives a polyurethane with high stiffness. Preferably is reacted a diol or dithiol of formula I with a diol of formula III to obtain a polyurethane exhibiting improved biocompatibility and more suitable as a material for contact lenses. In formula I, R<1> and R<2> are each H, methyl or phenyl; R<3> , R<4> , R<5> and R<6> are each H or halogen; and X is O or S. In formula II, X is a polycarbonate frame, a polyester frame or a polybutabiene frame. In formula III, Y is formula IV and n is 1-20.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyurethane (including polyurethane urea, polythiourethane, polythiourethane urea) suitable as, for example, a lens material for eyeglasses or a contact lens material, a lens material for eyeglasses using the same, and a contact lens. The present invention relates to a material, an eyeglass lens, a contact lens, and a method for producing the polyurethane.

[0002]

2. Description of the Related Art Various resins are used as eyeglass lens materials and contact lens materials. These materials are required to have a high refractive index, a low birefringence, an excellent transparency, an appropriate mechanical strength, and the like. Further, the lens material for glasses is required to have high hardness, and the contact lens material is required to have high flexibility and high oxygen permeability.

As a resin satisfying the above requirements, there is a polyurethane synthesized from diisocyanate and diol as raw materials. As an example of such a polyurethane, there is a polyurethane synthesized by a polyaddition reaction between various organic diisocyanates and a diol having a fluorene skeleton (for example, JP-A-8-3260).
No.).

[0004]

However, the conventional polyurethane has a refractive index of about 1.5. An object of the present invention is to provide a polyurethane which exhibits at least the same properties as those of the prior art in terms of transparency, mechanical strength, oxygen permeability, birefringence, etc., and has a higher refractive index than the conventional one. Another object of the present invention is to provide a spectacle lens material, a contact lens material, a spectacle lens, a contact lens made of such a polyurethane, and a method for producing such a polyurethane.

[0005]

In order to achieve the above object, the inventor of the present application has made various studies. As a result, as a diol to be reacted (urethane polymerization) with diisocyanate (organic diisocyanate),
: A specific diol having a fluorene skeleton, or
: The specific diol having a fluorene skeleton and a polymer diol having a carbonate skeleton or a polyester skeleton (a carbonate residue or a polyester residue);
Or: the specific diol having a fluorene skeleton, the polymer diol having a carbonate skeleton or a polyester skeleton (a carbonate residue or a polyester residue), and a polyurethane synthesized using a phosphoric acid diol have the above-mentioned objects. Have been achieved, and the present invention has been completed.

Accordingly, the present invention is a polyurethane obtained by reacting a diol or dithiol (also referred to as BPAF) represented by the following formula (1) with a diisocyanate.

Further, the present invention provides a method wherein a diol or dithiol represented by the following formula (1) (also referred to as BPAF) is reacted with a polymer diol represented by the following formula (2) and diisocyanate. The resulting polyurethane. In this case, advantages such as a polyurethane having higher hardness can be obtained than when only the diol represented by the formula (1) is used as the diol.

Further, the present invention provides a diol or dithiol represented by the following formula (1) (also referred to as BPAF), a polymer diol represented by the following formula (2), and a diol represented by the following formula (9):
Is a polyurethane obtained by reacting with a diol represented by the formula: When the diol represented by the formula (9) is used, biocompatibility is improved as compared with the case where the diol is not used. Therefore, it is more preferable as a contact lens material.

Further, the present invention is a lens material for eyeglasses, a contact lens material, a lens for eyeglasses or a contact lens made of any of the above polyurethanes.

[0010]

Embedded image

However, each of R ¹ and R ² in the formula (1) is
A hydrogen atom, a methyl group or a phenyl group, which may be the same or different. Further, each of R ³ , R ⁴ , R ⁵ , and R ⁶ is a hydrogen atom or a halogen atom, and may be the same, partially different, or all different. X is an oxygen atom or a sulfur atom. Also, X in the equation (2)
Is a polycarbonate skeleton, a polyester skeleton or a polybutadiene skeleton. Further, n in the formula (9) is 1-2.
0.

In the practice of the present invention, when the above three diols are used, the ratio of BPAF to the total amount of these diols is 5 mol% or more, preferably 30 mol% or more, and 90 mol% or less, preferably 80 mol% or less, PBD ratio is 5 mol% or more, preferably 10 mol% or more, 90 mol% or less, preferably 50 mol% or less,
The content of BESP is 5 mol% or more, preferably 10 mol%.
As described above, the content is preferably 90 mol% or less, more preferably 40 mol% or less. Polyurethane suitable as a material for spectacles or contact lenses can be obtained.

One preferred embodiment of the present invention is represented by the following formula (10):
And a polyurethane having a repeating unit (also referred to as a BPAF unit) represented by the following formula (11) and a repeating unit (also referred to as a PBD unit) represented by the following formula (11); It is a lens for contact lenses.

Another preferred embodiment of the present invention is represented by the following formula (1)
0), and a repeating unit (PB) represented by the following formula (11).
Also called D unit. ) And a repeating unit (also referred to as a BESP unit) represented by the following formula (12), and a lens material for eyeglasses, a contact lens material, and a lens for eyeglasses or contact lenses made of the polyurethane.

[0015]

Embedded image

However, each of R ¹ and R ² in the formula (10) is a hydrogen atom, a methyl group or a phenyl group, and they may be the same or different. Also, R ³ , R ⁴ , R ⁵ , R
⁶ each is a hydrogen atom or a halogen atom, and may be the same, partially different, or all different. Also, Y
Is an oxygen atom or a sulfur atom. X is an aryl group or an alkylene group which is a residue of diisocyanate. Further, X in the formula (11) is an aryl group or an alkylene group which is a residue of diisocyanate. X in the formula (12) is an aryl group or an alkylene group which is a residue of diisocyanate, and Z is an alkylene group having 1 to 20 carbon atoms.

In the case of a configuration having a BPAF unit, a PBD unit and a BESP unit, the ratio of the BPAF unit to the total amount of these units is 5 mol%.
Or more, preferably 30 mol% or more and 90 mol% or less, preferably 80 mol% or less, and the ratio of PBD units is 5 mol% or more, preferably 10 mol% or more and 90 mol% or less, preferably 50 mol% or less. It is preferable that the ratio of the BESP unit is 5 mol% or more, preferably 10 mol% or more, and 90 mol% or less, preferably 40 mol% or less. This is because a polyurethane suitable as a material for glasses or a contact lens can be obtained.

In the case of a configuration having these BPAF units, PBD units and BESP units, the ratio of the BPAF units to the total amount of these units is 5 mol% or more, preferably 20 mol% or more, more preferably 30 mol%. Above, particularly preferably 40 mol% or more, 90 mol% or less, preferably 80 mol% or less, more preferably 70 mol% or less, and the ratio of PBD units is 5 mol% or more, preferably 10 mol% or more, and more preferably It is preferably at least 15 mol%, at most 90 mol%, preferably at most 70 mol%, more preferably at most 50 mol%, and the ratio of BESP units is at least 5 mol%, preferably at least 10 mol%, more preferably at least 15 mol%. Mol% or more, 9
It is preferably at most 0 mol%, preferably at most 70 mol%, more preferably at most 50 mol%, particularly preferably at most 40 mol%. This is because a polyurethane suitable as a material for glasses or a contact lens can be obtained.

The weight average molecular weight of the polyurethane of the present invention is 10,000 or more, preferably 20,000 or more,
It is suitable to be 00000 or less, preferably 100,000 or less. This is because a polyurethane suitable for eyeglasses and as a material for contact lenses can be obtained.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of each invention of this application will be described below. The polyurethane of the present invention is BP
AF and diisocyanate, or BPAF and PB
It can be produced by reacting (urethane polymerization) D with diisocyanate or BPAF, PBD and BESP with diisocyanate.

Specifically, the polyurethane of the present invention can be efficiently produced by reacting about the same mole of the diol with the diisocyanate.

For example, a BPAF-PBD prepolymer having isocyanate groups at both terminals can be produced by reacting BPAF and PBD with an organic diisocyanate. By reacting the BPAF-PBD prepolymer with BESP, the polyurethane of one embodiment of the present invention can be efficiently produced.

The BPAF and PBD and the organic diisocyanate may be mixed with or without a solvent at a temperature of 50 ° C. or higher, preferably 60 ° C. or higher, more preferably 70 ° C. or higher while stirring as necessary. Usually below 200 ° C,
Preferably at 150 ° C. or lower, for 2 hours or longer, preferably 4 hours or longer, more preferably 12 hours or longer, usually 48 hours or more.
Hours or less, preferably 36 hours or less, more preferably 2 hours or less.
By heating for 8 hours or less, urethane polymerization can be performed.

BPAF-PBD prepolymer and BESP
Is a temperature of 60 ° C. or higher, preferably 70 ° C. or higher, more preferably 90 ° C. or higher and 200 ° C. or lower, preferably 1
Urethane polymerization can be performed by heating at 50 ° C. or lower, more preferably 110 ° C. or lower, for 1 hour or longer, preferably 2 hours or longer, more preferably 3 hours or longer, 24 hours or shorter, preferably 12 hours or shorter. .

The solvent is not particularly restricted but includes, for example, benzene, toluene, chlorobenzene,
o-dichlorobenzene, dimethylformamide (DM
F), dimethylacetamide (DMAC), dimethylsulfoxide, or the like can be used.

The diisocyanate is not particularly limited, but a diisocyanate represented by the formula OCN-G-NCO can be used. G in this formula is an organic group, and represents, for example, an aliphatic hydrocarbon residue (for example, an alkylene group), an alicyclic hydrocarbon residue (for example, a cycloalkylene group), or an aromatic hydrocarbon residue.

Specific examples of this diisocyanate include:
Linear or branched aliphatic diisocyanates such as hexamethylene diisocyanate, tetramethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate Aliphatic diisocyanates such as naphthalate (hydrogenated MD), isophorone diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 3,3'-methyleneditolylen-4,
Aromatic diisocyanates such as 4'-diisocyanate (TODI), naphthalene diisocyanate and xylylene diisocyanate can be used.

Further, as the diisocyanate, a compound represented by the formula: OC
A diisocyanate represented by NR-NCO can also be used. In particular, when this diisocyanate is used, a polyurethane having a higher refractive index can be produced. Note that R in the formula represents a diphenylmethane group that can have an alkyl group or a dicyclohexylmethane group that can have an alkyl group.

The BPAF is not limited thereto, but, for example, 9,9-bis (4- (2-hydroxyethoxy)) in which R ¹ and R ² in the formula (1) are each a hydrogen atom.
Phenyl) fluorene (this is also called BPEF),
Alternatively, 9,9-bis (4- (2-hydroxypropoxy) phenyl) fluorene in which each of R ¹ and R ² is a methyl group (this is also referred to as BPPF) can be used. BPAF can be produced, for example, by reacting fluorenone with phenoxyethanol or phenoxypropanol. Fluorenone and phenoxyethanol or phenoxypropanol,
For example, the reaction can be performed by using sulfuric acid or thiol as a catalyst.

The PBD is not limited to this, but has a weight average molecular weight of 500 or more, preferably 1000
Or more, more preferably 2,000 or more, 10,000 or less,
Preferably 5000 or less, more preferably 3000 or less can be used.

In addition, Y in BESP expressed by equation (9)
The alkylene group having 1 to 20 carbon atoms represented by can be a linear or branched alkylene group, is preferably a linear alkylene group, preferably has 5 or more carbon atoms, particularly preferably 10 or more, and is preferably It is an alkylene group of 18 or less.

[0032]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to several embodiments. In addition, the chemicals used in the following examples, the amount used,
Numerical conditions, such as temperature and time during processing, are merely examples within the scope of the present invention. Therefore, the present invention is not limited to the following embodiments, and many changes or modifications can be made.

1. Example 1 <Synthesis of Polyurethane> 2 g of a diol having a polycarbonate skeleton represented by the above chemical formula (3) having a weight average molecular weight of 3,500 and 9,9- which is one of the diols represented by the above chemical formula (1) Bis (4- (2-hydroxyethoxy) phenyl) fluorene (BPEF) 1.3
2 g and dimethylacetamide (DMA
C) 30 ml was prepared in a four-necked flask.

4,4'-, a kind of diisocyanate
Diphenylmethane diisocyanate (MDI) 1.25
g dissolved in DMAC was added to the four-necked flask, and the mixture was reacted at 110 to 120 ° C under a nitrogen stream for 24 hours, and further reacted at 115 to 125 ° C under a nitrogen stream for 3 hours. After this reaction, the sample was concentrated by an evaporator and further subjected to methanol precipitation to obtain a white solid. The amount of this white solid was 4.73 g, and the yield was 93.
%Met.

The results of elemental analysis of the obtained white solid are shown below.

Obtained value: C; 65.70 H; 5.64 N; 2.84 Calculated value: C; 65.41 H; 5.87 N; 3.01 The IR spectrum of this white solid was measured. . As a result, absorption attributable to a urethane wavenumber ^1720cm-1, but also, absorption attributable to carbonate wavenumber ^1740cm-1 were confirmed respectively.

The glass transition point of this white solid is 9
0.2 ° C.

The weight average molecular weight of this white solid is:
8 × 10 ⁴ , and the degree of dispersion of the molecular weight distribution is 1.5.
It was 0.

<Preparation of Film> The white solid obtained by the above synthesis is dissolved in a solvent so as to be 10% (w / v). A glass plate is placed in an oven at 60 to 70 ° C. in advance, and the solution is spread on the plate. The plate was left at a temperature of 60 to 70 ° C. overnight to produce the white solid film.

The refractive index of this film was measured.
Refractive index is 1.790 (z: 1.788, x: 1.78)
0, y: 1.779). It can be understood that the polyurethane of the present invention has low birefringence and a higher refractive index than conventional ones.

The glass transition temperature was measured by TG / DTA and DSC. For TG / DTA, TG / DTA320U manufactured by Seiko Denshi Kogyo was used as a device, the measurement temperature range was from room temperature to 500 ° C. (furnace temperature), the heating rate was 10 ° C./min, and the atmosphere was 200 ml / min.
Min atmosphere. For DSC, Seiko Denshi Kogyo DSC220 was used, and the measurement temperature range was from room temperature to 250 ° C.
° C, the rate of temperature rise is 10 ° C / min, and the atmosphere is a flow rate of 20 ° C.
A nitrogen atmosphere of ml / min was used.

The number average molecular weight for calculating the weight average molecular weight and the degree of dispersion of the molecular weight distribution was measured by GPC. According to GPC, polyurethane is used as an analysis sample in an amount of 0.1%.
After adjusting the solution to a 1% tetrahydrofuran solution, a solution filtered through a membrane filter (0.45 μm) was used. HLC-8120G manufactured by Tosoh Corporation
PC type, UV-8020 type and SC-8020 type were used, and TSKgel GMHXL × 2 (7.
8φ × 300mm), tetrahydrofuran (special grade reagent) is used for the dissolution solution, a differential refractometer is used for the detector,
Using a UV-visible detector (254 nm), the measurement temperature was 40 ° C., the measurement flow rate was 1.00 ml / min, polystyrene manufactured by Tosoh Corporation was used as the molecular weight standard, and the injection amount was 100 μl.

For the measurement of the refractive index, an Appe refractometer 4T manufactured by Atago Co., Ltd. was used as an apparatus, and the measurement wavelength was 589.3.
nm (sodium D line) was used, and the lysing solution was jod methane.

The measurement of the glass transition temperature, the weight average molecular weight, the degree of dispersion of the molecular weight distribution and the refractive index in each of the following Examples 2 and 3 were also carried out under the same conditions as in Example 1.

2. Example 2 <Synthesis of Polyurethane> 2 g of a diol having a polycarbonate skeleton represented by the above chemical formula (3) having a weight average molecular weight of 3500 and 9,9- which is one of the diols represented by the above chemical formula (1) 1.34 g of bis ((3,5-dibromo) 4- (2-hydroxyethoxy) phenyl) fluorene and 30 ml of DMAC as a solvent were prepared in a four-necked flask.

One of the diisocyanates, MDI1.
A solution of 25 g in DMAC was added to the four-necked flask, and the solution was added at 110 to 120 ° C under a nitrogen stream for 2 hours.
The reaction was performed for 4 hours, and further performed at 115 to 125 ° C. under a nitrogen stream for 3 hours. After this reaction, the sample was concentrated by an evaporator and further subjected to methanol precipitation to obtain a white solid. The amount of this white solid was 4.73 g, and the yield was 93%.

The results of elemental analysis of the obtained white solid are shown below.

Found: C; 53.30 H; 5.16 N; 2.45 Br; 17.05 Calculated: C; 53.51 H; 5.03 N; 2.63 Br; 15.98 The IR spectrum of this white solid was measured. As a result, absorption attributable to a urethane wavenumber ^1720cm-1 is also absorbed attributable to carbonate wavenumber ^1740cm-1, but also, absorption attributable to C-Br bond in the vicinity of a wave number of ^640cm-1 was confirmed respectively .

The glass transition point of this white solid is 7
5.3 ° C.

The weight average molecular weight of this white solid is:
It was 8.1 × 10 ⁴ , and the degree of dispersion of the molecular weight distribution was 1.52.

<Preparation of Film> The white solid obtained in the above synthesis is dissolved in a solvent so as to have a concentration of 10% (w / v). A glass plate is placed in an oven at 60 to 70 ° C. in advance, and the solution is spread on the plate. The plate was left at a temperature of 60 to 70 ° C. overnight to produce the white solid film.

The refractive index of this film was measured.
The refractive index is 1.793 (z: 1.791, x: 1.78)
9, y: 1.795). It can be understood that the polyurethane of the present invention has low birefringence and a higher refractive index than conventional ones.

3. Example 3 <Synthesis of Polyurethane> 2 g of a diol having a polycarbonate skeleton represented by the above chemical formula (3) having a weight average molecular weight of 3500 and 9,9- which is one of the diols represented by the above chemical formula (1) 1.32 g of bis (4- (2-hydrothioxyethoxy) phenyl) fluorene;
30 ml of DMAC as a solvent was prepared in a four-necked flask.

One of the diisocyanates, MDI1.
A solution of 25 g in DMAC was added to the four-necked flask, and the solution was added at 110 to 120 ° C under a nitrogen stream for 2 hours.
The reaction was performed for 4 hours, and further performed at 115 to 125 ° C. under a nitrogen stream for 3 hours. After this reaction, the sample was concentrated by an evaporator and further subjected to methanol precipitation to obtain a white solid. The amount of this white solid was 4.73 g, and the yield was 93%.

The results of elemental analysis of the obtained white solid are shown below.

Obtained: C; 61.27 H; 5.87 N; 2.88 S; 6.64 Calculated: C; 60.38 H; 5.98 N; 3.10 S; 6.00 The IR spectrum of this white solid was measured. As a result, absorption attributable to a urethane wavenumber ^1720cm-1 is also absorbed attributable to carbonate wavenumber ^1740cm-1, but also, the absorption attributable to C-S bond in the vicinity of a wave number of ^760cm-1, wave number 2560cm ^{chromatography The} absorption attributed to the SH bond was confirmed near ¹ respectively.

The glass transition point of this white solid is 7
8.1 ° C.

The weight average molecular weight of this white solid is:
It was 8.0 × 10 ⁴ , and the degree of dispersion of the molecular weight distribution was 1.49.

<Preparation of Film> The white solid obtained by the above synthesis is dissolved in a solvent so as to be 10% (w / v). A glass plate is placed in an oven at 60 to 70 ° C. in advance, and the solution is spread on the plate. The plate was left at a temperature of 60 to 70 ° C. overnight to produce the white solid film.

The refractive index of this film was measured.
The refractive index is 1.797 (z: 1.801, x: 1.80)
0, y: 1.795). It can be understood that the polyurethane of the present invention has low birefringence and a higher refractive index than conventional ones.

[0061]

As is apparent from the above description, the polyurethane of this application is a polyurethane synthesized by reacting a diisocyanate with one or more specific diols. Therefore, a polyurethane exhibiting a higher refractive index than that of the related art is realized.

Further, it exhibits at least the same low birefringence, high transparency, and appropriate mechanical strength required for eyeglass lens materials and contact lens materials as in the prior art. Also,
High hardness required for eyeglass lens materials, high flexibility required for contact lens materials, high oxygen permeability, and biocompatibility are also obtained. Therefore, a lens material for eyeglasses and a contact lens material which are superior to conventional materials are realized.

Further, according to the polyurethane production method of the present application, it is possible to efficiently produce a polyurethane which is provided with biocompatibility and which is superior to the conventional lens materials for eyeglasses and contact lenses.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G02B 1/04 G02B 1/04 G02C 7/02 G02C 7/02 7/04 7/04

Claims (26)

[Claims] A polyurethane synthesized by reacting a diisocyanate with a diol or dithiol represented by the following formula (1) (provided that R ¹ and R ² in the formula (1) Is a hydrogen atom, a methyl group or a phenyl group, and may be the same or different.
R ³ , R ⁴ , R ⁵ , and R ^{6 are} each a hydrogen atom or a halogen atom, and may be the same, partially different, or all different. X is an oxygen atom or a sulfur atom. ). Embedded image 2. Polyurethane, characterized by being synthesized by reacting a diisocyanate, a diol or dithiol represented by the following formula (1), and a polymer diol represented by the following formula (2): , R ¹ and R in the formula (1)
² each is a hydrogen atom, a methyl group or a phenyl group,
Each may be the same or different. Also, R ³ , R ⁴ , R
Each of ⁵ and R ⁶ is a hydrogen atom or a halogen atom, and may be the same, partially different, or all different. X is an oxygen atom or a sulfur atom. Also,
(2) X in the formula is a polycarbonate skeleton, a polyester skeleton or a polybutadiene skeleton. ). Embedded image 3. The polyurethane according to claim 1, wherein each of R ^{1 to} R ⁶ is a hydrogen atom. 4. The polyurethane according to claim 3, wherein the high molecular weight diol is a diol having a polycarbonate skeleton and having a weight average molecular weight of 500 to 9000 and represented by the following formula (3). Embedded image 5. The polyurethane according to claim 3, wherein the polymer diol is a diol having a polyester skeleton and having a weight average molecular weight of 1,000 to 4,000 and represented by the following formula (4). Embedded image 6. The polyurethane according to claim 3, wherein the high molecular weight diol is a diol having a polybutadiene skeleton and having a weight average molecular weight of 500 to 3000 and represented by the following formula (5). Embedded image 7. The polyurethane according to claim 3, wherein the high molecular diol is a diol having a polyester skeleton and having a weight average molecular weight of 500 to 5,000 and represented by the following formula (6). Embedded image 8. The polyurethane according to claim 3, wherein the high molecular weight diol is a diol having a polyester skeleton and having a weight average molecular weight of 500 to 3000 and represented by the following formula (7). Embedded image 9. The polyurethane according to claim 3, wherein the high molecular diol is a diol having a polyester skeleton and having a weight average molecular weight of 500 to 5,000 and represented by the following formula (8). Embedded image 10. A polyurethane having a repeating unit represented by the following formula (10) (wherein each of R ¹ and R ² in the formula (10) is a hydrogen atom, a methyl group or a phenyl group) , May be the same or different.
Further, each of R ³ , R ⁴ , R ⁵ , and R ⁶ is a hydrogen atom or a halogen atom, and may be the same, partially different, or all different. Y is an oxygen atom or a sulfur atom. X is an aryl group or an alkylene group which is a residue of diisocyanate. ). Embedded image 11. A repeating unit represented by the following formula (10) and a compound represented by the following formula (1) having a weight average molecular weight of 500 to 4,000.
(1) wherein each of R ¹ and R ² in the formula (10) is a hydrogen atom, a methyl group or a phenyl group, and R ³ , R ⁴ , R ⁵ ,
Each R ⁶ is a hydrogen atom or a halogen atom, and may be the same, partially different, or all different. Also, Y
Is an oxygen atom or a sulfur atom. X is an aryl group or an alkylene group which is a residue of diisocyanate. (11) In the formula, X is an aryl group or an alkylene group which is a residue of diisocyanate. ). Embedded image 12. The polyurethane according to claim 1, wherein the diisocyanate is a diisocyanate represented by the formula: OCN-R-NCO (wherein R is a diphenylmethane group that can have an alkyl group or a dicyclohexylmethane group that can have an alkyl group.). 13. A reaction between a diisocyanate, a diol or dithiol represented by the following formula (1), a polymer diol represented by the following formula (2), and a diol represented by the following formula (9): polyurethane, characterized in that it is synthesized (wherein, R ^1, R ² wherein each of (1) is a hydrogen atom, a methyl group or a phenyl group, may be different even each other are the same. in addition, R ³ , R ⁴ , R ⁵ , and R ^{6 are} each a hydrogen atom or a halogen atom, and may be the same, partially different, or all different, and X is an oxygen atom or a sulfur atom. X in 2) is a polycarbonate residue, a polyester residue or a polybutadiene residue, and n in the formula (9) is 1 to 20). Embedded image 14. The polyurethane according to claim 13, wherein the ratio of the diol represented by the formula (1) to the total amount of the diols represented by the formulas (1), (2), and (9) is 5 to 5. A polyurethane characterized by 90% by mole, 5 to 90% by mole of a diol represented by the formula (2), and 5 to 90% by mole of a diol represented by the formula (9). 15. The polyurethane according to claim 13, wherein the ratio of the diol represented by the formula (1) to the total amount of the diols represented by the formulas (1), (2), and (9) is 30 to 30. 80% by mole, a ratio of the diol represented by the formula (2) is 10 to 50% by mole, and a ratio of the diol represented by the formula (9) is 10 to 40% by mole. 16. A repeating unit represented by the following formula (10) and a compound represented by the following formula (1) having a weight average molecular weight of 500 to 4,000.
A polyurethane having a repeating unit represented by the formula (1) and a repeating unit represented by the following formula (12) (provided that R ¹ and R ² in the formula (10) each represent a hydrogen atom or a methyl group) And R ³ , R ⁴ , R ⁵ , and R ^{6 are} each a hydrogen atom or a halogen atom, and are the same or partially different, and all are different. Further, Y is an oxygen atom or a sulfur atom, X is an aryl group or an alkylene group which is a residue of diisocyanate, and X in the formula (11) is a residue of diisocyanate. And an aryl group or an alkylene group.
X in 2) is an aryl group or an alkylene group which is a residue of diisocyanate, and Z is an alkylene group having 1 to 20 carbon atoms. ). Embedded image 17. The polyurethane according to claim 16, wherein the repeating unit represented by the formula (10) and the formula (1)
The formula (10) with respect to the total amount of the repeating unit represented by 1) and the repeating unit represented by the formula (12)
Wherein the proportion of the repeating unit represented by the formula (5) is 5 to 90 mol% and the proportion of the repeating unit represented by the formula (11) is 5 to 90 mol%. 18. The polyurethane according to claim 16, wherein the repeating unit represented by the formula (10) and the formula (1)
The formula (10) with respect to the total amount of the repeating unit represented by 1) and the repeating unit represented by the formula (12)
Is 30 to 80 mol%, the proportion of the repeating unit represented by the formula (11) is 10 to 50 mol%, and the proportion of the repeating unit represented by the formula (12) is 10 to 40 mol%. A polyurethane characterized by the following. 19. The polyurethane according to claim 16, wherein the repeating unit represented by the formula (10) and the formula (1)
The formula (10) with respect to the total amount of the repeating unit represented by 1) and the repeating unit represented by the formula (12)
Is 5 to 90 mol%, and the proportion of the repeating unit represented by the formula (11) is 5 to 90 mol%.
And a proportion of the repeating unit represented by the formula (12) is 5 to 90 mol%. 20. The polyurethane according to claim 1, wherein the polyurethane has a weight average molecular weight of 10,000 to 300,000. 21. The polyurethane according to claim 1, which has a refractive index of 1.78 or more. 22. A lens material for spectacles, comprising the polyurethane according to claim 1. Description: 23. A contact lens material comprising the polyurethane according to any one of claims 1 to 21. 24. A spectacle lens comprising the polyurethane according to any one of claims 1 to 21. A lens for a contact lens, comprising the polyurethane according to any one of claims 1 to 21. 26. A urethane prepolymer obtained by reacting a diol represented by the following formula (1) with a diol represented by the following formula (2) and an organic diisocyanate, and a urethane prepolymer represented by the following formula (9) A method for producing a polyurethane, comprising reacting a diol with a diol. Embedded image