JPS60188426A - Material for optical instrument and device - Google Patents

Abstract

PURPOSE:The titled material having a small photoelastic constant and a high sensitivity of reading information recorded on a disk, obtained by reacting a specified compound with a halogenated methane. CONSTITUTION:4,4'-Dihydroxytetraphenylmethane of formula I , 1-phenyl-1,1-bis(4- hydroxyphenyl)ethane of formula II, or a compound of formula III (wherein m is 4-10) is reacted with a halogenated methane (e.g., CH2Cl2) in the presence of a catalyst and an MW modifier to obtain a material for optical instruments and devices comprising a polyformal polymer having repeating units of formula IV(wherein R<1> is a group of one of formulas V-VII) and a reduced viscosity [etasp/ c] as measured in a methylene chloride solution at a concentration of 0.5g/dl at 20 deg.C, >=0.2dl/g. USE:Audiodisk and optical memory disk.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an optical device 6 material, and particularly to a material suitable for digital audio discs and optical memory discs.

Generally, materials for optical devices as mentioned above are required to have various performances, such as transparency, heat resistance, moisture resistance, excellent mechanical strength, and optical properties such as low photoelastic coefficient. things are suitable. Although methacrylic resin and the like have been known as materials having such properties, this material has the disadvantage that it is still difficult to say that it is sufficient in terms of heat resistance, moisture resistance, and impact resistance. In addition, polycarmenate resin obtained by reacting bisphenol A (2,2-bis(4'-hydroxyphenyl)propane) with phosgene, diphenyl carbonate, etc. has excellent heat resistance, moisture resistance, and impact resistance. However, since the photoelastic coefficient is large, birefringence becomes large due to this, and there are problems in that the sensitivity of reading information recorded on the disk decreases and errors occur.

The purpose of the present invention is to provide a material for optical equipment that eliminates the above-mentioned conventional drawbacks, and in particular, to provide a material for optical equipment that has a small photoelastic constant as an optical property and has high sensitivity for reading information recorded on a disk. The purpose is to provide

That is, the present invention first shows any one of the general formulas. However, m indicates 4 to 10. ), and the concentration is 0.5P/J.
The reduced viscosity at 20°C of a methylene chloride solution of ['7
sp/') is o, 2''/tJA on o Ho!J
The present invention provides a material for optical equipment made of a hopv Y medium-based polymer.

5- Furthermore, the present invention secondly shows the general formula. However, m represents 4 to 1o. ) and the general formula. However, m represents 4 to 1o. ), and the repeating unit C
When the molar fractions of I) and [■] are 4- and t, respectively, the value of 2/10t exceeds 0.5, and the tyrene chloride solution has a concentration of 0.5 f/di. The reduced viscosity [η, 1p10) at 20°C of
．． The present invention provides a di material for optical equipment made of a polyformal copolymer with a yield of 2 dl/f or more.

In the first aspect of the present invention, the degree of polymerization of the polyformal polymer having the above-mentioned repeating unit [I] may be appropriately selected depending on the type of optical equipment. Reduced viscosity at 2o”C [ηsp/
a) is 0.2d/1 or more, preferably 0.6 to 0.
It should be polymerized so that it becomes 8 dl/f.

In addition, m is 4 to 1° in the above repeating unit CI), but if m is less than 4, the fluidity of the obtained polymer during molding will decrease, and if m is less than 10
Exceeding this is not preferable because heat resistance decreases.

Moreover, the second invention has the repeating unit (II) in addition to the repeating unit CI in the first invention.
It is made of a fluoroformal copolymer. In the second aspect of the present invention, the repeating unit [■] is adjusted to contain more than 50% of the total mole fraction. That is, the mole fraction of the above-mentioned repeating unit CI) is adjusted so that the value of t exceeds 0.5, where t is the mole fraction of one repeating unit [■]. The value of 10t in k/ is 0
．． If it is less than 5, the photoelastic constant and moldability decrease, resulting in an increase in birefringence due to molding distortion, which is not preferable.

In the second aspect of the present invention, the degree of polymerization of the polyformal copolymer having the repeating unit CI) and the repeating unit (If) may be appropriately selected depending on the type of optical equipment. As in the invention, the reduced viscosity [ηap
/O) is 04#/7 or more, preferably 0.5 to 0.8
It should be polymerized so that it becomes dt/f.

The polyformal polymer having the above-mentioned repeating unit [I] can be produced by various methods, and for example, 4,4'-dihydroxytetra-7enylmethane.

1-phenyl-1,1-bis(4-hydroxyphenyl)ethane having the formula (wherein m is the same as above) is added to a suitable catalyst (9) and a molecular weight regulator. It can be produced by reacting with halogenated methylene such as OH204+ OH2B rfi, or by reacting this halogenated methylene with a base such as NaOH. Here, various molecular weight modifiers can be used, and examples thereof include (P3 represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group). In addition, the degree of polymerization of the polyformal polymer having the above-mentioned repeating unit CI) can be made to be as described above by appropriately selecting the amount of halogenated methylene, etc., without using a molecular weight regulator. can.

In addition, there are various compounds represented by the above general formula [■], but for example, 1,1-bis(4-hydroxy7E B
- cyclopentane.

1,1-bis(4-hydroxyphenyl) represented by the formula
Cyclohexane.

1,1-bis(4-hydroxyphenyl) represented by the formula
Examples include cycloheptane.

Furthermore, polymers having the above-mentioned repeating unit [11) can also be produced by various methods, such as 4,4'-dihydroxytetraphenylmethane represented by the above-mentioned formula Cm), and 4,4'-dihydroxytetraphenylmethane represented by the formula (IV). 1-phenyl-1
, 1-bis(4-hydroxyphenyl)ethane and a compound represented by the general formula [■], using phosgene. In addition to the method for producing polycarbonate using the phosgene method, it can also be carried out according to the method for producing polycarbonate using the transesterification method using diphenyl carbonate, etc.1 Therefore, the repeating unit (CI) as well as the repeating unit
In order to produce the second polyformal copolymer of the present invention having II), for example, as described above, 4,4'-dihydroxytetraphenylmethane represented by the formula Cm), 4,4'-dihydroxytetraphenylmethane represented by the formula [, IV) 1-7 enyl 1,1-bis(
4-Hydroxyphenyl)ethane and a compound represented by the general formula (V), alone or in a mixture thereof, are reacted with halogenated methylene, etc. to produce a polyformal-based low polymer having linear return units CI). It is sufficient to produce a polycondensate, and polycondense the terminal 7-enolic hydroxyl group using phosgene or the like.

Although the conditions for this polymerization cannot be determined uniquely depending on the degree of polymerization of the desired copolymer, etc., a suitable catalyst bimolecular regulator may generally be used. Here, the molecular IT regulators include those mentioned above.

The repeating unit CI) constituting the second polyformal copolymer of the present invention is 4゜4'-dihydroxytetraphenylmethane represented by formula (m), 1-phenyl-1 represented by formula [IV), It is formed by the reaction of 1-bis(4-hydroxyphenyl)ethane and any of the compounds represented by the general formula (V) with halogenated methylene, etc., and the repeating unit (n) is represented by the formula [1]. 4 represented
, 4'-nohydroxytetraphenylmethane formula 1 (IV
) is formed by the reaction of 1-phenyl-1,1-bis(4-hydroxyphenyl)ethane represented by formula [V] with phosgene or the like.

Therefore, repeating units CI), (II
), 4°4'-dihydroxytetraphenylmethane of formula (III), 4°4'-dihydroxytetraphenylmethane of formula (III),
1-phenyl-1,1-bis(4-
The amount of hydroxyphenyl)ethane and the compound represented by the general formula (V) to be used may be appropriately selected, and the type of the compound represented by the above general formula EV) can also be changed to the desired repeating unit CI) or repeating unit mark] Depending on the type of
It may be selected from the above-mentioned Specification 1] or other than Specification 1-11-.

In addition, when molding a disk or the like using the material for optical equipment of the present invention, usual additives such as antioxidants and ultraviolet absorbers may be added.

The first polyformal polymer of the present invention obtained in this way has a smaller photoelastic constant than conventional polycarbonate resins, and a molded article with a smaller optical birefringence can be obtained. In addition, this polymer has heat resistance that is equivalent to or slightly inferior to conventional polycarbonate resins, but is sufficiently higher than that of methacrylic resins (glass transition temperature: 105°C).

Furthermore, the second polyformal copolymer of the present invention is significantly superior to conventional polycarbonate resins in both photoelastic constant and heat resistance.

Therefore, if the polyformal polymer or copolymer of the present invention is used as a material for various optical devices, the improved optical properties will improve the reading sensitivity of information recorded on the disk, and error 12- Since it is a material that has good thermal and strength properties, optical devices that are made using it operate stably under a variety of conditions.

Therefore, the material of the present invention can be effectively used as a material for optical equipment such as digital audio discs and optical memory discs.

Next, the present invention will be explained with reference to examples.〇Example 1 4.4'-dihydroxytetraphenylmethane 55.2
7 (0.1 mol), methylene chloride 40 fco, 47
mole), sodium hydroxide 16. A mixture of o'j (o, 4 mol) and 80 icj of N-methylpyrrolidone was reacted for 5 hours at 80'C with stirring.

After the reaction was completed, the product was diluted with 200 d of methylene chloride, washed successively with dilute hydrochloric acid and water, and then poured into methanol to precipitate and collect the polymer.

The resulting polymerized product had a reduced viscosity of C? measured at 2o'C for a solution of concentration o and 5i/# using methylene chloride as a solvent. sp/a) was 0.46 dt/l.

Moreover, the glass transition temperature of this polymer was 160°C. Furthermore, this polymer was press-molded at 500''C to form a sheet with a wall thickness of about 0.5 mm, and the photoelastic constant was measured at a wavelength of 635 mm, and it was found to be 26.6 x 10
-" CD/dyne.

Example 2 The same procedure as in Example 1 was carried out except that 26.87 (0.1 mol) of bis(4-hydroxyphenyl)cyclohexane was used in place of 4,4'-dihydroxytetraphenylmethane. A polymer was obtained.

The reduced viscosity [ηsp/O) at 20°C of a methylene chloride solution with a concentration of 0.5 f/dl of the obtained polymer is o, 4
5 dll? Met. Further, the glass transition temperature of this polymer was 116°C. Furthermore, when the photoelastic constant was measured in the same manner as in Example 1, it was 50. Ox 1o −
” It was CD/Dyne.

Example 5 4.4'-dihydroxytetraphenylmethane 55.2
A mixture of 7 (0.1 mol), methylene chloride 25SNo, 5 mol) and N-methylpyrrolidone (40 tt+l) was heated with stirring and reacted under reflux for 1 hour.

After the reaction was completed, the reaction product was diluted with 100 d of methylene chloride, washed with dilute hydrochloric acid and then with water, and then poured into methanol to precipitate and recover a polyformal low polymer.

The obtained polyformal low polymer was mixed with 150% methylene chloride.
It was dissolved in a mixed solvent of Kl and 5 oiu of pyridine, 200 Hl of phosgene gas was blown into it at room temperature, and the mixture was reacted for 1 hour. After the reaction is complete, the product is diluted with 1N salt i! The resin was washed successively with water and water, and then poured into methanol to precipitate and recover the polyformal/polycarbonate resin.

The reduced viscosity ('7 sp/O) of the resulting resin in methylene chloride solution with a concentration of 0.5 p/J at 20°C is '
0.56 dll 54, and the glass transition temperature was 189°C. Furthermore, when the photoelastic constant was measured in the same manner as in Example 1, it was found that 2 C5X 10-'cd
/dyne.

Comparative Example 1 A polycarbonate resin was produced using 15-2.2-bis(4-hydroxyphenyl)propane by a normal phosgene method. The reduced viscosity [η8p10] of a methylene chloride solution with a concentration a and 5 f/dl at 20°C is 0.
．． 51 J/p, and the glass transition temperature is 148
It was ℃. Furthermore, when the photoelastic constant was measured in the same manner as in Example 1, it was found to be 71.9X 1 o ” cd/
It was dyne.

Patent applicant: Idemitsu Kosan Co., Ltd. 16 one

Claims (1)

[Claims] 1. Any of the general formulas is shown. However, m indicates 4 to 10. ), and has a concentration of 0.5 f/d.
Reduced viscosity (?) of methylene chloride solution of i at 20°C
An optical equipment ml material made of a polyformal polymer having ap/O) of o, 2 dl/g- or more. Show either of the two general formulas. However, m indicates 4 to 10. ) and any of the general formulas are shown. However, m represents 4 to 10. ) has a repeating unit [■], and the repeating unit C
k/k-) where the molar fractions of I) and [II) are k and t, respectively, the value of t is greater than 0.5, and the methylene chloride solution with a concentration o, sy-/dt is Optical equipment II material made of a polyformal copolymer having a reduced viscosity C9ap/O) of 0.2 d//g or more at 20°C.