JPH01201306A - Optical material - Google Patents

Abstract

PURPOSE:To provide an optical material having a low water absorptivity, excelling in optical homogeneity, abrasion resistance, etc., and suited for lenses, optical disc bases, etc., by constituting it from a (co)polymer of a specified alicyclic (meth)allyl ether compound. CONSTITUTION:This optical material is prepared from a polymer of a compound of formula I (wherein R1 and R2 are each H or methyl, l is 1-3, m and n are each 0-8, and 0<=m+n<=8), e.g., formula II or III, or a copolymer of this compound with a copolymerizable compound (e.g., ethylene glycol diacrylate). Said compound of formula I is produced by reacting a diol of formula IV (wherein l is 1-3) or a diol of formula V (wherein p and q are each 0-8, and 1<=p+q<=8) each of which is derived from an adduct of cyclopentadiene is converted into a dialkoxide with, for example, sodium hydride and reacting this dialkoxide with an allyl halide and/or methallyl halide.

Description

[Detailed description of the invention] <Industrial application field> The present invention has low water absorption, optical uniformity, heat resistance, 4Q This invention relates to optical materials with excellent wear resistance.

<Prior Art> Synthetic resins have advantages over glass, such as being lightweight, having excellent moldability, and being mass-producible.In recent years, synthetic resins have been used for lenses. Demand for optical materials such as rhythm and optical disk substrates is increasing.

Conventionally, as optical materials, thermoplastic resins such as polystyrene resin, methyl methacrylate resin, I-recarbonate resin, and thermosetting resins such as diethylene glycol bisallyl carbonate have been used.

<Problems to be Solved by the Invention> However, the above resins do not have all of the optical uniformity, low water absorption, heat resistance, and abrasion resistance required of optical materials. For example, when each of the above resins is used for lenses, optical disk substrates, etc., /IJ styrene has poor optical uniformity, heat resistance, and abrasion resistance, and polymethyl methacrylate has problems with water absorption and heat resistance. .

Polycarbonate lacks optical uniformity, and diethylene glycol bisallyl carbonate has a large water absorption property, so it is easily deformed by water absorption.

In order to improve these drawbacks, Japanese Patent Application Laid-Open No. 61-2879
In Publication No. 13, bis(oxymethyltricyclo(
An optical material made of a copolymer of 5,2,1,0''' E-decane di(meth)acrylate and fullkylene glycol di(meth)acrylate has been proposed. However, the copolymer of this alicyclic compound Although there are improvements in low water absorption, heat resistance, and abrasion resistance, optical materials made of This method has the disadvantage of poor uniformity, which poses a practical problem.

The purpose of the present invention is to overcome the drawbacks of the conventional optical materials made of synthetic resins, to have various physical properties desired as optical materials such as optical uniformity, low water absorption, heat resistance, and abrasion resistance. The objective is to provide a well-balanced optical material.

tth Means for Solving the Problem> As a result of intensive research in view of the current situation, the present inventors have found that
We have found a means to solve the problem and have arrived at the present invention.

) That is, the gist of the present invention is a polymer of at least one compound selected from the compounds represented by the following general formula (I), or a compound represented by the following general formula (I) and the compound. This is an optical material characterized by being made of a copolymer of a compound and another copolymerizable compound.

[In the formula, R1 and R2 are the same, or t is different, and the hydrogen atom is a methyl group. A#i indicates an integer from 1 to 3. m and n represent integers of 0 to 8. We are friends, m and 1
The total number of is O≦m−)−n≦8. ] The compound represented by the general formula (I) is an alicyclic (meth)allyl ether compound, and is a diol represented by the following general formula (I) derived from an adduct of cyclopentadiene. A long-chain diol represented by the following general formula (III) obtained by synthesizing the diol and ethylene oxide using a basic catalyst is mixed with dialkoxy using, for example, sodium hydrite, and then 1, for example, allyl bromide is added. 71 full halide and/or may be obtained by reacting methallyl halide such as methallyl chloride.

[In the formula, t represents an integer of 1 to 3. ] [In the formula, t represents an integer of 1 to 3. p and q are θ~8
indicates an integer. t, total number of p and q 1≦p+q
≦8. ] Specific examples of the compound represented by the general formula (I) include the following. Two or more of these alicyclic (meth)allyl ether compounds may be used in combination.

The alicyclic (meth)allyl ether compound represented by the above-mentioned (I) can be used to adjust the viscosity of the compound and improve the hardness, impact resistance, etc. of the polymer. Other compounds copolymerizable with can be blended. Any other compound may be used as long as it has radical polymerizability, forms a three-dimensional network structure, and does not impair the transparency of the polymer after polymerization. Specific examples include the following.

(I) Allyl compounds and allylidene compounds ethylene dalycol bisallyl carbonate, diethylene glycol bisallyl carbonate (CR-39),
) 17 ethylene glycol bisallyl carbonate,
Tetraethylene glycol bisallyl carbonate, Hentaethison glycol bisallyl carbonate, polypropylene glycol bis7lyl carbonate, trimethylene glycol bisallyl carbonate, 3-hydroxyl glycol bisallyl carbonate, glycerin bis Allyl Cargonate, Triglycerin Bisallyl Cargonate, Zoallyl Cargonate,
Diarylidene (metaerythritol, triarylidene sorbitol, diarylidene-2,2,6,6-titramethylolcyclohexanone, triarylidene hexamethylol melamine, diarylidene-D-glucose, bisphenol A-/allyl ether, bisphenol S diallyl ether, ethylene glycol Diallyl ether, diethylene glycol diallyl ether, triethylene dalycol diallyl ether, 18111-) Rimer? el - Ruderono Tsuen) +77 Lil Ether,
tx is a preliminary reaction product of neohentyl glycol diaryether, diallyl phthalate, triallyl isocyanurate, etc.

[l] (Meth)acrylate compounds ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, glycerin di(meth)acrylate
acrylate), 1-(meth)acryloyl-2-hydroxy-3-(meth)acryloylgulonone, pentaerythritol tetra(meth)acrylate, 1,1.1
-Trimethylolguronoyatri(meth)acrylate, 947 taerythritol hexaacrylate, 4g4
1-bis(2-[:2-7 chloroyloxyethyloxy]ethyloxy]-2,2-diphenylgronodan,
Hexamethylolmelamine hexa(meth)acrylate, N,N',N1-)lis(2-(meth)acryloylxyethyl)isocyanurate, neobentylglycol di(meth)acrylate, etc., or preliminary reactants thereof.

The compounds (I) and (II) above may be used in combination.

(III) The above (I) and/or t are a mixture or preliminary reaction product a) of the compound of (II) and a polythiol compound! Lithiol compound 4-taerythritol tetrathioglycolate, 1.1
．． 1- Trimethylol glonotrithioglycolate, pentaerythritol trithioglycolate, ethylene glycol dithioglycolate, diethylene glycol notiodarico L/-), triethylene glycol dithioglycolate, tetraethylene glycol dithioglycolate, neopentyl The mixing ratio of the compound [I] and/or [11) above, such as glycol dithioglycolate, and the polythiol compound is not particularly limited, but the ratio of thiol is within the range of the equivalent functional group amount with the compound of (I) or C1l]. It is preferable that it be within.

Note that the above specific examples are just a few examples used in the present invention, and the present invention is not limited to these in any way.

The mixing ratio of other compounds used in combination is determined based on the optical uniformity, low water absorption, and
Any mixing ratio may be used as long as it does not impair heat resistance etc., and it is usually at most 85 parts by weight, preferably at most 50 parts by weight, based on 100 parts of the total amount of the alicyclic (meth)allyl ether compound and other compounds. be.

At least a part of the compound selected from the alicyclic (meth)allyl ether compounds represented by the above-mentioned - Monana (I), and other compounds copolymerizable with the alicyclic (meth)allyl ether compound and said compound. The following method can be used to combine the mixture with the compound.

(I) Method using heat When the raw material compounds are polymerized using heat, a polymerization initiator may or may not be used. Specific examples of 1 combination initiators include 2.2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2.2 '-Azobisisotrichronitrile, dimethyl-2,2'-azobisinputylene), 2,2'-7zobis(2-methylpf-nitrile)
, 1.1'-azobis(I-cyclohexanecargenitrile), 2-phenyla:/-2,4-cymefk-4-
methoxypaleroni) Li/l/% 2#2'-7 Azo polymerization initiator such as zobis(2-methylzolopane), O! Hill, 1-bis(tert-butylperoxy)
-3,3,5-)limethylcyclohexane, 1.1-
Bis(tertiary-butyloxy)cyclohexane, n-butyl-4,4'-his(tertiary lactyl/benzo-oxy)valerate, r-kayl/mara-oxide, lauroyl 14-oxide, benzoyl peroxide, meta-toluoyl oxide Oxide, diisoderopirno! -oxydicar Mne), di-2-ethylhexyloxycarnate, di-normalzolobyrno-oxycarnate, dimethoxyisozolobyrno-e-oxycaranoate, cumyl-oxyneodecanoate, Tertiary Ptyrno Arm - Oxy -
Peroxides such as 2-ethylhexanoate, tert-butylperoxy-3,5,5-)listylhexanoate, ditertiarybutyldiperoxyisophthalate, tertiarybutylnoyoxyisozolopyrcarnate, etc. Examples include physical polymerization initiators.

Also, two or more of these polymerization initiators may be used in combination.

The above polymerization initiators vary depending on their type, but
It is used in an amount of 0.001 to 10 parts by weight per 100 parts by weight of the raw material compound, and preferably 0.001 to 5 parts by weight in consideration of weather resistance.

The heating temperature varies depending on whether or not a polymerization initiator is used, their type and blending ratio, but is usually between room temperature and 30°C.
0°C is preferable, but 50 to 130°C is preferable. The heating temperature may be increased in steps. If the heating temperature is lower than room temperature, the polymerization time will be longer, resulting in poor productivity.

On the other hand, if the temperature exceeds 300°C, it will deteriorate due to heat.

Nine, the heating time depends on the temperature and whether or not a polymerization initiator is used.
Although it varies depending on the type and usage ratio, it is generally 0.1 to 100 hours, and particularly preferably 1 to 20 hours.

(2) Method of irradiating active energy rays This method:
This is a method of polymerizing raw material compounds by irradiating them with active energy rays such as r-rays, X-rays, ultraviolet rays, and electron beams. The amount of irradiation energy is generally 0. OI Jlcd
' or more and 500 J/m2 or less, especially 0.
It is preferably within the range of 1 to 100 J/cm;'. The amount of irradiation energy is 0. If the OI is less than J/crs2, polymerization is incomplete. On the other hand, if irradiation exceeds 500 J/aR2, a part of the resulting polymer will deteriorate or become colored, making it impossible to obtain a good optical material.
``Irradiation may be divided into two or more times or may be performed at once. If necessary, additives such as photopolymerization initiators and stabilizers described in JP-A-58-175877 may be added. This method is described in Japanese Unexamined Patent Publication No. 5
It is described in detail in the specifications of each publication of No. 9-86001 and Japanese Patent Application Laid-open No. 59-89330.

The above method using heat and the method of irradiating active energy rays can also be used in combination.

Also, in the present invention, polymerization inhibitors, ultraviolet haze absorbers,
Antioxidants, mold release agents, antistatic agents, color-adjusting dyes, and the like can be optionally added and used.

The optical material according to the present invention is produced by a cast polymerization method or the like. A raw material compound is poured into a mold of a predetermined shape made of, for example, glass, ceramic, plastic, etc., and polymerized using the method described above.

A colored optical material can be produced by adding a dye or pigment to the raw material compound according to the present invention, or by forming a polymer and then dyeing it.

The optical materials obtained in the present invention include, for example, so-called lenses for still cameras, video cameras, telescopes, glasses, etc., optical disk substrates for VD substrates, DRAW substrates, magneto-optical disk substrates, etc. , refers to an optical element that functions by transmitting or reflecting light.

<Examples> Hereinafter, the present invention will be explained in more detail by giving Examples and Comparative Examples.

The physical properties obtained in the examples and comparative examples are as follows:
Measured using the method below.

(I) Refractive index: 20
Measure the refractive index at 9°C.

(2) Using a light transmittance spectrophotometric needle (Hitachi Model 124),
The transmittance of the sample was measured using light at a wavelength of 550 nm.

(3) Glass transition temperature T2 Viscoelasticity measuring device (Rheopyturon D manufactured by Orientic Co., Ltd.
-1 peak (inflection point) using DV-n-EP type)
By reading the value, the glass transition temperature of the sample (thickness: 0.1 mm) was determined.

(4) Sample with +0000 steel wool at abrasion resistance load soo, p (
Thickness 3-) Surface t-10 reciprocating rubbing, Irf lever h without scratches, diethylene glycol bisallyl carmenate resin grade B, intermediate between diethylene glycol bisallyl carmenate resin and pre-methyl methacrylate resin C
1 polymethyl methacrylate resin was designated as D.

(5) Polymerization unevenness A glass mold of 80 mm diameter was assembled with a gasket to a thickness of 15 m, and during polymerization according to the conditions of the example, the presence or absence of polymerization unevenness due to oxygen inhibition that appeared especially in the peripheral area was checked.

(6) Using a sample piece of water absorption JIS-K-7209,
The rate of weight increase when the sandals were dried under reduced pressure for one day and immersed in water at 100° C. for 2 hours is shown based on the dry weight.

Examples 1 to 10 Other compounds that can be copolymerized with the telecycloaliphatic (meth)allyl ether compounds shown in Table 1 and the eam (meth)allyl ether compounds shown in Table 2 are shown in Table 3. To 100 parts by weight of the raw material compounds blended in the following proportions, 3.5 parts by weight of diisopropyl oxydicargenate was added and dissolved with stirring. After filtering this monomer solution, it was degassed at 15 Hg for 30 minutes using a vacuum I ring. Injected into a T-type assembled to a thickness of .11, the temperature was raised at 3°C/hour from 35°C to 50°C, the temperature was raised at 6°C/hour from 50°C to 80°C, and from 80°C to 900°C. The temperature was raised at 10°C/hour, then held at 90°C for 3 hours, and after step 7, removed from the mold.
Annealed at 100℃ for 1 hour. The casting, polymerization, and annealing steps were all performed in normal atmospheric conditions. Obtained polymer (flat plate)
is colorless and transparent. The physical properties of each polymer of Examples 1 to 1O are shown in Table 4.

Table 2 Table 3 Comparative Example 1 Polymerization was carried out in the same manner as in Example 1, except that diethylene glycol bisar 1'alkate was used in place of the alicyclic allyl ether compound used in Example 1. Obtained union. Physical property values are shown in Table 4.

Comparative Example 2 0.2 parts by weight of azobisisobutyronitrile was added to 100 parts by weight of methyl methacrylate, and the mixture was thoroughly dissolved and mixed. This monomer solution was filtered in the same manner as in Example 1,
Degassed, cast, held at 35℃ for 6 hours, and then heated to 50℃ from 35℃.
℃ to 2.5℃/hour, 50℃ to 80℃ 6
The temperature was raised at 80°C/hour, then held at 80°C for 2 hours, and after t0 demolding, annealing was performed at 80°C for 1 hour to obtain a polymer. Physical property values are shown in Table 4.

Comparative Example 3 100 parts by weight of 4.8-bis(methacryloyloxymethyl)tricyclo(5,2,1,021′)decane,
Benzoyl peroxide 1. A polymer was obtained in the same manner as in Comparative Example 2, except that 1 part of θ polymer was dissolved and mixed and the monomer was used. Physical property values are shown in Table 4.

Table 4 <Effects of the Invention> The optical material of the present invention has excellent optical uniformity, heat resistance, abrasion resistance, etc., and low water absorption compared to conventional optical materials, and can be used as an optical material. It is an extremely well-balanced optical material that satisfies all required properties. Therefore, the lens! It can be widely used in rhythm, optical disk substrates, and other applications that require transparency.

Patent applicant: Showa Denko Co., Ltd.

Claims (1)

[Claims] 1. A polymer of at least one compound selected from the compounds represented by the following general formula (I), or a polymer copolymerizable with the compound represented by the following general formula (I). An optical material characterized by being made of a copolymer with a chemical compound. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, R_1 and R_2 are the same or different and are hydrogen atoms or methyl groups. l represents an integer of 1 to 3. m and 1 represent integers of 0 to 8. However, the total number of m and n is 0≦m+n≦8. ]