JPS6315811A - Optical resin having high refractive index - Google Patents

Abstract

PURPOSE:To obtain an optical resin excellent in transparency, high refractive index, heat resistance, impact resistance, etc., by polymerizing a monomer comprising a specified ether or ester or copolymerizing it with a radical- polymerizable vinyl monomer. CONSTITUTION:This optical resin is one obtained by polymerizing at least one monomer selected from among those of formula I (wherein A is a group of formula II, III, IV or the like, R1 and R2 are each H or methyl, m and n are each 0 or an integer of 1-10) or copolymerizing at least one of said monomers with a radical-polymerizable vinyl monomer. Examples of said vinyl monomers include styrene, alpha-methylstyrene, divinylbenzene and alkyl(meth) acrylates. The proportion of the radical-polymerizable vinyl monomer in the copolymer is preferably 1,000-1pt.wt. per 100pts.wt. monomer of formula I.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to an optical resin having a high refractive index, and more particularly, to an optical resin having excellent heat resistance and impact resistance. Regarding resin for use.

<Conventional technology and problems> In recent years, plastic materials have been used as a substitute for inorganic glass due to their excellent properties such as transparency, lightness, workability, and safety, and are actually used in plastic lenses and optical fibers. , optical disk substrates, etc. Taking advantage of this transparency, JF currently has polymethymethacrylate, polydiethylene glycol bisallyl carbonate-1, polystyrene, polyno J-bony-1,
... etc. are used.

However, for example, polymethylmethacrylate-1 and boridiethylene glycol bisallyl carbonate have a refractive index of n. = 1.49 to 1.50, and has low heat resistance, so when used in fields that utilize refractive index and heat resistance such as lenses, it needs to be thicker than inorganic glass. However, the field of use is limited, and the disadvantage is that it is not suitable for applications in which high-magnification total internal reflection is desired, weight reduction, and general-purpose use.

Furthermore, although polystyrene and polycarbonate have a high refractive index of around 1.58 to 1.59, these resins are thermoplastic and therefore lack heat resistance.During molding, optical distortion due to birefringence is likely to occur. There is a problem,
Other drawbacks include poor solvent resistance and scratch resistance.

Recently, it has been proposed to use a crosslinking agent having a high refractive index as a main component or a modifier in order to improve these conventional drawbacks.

For example, divinylbenzene, diallyl phthalate (JP-A-59-81318).

Dimethacrylate with bisphenol A (JP 55-13747), diallyl carbon-1 with bisphenol 8 (JP 56-166214, )
An example is given in which a polyfunctional monomer such as the following is used as a main component or a copolymer component. However, when divinylbenzene is used as a crosslinking agent, a resin with a high refractive index can be obtained, but the impact resistance is extremely low (IF!).
J m and other diallylphthale-1-, bisphenol-8-containing dimethacrylate t9 and diallyl carbonate are used, the refractive index of the cured resin is 1.
There was a drawback that the value was as low as 52 to 1.57.

<Objective of the Invention> 7 The object of the present invention is to provide an optical 11*1 resin which is excellent in transparent P1, +l'l+ All refractive index, heat resistance, impact resistance, etc.

<Lower 1st step for solving the problem> According to the present invention, the general formula 〇→ 0−+cH2+WO−,0fCH2CHOkR,R2
, represents hydrogen or a methyl group, m and n are O or 1 to 10
A high refractive index product obtained by polymerizing one or more monomers represented by (representing an integer of Provided is an optical resin having a

Hereinafter, the present invention will be explained in detail.

According to the present invention, the Ill mer represented by the following general formula (I) (% formula % R-, Rz represents hydrogen or a methyl group, m, n4 represents O or an integer from 1 to 10) Use type 1 or type 2 inserts. MatabanyonlmaO or 1
It is an integer from 10 to 10, but if it exceeds 10, the refractive index will drop significantly and the heat resistance will deteriorate, so it cannot be used. A force 1-o-(cx-h, radiation o-,
-o-+cn2CI-■oy.

Specific examples of R2 include ethylene glycol distyryl methyl ether, 1. /]-butanediol distyryl methyl ether, diethylene glycol distyryl methyl ether, propylene glycol distyryl methyl ether, dipropylene glycol distyryl methyl ether, 2,2-bis(4-styryl methyloxy)
-xyphenyl)propane, di(4-styrylmethyloxyel-1-xyphenyl)methane, 2,2'-bis(4
-styrylmethyloxypropoxyphenyl)propane, 2,2'-bis(/I-styrylmethyloxy1-lye1-xyphenyl)propane, 2,2'-bis(4
-styrylmethyloxypropoxyphenyl)propane, 2,2'-bis(4-styrylmethyloxydipropoxyphenyl)propane, di(4-styrylmethyloxydipropoxyphenyl)methane, and the like. To synthesize this monomer, chloromethylstyrene and a given diol, such as ethylene glycol, diethylene glycol, propylene glycol, 4,4'-
It is obtained by heating and reacting dihydroxyethylbisphenol A and the like in the presence of a base such as sthorium hydroxide, potassium hydroxide, pyridine, or 1-ethylamine M. In this case, a solvent, a polymerization inhibitor, etc. may be used as appropriate.

A in the above general formula (I) has an unsaturated group and does not have to be 1'J, but it is better to have an unsaturated group to improve the refractive index and heat resistance of the polymer when 1F is combined. It would be nice if she had a good gender. As a specific example,
Malonic acid di(styrylmethyl) ester, succinic acid di(
styrylmethyl) ester, maleic acid di(styrylmethyl) ester, fumaric acid di(styrylmethyl) ester, itaconic acid di(styrylmethyl) ester, citraconic acid di(styrylmethyl) ester, mesaconic acid di(styrylmethyl) ester,
Examples include styrylmethyl) ester, orthophthalic acid di(styrylmethyl) ester, isophthalic acid di(styrylmethyl) ester, and terephthalic acid di(styrylmethyl) ester. To synthesize these monomers, chloromethylstyrene and a given dicarboxylic acid are hydroxylated.
It can be obtained by carrying out a reaction at room temperature or with heating in the presence of a base catalyst such as -lium, potassium hydroxide, pyridine, or triethylamine. In this case, it is preferable to use a solvent and a polymerization inhibitor in combination as appropriate.

In the present invention, one of the monomers represented by general formula (I)
The species or two or more monomers are polymerized or one of the monomers is
The species or two or more species are copolymerized with a radically polymerizable vinyl monomer. Such radically polymerizable vinyl monomers (e.g. styrene).

Methyl nucleus substituted styrene, halogen nucleus substituted styrene, α-
Methylstyrene, divinylbenzene, alkyl (meth)
to acrylate-1, phenyl (meth)ai-1 rylate, benzyl (meth)acrylate, vinyl benzoate, vinyl acetate, acrylonitrile, ethylene glycol di(meth)acryle-1-, diethylene glycol di(meth)acrylate-1-, bisphenol A dimethacrylate-1~,
2,2-bis(4-(meth)acryloyloxy1~
A mixture of one or more of (xyphenyl)propane, diallyl phthalate (1), diethylene glycol bisallyl carbonate (1), etc. is used (I'). radical i
f (composite 11 of the synthetic vinyl monomer (as a present ratio,
It is desirable to use 1 part by weight of 1 part by weight per 100 parts by weight of lli represented by the general formula (I).

The polymerization or copolymerization is carried out by a radical polymerization method using a general radical polymerization initiator, and can be carried out by known techniques such as bulk polymerization, suspension polymerization, and emulsion polymerization. Polymerization or copolymerization is carried out using diisopropyl peroxydicarbonate 1 to 1 as a radical initiator.
-butylperoxypivale-1-, isobutyryl peroxide, benzoyl peroxide, lauroyl peroxide,
This can be carried out using azobisisobutyronitrile, azobisdimethylvaleronitrile, persulfates, persulfate-bisulfite systems, and the like. It is desirable to use the radical polymerization initiator in an amount of 0.01 to 10% by weight, more preferably 0.1 to 5% by weight based on the total monomer weight, and 0.3 to 72% by weight at a polymerization temperature of 20 to 100°C. It is desirable to react for about an hour.

<Effects of the Invention> The optical resin having a high refractive index of the present invention is a crosslinkable monomer with a molecular structure in which two polymerizable styrene units are bonded together by a long molecular chain, and is made by radical polymerization. When polymerized, optical crosslinkable resins with transparency, high refractive index, and heat resistance can be synthesized, and when copolymerized with other polymerizable vinyl monomers, they can be used as crosslinking agents to increase the refractive index of optical resins. It can also be used to modify heat resistance, solvent resistance, mechanical strength, etc.

The crosslinkable resin obtained in this way has excellent physical properties as an optical resin, and is suitable for use in plastic lenses, plastic lenses, etc.
It can be applied to prisms, optical fibers, optical elements, etc.

<Examples> The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

In addition, various physical properties were measured by the methods described below.

Refractive index - Abbe Ail refractometer Heat resistance - Glass transition temperature determined by dynamic viscoelasticity measurement.

Impact Resistance - 2 nyn thick cured boards were tested I~ according to FDA specifications.

Solvent Resistance - Cured resin is dissolved in acetone, benzene at room temperature.
[Those that did not swell or dissolve in the solvent after being immersed overnight were rated ○.

Examples 1 to 4 2 mol of chloromethylstyrene and 1 mol of ethylene glycol, diethylene glycol, dipropylene glycol, or bisphenol A di(hydroxyethyl) ether as a diol, and 3 mol of thorium hydroxide, 1 g of hydroquinone, and 20' of toluene.
Place Occ into IQ autoclave 1. 0℃
The mixture was allowed to react for 3 hours. After the reaction was completed, it was cooled, neutralized and washed with water, and a purified product was taken out from the oil layer by distillation. However, only when bisphenol A di(hydroxyethyl) ether was used as the diol, the residue after removing toluene and chloromethylstyrene by distillation was used as the target product. Structural formula and H'-NMR of each obtained monomer
The analytical values are shown below.

=5.22 PPM (411◇HICI+2)=13
- =6.41~6.90 PPM (211C1122G! member-)7'" δ==7.28 PPM <an @ )=5;25
PPM (411o-cB!7) narrow δ = 7.25 PPM (8110) = 5.20 PPM (411@-el+,) = 3.5
~4. I PPM (411-0C1jl□cn”0-
)■ CI+3' =1.1~1.45 PPM (6+1 -0CII2
CIIO-)■ CIL.

=5.25r'PM (411-C1j2-@) 2 mol of glormethylstyrene and dibasic acid such as fumaric acid, itaconic acid, or isophthalic acid], mol, further 2.2 mol of 1-ethylamine, and 1 g of 1-ethylamine , benzene was charged into a four-volume IQ flask and reacted at 50 to 60°C for 3 hours.

After the reaction was completed, the mixture was cooled, neutralized, washed with water, and benzene and unreacted components were distilled off from the oil layer. The structural formulas and II'-NMR analysis values of each Qt Ji body obtained are shown below.

=5.20 PPM (411@HII,-)=6.9
I PPM (211Cl1=C11)0 (
I'17M5) =5.2] 1)l)M (411jo co, -) = 3.
441) l) M (211CI+, -C-)C11□ =5.72.6.4 P gate (211CI+,,C) = 7
．． 32-7.55 PPM (I211G) = 5.22
11°C 1M (4+1 @-CI+,-) Disappearance Example-Kai T-4]-Reli Jagakawa-Compared, 2T (The monomers obtained in Examples 1 to 8 were Polymerization or copolymerization was carried out with methyl methacrylate, styrene, ethylene glycol dimethacrylate, divinylbenzene, and vinyl benzoate according to the composition shown in Table 1. 2 weight% benzoyl peroxide was used as a radical polymerization initiator, and two 10 cm x 10 a.
After charging the monomer composition with the addition of a polymerization initiator into a mold composed of a hard glass plate and a silicone packing,
It was cured for 10 hours in a constant temperature bath at .

After curing, the cured resin was taken out from the sealed tube and evaluated using the physical property test 1 described above.

In addition, as comparative examples, methyl methacrylate, styrene,
Homopolymerization of ethylene glycol dimethacrylate and divinylbenzene was carried out in exactly the same manner as in Examples 8 to 21-, and the cured resin was tested for physical properties.

The results are shown in Table 1.

Examples Monomer (g) 8 EGMS (I0) 9 0EGMS (I0) 10 0PGMS (I0) 11 EPMS (I0) 12 FAMS (I0) 13 ITMS (I0) 14 IPMS (I0) 15 EGMS/Styrene (515) 16 0EGM
S/methyl methacrylate (515) 17 DPGM
S/ethylene glycol dimethacrylate (515) 18 EPMS/styrene (515) 19 FAM
S/vinyl benzoate (515) 20 ITMS/divinylbenzene (515) 21 IPMS/styrene (
515) Comparative Example 1 Methyl methacrylate (I0) 2 Styrene (I0) 3 Ethylene glycol methacrylate (io) 4
Divinylbenzene (I0) Table 1

Claims (1)

[Claims] The following general formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (I) (In the formula, A is -O-(CH_)_2-O-, ▲ Numerical formula, chemical formula There are , tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R_1 and R_2 represent hydrogen or methyl groups, m and n are 0
or an integer from 1 to 10)
An optical resin having a high refractive index obtained by polymerizing one or more of these monomers or copolymerizing one or more of the monomers with a radically polymerizable vinyl monomer.