JPS62161806A - High-refractive index resin composition - Google Patents

Abstract

PURPOSE:A resin, consisting of a copolymer obtained by polymerizing specific three kinds of monomers as principal components, having optical characteristic of high refractive index and low dispersion, high hardness and excellent light resistance and good properties of cutting, grinding properties, dyeability, etc. CONSTITUTION:10-80pts.wt. of the first monomer expressed by formula I (X is H, CH3, Cl or Br; n is 0, 1 or 2), e.g. dicyclopentanyl acrylate, etc., 10-80pts. wt. of the second monomer expressed by formula II (Y is H, CH3, Cl or Br; m is 1 or 2), e.g. 6,6-dimethyl-2-(2-methacryloxyethyl)bicyclo[3.1.1] help-2-ene, etc., and 10-80pts.wt. of the third monomer expressed by formula III (Z1 and Z2 are H, CH3, Cl or Br; W1-W4 are H, Cl or Br; l1 and l2 are 0-3), e.g. bisphenol a derivative, etc., and capable of radical copolymerization therewith, preferably giving >=1.55 refractive index of the homopolymer as principal components are polymerized to give the aimed resin.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel resin composition, particularly a novel high refractive index resin composition with little chromatic aberration.

[Conventional technology]

Conventionally, various synthetic resins to replace inorganic glass have been studied and proposed.

For example, polymers containing diethylene glycol bisallyl carbonate as a main component have been put to practical use as optical lenses. This polymer has advantages that inorganic glass cannot satisfy, such as light weight, safety, easy processability, and dyeability, and because it is crosslinked, it also has good mechanical properties.

[Problem that the invention seeks to solve]

However, the refractive index of the polymer is about! It has the disadvantage of being low.

On the other hand, high refractive index resins that have improved this drawback have also been proposed. For example, resins containing a large amount of benzene nuclei and halogens, such as those found in JP-A-36-/662/ψ, have a high refractive index, and when made into lenses, they can be made thinner than conventional products.

However, these resins have extremely low Atsube numbers of 3j or less. When the Abbe number becomes low, the difference in refractive index depending on each wavelength becomes large (high dispersion), which is not preferable in terms of lens design. Recently, resins that have both a high refractive index and a high Abbe number have been developed, as seen in JP-A No. 39-790/, but the main component of this resin is a copolymer of heptamer having a dicyclopentene skeleton. Many of the lens materials used in combination are insufficiently hard. Further, even after polymerization, double bonds remain within the molecule, and this portion is susceptible to chemical reactions, resulting in coloring, etc.

An object of the present invention is to provide a resin for optical lenses that has optical properties of high refractive index and low dispersion, has high hardness, is excellent in light resistance, and has excellent cutting, polishing, and dyeing properties. be.

[Means for solving problems]

The present inventors completed the present invention as a result of intensive research to improve the defects caused by conventional T fat. That is, the present invention comprises one or more first monomers represented by the general formula (1), a second monomer of 1& or 2&1 or more represented by the general formula (n), and a radical This is a high refractive index resin composition characterized by containing as a main component a copolymerizable copolymer or a copolymer with a third single lid having a length of 2 m or more.

Here, the general formula (1) is (X-H, an, , C1 or Br, n-0, /
'! , Take 2), and the general formula []] is 4-J countries (Zl and z2 are each independently He0HsvC1 or Br, Wl to W4 are each independently H, C1 or Br, jl and 12 are each independently KO ,/,2
or 3) Alternatively, a divinylbenzene derivative represented by the general formula CF/), (R1 and R2 are each independently H*CHs*
C1 or Br) etc. are used, but in addition to these, styrene, chlorostyrene, dichlorostyrene, bromostyrene.

Methyl 4 conductors such as methylstyrene, methoxystyrene, etc.: phenyl acrylate, chlorine 722 acrylate, dichlorophenylacrylate.

Trichlorophenyl acrylate, bromo7 enyl acrylate, benzyl acrylate, P-chlorobenzyl acrylate, 0-chlorobenzyl acrylate, dichlorobenzyl acrylate.

Esters of acrylic acid such as trichlorobenzyl acrylate, bromobenzyl acrylate, bromophenyloxyethyl acrylate: phenyl methacrylate, chlorophenyl methacrylate.

Dichlorophenyl methacrylate, trichlorophenyl methacrylate, bromophenyl methacrylate, dibromophenyl methacrylate, benzyl methacrylate, P-chlorobenzyl methacrylate IJL/-) 10-chlorobenzyl methacrylate.

Esters of methacrylic acid such as dichlorobenzyl methacrylate, trichlorobenzyl methacrylate, bromobenzyl methacrylate, bromophenyloxyethyl methacrylate, dibromophenyloxyethyl methacrylate, tribromophenyloxyethyl methacrylate: allyl cinnamate, diallyl phthalate, diallyl isoheptalate, triaryl Allyl compounds such as lucyanurate and triallylisocyanurate are used. When any of the above-mentioned third monomers becomes a polymer by itself! ! The present invention will be described in detail below.

Used in a resin composition containing a copolymer of one or more first monomers, one or more second monomers, and seven or more third monomers as a main component of the present invention. When the composition ratio of the first monomer is too large or when the composition ratio of the second monomer is too small, the hardness of the resin decreases. Furthermore, if the total composition ratio of the first monomer and the co-monomer is too small, the Abe number of the resin decreases. On the other hand, if the total composition ratio of the first monomer and the second monomer is too large, the refractive index of the resin decreases. Therefore, in the resin composition of the present invention, the first monomer is 7O-rO
weight ratio, preferably 60% to lO, the second monomer 1
0-40% by weight, preferably 10-70% by weight and 10-40% by weight, preferably 70-70% by weight of the third monomer.
It can be obtained by copolymerizing a mixture of monomers containing.

In addition, the resin composition of the present invention may contain an ultraviolet absorber of 0.03 to improve its weather resistance and light resistance, if necessary.
It is preferable to contain up to 3.0% by weight.

mW when the concentration of ultraviolet absorber is less than 0.0/wt%
However, it has little effect on improving weather resistance and light resistance, and if it exceeds 3.0% by weight, yellow coloring becomes noticeable and the commercial value tends to decrease.

The ultraviolet absorbers used in the present invention include benzotriazole-based, benzophenone-based, salicylic acid-based, cyanoacrylate-based, hindered amine-based as ultraviolet stabilizers, and Niw! ! A wide variety of salts, benzoates, etc. can be used.

The method of polymerizing the composition of the present invention is not particularly limited, and any known polymerization method can be employed. For example, between the molds held by an elastomer gasket or spacer, the The composition is produced by adding a polymerization initiator to the second and third monomers and the ultraviolet absorber and heating the mixture, but the composition can also be produced by photopolymerization or radiation polymerization. Furthermore, by selecting the type and amount of polymerization initiation, it is possible to manufacture by a reaction injector molding method (RIM), and the method is not limited to the casting method.

The above polymerization initiator is benzoyl peroxide diisopropyl peroxide dicarbonate.

From 0.03 to lauroyl peroxide, organic peroxide, or azo compounds such as azobisisobutyronitrile
It is used by mixing r and o weight %. The type and concentration of the polymerization initiator used depends on the composition of the monomer mixture,
It is determined by considering reactivity, reaction rate control, etc.

〔Effect of the invention〕

The resin composition of the present invention has excellent optical properties such as a high Atsube number and a high refractive index at the same time as compared to conventionally proposed high refractive index resins, and has excellent hardness, light resistance, impact resistance, It also had excellent soil tank processability.

Furthermore, it has good dyeability and can be used for various optical lenses and optical elements such as cameras and eyeglasses.

〔Example〕

Examples of the present invention will be described below, but it goes without saying that the scope of the present invention is not limited thereby.

Example/Dicyclopentanyl acrylate 3otr@%, which is X-H, n-0 in general formula (I), general formula cn]'
, Y-CH3,n-/6,6-dimethyl-2-(2-methacryloxyethyl)bicyclo[3,
l, l] Hebdo2en [hereinafter abbreviated as Nopol-MA]! θ weight 11%, i + 2-bis(gumethacryloxy-jJ-dichlorophenyl)propane 20% by weight, azobisisobutyronitrile O as a polymerization initiator.
A mixed solution consisting of 9% by weight was heated at 65° C. for 1 hour in a nitrogen atmosphere to carry out 1,111 polymerization to obtain a colorless and transparent prepolymer.

This prepolymer was poured into a glass mold and polymerized in hot air. Polymerization conditions are 50℃ and approximately 1o
After holding for FI#, the temperature was raised to 0°C over about 2 hours, and the temperature was kept at 190''C for 2 hours.

The lenses were removed from the glass mold and then post-cured. The obtained lens has good optical performance with a refractive index of /,j'll and an Atsbe's number II of <,7, as well as a pencil hardness of 2H and excellent impact resistance and potability. Ta. In addition, the dyeability and light resistance were also good.

Example 2 In the compound of general formula CI), instead of dicyclopentanyl acrylate, dicyclopentanyl methacrylate j of
Polymerization was carried out in exactly the same manner as in Example 1 using the same liquid mixture as in Example 1 except that the amount of A was 30% by weight.

The obtained lens had a refractive index of 8jS3 and an Abbe number of ≠6.0, and also had excellent properties such as light resistance, hardness, and machinability.

Claims (4)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [I] First monomer represented by (X=H, CH_3, Cl or Br, n=0, 1, or 2) 10 to 80 weight Department and
General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] (Y=H, CH_3Cl or Br, m=1 or 2)
A high refractive index resin composition consisting of a copolymer mainly composed of 10 to 80 parts by weight of a second monomer represented by the formula and 10 to 80 parts by weight of a third monomer radically copolymerizable with these monomers. (2) The refractive index of the homopolymer of the third monomer is 1.5
The high refractive index resin composition according to claim 1, which has a refractive index of 5 or more. (3) The third monomer has the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (II) (Z_1 and Z_2 are each independently H, CH_3,
Cl or Br, W_1 to W_4 are each independently H,
Cl or Br, l_1 and l_2 are each independently represented by 0, 1, 2 or 3) Claim 2
High refractive index resin composition described in section (4) The third monomer has the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [IV] (R_1 and R_2 are each independently H, CH_3,
Cl or Br) High refractive index resin composition according to claim 2