JPS6026013A - Optical resin object - Google Patents

Abstract

PURPOSE:To obtain the titled object of a high refractive index, by using, as a principal component, a polymer obtained by copolymerizing a thioether group- containing monomer with a styrene compound. CONSTITUTION:An optical resin object for optical materials and optical elements which has, as a principal component, a copolymer comprising 5-98wt% monomer component of formula I (wherein R1 is H or methyl, R2 is H, alkyl, alkoxyl, amino, halogen, sulfide, sulfoxy, sulfonate, aryl, or heterocyclic group, Ar is arylene) and 5-98wt% monomer component of formula II (wherein R3 is H, alkyl, alkoxyl, amino, halogen, sulfide, sulfoxy, sulfonate, aryl, or heterocyclic group, and Ar is arylene). By the term ''contain as a principal component'' is meant ''contain in an amount of 50wt% or more''.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an optical resin object, and more specifically, to an optical resin object, which mainly comprises a polymer obtained by copolymerizing a monomer containing a thioether group with another monomer. The present invention relates to an optical material having a high refractive index and an optical resin object for an optical element, which has a high refractive index.

i-no! - Optical elements such as conventional lenses, prisms, and optical fibers are sometimes made of glass;
It is also being made from plastic. Optical elements made from this plastic are lighter than glass products and can be easily molded from the material, making it possible to mass produce them, and the demand for them has increased in recent years. The resin used to make such optical elements needs to be colorless and transparent. Conventionally, general-purpose resins such as polystyrene resin, polycarbonate resin, and acrylic resin have been used as such resins. However, the refractive index of these resin materials is in the range of 1.49 to 1.59,
Polystyrene resin, polycarbonate 1, which is said to have a relatively high refractive index behind the resin material, is lower than the refractive index of glass material A, which can be varied over a wide range of 1.4 to 1.9.
Even -4A4 resin cannot have a refractive index higher than the above-mentioned 1.59. In this way, the high refractive index element (,4 is (!
For example, L/
This means that lenses must be thicker in order to have the same focal length as lenses made from materials with high refractive indexes such as glass. If the wall thickness of an optical element, such as a lens, becomes thicker, it will not be possible to make good use of the lightweight characteristic of plastic products, and the space occupied by the lens will become larger, making it difficult to make the optical system lighter and smaller. However, it is not possible to meet the recent demands for compact optical equipment. Therefore, it is desired to develop a resin having a refractive index higher than the refractive index of 1,59 which has reached 1/2 (as the resin element 1), which makes it possible to reduce the weight and size.

An object of the present invention is to provide a novel optical resin element +A having an unprecedentedly high refractive index and an optical object of an optical resin element.

Structure of the Invention The above-mentioned object of the present invention is to provide a monomer component represented by the following general formula CI) containing 2 to 95% by weight of a monomer component and 5 to 98% by weight of a monomer component represented by the general formula (n). This is achieved by having coalescence as the main component.

General formula (1) General formula (IT) 1 / CH2=CR2CI 2=CH 1/I C-3-ArAr ]1 \ ORa [In the formula, R1 represents a hydrogen atom or a methyl group, and R2 and R9 are hydrogen atoms , an alkyl group, an alkoxy group, an amino group, a halogen atom, a sulfide group, a sulfoxy group, a sulfone-1 group, an aryl group or a heterocyclic group, and Ar represents an arylene group. ] R2 and R3 in the above general formula of the monomer used in the present invention are hydrogen atoms, preferably alkyl groups having 1 to 20 carbon atoms, such as methyl group, ethyl group, isopropyl group, tert-butyl group, hexyl group Ring; alkoxy group, preferably an alkoxy group having 1 to 20 carbon atoms, such as methoxy group, ethoxy group, etc.; amino group; hydrogen atom, such as chlorine, bromine, etc.; sulfide group; sulfoxyne-1- group; sulfone I・Group: Aryl group, preferably an aryl group having 6 to 18 carbon atoms, such as phenyl group; Heterocyclic group, preferably 5- to 7-membered 1'
Tetracyclic groups (even if substituted, one is substituted), such as pyrazolinyl, morpholinyl, piperidylnotyl, lahydrofuryl, dioxanyl, quinardyl, pyrrolyl, isoxazolyl, imidazolyl, isothiazolyl, furazanyl , pyrazolinyl group, etc., and A
r represents an arylene group, preferably an arylene group having 6 to 22 carbon atoms, such as a phenylene group, a naphthylene group, anthrylene group, a perylene group, an acenaphthenylene group, and the like.

In the present invention, 1.1: Preferred monomers of the monomer represented by the general formula (1) are exemplified, but the invention is not limited thereto.

(1) Phenylthiol acrylate ○ (2) Phenylthiol methacrylate H3 Cloudy (3) 4-Chlorphenylthiol acrylate (4)
4-Chlorphenylthiol metharylate H9 (5) Pentachlorphenylthiol acrylate (6
) Pentachlorpheni month 4-all, meta sentence 1 ru 1
・(7) Naf Senzuki=f-all acrylic l/-1・Cl2
-C11 (8) Naphthylthiol MEC January Notes CI (3 "CI22C The above general formula CI+ in the present invention) is exemplified by styrene, 2-methylstyrene, 4-
Methylstyrene, 2-dichlorostyrene, 2-dichlorstyrene, 24-dichlorostyrene, pentachlorstyrene, 2-bromostyrene, 4-bromostyrene, 2
4-dipromostyrene, pentabromostyrene, ■! −
Dostyrene, 4-phenylstyrene, aminostyrene,
Nitrostyrene, vinylnaphthalene, vinylanthracene, vinylphenanthrene, vinyl/I/; IJ luhaso/I/, preferably styrene, methylstyrene, and chlorstyrene.

In the present invention, the polymer consisting of the general formula CI) and the general formula (n) can obtain a high refractive index by the monomer represented by the general formula [■], but the monomer represented by the general formula (IT) has a high refractive index. It is advantageous to increase the Ui'T refractive index of the iron.

From this point of view, the copolymerization ratio of the monomers represented by these general formulas is 2 to 95% by weight of the 117mer of the general formula [■],
It is appropriate that the amount of @mer shown in [II] is 5 to 98% by weight. If the monomer of general formula (1) is less than 1%, a polymer with a high refractive index cannot be obtained, and the general formula (1)
When the fl'L content exceeds 95% by weight, moldability deteriorates.

The polymer in the present invention is represented by the general formula -! l'
Contains the tm isomer as the main component, and "containing it as the main component" means containing 50 tm-1-1. If the monomer shown in General 1 (indicated by
Examples of the polymer include 1,000 liters/ton type unsaturated monomer.

Examples of the ethyl L/one-based non-1i[11N-forms include alkyl)'-1- and alkyl methacrylates, specifically methyl acrylate, ethyl acrylate-1, propyl acrylate, and butyl acrylate. 1, hensyl acrylate-1-, methyl methacrylate-1, butyl methacrylate, cyclohedyl-1-syl methacrylate-1, benzyl methacrylate-1, diallyl phthalate, !-lylyl cyanerate, triallyl 1
~ Limerite-1・, Ethi 1/Nglycol dimethacrylic I
/-1-, butylene glycol dimethacrylate and 2
．． 2bis(4-methacryloxypolyethoxyphenyl)
Examples include, but are not limited to, propane.

Furthermore, examples of copolymerizable ethylenically unsaturated r(ii) useful in the present invention include vinyl ester, vinyl amide, vinyl nitrile, vinyl ketone, vinyl halide, vinyl ether, olefin, and diolefin. Acrylic acid to tolyld, methacrylamide, vinyl chloride, methyl vinyl ketone, thumaric acid ester, maleic acid ester and hytaconic acid ester, 2-chloroethyl vinyl ether, 2
Examples include, but are not limited to, -hydroxyethyl methacrylate, N-vinylsuccinamide, N-vinylphthalimide, N-vinylpyrrolidone, butadiene, and ethylene.

Preferred copolymerizable ethylenically unsaturated monomers utilized in the synthesis of the polymers of the present invention include acrylates,
These include methacrylate and aromatic vinyl compounds, and more preferably benzyl methacrylate-1, styrene, and methylstyrene.

Next, specific examples of the polymer in the present invention will be illustrated using structural formulas. Note that the numbers are weight %.

(1) (Phenyl methacrylate/styrene) copolymer (2) (Naphthylthiol acrylate-1-/styrene)
Copolymer (3) (4-Cromo d-fuchizuki d-ol acrylate-1-/styrene) Copolymer (4) (Leaf-thylthiol acrylate-1/vinylnaphthalene) Copolymer (5) (Phenylthiol acrylate-1 -/4-
Chlorstyrene) copolymer 〇! (6) (Phenylthiol acrylate barvinylcarbazole) copolymer (7) (4-Chlorphenylthiol methacrylate/4-methylstyrene) copolymer H3 (8) (Phenylthiol acrylate/4-phenylstyrene) copolymer (9) (Phenylthiol (acrylate/styrene) copolymer (10) (4-chlorophenylthiol methacrylate/4-methylstyrene) copolymer 113 ■ H9 (11) (thiol acrylate for edges -1/4-
Chlorstyrene) Copolymer (12) (Phenylthiol acrylate/4-methylstyrene/Methyl acryle-1-) Copolymer I (13) (Phenylthiol acrylate-1-,/4-
Chlorphenylthiol methacrylate/styrene) copolymer Ii3 The polymer of the present invention thus obtained is substantially colorless and transparent, and the refractive index of the molded product is 1.6O-
It has a refractive index greater than t.

The method of polymerizing the polymer in the present invention includes, for example, bulk polymerization,
Examples include, but are not limited to, suspension polymerization, photopolymerization, solution/&flt polymerization, radiation polymerization, and the like.

Molding methods for producing the optical element of the present invention include injection molding, positive phase molding, injection molding and compression molding, such as the low-links method, 4-micro molding method, etc. 1. Any method of molding a resin in a molten or semi-molten state can be applied.

Furthermore, the LJ ttt composite according to the present invention exhibits good properties even when molded by the cast polymerization method.

The optical table made from the optical material consisting of 111 combinations according to the present invention has improved refractive index as shown in -1-, but it has the characteristics as an optical element, namely, 5 deformability, birefringence, etc. , bending strength, surface hardness, etc., and can be used alone; however, in order to further stabilize these properties, a coating may be applied to the element surface.

The optical element of the present invention includes so-called lenses for still cameras, video cameras, telescopes, television projectors, big amplifier lenses, eyeglasses, contact lenses, sunlight condensing lenses, etc. Prisms such as pentaprisms, mirror elements such as concave mirrors, convex mirrors, and polygons, leading elements such as optical fibers and optical waveguides, and discs such as optical video discs and audio discs function by transmitting light. An element that exhibits

As described in detail, according to the present invention, the general formula (r)
By synthesizing a polymer containing monomers represented by and (IT) as main components and creating optical resin objects for optical materials and optical elements, the refractive index can be changed from that of conventional optical resins. It can be made even higher than the optical resin object created. For this reason, for example, the same focal length can be achieved even if the thickness of the lens is made thinner than that of a conventional lens made of resin, or the curvature of the lens is reduced. The occupied volume can be reduced. As a result, the number of lenses of the optical system provided in the limited space of the optical device and the selection range of their arrangement can be greatly expanded, and the weight and size of the optical device can be further reduced.

EXAMPLES The present invention will be explained in detail with reference to some examples below, but the present invention is not limited to these examples.

Actual jjffi Examples 1 to 3 "1" of t'1'1141 bodies represented by the above general formula (f)
The phenylthiol acrylate and styrene of Example (1) were mixed with sea urchin according to the formulation shown in Table 1 to give a total of 100 g, and this was mixed with lauroylperoxylic acid F'0. ] g and dissolve to prepare a monomer blend solution, which is then placed in a container that can be depressurized.

Separately, two glass plates measuring 100 m x 150 m and 61% thick were lined with flexible vinyl chloride gaskets, and the distance 1i111 between the two glass plates was 3. Assemble the °ζ cell so that it is completely inebriated.

Next, the above monomer mixture solution was stirred under a reduced pressure of 3 Qtorr.
The mixture was degassed for 2 minutes, and then the pressure was returned to normal, and immediately poured into the glass cell prepared above.

Then, it is kept in a constant temperature bath set at 65-70°C for 10 hours, and then kept in a hot air circulation oven set at 1&105-110°C for 3 hours. Then, after cooling at room temperature, the glass plate was removed to obtain a sheet-like resin object.

The refractive index n and Atsube number ν of this resin object. The results of A11 determination are shown in Table 1. Here, the refractive index and Atsube's number were measured using Asohe Refractive IT (NAI?-3>).

Table 1 Examples 4 to 6 -1-General''(tl'j !it body of the above example (7) of the i1''! body shown in [1] and 4,,)t
□Example 1 to 3 except that Rustyrene was used.
A sheet-like resin object (II) was made in the same manner as in Example 1. The refractive index and vertical number of this object were also measured in the same manner as in Examples 1 to 3, and the results are shown in Table 2.

Table 2 Examples 7 to 9 The above examples (4) of monomers represented by general formula (T)
Polymerization was carried out in the same manner as in Examples 1 to 3 except that the monomer and 4-methylstyrene were used.
It's il. This was also evaluated in the same manner as Examples 1 to 3, and the results are shown in Table 3.

Table 3 Patent applicant Konishiroku Photo Industry Co., Ltd.

Claims (1)

[Claims] (1) Monomer components 2 to 95 represented by the following general formula (1)
Monomer components 5 to 5 represented by weight deposit % and general formula CII)
1. An optical resin object characterized by having as a main component a polymer having a weight ratio of 98%. General formula (1) General formula (II) 1 / CH2=CR2CH2=CH 1/I C-3-Ar 8r 11 \ R3 [In the formula, R1 represents a hydrogen atom or a methyl atom, and R2 and R3 are hydrogen atoms , an alkyl group, an alkoxy group, an amino group, a halogen atom, a sulfide group, a sulfoxy group, a sulfonate group, an aryl group, or a heterocyclic group, and Ar represents an arylene group. (2) The optical resin object according to claim 1, which is a molded optical element.