JPH0568681B2 - - Google Patents

Description

[Detailed description of the invention]

[Field of Application of the Invention] The present invention relates to an optical resin that is transparent and has excellent heat resistance and adhesive properties. [Background of the Invention] Since resins containing fluorine have a low refractive index, their use as various optical materials including optical fibers has been studied. Among these, a copolymer of vinylidene fluoride and a fluorine-containing olefin monomer such as tetrafluoroethylene, as described in Japanese Patent Publication No. 53-42260, has excellent heat resistance and adhesiveness, but These polymers are crystalline and cloudy, resulting in large light scattering. On the other hand, polyfluoromethacrylates and acrylates are known as fluorine-containing resins with excellent transparency, but these polymers generally have poor heat resistance and adhesive properties. Therefore, as a method to solve these drawbacks, a method of copolymerizing vinyl monomers capable of forming a hydrophilic homopolymer has been proposed in JP-A-59-15411, JP-A-59-7906, and JP-A-59.
-9604 and No. 59-7311. These methods can improve heat resistance and adhesion to a certain extent compared to the case where a vinyl monomer capable of forming a hydrophilic homopolymer is not used, but the heat decomposition resistance increases at high temperatures for a long time. Additionally, the glass transition temperature of the resin is low at 90°C or less. Furthermore, since the types of fluoromethacrylates used are limited to two to three types, such as ethyl and propyl esters, it becomes difficult to freely adjust the optical properties depending on the type of material. [Object of the Invention] An object of the present invention is to provide an optical resin that is transparent and has excellent heat resistance and adhesive properties. [Summary of the Invention] To briefly summarize the present invention, the present invention relates to an optical resin, and includes a metal other than an alkali metal,
The resin has at least the following general formula:

[Embodiments of the invention]

EXAMPLES In order to explain the present invention more specifically, Examples and Comparative Examples will be described below, but the present invention is not limited to these Examples. In addition, various physical properties of the resins obtained in Examples and Comparative Examples were measured by the following test methods. (1) Refractive index The refractive index at 25°C was measured using Atsube's refractive index (n ²⁵ _D ) (2) Light transmittance Test on a 2 mm thick film using a haze meter (manufactured by Suga Test Instruments Co., Ltd.) Measured on a piece (according to ASTM-1003) (3) Heat distortion temperature (Tg) Heat distortion temperature (Tg) was measured using a thermophysical testing machine TMA.
(manufactured by Shinku Riko Co., Ltd.) from the change in linear expansion coefficient with temperature. (4) Heat resistance Heat resistance was determined by the weight loss rate of the resin in % after being left at 250°C for 3 hours (in air), and the appearance was observed with the naked eye. (5) Adhesion Using two optically polished 2 x 4 cm quartz glass plates, the above monomer composition was applied to a 2 x 2 cm area, and the plates were bonded together. These two glass plates were fixed with compression springs and heated at 60°C for 3 hours and at 80°C for 2 hours. After performing a heat cycle test 500 times by immersing this product in a 0°C cold water bath and an 80°C hot water bath alternately,
The state of adhesion was examined. Hereinafter, methods for producing resins are shown in Examples 1 to 8 and Comparative Examples 1 and 2, and characteristics of these resins are shown in Table 1. In addition, in each example, parts mean parts by weight. Example 1 12 parts of methacrylic acid in 100 ml of methyl alcohol,
After 57 parts of perfluorooctanoic acid was dissolved and maintained at 55°C, 31 parts of lead monoxide was gradually added to cause a reaction. After this solution was filtered, water and methyl alcohol were removed under reduced pressure to obtain a monomer composition. 50 parts of this monomer composition, 2,2,3,3,4,4,
50 parts of 4-heptafluorobutyl methacrylate,
0.3 part of dimyristyl peroxydicarbonate was uniformly mixed as a polymerization initiator, and a bulk polymerization reaction was carried out at 60°C for 3 hours and at 80°C for 3 hours in a nitrogen gas atmosphere. Example 2 25 parts of methacrylic acid in 100 ml of methyl alcohol,
After 45 parts of perfluorooctanoic acid was dissolved and maintained at 50°C, 30 parts of lead monoxide was gradually added to cause a reaction. After this solution was filtered, water and methyl alcohol were removed under reduced pressure to obtain a monomer composition. To 100 parts of this monomer composition, 0.1 part of dimyristyl peroxydicarbonate was added and mixed at 60°C,
Bulk polymerization reaction was carried out in nitrogen for 3 hours at 60°C and 3 hours at 80°C. Example 3 20 parts of the monomer composition obtained in Example 1, 2,
2,2-trifluoroethyl methacrylate 80
part, dimyristyl peroxydicarbonate 0.2
Mix the parts uniformly and incubate at 55℃ for 3 hours and 80℃ for 3 hours in nitrogen.
The bulk polymerization reaction was allowed to take place for an hour. Example 4 26 parts of acrylic acid in 100ml of methyl alcohol,
After dissolving 55 parts of perfluorooctanoic acid and keeping it at 55°C, barium hydroxide monohydrate [Ba
19 parts of (OH) ₂ .H ₂ O] was gradually added to carry out the reaction. After this solution was filtered, water and methyl alcohol were removed under reduced pressure to obtain a monomer composition. Example 3: 60 parts of this monomer composition, 40 parts of 2,2,2-trifluoroethyl methacrylate, and 0.2 parts of dimyristiperoxydicarbonate were uniformly mixed.
The polymerization reaction was carried out in the same manner. Example 5 11 parts of methacrylic acid in 100ml of methyl alcohol,
After dissolving 48 parts of perfluoroheptanoic acid and keeping it at 55°C, barium hydroxide octahydrate [Ba
41 parts of (OH) ₂ ·8H ₂ O] was gradually added to carry out the reaction. After this solution was filtered, water and methyl alcohol were removed under reduced pressure to obtain a monomer composition. 20 parts of the monomer composition, 80 parts of 2,2,2-trifluoroethyl methacrylate, and 0.2 parts of dimyristyl peroxydicarbonate were uniformly mixed, and a polymerization reaction was carried out in the same manner as in Example 3. Example 6 11 methacrylic acid in 100 ml of methyl ethyl ketone
54 parts of perfluorooctanoic acid at 55°C.
35 parts of strontium hydroxide was gradually added to carry out the reaction. After this solution was filtered, water and methyl ethyl ketone were removed under reduced pressure to obtain a monomer composition. 15 parts of this monomer composition, 2,
85 parts of 2,3,3,3-pentafluoropropyl methacrylate and 0.3 parts of dimyristyl peroxydicarbonate were mixed uniformly, and a polymerization reaction was carried out in the same manner as in Example 3. Example 7 31 parts of methacrylic acid in 100ml of methyl alcohol,
After 54 parts of perfluorooctanoic acid was dissolved and maintained at 55°C, 15 parts of barium hydroxide monohydrate was gradually added to carry out the reaction. After this solution was filtered, water and methyl alcohol were removed under reduced pressure to obtain a monomer composition. 15 parts of this monomer composition, 10 parts of methyl methacrylate, 75 parts of 2,2,3,3,3-pentafluoropropyl methacrylate, and 0.3 parts of dimyristyl peroxydicarbonate were mixed uniformly, and the same method as in Example 3 was carried out. A polymerization reaction was carried out. Example 8 26 parts of itaconic acid monomethyl ester and 67 parts of perfluoroheptanoic acid in 100 ml of methyl ethyl ketone
After dissolving 1 part and maintaining the temperature at 55°C, 7 parts of magnesium oxide were gradually added to carry out the reaction. After this solution was filtered, water and methyl ethyl ketone were removed under reduced pressure to obtain a monomer composition. This monomer composition
30 parts of 2,2,2-trifluoroethyl methacrylate, and 0.2 parts of dimyristyl peroxydicarbonate were uniformly mixed, and a polymerization reaction was carried out in the same manner as in Example 3. Comparative Example 1 0.3 parts of dimyristyl peroxydicarbonate was dissolved in 100 parts of 2,2,3,3-pentafluoropropyl methacrylate, and a bulk polymerization reaction was carried out at 60°C for 5 hours and 80°C for 3 hours in a nitrogen gas atmosphere. I made it happen. Comparative Example 2 70 parts of 2,2,3,3,3-pentafluoropropyl methacrylate, 28 parts of methyl methacrylate
1 part, 2 parts of methacrylic acid and 0.3 part of dimyristyl peroxydicarbonate were uniformly dissolved,
The polymerization reaction was carried out in the same manner.

〔Effect of the invention〕

As explained in detail above, the optical resin containing metal and fluorine according to the present invention is transparent and has a refractive index of n ²⁵ _D.
It has a low refractive index of 1.55 or less, and has excellent heat resistance and adhesive properties, so it is used not only as a cladding material for optical fibers and general optical resin plates, but also as optical adhesives, lenses, optical waveguides, etc. It can be used as a material for various optical components. Therefore, the present invention is an invention that has remarkable effects in terms of its usefulness.

Claims (1)

[Scope of Claims] 1. Consisting of a resin containing a metal other than an alkali metal and fluorine, the resin has at least the following general formula: [Chemical formula] (where M is a metal other than an alkali metal, R ₁ is hydrogen or a methyl group, R ₂ is a fluorine-containing group, n indicates the oxidation number of the metal M), and the content of the metal is relative to the total weight of the resin. 1% by weight or more, the resin has a light transmittance of 80% or more and a refractive index of 1.55 or less.