JPS61166804A - Production of transparent thermosetting metal-containing resin - Google Patents

Abstract

PURPOSE:To produce a transparent resin having high refractive index and low dispersion, by reacting a lanthanoid metal or yttrium salt of a mercapto- containing carboxylic acid with an epoxy-containing vinyl monomer and thermally curing the reaction product. CONSTITUTION:(A) 10-70(wt)% lanthanoid metal or yttrium salt of a mercapto- containing carboxylic acid [preferably a reaction product of a lanthanoid metal oxide or yttrium oxide with the compound of formula HSCnH2nCOOH (n is 1-5)] is mixed and made to react with (B) 30-90% vinyl monomer having epoxy group [e.g. the compound of formula (X is H or CH3)] or a mixture of said monomer and other copolymerizable monomer and the reaction product is cured with heat. USE:An optical material for the parts such as lens, prism, filter, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a transparent thermosetting resin containing metal. This metal-containing transparent thermosetting resin can be used as an optical material for optical components such as lenses, prisms, and filters.

[Conventional technology]

Various optical parts such as lenses, prisms, filters, etc.
Conventionally, optical glass, which is an inorganic substance, has been mainly used, but plastic materials such as polymethyl methacrylate, polystyrene, polycarbonate, and CR-39 (diethylene glycol bisallyl carbinate) are now used in some applications. ing.

[Problem that the invention seeks to solve]

Optical glasses conventionally used in various optical components are
There are more than 200 types with different refractive indexes and dispersion values (Atsube number)] When designing optical components such as lenses, high-precision optical performance is achieved by combining several types of materials with different optical properties. can be achieved. However, it has a drawback that it has a high specific gravity, is heavy when large in size, and is easily broken, making it inconvenient to handle.

On the other hand, glass materials used in some applications have the advantage of being relatively inexpensive as they are lightweight, hard to break, and easy to mass produce, but on the other hand, they only have a limited refractive index and dispersion value. However, it has the disadvantage that it can only be used in a limited number of optical parts that require high-precision optical performance.

An object of the present invention is to provide a metal-containing thermosetting resin that has the characteristics of conventional plastic optical materials and has a relatively high refractive index, a low dispersion value, and is transparent.

[Means for solving problems]

10-70% by weight of a lanthanide metal or yttrium carboxylate having a mercapto group according to the invention
30 to 90% by weight of a mixture of and a vinyl monomer having an epoxy group or another monomer copolymerizable with the monomer
Provided is a method for producing a transparent thermosetting metal-containing resin, which is specially designed to mix and react with the metal-containing resin and heat-cure it.

In the usual case, when a large amount of metal ions are introduced into a resin, it often causes cloudiness and impairs transparency. However, according to the present invention, metal ions are introduced in the form of a carboxylic acid salt having a mercapto group. A transparent metal-containing resin having a high refractive index and a low dispersion value can be obtained for the first time by mixing and reacting with a vinyl monomer containing an epoxy group that is reactive with the resin.

The lanthanide metals used in the present invention are:

Examples include lanthanum, gadolinium, ytterbium, ruthenium, etc., which are introduced into the resin in the form of carnate. Carboxylate salts of lanthanoid metals or yttrium having mercapto groups are, for example,
Lanthanide metal oxide or yttrium oxide and the following general formula H8CnH2,C0OH (in the formula n Fil
A reaction product with mercaptocargenic acid represented by the formula (an integer of 5 to 5) is preferably used. Examples of such mercadetocardic acid include β-mercatoderobionic acid, thioglycolic acid, and the like.

The above reaction may be carried out by directly mixing the two or in a polar medium such as dimethylsulfoxide or N,N-dimethylacetamide. The reaction is completed when the reaction solution becomes a clear solution. After dropping the reaction solution into a poor solvent, such as ethyl ether, to precipitate the salt,
By filtering and drying, a lanthanide metal or yttrium carboxylate having a mercapto group can be obtained.

These salts may be used singly or in combination.

In the present invention, the vinyl monomer having an epoxy group used alone or in mixture with other copolymer monomers is 1, for example, the following general formula (wherein X and Y are H or -CH, respectively): Preferably, the compound is vomiting.

Examples of such vinyl monomers used include β-methylglycidyl methacrylate, glycidyl methacrylate, β-methylglycidyl acrylate, and glycidyl acrylate.

Monomers that can be used in combination with the vinyl monomer having an epoxy group include methacrylic acid, acrylic acid, itaconic acid, methyl methacrylate, cyclohexyl methacrylate, hydroxyethyl methac')L/-), hydroxyethyl acrylate, Examples include ethylene glycol dimethacrylate. These are selected in consideration of solubility with the lanthanide metal or yttrium carboxylate having a mercapto group.

Cal of mercapto group-containing lanthanide metal or yttricum? The amounts of the phosphate salt and the epoxy group-containing vinyl monomer or a mixture thereof with other monomers copolymerizable therewith are in the range of 10 to 70% by weight and 30 to 90% by weight, respectively. If the amount of the former is less than 10% by weight, the effect of adding the metal salt will be small and a resin with a high refractive index will not be obtained.

If it exceeds 70%, the curing reaction will not proceed sufficiently during heat curing, resulting in a brittle resin and poor water resistance.

During the mixing and reaction of the above metal salt and monomer, the mercapto group and the d? It is permissible to add a small amount of a catalyst such as triethylamine, birinone, or piperidine to accelerate the reaction with the xyl group.

However, since adding a large amount of such a catalyst causes coloring of the resin, it is preferable to keep the amount as small as possible. Further, in order to accelerate heat curing of the vinyl group, it is preferable to use a polymerization initiator in combination. Usable polymerization initiators include commonly used radical polymerization initiators, but azo initiators such as azobisisobutyronitrile are particularly preferred because they do not cause side reactions with acids or bases. be.

In the method of the present invention, in a preferred embodiment of the curing reaction, the mercazoto group-containing compound is The essential components are diluted salt and an epoxy group-containing vinyl monomer, to which other vinyl monomers and catalysts are added, and after stirring and mixing thoroughly at a relatively low temperature, the mixture is poured into a mold, defoamed, and kept at a constant temperature. This is done by immersing it in a tank.

At this time, in order to minimize the unevenness of the refractive index in the resin, stirring is carried out for a long time at low temperature to allow the reaction between the mercapto groups and epoxy groups to proceed sufficiently, and then the temperature is raised to carry out the polymerization reaction of the vinyl groups. preferable.

The transparent thermosetting metal-containing resin thus cured can be processed into various optical components by cutting and polishing using conventional methods.

The present invention will be explained in more detail with reference to Examples below.

Example 1 163.9 g of optical grade lanthanum oxide was added to 1 g of β-mercapdog a-pionic acid, and the mixture was stirred and reacted at 60° C. for 20 hours to obtain a clear reaction solution. This reaction solution was mixed with ethanol 101
The mixture was dropped into the solution to precipitate, and then dried under reduced pressure at 80° C. to obtain white lanthanum β-mercaptopropionate salt 410f1. The infrared absorption spectrum was measured and found a peak at 2,550α caused by the stretching vibration of the mercapto group, and a peak at 1,550 cm and 1,420 cI, which is characteristic of calgenate.
The stretching vibration of the carbinyl group of n was observed, and the formation of a salt was confirmed, but the 3*40
A 2-reel of 0 cm2 was also observed, suggesting that the salt contained water of crystallization. This salt is triethylamineLOOO
ppm and azobisisobutyronitrile 200 ppm
A monomer mixture containing β-methylglycidyl methacrylate and methacrylic acid in a weight ratio of 7:3 and a weight ratio of 1=1 were charged into a polypropylene precipitation tube with an inner diameter of 15 m and mixed with stirring, After defoaming under reduced pressure, 8
The resin was thermally cured at 0°C for 2 hours and then at 100°C for 2 hours to produce a transparent thermosetting metal-containing resin. The refractive index and Atsube number of this resin for sodium DllJ are each 15.
They were 53 and 47.

Examples 2 to 5 The same conditions as in Example 1 were used except that the same β-mercapto 7'a pionic acid lantum salt and monomer mixture as in Example 1 were used, and the mixing ratio of salt and monomer was changed. This was thermally cured to obtain a transparent thermosetting metal-containing resin.

Table 1 shows the relationship between the mixing ratio, refractive index (17D), and Atsube number.

Table 1 * MGMA: β-methylglycidyl methacrylate * MAA: Methacrylic acid ** ηD: Refractive index measured with sodium D line Example 6 Using the same β-mercagutopropionic acid silanthanate salt as in Example 1, triethylamine 1,000 Example 1 was prepared by mixing glycitul methacrylate and methacrylic acid in a 1:1 weight ratio with a monomer mixture containing 200 ppm of pFl and asobisisobutyronitrile in a weight ratio of 7=3. A transparent thermosetting metal-containing resin was prepared by curing under the same conditions.

The refractive index and Abbe number of this resin with respect to the sodium D line were 1.555 and 42, respectively.

Example 7 A lanthanum thioglycolic acid salt was prepared under the same conditions as in Example 1 except that thioglycolic acid was used instead of β-mercaptopropionic acid. This salt was mixed and thermosetted with a monomer mixture under the same conditions as in Example 1 to produce a transparent thermosetting metal-containing resin. This resin) IJum D
The refractive index and Atsube number for the line were 1.562 and 41, respectively.

Example 8 Yttrium oxide (113JF) as a substitute for lanthanum oxide
A yttrium β-mercaptopropionate salt was prepared under the same conditions as in Example 1 except that .beta.-mercaptopropionate was used. This salt was mixed with a monomer mixture under the same conditions as in Example 1 and thermally cured to produce a transparent thermosetting metal-containing resin. The refractive index and Abbe number of this resin for the sodium D line were 1.549 and 48, respectively.

Comparative Example 1 A transparent thermosetting metallized resin was prepared under the same conditions as in Example 1, except that the mixing ratio of β-mercaptogropio/acid clanthan salt monomer mixture was 5:95 by weight. . The refractive index and Abbe number of this resin with respect to the sodium D line were 1.523 and 50, respectively.

Comparative Example 2 A transparent thermosetting metallized resin was prepared under the same conditions as in Example 1, except that the mixing ratio with the monomer mixture of β-mercagtoglobionic acid clanthan salt was 75:25 by weight. did. This resin had uneven refractive index and was hygroscopic and brittle, making it difficult to measure its optical properties.

Claims (3)

[Claims] (1) A mixture of 10 to 70% by weight of a lanthanoid metal or yttrium carboxylate having a mercapto group and a vinyl monomer having an epoxy group or another monomer copolymerizable with the monomer 30 to 70% by weight 90% by weight of a transparent thermosetting metal-containing resin, which is characterized by carrying out a mixing reaction and thermosetting. (2) The above mercapto group-containing lanthanoid metal or yttrium carboxylate is combined with a lanthanoid metal oxide or yttrium oxide and the following formula HSC_nH_2
The manufacturing method according to claim 1, which is a reaction product with a compound represented by _nCOOH (n is an integer of 1 to 5). (3) The above-mentioned vinyl monomer having an epoxy group is a compound represented by the following general formula, ▲Mathematical formula, chemical formula, table, etc.▼ (wherein X is H or -CH_3) Manufacturing method in Section 1.