JPH07216022A - Polymerizable composition and its utilization thereof - Google Patents

Abstract

PURPOSE:To obtain a polymerizable composition containing a specific dithian ring-containing unsaturated monomer, excellent in low specific gravity, high refractive index, low dispersion, weather resistance and heat resistance, capable of curing by action of heat and active energy beam and useful for producing optical parts, optical elements, etc. CONSTITUTION:A diallyldisulfide expressed by formula I is reacted with bromine to afford 2,5-dibromo-dithian and addition reaction of the resultant compound with thiourea is carried out and the product is hydrolyzed to give a dithian ring-containing dithiol compound of formula II, and then, the compound of formula II is reacted with chloromethylstyrene, etc., to afford a dithian ring- containing unsaturated monomer expressed by the formula III [(b1) and (b2) are each an integer of 1-5; C1 and C2 are each an integer of 0-2; W and X are each CH3, formula IV [(d) is an integer of 1-5; (e) is an integer of 0-2] or a group of the formula V; A and B are each H or CH3]. Then, this monomer is blended with a polymerization initiator (e.g. tert-butylperoxy-2-ethylhexanoate) to provide the objective polymerizable composition capable of providing a resin material, etc., for optical materials.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymerizable composition which is cured by the action of heat and / or active energy rays, and a resin material obtained by polymerizing and curing the polymerizable composition. More specifically, the present invention relates to a cast polymerizable composition suitable for producing optical parts or optical elements such as lenses, prisms, mirrors and optical disks.

[0002]

2. Description of the Related Art Heretofore, various resins for plastic lenses have been studied as substances that replace inorganic glass. For example, a resin material obtained by polymerizing methyl methacrylate or a monomer whose main component is diethylene glycol bisallyl carbonate is used as an optical component such as a lens. However, these have many problems and are not of a sufficiently satisfactory property. For example, some of these resin materials have a refractive index of 1.50, which is lower than that of glass. Therefore, in order to obtain a desired refractive index, the lens must be made thick and the weight reduction is not sufficient. Absent. Further, particularly in the case of a concave lens, the thickness around the lens becomes thick and chromatic aberration occurs, which is not preferable. In addition, various resins such as polystyrene and polycarbonate have been used, but since these are thermoplastic resins, there are problems that optical distortion due to birefringence is likely to occur during injection molding and that they are easily colored.

Therefore, there is a demand for a material which realizes a high refractive index and a low dispersion while making the best use of the characteristic of plastic having a low specific gravity. As a material therefor, a polymer of tetrachlorometa-xylylenedithiol, 1,3,5-trimercaptobenzene and diisocyanate is disclosed in JP-A-63-46213. Further, a polymer of pentaerythritol tetrakisthiopropionate and diisocyanate is disclosed in JP-A 64-26622. Further, a polymer of pentaerythritol tetrakisthiopropionate and a vinyl compound is disclosed in JP-A-63-309509.

However, even though these proposals have made some contributions, the inventors of the present invention know that they are not completely satisfactory. For example, the thiol compound described in JP-A-63-46213 is
Although the polymer obtained from this as a raw material has a high refractive index, it is thought to have problems such as a low Abbe number and poor weather resistance. Further, the thiol compounds described in JP-A 64-26622 and 63-309509 are
A polymer using this as a raw material has a large Abbe's number but a low refractive index, and it is considered to have problems of poor heat resistance.

[0005]

The above-mentioned problems have been found in the prior art.

[Outline of Invention]

[0007]

[Means for Solving the Problems]

<Summary> The present invention is an improvement over the problems of the prior art such as the resin for plastic lenses described above, and is a resin material having low specific gravity, high refractive index, low dispersion, and excellent weather resistance and heat resistance. The present invention aims to provide a polymerizable composition suitable for producing an optical component, which is obtainable from the above, and a resin material obtained by polymerizing and curing the same.

Accordingly, the polymerizable composition according to the present invention is characterized by containing a dithiane ring-containing unsaturated monomer represented by the following general formula [I].

[0009]

[Chemical 4] [The integers and chemical formulas represented by the symbols in the formulas may be the same or different, and each independently, b
1 and b2 are integers of 1 to 5, and c1 and c2 are 0 to
An integer of 2, W and X are hydrogen atoms, CH ₃ ,

[0010]

[Chemical 5] Or

[0011]

[Chemical 6] [D represents an integer of 1 to 5 and e represents an integer of 0 to 2]
And A and B represent a hydrogen atom or CH ₃ , respectively.] Further, the resin material according to the present invention comprises a polymerizable composition containing the above-mentioned dithiane ring-containing unsaturated monomer under heat and / or activity. It is characterized by being polymerized and cured by the action of energy rays.

Another resin material according to the present invention is at least one of the above dithian ring-containing unsaturated monomers.
A polymerizable composition comprising a seed and at least one radical polymerizable monomer having at least one vinyl group in one molecule, which is polymerized and cured by the action of heat and / or active energy rays. , Are characterized. <Effect> The polymerizable composition of the present invention and the resin material obtained by polymerizing and curing the same have low specific gravity, high refractive index, low dispersion, and excellent weather resistance and heat resistance. This is a solution to the problems found in resin for lenses and the like. [Detailed Description of the Invention] (1) Polymerizable composition The polymerizable composition according to the present invention comprises a dithiane ring-containing unsaturated monomer represented by the following general formula [I],
It is characterized by.

[0013]

[Chemical 7] [The integers and chemical formulas represented by the symbols in the formulas may be the same or different, and each independently, b
1 and b2 are integers of 1 to 5, preferably 1 or 2, and c1 and c2 are 0 to 2, preferably 0 or 1,
W and X are hydrogen atoms, CH ₃ ,

[0014]

[Chemical 8] Or

[0015]

[Chemical 9] [D represents an integer of 1 to 5, preferably 1 or 2, and e represents an integer of 0 to 2, preferably 0 or 1]
(Preferably W and X are hydrogen atoms)
And B each represent a hydrogen atom or CH ₃ , preferably a hydrogen atom.] In the formula [I], the phenylene group may be any of o-, m- and p-, but m-, p Mixtures of p-forms and p-forms, especially m-, p-mixtures, are preferred.

The term "comprising" as used herein means that, in addition to the components listed above, auxiliary components (details described later) may be contained unless the gist of the present invention is impaired.

The following compounds may be mentioned as specific examples of the dithiane ring-containing unsaturated monomer used in the composition of the present invention.

[0018]

[Chemical 10]

[0019]

[Chemical 11] Among these, the compounds (1) and (2) are preferable.

In the present invention, only one type of dithian ring-containing unsaturated monomer may be used, or two or more types may be appropriately selected and used.

The integers and chemical formulas represented by the symbols in formula [I] are defined as "independently" as described above. Therefore, the compound of the formula [I] includes all possible combinations thereof, and for example, the disclosure of the above-mentioned compounds (1) to (7) indicates that the specific "symbols" in these compounds are It is to be understood that all other combinations of "integer and formula shown" are also disclosed.

The dithiane ring-containing unsaturated monomer represented by the formula [I] can be produced by any method.

One of the preferable methods is, for example, the following.

A dithiol compound is produced by the reaction of the following formula (see, for example, Japanese Patent Application Laid-Open No. 3-236386),

[0025]

[Chemical 12] The obtained dithiol compound can be reacted with chloromethylstyrene under a dehydrochlorinating agent to obtain the desired dithian ring-containing unsaturated monomer.

[0026]

[Chemical 13] (2) Resin Material (No. 1) The resin material according to the present invention is obtained by applying heat and / or heat to the polymerizable composition containing the dithian ring-containing unsaturated monomer.
It is characterized by being polymerized and cured by the action of active energy rays.

For the polymerization and curing of the polymerizable composition of the present invention, polymerization by heat, polymerization by active energy rays, and a method of using these in combination are adopted, and it is carried out by applying such an exciting action. You can In the case of thermal polymerization, it is preferable to use a thermal polymerization initiator, and in the case of active energy rays such as ultraviolet rays, it is preferable to use a photo (ultraviolet) polymerization initiator. That is, in the present invention, the term "action of heat" or "action of active energy rays" includes the combined use of a thermal polymerization initiator or a photopolymerization initiator. In addition to these polymerization initiators, a radical generator can be used in combination, and this radical generator may overlap with the above-mentioned polymerization initiator. When the polymerization initiator is an oxidizing agent, it includes a case in which it is combined with a reducing agent to form a so-called redox system.

More specifically, in the case of thermosetting, a thermopolymerization initiator such as benzoyl peroxide, diisopropyl peroxycarbonate, lauroyl peroxide, t-butylperoxy (2-) is preferably added to the polymerizable composition. Ethyl hexanoate), azoisobutyronitrile, etc. are added and dissolved, and the polymerization is carried out at a heating temperature of 20 ° C. to 150 ° C., preferably 30 to 130 ° C. for 1 to 30 hours, preferably 10 to 20 hours. It is preferable to react. The reaction atmosphere may be either air or an inert gas, but is preferably air in terms of operation.

In the case of ultraviolet curing, a photopolymerization initiator such as benzophenone, benzoin methyl ether, benzoin isopropyl ether, diethoxyacetophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide is preferably added to the polymerizable composition. Are added and dissolved, and ultraviolet rays are irradiated in the atmosphere or an inert gas to cause a polymerization and curing reaction. The irradiation light amount is appropriately selected depending on the type of the composition and the photopolymerization initiator, but is 0.0
1 to 300 J / cm ² , especially 20 to 100 J / cm ² ,
Is preferred. As the light source, a chemical lamp, a xenon lamp, a low pressure (high pressure) mercury lamp, a metal halide lamp or the like is used. It is possible to polymerize and cure with an active energy ray other than ultraviolet rays, such as an electron beam, without a photopolymerization initiator.

The amount of photopolymerization initiator and thermal polymerization initiator used is in the range of about 0.01 to 5%, preferably 0.03 to 2%, based on the total weight of the composition. If the amount is too small, the curing will be insufficient, and if it is too large, the cured resin will easily turn yellow and the control of polymerization will be difficult.

In the polymerizable composition of the present invention, a radical polymerization accelerator, a polymerization regulator, an ultraviolet absorber, a release agent, an antioxidant, and other additives can be appropriately added as an auxiliary agent. As these additives, known commercial products can be used, but phosphorus-based antioxidants are particularly preferable as the antioxidant. (3) Resin Material (Part 2) The present invention also provides at least one dithiane ring-containing unsaturated monomer and at least one radically polymerizable monomer having at least one vinyl group in one molecule. The present invention relates to a resin material, which is obtained by polymerizing and curing a polymerizable composition containing and by the action of heat and / or active energy rays.

Typical examples of preferable radical polymerizable monomers include (a) vinyl compounds, specifically styrene, vinyltoluene, methoxystyrene,
Chlorostyrene, bromostyrene, dichlorostyrene,
Dibromostyrene, divinylbenzene, vinylnaphthalene, etc., and (b) (meth) acrylate compounds, specifically phenyl methacrylate, 2,2-bis (4-
(Meth) acryloyloxyphenyl) propane, its halogen derivative, 2,2-bis (4- (2- (meth) acryloyloxyethoxy) phenyl) propane, p-
There are bis (β- (meth) acryloyloxyethylthio) xylylene, m-bis (β- (meth) acryloyloxyethylthio) xylylene and the like. Here, "(meth) acryloyl" means both acryloyl and methacryloyl. Two or more kinds of these radically polymerizable monomers can be used.

The content of the radical-polymerizable monomer is arbitrary as long as it does not impair the gist of the present invention, but in general, 1 to 80 parts by weight per 100 parts by weight of the total amount of the radical-polymerizable monomer and the dithian ring-containing unsaturated monomer, Preferably 1 to 40 parts by weight,
Is adopted.

By blending such a radically polymerizable monomer with an unsaturated monomer, the physical properties or viscosity of the resin material can be adjusted.

As the polymerization and curing method, and the polymerization initiator, auxiliary agent and the like, the same ones as described above in the resin material (No. 1) can be used. (4) Molding / Polymerization of Optical Element (Continued) The polymerizable composition containing the dithiane ring-containing unsaturated monomer as an essential component according to the present invention is contained in a mold having a cavity corresponding to a target optical element. By carrying out so-called cast polymerization, the desired optical element can be produced immediately or in a state where only simple post-treatment such as surface polishing is required. This is the preferred polymerization method in the invention.

In the case of cast polymerization, the polymerizable composition may be injected into the mold as it is according to a conventional method, or the polymerization may be carried out outside the mold to a certain degree to form a viscous so-called syrup and then the mold is formed. It is also possible to inject into. In the latter case, it is possible to carry out the syrup formation and the polymerization in the mold by different polymerization initiation means.

In order to complete the polymerization, the polymerization cured product is
It is also possible to carry out further heating and / or irradiation with an active energy ray or other polymerization accelerating treatment in the mold or after removing it from the mold.

Another method of making an optical element using the present invention is to obtain a polymer in the form of a lump, a plate or another shape,
Then, the desired optical element is manufactured by cutting or other processing means.

Regardless of which manufacturing method is used, the optical element comprising the polymerized and cured product of the polymerizable composition according to the present invention, that is, the resin material according to the present invention, has any shape that a synthetic resin optical element can adopt. sell. In particular,
For example, a lens (including a Fresnel lens), a prism, a mirror, an optical disk, and the like can be used.

[0040]

EXAMPLES The following examples and comparative examples serve to further explain the present invention. In these examples "part"
Means parts by weight. The physical properties of the resins in these examples are measured by the following test methods.

Appearance By visual inspection.

Refractive Index Measured with an Abbe refractometer. (Measurement temperature: 25 ° C) Hardness Depends on pencil hardness. Example 1 To 100 parts of the compound represented by the formula (1), 0.3 part of t-butylperoxy-2-ethylhexanoate (manufactured by NOF CORPORATION, trade name "Perbutyl O") was added and defoamed. rear,
It was poured into a mold having a thickness of 2 mm composed of a glass plate and silicon rubber. Then, from 30 ℃ to 100 ℃ 1
The temperature was raised over 5 hours.

After removing the obtained cured product from the mold, the physical properties were measured. The results are as shown in Table 1. Example 2 To 100 parts of the compound represented by the formula (2), 0.3 part of t-butylperoxy-2-ethylhexanoate (manufactured by NOF CORPORATION, trade name "Perbutyl O") was added and defoamed. rear,
It was poured into a mold having a thickness of 2 mm composed of a glass plate and silicon rubber. Then, from 30 ℃ to 100 ℃ 1
The temperature was raised over 5 hours.

After removing the obtained cured product from the mold, the physical properties were measured. The results are as shown in Table 1. Example 3 85 parts of the compound represented by the formula (1) and 15 parts of styrene were mixed and stirred, and t-butylperoxy-2-ethylhexanoate (trade name “Perbutyl O” manufactured by NOF CORPORATION).
After adding 3 parts and defoaming, it was poured into a mold having a thickness of 2 mm composed of a glass plate and silicon rubber. Next, the temperature was raised from 30 ° C. to 100 ° C. over 15 hours.

After removing the obtained cured product from the mold, the physical properties were measured. The results are as shown in Table 1. Example 4 85 parts of the compound represented by the formula (1) and 15 parts of p-bis (β-methacryloyloxyethylthio) xylylene were mixed and stirred, and 0.1 part of 2,4,6-trimethylbenzoyldiphenylphosphine oxide and After adding 0.2 part of t-butyl peroxy-2-ethylhexanoate (trade name "Perbutyl O" manufactured by NOF CORPORATION) and defoaming, a thickness composed of a glass plate and silicon rubber 2 mm
Was poured into the mold. Next, in an atmosphere at 110 ° C,
Using a high-pressure mercury lamp with an output of 80 W / cm, a height of 40 cm
Light was applied from both sides of the glass for 3 minutes.

After removing the obtained cured product from the mold, the physical properties were measured. The results are as shown in Table 1. Comparative Example 1 85 parts of the compound represented by the formula (1) and benzenethiol 1
The composition was cured as in Example 1 using 5 parts.
The appearance of the cured product was colorless and transparent. However, the cured product was rubbery, and it was impossible to measure the refractive index and other physical properties.

[0047]

[Table 1]

[0048]

INDUSTRIAL APPLICABILITY The polymerizable composition of the present invention and the resin material obtained by polymerizing and curing the composition have low specific gravity, high refractive index and low dispersion, and are excellent in weather resistance and heat resistance. What is preferable as the resin for the lens is as described above in the section "Outline of the Invention".

Claims (3)

[Claims] 1. A polymerizable composition comprising a dithiane ring-containing unsaturated monomer represented by the following general formula [I]. [Chemical 1] [The integers and chemical formulas represented by the symbols in the formulas may be the same or different, and each independently, b
1 and b2 are integers of 1 to 5, and c1 and c2 are 0 to
An integer of 2, W and X are hydrogen atoms, CH ₃ , Or [Chemical 3] [D represents an integer of 1 to 5 and e represents an integer of 0 to 2]
And A and B represent a hydrogen atom or CH ₃ , respectively.] 2. A polymerizable composition comprising the dithiane ring-containing unsaturated monomer according to claim 1, which is polymerized and cured by the action of heat and / or active energy rays. Resin material. 3. A polymerization comprising at least one dithiane ring-containing unsaturated monomer according to claim 1 and at least one radically polymerizable monomer having at least one vinyl group in one molecule. A resin material, which is obtained by polymerizing and curing a functional composition by the action of heat and / or active energy rays.