JPH07278243A - Polymerizable composition and optical material - Google Patents

Abstract

PURPOSE:To obtain a polymerizable composition excellent in optical, mechanical and thermal properties, weatherability, etc., by using a prepolymer having specified structural units and a specified degree of polymerization as the essential component. CONSTITUTION:A polymerizable composition is produced by using a prepolymer comprising structural units represented by formula I (m is 2-20) and having a degree of polymerization of 2-1000 (e.g. a prepolymer of formula II or III (n is the degree of polymerization, and n<1>+n<2>=n) as the essential component. This composition may further contain a monomer (e.g. styrene or ethylene glycol bisacrylate) copolymerizable with the above prepolymer. The prepolymer having structural units of formula I can be produced by reacting vinylbenzaldehyde with HS(CH2CH2S)2H or the like in the presence of an acid catalyst. By curing the above composition by polymerization, a plastic lens or the like having a refractive index as high as 1.55 or above and excelling in optical transparency, etc., can be produced.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention is applicable to a polymerizable composition which can be used as a polymerization component such as an optical resin, a coating resin and a decorative resin, and a plastic lens for spectacles and OA equipment. It relates to optical materials.

[0002]

2. Description of the Related Art In recent years, synthetic resin materials excellent in light weight, moldability, impact resistance and dyeability have been used as plastic lens materials instead of inorganic glass. Known examples of such synthetic resin materials include polymethyl methacrylate, polydiethylene glycol bisallyl carbonate, polystyrene, and polycarbonate. However, polymethylmethacrylate and polydiethylene glycol bisallyl carbonate are excellent in lightness and impact resistance, but when used as a lens because of their low refractive index of about 1.49, a thicker lens than inorganic glass is required, It has the drawback of not being suitable for higher magnification and lighter weight. Polystyrene and polycarbonate have a high refractive index of about 1.58 to 1.59, but since these resins are thermoplastic, there is a problem that optical distortion due to birefringence is likely to occur during injection molding. It has the drawback of poor solvent resistance and scratch resistance.

Therefore, recently, various proposals have been made in order to improve these drawbacks. For example, JP-A-53
-7787 discloses a copolymer of diethylene glycol biscarbonate and diallyl isophthalate, and JP-A-59-81318 discloses a copolymer of diallyl phthalate and an unsaturated fatty acid alcohol benzoate. JP-A-59-191708 discloses a copolymer of di (meth) acrylate having bisphenol A, diallyl isophthalate, and diethylene glycol bisallyl carbonate. These copolymers have a refractive index of about 1.52 to 1.55, but have the drawback that unreacted allyl monomer is likely to remain.

Further, Japanese Patent Application Laid-Open No. 57-28115 discloses that
A copolymer of a styrene-based vinyl monomer and an unsaturated carboxylic acid heavy metal salt is disclosed in JP-A-60-55007.
Copolymers of halogen-substituted diallyl phthalates and halogen-substituted allyl benzoates are shown. These copolymers have a high refractive index of about 1.58 to 1.60, but since they use a metal salt or an allylic monomer having a halogen-substituted aromatic ring, they have a large specific gravity and a heavy lens. Therefore, there is a drawback that weight reduction is impaired.

Further, Japanese Patent Laid-Open No. 2-160762 discloses that
Dimercaptodiphenyl sulfide dimethacrylate and 2- (vinylbenzyl sulfide) benzothiazole are proposed in JP-A-2-29401. The refractive index of these polymers is as high as about 1.60 to 1.70, but the chromatic aberration and dimensional stability are poor, the polymerization reaction is difficult to control, the specific gravity is large, and the weather resistance is also problematic. .

[0006]

The object of the present invention is to provide an optical material having excellent weather resistance, solvent resistance, etc., excellent dimensional stability, low specific gravity, high refractive index and optical transparency. An object of the present invention is to provide a polymerizable composition that can be used as a raw material for a coating material, a coating resin, a decorative resin, and the like.

Another object of the present invention is to provide an optical material having excellent weather resistance, solvent resistance, etc., excellent dimensional stability, low specific gravity, high refractive index and optical transparency. To do.

[0008]

According to the present invention, the polymer has a structural unit represented by the following structural formula 2 and has a degree of polymerization of 2 to 100.
No. 0 prepolymer (hereinafter referred to as prepolymer A) and, if necessary, a polymerizable monomer copolymerizable with the prepolymer A are provided.

[0009]

[Chemical 2]

Further, according to the present invention, there is provided an optical material obtained by polymerizing and curing the above-mentioned polymerizable composition and having a refractive index of 1.55 or more.

The present invention will be described in detail below. The polymerizable composition of the present invention contains the prepolymer A represented by the structural formula 2 as an essential component.

In the prepolymer A, when m is 21 or more, the production is difficult. The polymerization degree of the prepolymer A is 2 to 1000, the preferable lower limit is 5 from the viewpoint of performance, and the preferable upper limit is 100 from the viewpoint of workability. Further, the lower limit of the molecular weight of the prepolymer A is preferably 500 in order to express the properties of the prepolymer, particularly preferably 1000 in order to further express the properties, and the upper limit of the molecular weight is preferably due to high viscosity. From the viewpoint of preventing a decrease in handling, it is preferably 100,000, and particularly preferably 20,000 to further improve the handling property.

Examples of the prepolymer A include compounds represented by the following general formula 3.
At this time, n represents the degree of polymerization and n ¹ + n ² = n.

[0014]

[Chemical 3]

To prepare the prepolymer A, vinylbenzaldehyde and HS (CH ₂ CH ₂ S) mH (m is 2 to 20)
And represents an integer of) and a reaction method in the presence of an acid catalyst.

The above-mentioned vinylbenzaldehyde is p
-Vinylbenzaldehyde, m-vinylbenzaldehyde, o-vinylbenzaldehyde or a mixture thereof can be used.

The above HS (CH ₂ CH ₂ S) mH means HS (CH ₂ CH ₂ S) ₂ H, HS
(CH ₂ CH ₂ S) ₃ H, HS (CH ₂ CH ₂ S) ₄ H, HS (CH ₂ CH ₂ S) ₅ H, HS (CH ₂ C
H ₂ S) ₆ H, HS (CH ₂ CH ₂ S) ₇ H, HS (CH ₂ CH ₂ S) ₈ H, HS (CH ₂ CH ₂ S) ₉
H, HS (CH ₂ CH ₂ S) ₁₀ H, HS (CH ₂ CH ₂ S) ₁₁ H, HS (CH ₂ CH ₂ S)
₁₂ H, HS (CH ₂ CH ₂ S) ₁₃ H, HS (CH ₂ CH ₂ S) ₁₄ H, HS (CH ₂ CH ₂ S) ₁₅
H, HS (CH ₂ CH ₂ S) ₁₆ H, HS (CH ₂ CH ₂ S) ₁₇ H, HS (CH ₂ CH ₂ S)
₁₈ H, HS (CH ₂ CH ₂ S) ₁₉ H, HS (CH ₂ CH ₂ S) ₂₀ H and the like can be mentioned, and they can be used alone or as a mixture in the reaction.

As the acid catalyst, TiCl ₄ , AlC
l _3, FeCl _3, Lewis acids such as ZnCl _2, BF _3; hydrochloride, mineral or sulfuric; p-tosylate, benzenesulfonate, and organic acids such as trifluoroacetic acid; and include cation exchange resins such as However, TiCl ₄ is used because it is easy to handle and has high activity.

In order to carry out the reaction for obtaining the prepolymer A, it can be easily obtained by a method of stirring and reacting without solvent or in the presence of an organic solvent such as chloroform, methylene chloride, acetonitrile, benzene and toluene. You can At this time, vinyl benzaldehyde and compound B
It is preferable that the molar ratio of the ingredients to be charged is 1: 0.5 to 1: 2 mol, particularly 1: 0.8 to 1: 1.2 mol. The reaction temperature is preferably -100 to 120 ° C, particularly 0 to 60 ° C. Further, the reaction time is 1 minute to 48 hours, particularly 30 minutes to 24 hours.
Time is preferred.

The obtained prepolymer A can be easily isolated / isolated by known methods such as washing / extracting operation, reprecipitation operation, column separation operation, adsorbent treatment, ion exchange resin treatment and the like.
It can be purified.

Since the prepolymer A also has excellent addition reactivity to the styryl group of the side chain, for example, mercapto-containing compounds such as thiophenol and mercaptoethanol,
Alternatively, amino-containing compounds such as dimethylamine and diethylamine can be easily added.

To carry out such an addition reaction, solvent-free or acetonitrile, methanol, ethanol, N, N in the presence of an oxidizing agent such as oxygen, air or peroxide, or a basic catalyst such as amine or alkoxide. -In an organic solvent such as dimethylformamide, dimethylsulfoxide, tetrahydrofuran and chloroform, preferably at a reaction temperature of -100 to 150 ° C, particularly 0 to 100 ° C, and a reaction time of 10 minutes to 100 hours, particularly 10 minutes to 12 hours, Stirring,
It can be easily performed by a reaction method or the like.

In addition to the prepolymer A, the polymerizable composition of the present invention may contain, if necessary, another polymerizable monomer copolymerizable with the prepolymer A. Examples of the other polymerizable monomer that can be copolymerized include styrene, p-methylstyrene, p-chlorostyrene, o-chlorostyrene, p-bromostyrene, o-bromostyrene, α-methylstyrene, p-chlorostyrene. Methyl styrene, vinyl acetate, vinyl propionate, methyl (meth) acrylate, butyl methacrylate, ethyl acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, bromphenyl methacrylate, (meth) acrylonitrile, (meth) acrylic acid, 2 -Monofunctional monomers such as hydroxyethyl methacrylate; 2,2-bis (4
-(Meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloylpoly (n = 2-20) ethoxyphenyl) propane, 2,2
-Bis (4-2'-hydroxy-3 '-(meth) acryloyloxypropoxyphenyl) propane, diethylene glycol bisallyl carbonate, diallyl tetrachlorophthalate, diallyl phthalate, p-divinylbenzene, m-divinylbenzene, divinylbiphenyl,
Ethylene glycol bis (meth) acrylate, diethylene glycol bis (meth) acrylate, triethylene glycol bisacrylate, tetraethylene glycol bis (meth) acrylate, polyethylene glycol bis (meth) acrylate, dipropylene glycol bismethacrylate, propylene glycol bisacrylate, bisphenol A bis (meth) acrylate,
Preferred examples include polyfunctional monomers such as diallyl tetrachlorophthalate, diallyl isophthalate, allyl methacrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, and tetramethylolmethane tetra (meth) acrylate. It can be used alone or as a mixture.

The essential components of the polymerizable composition include prepolymer A alone, a combination of prepolymer A and the monofunctional monomer, a combination of prepolymer A and the polyfunctional monomer, and prepolymer A. It may be any combination of the monofunctional monomer and the polyfunctional monomer, etc., but in order to prepare a cured product having particularly excellent mechanical strength, the polyfunctional monomer is contained. Is desirable.

In the polymerizable composition, the mixing ratio of the prepolymer A is 1 so that the lower limit of the content of the prepolymer A with respect to the total amount of the composition is preferably 1 so that the optical properties of the prepolymer A can be exhibited. %, Particularly preferably 20% by weight in order to sufficiently exhibit the characteristics, while the upper limit is preferably 100% by weight, particularly preferably 80% by weight in order to improve mechanical strength and the like. The blending ratio of the other polymerizable monomer that can be copolymerized is 0 to 99% by weight, particularly 20 to 80% by weight based on the total amount of the composition.
Is preferred.

In order to polymerize and cure the polymerizable composition of the present invention, the conditions can be appropriately selected according to the intended cured product, and the composition can be polymerized according to the method for preparing an optical material described later.

The optical material of the present invention has a refractive index of 1.55 or more, preferably 1.56 to 1.68, obtained by polymerizing and curing the above-mentioned polymerizable composition. That is, it is a homopolymer of the prepolymer A or a copolymer of a composition containing the prepolymer A and the other polymerizable monomer capable of copolymerization and having the specific refractive index.

To prepare the optical material of the present invention, for example, the polymerizable composition is added in the presence of a radical polymerization initiator.
It can be obtained by a method such as photopolymerization or heat polymerization.

As the radical polymerization initiator, it is preferable to use an organic peroxide and / or an azo compound having a 10-hour half-life temperature of 160 ° C. or lower. Specifically, for example, benzoyl peroxide, diisopropyloxydioxide. Carbonate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxypivalate, tert-butyl peroxydiisobutyrate, lauroyl peroxide, tert-butyl peroxyacetate, tert-peroxy octoate, tert-butyl peroxybenzo Examples thereof include eight, azobisisobutyronitrile, and a mixture thereof. The amount of the radical polymerization initiator used is preferably 10 parts by weight or less, more preferably 5 parts by weight or less with respect to 100 parts by weight of the polymerizable composition.

The above-mentioned polymerization conditions and the like can be appropriately selected according to the intended optical material. For example, in the production of plastic lenses for spectacles, the above-mentioned polymerizable composition and radical polymerization initiator can be directly desired. It is possible to employ conditions such as charging in a mold and heating and polymerizing at 0 to 200 ° C. for 1 to 48 hours. At this time, the polymerization system is preferably replaced with an inert gas such as nitrogen, carbon dioxide or helium or under an atmosphere. Alternatively, the polymerizable composition may be preliminarily polymerized at 0 to 200 ° C. for 0.5 to 48 hours in advance, charged in a desired mold and then polymerized. Further, during the above-mentioned polymerization and curing, additives such as UV absorbers and anti-coloring agents may be added, and in order to improve the surface physical properties of the obtained polymerized and cured product, various surface treatments are conducted on the surface after curing. Can also be applied.

[0031]

Since the polymerizable composition of the present invention contains a prepolymer having an alkylene sulfide group in the main chain and a reactive styryl group in the side chain as essential components, it has excellent optical properties and mechanical properties. Properties, thermal properties, chemical stability,
It is possible to obtain an optical material having weather resistance and the like, a resin for paint, a resin for decoration, and the like. Further, the optical material of the present invention is a cured product of the polymerizable composition, and thus has a refractive index, transparency,
It has excellent optical properties such as solvent resistance, and is extremely useful for plastic lenses for spectacles and OA equipment.

[0032]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[0033]

Synthesis Example 1 1.0 g (7.6 mmol) of p-vinylbenzaldehyde and bis-in 5 ml of chloroform.
1.4 g of (2-mercaptoethyl) sulfide (9.0
mmol), and after cooling to -10 ° C, TiCl
₄ 0.19 g (1 mmol) was added, and the mixture was stirred at 30 ° C. for 4 hours. The progress of the reaction, the IR spectrum was confirmed by the disappearance of the absorption of 1700 cm ~ ¹ from aldehydes. After completion of the reaction, the mixture was washed with a 5 wt% sodium hydroxide aqueous solution and distilled water, and the organic layer was concentrated under reduced pressure to obtain a target prepolymer (hereinafter referred to as prepolymer (I)) liquid. The yield was 92%. The molecular weight of the obtained prepolymer (I) was measured by GPC (gel permeation chromatography) (column: developing solvent: tetrahydrofuran, standard sample: polystyrene), and as a result, it was about 9000. Prepolymer obtained below
The measurement results of ¹ H-NMR, ¹³ C-NMR, IR and elemental analysis of (I) are shown.

[0034]

[Chemical 4]

IR (KBr; cm ~ ¹ ) 1510, 860 (para or disubstituted benzene) 2990, 1408, 990 (vinyl) Elemental analysis (C ₁₃ H ₁₆ S ₃ ) theoretical value; H: 6.02, C: 58.20, S: 35.7
8 Measured value; H: 6.00, C: 58.28, S: 35.7
Two

[0036]

Synthesis Example 2 The target prepolymer (hereinafter referred to as prepolymer) was prepared in the same manner as in Example 1 except that 2,2 ′-(ethylenedithio) diethanethiol was used instead of bis- (2-mercaptoethyl) sulfide. A colorless and transparent viscous liquid of a polymer (II) was obtained. The yield was 91% and the molecular weight was 11,500. The structural unit of the prepolymer (II) obtained below is shown in Formula 5.

[0037]

[Chemical 5]

[0038]

Examples 1 to 10 are shown in Table 1 using the prepolymer (I) synthesized in Synthesis Example 1 and Examples 6 to 10 are the prepolymer (II) synthesized in Synthesis Example 2. The polymerizable composition shown was prepared. Each polymerizable composition obtained (total amount: 1 g)
After adding 0.01 g of trade name "Perbutyl O" (manufactured by NOF CORPORATION) to the test tube and substituting with nitrogen, 70
It was cured by heating at ℃ for 12 hours. The refractive index and Abbe number of the obtained resin were measured using an Abbe refractometer (manufactured by Atago Co., Ltd., trade name "2T"). The appearance and the presence or absence of apparent denaturation were visually evaluated after immersion in boiling water for 10 minutes. The measurement results are shown in Table 1.

[0039]

Comparative Examples 1 to 3 Each of the polymerizable compositions prepared in the blending ratios shown in Table 1 was polymerized and cured in the same manner as in Example 1, and the refractive index, Abbe number, appearance and apparent modification were measured. The measurement results are shown in Table 1.

[0040]

[Table 1]

Claims (3)

[Claims] 1. A polymerizable composition containing a prepolymer having a structural unit represented by the following structural formula 1 and having a degree of polymerization of 2 to 1000. [Chemical 1] 2. The polymerizable composition according to claim 1, further comprising a polymerizable monomer copolymerizable with the prepolymer. 3. An optical material having a refractive index of 1.55 or higher, which is obtained by polymerizing the polymerizable composition according to claim 1 or 2.