JPH04159275A - Polyisocyanate compound, optical material and product obtained by using the same - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (n1 is 0-3; n2 is 2-4; only one each of the substituent groups in the parenthesis can optionally be added to the 2,3,5 or 6-position of the 1,4-dithian ring). EXAMPLE:2,5-Isocyanatomethyl-1,4-dithian. USE:An optical material, especially preferred as plastic lenses. PREPARATION:A compound expressed by formula II is reacted with a compound expressed by formula III according to the reaction formula to provide a compound expressed by formula IV, which is then reacted with Triton B(R) to afford a compound expressed by formula V. The resultant compound expressed by formula V is further reacted with NaOH, HCl, etc., to provide a compound expressed by formula VI, which is subsequently reacted with a compound such as CH3CH2OOCl or (CH3CH2)3N to afford the objective compound such as a compound expressed by formula VII.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polyisocyanate compound, and optical materials and optical products obtained using the same. The polyisocyanate compound of the present invention is used, for example, as a useful raw material for optical plastic lens materials. In addition, the optical material of the present invention obtained using the above polyisocyanate compound has a high refractive index, low dispersion, and excellent optical properties, and is used for optical applications such as lenses, prisms, optical fibers, recording medium substrates, filters, etc. Preferably used in products. Furthermore, decorative items such as glasses and flower vases that take advantage of their high refractive index are also included in the optical products referred to here.

[Conventional technology]

Plastic lenses are lighter than glass, less likely to break, and are easier to dye, so they have been used in optical applications such as various lenses in recent years. The plastic material for this purpose is polyethylene glycol bisallyl carbonate (CR).
-39) and polymethyl methacrylate (PMMA) are commonly used. The refractive index of these plastic materials is 1°50 or less, and when used in lens materials, for example, as the power increases, the lens must be made thicker, which not only loses the advantage of lightweight plastics. However, when used as a lens for spectacles, the esthetics deteriorated, which was not preferable.

Further, in particular, in the case of a concave lens, the thickness around the lens becomes thick, causing birefringence and chromatic aberration, which is not desirable. Therefore, there is a need for a high refractive index, low dispersion plastic material that can reduce the thickness of the lens while taking advantage of the characteristics of plastic with low specific gravity, and has less brown color aberration. Materials for this purpose include tetrachloromethaxylylenedithiol and I
, 3,5-trimercaptobenzene and a diisocyanate compound are disclosed in JP-A-63-46213. Further, a polymer of pentaerythritol tetrakisthioprobionate and diisocyanate is disclosed in JP-A-64-26622. Furthermore, a polymer of pentaerythritol tetrakisthioprobionate and a vinyl compound was disclosed in JP-A-63-3095.
It is disclosed in Publication No. 09.

[Problem to be solved by the invention]

However, although the isocyanate compounds described in JP-A-63-46213 and JP-A-64-26622 have a high refractive index, they have a low Atsube number, and polyadducts of these and thiol compounds have a It has the disadvantages of low heat resistance and poor weather resistance. Also, JP-A-63-
The polymer described in Japanese Patent No. 309509 has drawbacks such as a low refractive index and a low Abe's number, and poor heat resistance.

Therefore, an object of the present invention is to provide a new isocyanate compound that eliminates the above-mentioned drawbacks, and new optical materials and optical products using the same as a raw material.

[Means to solve the problem]

The present invention was made to achieve the above-mentioned object, and the novel thiol compound of the present invention is characterized by being represented by the general formula (1).

[In the formula, nl is an integer of 0 to 5. Also, n.

is an integer from 2 to 4, and the substituent in [ ] is I.

Only one can be optionally added to each of the 2.3 and 5.8 positions of the 4-dithiane ring. ] Further, the novel optical material of the present invention comprises a component (A) containing at least the isocyanate compound (a2) represented by the above general formula (1), and a compound having two or more hydroxyl groups in one molecule (
b2), containing at least one of the following: a compound (b2) having two or more mercapto groups in one molecule; and a compound (b2) having one or more hydroxyl groups and one or more mercapto groups in one molecule. It is characterized by being obtained by polymerizing component (B).

The present invention will be explained in detail below.

The novel thiol compound of the present invention is characterized by having a 1,4-dithiane ring which is an alicyclic sulfide. This 1,4-dithiane ring increases the refractive index and Atsube number of the polyisocyanate compound itself, so when an optical material is manufactured using this polyisocyanate compound, it also increases the refractive index and Atsube number of the optical material. . Further, since the 1,4-dithian ring of this polyisocyanate compound is rigid, when an optical material is manufactured using this polyisocyanate compound, it provides high heat resistance and excellent mechanical properties to the optical material. The reason why nl is limited to an integer of 0 to 3 in general formula [1] will be described. When nl is 4 or more, the refractive index of the polyisocyanate compound decreases, and the refractive index of the optical material obtained using the polyisocyanate compound as a raw material tends to decrease, and the heat resistance also tends to decrease, which is not preferable. Also, in formula (1), n2 is written as 2 to 4 because [
2゜3.5.6- of the 1,4-dithiane ring
This shows that only one can be added to each position arbitrarily. In the general formula (1), the polyisocyanate compound of the present invention has n+ = 1. , n9 = 2
In the case of (2,5-position), it can be synthesized by the method shown in the following formula.

(Left below) The synthesis method shown above, n+ = l, n* -2(2
, 5-position) other than the polyisocyanate compound represented by formula (1), the following may be mentioned.

Next, the optical material of the present invention obtained using the polyisocyanate compound of the above formula [1] will be described. This optical material contains at least the polyisocyanate compound (a1) shown by the above general formula [1]. Ingredient (A) and
Compounds with two or more hydroxyl groups in one molecule (
b1), a compound (b2) having two or more mercapto groups in one molecule, and a compound (b2) having one or more hydroxyl groups and one or more mercapto groups in one molecule; It is obtained by polymerizing the component (B) contained therein.

Since the compound of general formula [1] in component (A) has already been described in detail here, its explanation will be omitted.

Component (A) may contain, in addition to the compound represented by the general formula [1], a compound having two or more iso(thio)cyanate groups in one molecule in order to appropriately improve the physical properties of the optical material. It may contain one kind or two or more kinds. These compounds specifically include xylylene diiso(thio)cyanate, 3゜3'-dichlorodiphenyl-4,4'-
Diiso(thio)cyanate, 4,4'-diphenylmethane diiso(thio)cyanate, Hexamethylene diiso(
thio)cyanate, isophorone diiso(thio)cyanate, 2.2',5.5'-tetrachlorodiphenyl-4,4'-diiso(thio)cyanate, tolylene diiso(thio)cyanate, 1.3-bis( Examples include iso(thio)cyanatomethyl)cyclohexane. In addition, the above-mentioned iso(thio)cyanate means both an isocyanate and an isothiocyanate, and the iso(thio)cyanate group means both an isocyanate group and an isothiocyanate group. The amount of the compound represented by the general formula [1] to be used is 0.000000 with respect to the total amount of component (A). 1-j
OOmo is 1%, preferably 5-15-1O0%.

Hydroxyl group-containing compound (b) used in component (B)
Specific examples of 1) include ethylene glycol, trimethylolpropane, glycerin, dihydroxybenzene, catechol, 4,4'-dihydroxyphenylsulfide, and 2-hydroxyethylsulfide. Further, the mercapto group-containing compound (b2) used in component (B) is 1,2-ethanedithiol, 1,3-
Propanedithiol, tetrakismercaptomethylmethane, pentaerythritol tetrakismercaptopropionate, pentaerythritol tetrakismercaptoacetate, 2,5-dimercaptomethyl-1,4-dithiane, 1,2-benzenedithiol, I,3-benzenedithiol, 1.4-benzenedithiol, I, 3.
5-benzene trithiol, 1,2-dimercaptomethylbenzene, 1,3-dimercaptomethylbenzene, 1
．． Examples thereof include 4-dimercaptomethylbenzene, 1,3°5-trimercaptomethylbenzene, toluene-3,4-dithiol, and tris(3-mercaptopropyl)isocyanurate.

In addition, the hydroxyl group- and mercapto group-containing compound (b3) used in component (B) includes 2-mercaptoethanol, 2,3-dimercaptopropanol, 1
．． Examples include 2-dihydroxy-3-mercaptopropane and 4-mercaptophenol.

The usage ratio of component (A) and component (B) (component (A)/component (B)) is such that the ratio of (iso(thio)cyanate group)/(mercapto group + hydroxy group) is 0.95 to 1. 05
It is preferable that it is within the range of . Furthermore, additives such as ultraviolet absorbers, antioxidants, color inhibitors, and fluorescent dyes may be added as appropriate to improve weather resistance. Further, a catalyst for improving polymerization reactivity may be used as appropriate, and organic tin compounds, amine compounds, etc. are effective.

- As an example, the production of the optical material of the present invention using the polyisocyanate compound of the present invention will be described as follows.

A homogeneous mixture of the above components (A), component (B), additives and catalysts is poured into a mold using a known cast polymerization method, that is, a mold made of a glass or metal mold and a resin gasket, and heated. and harden. At this time, in order to facilitate the removal of the resin after molding, the mold may be subjected to mold release treatment in advance, or a release agent may be mixed into the mixture of component (A) and component (B). The polymerization temperature varies depending on the compound used, but is generally -20 to +150°C, and the polymerization time is 0.5 to 72 hours. The optical material of the present invention can be easily dyed in water or an organic solvent using a conventional disperse dye.
A carrier may be added or heated.

The optical material thus obtained is particularly preferably used as a plastic lens, although it is not limited thereto.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

(Evaluation of physical properties) Physical properties of the polyisocyanate compounds and optical materials (polymers) thereof obtained in Examples and Comparative Examples were evaluated as follows.

Refractive index (n2) and Atsube number (vD) Measured at 20° C. using an Atago refractometer 3T.

exterior Observation was made with the naked eye.

Weather equipped with weather resistant sunshine carbon arc lamp
A lens (an optical product using an optical material) was set in the meter, and after 200 hours had elapsed, the lens was taken out and the hue was compared with the lens before the test. The evaluation criteria were: no change (○), slight yellowing (△), and yellowing (x).

TMA measurement was performed using a heat-resistant Rigaku TMA device using a 0.5 mmφ pin at a load of IOgf, and at a rate of 10°C/min.
Evaluation was made based on the peak temperature of the chart obtained by increasing the temperature.

optical distortion Macroscopic observation was performed using the Schlieren method.

Those with no distortion were rated 0, and those with distortion were rated ×.

(Example) (Carboethoxymethylene)triphenylphosphorane (91.68g, 0゜263mo 1), 2,5-dihydroxy-1,4-dithiane (22゜04g, 0.1
45 mo1) and benzene 500 mf.
The mixture was stirred at ℃ for 1 hour. The reaction mixture went from a suspension to a clear solution. Benzene was distilled off under reduced pressure, and the desired product was extracted from the precipitated crystals with isopropyl ether. After distilling off isopropyl ether from the extract, the residual aroma was distilled under reduced pressure to obtain a fraction of 62-67°C/15mmHg, 22-9.
g (yield 59.6%) was recovered.

Dissolve this in 310mf chloroform and
56 mA of Triton B was added and refluxed for 30 minutes. A viscous liquid was obtained by distilling off chloroform from the reaction mixture.

The above sticky liquid (57.73g, 0.198m).

] ) to] 15 wt % - sodium hydroxide aqueous solution! 58.
1 g (0,593 mo1) was added and stirred at room temperature for three days. Activated carbon was added to the reaction mixture and the mixture was filtered, and then acidified with concentrated hydrochloric acid until pH=1. The precipitate was filtered and dried to obtain 33.01 g of carboxylic acid (yield: 70.696).

The obtained carboxylic acid (17,00g, 0.072mol
) with 25 ml of water and 50 mI! suspended in acetone,
Triethylamine (17.45g.

0.173 mo1) in acetone solution at -5°C.
Added in. Ethyl chloroformate (18.75g,
43 ml of an acetone solution of 0.173 mo1) was added at -5°C, and stirred at that temperature for 30 minutes. Then sodium azide (14,04g, 0.216mol) in water 8
6rni solution was added at -10°C and stirred for 2.5 hours. The reaction mixture was poured into 500 mf of ice water, extracted with benzene, the extract was washed with water, and then dried over anhydrous magnesium sulfate. This benzene solution was passed through the mouth and the mouth was heated to 60°C. After 1 hour, no more nitrogen was generated, so the benzene was distilled off, and the residual aroma was recrystallized with ethyl ether to give 10.00 g of white needle-like crystals (yield from carboxylic acid: 60.0 g).
4%). This one had absorption due to isocyanate groups according to the TR spectrum (2257 cm-')
, it turned out to be the target object.

The TR spectrum of this new polyisocyanate compound is shown in FIG.

(Example 2) Preparation of 0 of I 2,5-diisocyanate methyl- obtained in Example I
1,4-dithiane (indicated as 5IC-1 in Table 1) 0.1
mol, 0.1 mol of 2.5-dimercaptomethyl-1,4-dithiane (denoted as DMMD in Table 1) and dibutyltin dilaurate (denoted as DBTL in Table 1) IX
The mixture of IO-'mol was stirred uniformly, poured into two lens molds, and heated at 50°C for 10 hours, then 6
Polymerization was performed by heating at 0°C for 5 hours and then at 20°C for 3 hours to obtain a plastic lens. Table 1 shows the physical properties of the obtained plastic lens. From Table 1, it can be seen that the polymer of Example 20 is colorless and transparent, has a very high refractive index (nD) of 1.68, has a high Abbe number (νD) of 37 (low dispersion), has good weather resistance, It had excellent heat resistance (120° C.) and no optical distortion.

(Examples 3 to 9) Example 2 except that the monomer composition shown in Table 1 was used.
A plastic lens was obtained by performing the same operation as above. The physical properties of these plastic lenses are shown in Table 1 together with the physical properties of the polymer of Example 2.

From Table 1, the plastic lenses of Examples 3 to 9 are colorless and transparent, have a very high refractive index (no) of 1.63 to 1.68, and have a high (low) Atsube number (ν0) of 39 to 42. Dispersion), weather resistance and heat resistance (106-124℃)
It had excellent properties and no optical distortion.

(Comparative Example 1) Pentaerythritol tetrakis mercaptopropionate (indicated as PETMP in Table 1) 0°1 mo 1, m
-0.2 mol of xylylene diisocyanate (designated as XDI in Table 1) and dibutyltin dilaurate (Table 1)
A mixture of I x 10-hmo 1 (indicated as DBTL) was stirred uniformly, poured into two lens molds, and heated at 50°C for 10 hours, then at 60°C for 5 hours, and then at 120°C. Polymerization was performed by heating for 3 hours to obtain a plastic lens.

Table 1 shows the physical properties of the obtained plastic lens. From Table 1, the plastic lens of this comparative example was colorless and transparent and no optical distortion was observed, but no/'ν. is 1,59/
The temperature was low at 36°C, and the heat resistance was also poor at 86°C.

(Comparative Examples 2 and 3) Comparative Example I except that the monomer composition shown in Table 1 was used.
A plastic lens was obtained by performing the same operation as above. The physical properties of these plastic lenses are shown in Examples 2 to 0,
Table 1 shows the various physical properties of the polymer of Comparative Example 1. From Table 1, the refractive index of the plastic lens of Comparative Example 2 is 1.6.
8 and excellent heat resistance (128° C.), but it was yellow in color, had a low heat resistance number, was poor in weather resistance, and optical distortion was observed. Further, the plastic lens of Comparative Example 3 was colorless and transparent, and had excellent heat resistance (113° C.) and weather resistance, but the refractive index was as low as 1.57, and optical distortion was observed.

(Left below) Abbreviations in Table 1 XDT: m-xylylene diisocyanate DMMD:
2,5-dimercaptomethyl-1,4-dithiane PETMP/pentaerythritol tetrakis mercaptoprobionate TMP 2)-limethylolpropane PETMA: pentaerythritol tetrakis mercaptoacetate IPDI: isophorone diisocyanate H,XDI
: 1.3-Di(isocyanatomethyl)cyclohexane DMP Nidimercaptopropanol TMPIC:) Lis(3mercaptopropyl)isocyanurate TG: Thioglycerol □ HES: 2-Hydroxyethyl sulfide XDT
:xylylene dithiol DBTL Nidibutyltin dilaurate TDI:) lylene diisocyanate MES: 2-mercaptoethyl sulfide [Effects of the invention] Since the novel polyisocyanate compound of the present invention has a 1°4-dithiane ring, the refractive index and Atsube number are low. Compounds with two or more hydroxyl groups in one molecule, compounds with two or more mercapto groups in one molecule, and compounds with one or more hydroxyl groups and one or more mercapto groups in one molecule. It easily undergoes a polymerization reaction with at least one of the above to provide an optical material. Moreover, the optical material of the present invention obtained using this polyisocyanate compound has 1
．． Contains a 4-dithiane ring in its main chain, so it has a high refractive index and Atsube number, and has excellent heat resistance, weather resistance, and transparency, so it can be used for lenses such as eyeglass lenses and camera lenses, prisms, optical fibers, optical disks, and magnetic disks. It is preferably used for optical products such as substrates for recording media, filters, etc.

Furthermore, it is also used in decorative items such as glasses and flower vases that take advantage of its high refractive index.

[Brief explanation of drawings]

FIG. 1 is a diagram showing an IR spectrum of the polyisocyanate compound obtained in Example 1.

Claims (1)

[Claims] 1. A polyisocyanate compound represented by the general formula [1]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [1] [In the formula, n_1 is an integer from 8 to 3. Further, n_2 is an integer of 2 to 4, and only one substituent in brackets can be arbitrarily added to the 2, 3, 5, and 6 positions of the 1,4-dithiane ring. ] 2. The polyisocyanate compound according to claim 1 (a_
Component (A) containing at least 1), a compound (b_1) having two or more hydroxyl groups in one molecule, and a compound (b_2) having two or more mercapto groups in one molecule.
and a component (B) containing at least one of the compounds (b_3) having one or more hydroxyl groups and one or more mercapto groups in one molecule. material. 3. An optical product characterized by using the optical material according to claim 2. 4. The optical product according to claim 3, wherein the optical product is a plastic lens.