JPH10268101A - Manufacture of resin for lens having large refraction factor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily manufacture a product having not only a large refraction factor and high impact resistance, but also rigidly at high temperature and a large Abbe number by pertinently selecting a diluting diol, using a manufacturing facility conventionally and generally in use. SOLUTION: This method manufactures resin for a lens having a large refraction number by causing reaction and copolymerization processes among the diols expressed by formula (wherein X stands for Br, Cl or H, m>=1, n>=1 and 2>=mfn>=6), diols and/or triols selected from aliphatic compounds, alicyclic compounds, heterocyclic compounds and aromatic compounds, when necessary, for diluting the diols in the formula, 3-ispopopenyl-α,α-dimenthyl benzyl isocyanate, and a monomar with an independent copolymer having a refraction factor ND equal to or above 1.55 and as well as the capability of radical polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a resin for lenses and other optical materials which has a high refractive index, has excellent impact resistance, and is easy to polish and perforate.

[0002]

2. Description of the Related Art Thermosetting resins and thermoplastic resins are known as resins for lenses and other optical materials, but thermosetting resins are advantageous for polishing and perforating. Diethylene glycol bis (allyl carbonate) has been used for a long time, but its refractive index N
_D is 1.50, the refractive index of the crown glass _N D 1.
When it is lower than 52 to 1.53, the use of this resin to form a spectacle lens has the disadvantage that the thickness increases rapidly with increasing altitude.

[0003] Polystyrene and polycarbonate are
While having a high refractive index (N _D from 1.58 to 1.59), since these are fusible soluble thermoplastic resin, not suitable for performing the polishing and drilling. In addition, it is vulnerable to strong pressure because permanent set is given by creep. That is, the spectacle lens requires cutting and polishing around the lens when being framed, and has the disadvantage that the spectacle frame is sometimes strongly tightened and easily causes a refractive error.

[0004] On the other hand, many conventional thermosetting resins for lenses and other optical materials generally have a drawback of low impact resistance. In order to overcome this drawback, thermosetting resins incorporating urethane production involving isocyanate have recently been developed. However, low yields due to severe temperature and other polymerization conditions, excessive costs for raw material synthesis, and odor and toxicity depending on the raw materials are significant, requiring large capital investment to counteract them. There were problems such as doing. (Japanese Unexamined Patent Publication No. 64-26222, 6
4-54021, JP-A-2-153302, 3-13
8601, 5-105677, 5-307101,
6-65193)

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems and disadvantages, and uses a reaction tank and a polymerization molding equipment which are conventionally widely used. By effectively combining raw materials of similar properties, by urethane formation reaction and radical polymerization,
An object of the present invention is to provide a method for producing a lens or other resin for an optical material, which has a high refractive index and excellent impact resistance, and can easily satisfy a demand for a high Abbe number or the like depending on a combination of raw materials.

[0006]

Means for Solving the Problems The inventor of the present invention has made intensive studies in order to solve this problem and has reached the present invention. That is, the present invention relates to a compound represented by the general formula:

(Wherein X represents a bromine atom, a chlorine atom or a hydrogen atom, and m and n are m ≧ 1, n ≧ 1 and 2 ≧ m
+ N ≧ 6. ) And one or more diols selected from aliphatic, alicyclic, heterocyclic and aromatic for diluting the diols, if necessary. and species or more diols and / or triols, 3-isopropenyl-.alpha., alpha-dimethyl benzyl isocyanate, further refractive index N _D homopolymer is 1.55 or more, radically polymerisable one Alternatively, there is provided a method for producing a resin for a high refractive index lens, which comprises reacting and copolymerizing two or more monomers.

The diols of the formula (I) used in the present invention may be obtained by bonding Br or Cl to the respective benzene nuclei of bisphenol A one or two at designated positions, or not bonding them. Then, ethylene oxide is added in an amount of 2 moles (1 mole per OH group of each benzene nucleus) to 6 moles (approximately 3 moles on average to each OH group of each benzene nucleus) of m + n of the formula (1). Value 6
Diols) obtained by the addition, and both ends of the molecule are primary OH groups.

[0008] Aliphatic diols for dilution and / or
Examples of triol include ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, and trimethylolpropane. Examples of the cyclic diol include tricyclo (5.2.1.0 ^2′6 ) ^{decane dimethanol} , 1,4
-Cyclohexane dimethanol, 1,3-cyclohexane dimethanol, and the like; examples of heterocyclic diols include 2,5-tetrahydrofurandimethanol; and examples of aromatic diols include 1,4-bis ( 2-
(Hydroxyethoxy) benzene, 1,3-bis (2-hydroxyethoxy) benzene, and the like.

The reason for using diols and / or triols for dilution is that the number of urethane groups is limited because the molecular weight of the diols of the formula (1) is so large that the number thereof is increased. It is expected that special useful properties will be imparted to the resin for high refractive index lenses, depending on the type of diols and / or triols for dilution, in order to improve the impact resistance. This is because the effect of lowering the formation temperature can be obtained.

3-Isopropenyl-α, α-dimethylbenzyl isocyanate is disclosed in Am. Cyanamid C
o. Developed a production method by developing a basic method for producing an isocyanate by reacting isocyanic acid with an olefin [US Pat. No. 4,377,530, JP-A-58-16].
2563], and a monomer which is considered to be used for paints and the like. [C. A. 102 , 149958a (19
85), ibid., 185676r (1985), C.I. A. 1
03 , 178679m (1985), and C.I. A. 10
5 , 62273m (1985)]

[0011] alone refractive index N _D in the polymer at 1.55 or more, a radically polymerizable, moreover compatible with the present invention, as monomer having a copolymerizable property, styrene, alpha-methyl styrene, chloro Styrene, divinylbenzene, benzyl methacrylate, 2,2-bis (acryloxy-
Polyethoxy-phenyl) propane, 2,2-bis (methacryloxy-polyethoxy-phenyl) propane, and the like.

[0012] Using the above various raw material monomers, the making a composition for making a high refractive index lens other optical materials for resin, which is an object of the present invention, the refractive index N _D homopolymer
Is 1.55 or more and 3-isopropenyl-
α, α-Dimethylbenzyl isocyanate, a diol of the formula (1) and, if necessary, a diol and / or a triol for dilution, are mixed with a known catalyst for accelerating a urethanization reaction (for example, diol). -N-butyltin dilaurate) and an appropriate temperature (usually 40 to 100).
℃). Here, the OH group of the diols and / or triols is 3-isopropenyl-α, α-
It reacts with the NCO group of dimethylbenzyl isocyanate to be urethanized, so that not only liquid but also solid diols and / or triols form a uniform liquid composition. This material is once cooled (usually allowed to cool) after the urethane-forming step is completed, but may solidify when cooled depending on the selection of the original raw material. At that time, the subsequent operation must be performed while the temperature is raised to an appropriate temperature and the liquid is maintained.

In this urethanization reaction, NCO is used.
When the molar ratio of groups / OH groups is about 1 ± 0.5, a resin of acceptable quality can be obtained. It is preferable that all OH groups are primary.
Even if the groups are mixed, the quality of the resulting resin is not often impaired.

Here, necessary additives such as an ultraviolet absorber are added and dissolved, a radical polymerization catalyst is further added, the mixture is poured into a mold such as a lens, and the mixture is heated in a polymerization furnace and polymerized.

As the ultraviolet absorber, 2- (3,5-di-
t-butyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-5- (1,1,3,3-
Good results can be obtained by using triazole compounds such as (tetramethylbutyl) phenyl] benzotriazole or benzophenone compounds such as 2-hydroxy-4-n-octoxybenzophenone and 2-hydroxy-4-benzyloxybenzophenone. it can. The amount used is 0.05 to 1% by weight based on the total raw material monomer mixture. This prevents yellowing and deterioration of physical properties due to aging under sunlight irradiation after molding into lenses, etc., and in particular, when used as eyeglass lenses, blocks out ultraviolet rays as much as possible to protect eyes. Can be helpful.

In the present invention, the radical polymerization reaction comprises:
It is performed after the urethane production reaction is completed or has sufficiently proceeded. As described above, the urethanization reaction is carried out at 40 to 100 ° C. However, when the reaction is carried out at a relatively high temperature, it is once cooled and kept at a temperature capable of maintaining a liquid state, and a radical exhibiting catalytic activity above this temperature A polymerization catalyst must be selected and added for polymerization.

Examples of suitable radical polymerization catalysts include t-butylperoxyisobutyrate, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate and the like. These polymerization catalysts are used alone or in combination of two or more. The amount used is required to be 0.1 to 5% by weight based on the total amount of the raw material monomers mixed (when two or more types are used as a mixture, a total thereof).

In the present invention, polymerization and molding are usually carried out by using two well-polished and surface-reinforced glass molds by means of a rubbery elastic material (for example, Via a gasket made of ethylene-butadiene copolymer, etc.), assembling them in parallel so that each of the above-mentioned raw materials and monomers, an ultraviolet absorber,
A liquid composition comprising a polymerization catalyst (a releasing agent, a dye for yellowing complementary color or the like is sometimes added) and the like is injected. The temperature at the time of the injection must be determined so that no solid is formed, the fluidity is suitable for the operation, and the temperature at which the activity of the radical polymerization catalyst develops.

After completion of the injection, the mixture is placed in a polymerization furnace and polymerized.
The polymerization time is generally 10 to 30 hours, but is preferably 15 to 30 hours.
In many cases, 20 to 20 hours are preferable from the viewpoint of operation. The temperature control of the polymerization furnace depends on the type of polymerization catalyst used.
The temperature rise curve should be chosen so as to obtain the polymer with the best physical properties and to optimize the operating efficiency.

For example, if t-butyl peroxyisobutyrate is used as a polymerization catalyst and the injection temperature of the liquid composition and the initial temperature of the polymerization furnace are 50 ° C., the first 2
The temperature is raised to 60 ° C. over a period of time (linearly, the same applies hereinafter), the temperature is raised to 70 ° C. in the next 3 hours, the temperature is raised to 90 ° C. in the next 9 hours, and then to 105 ° C. in the next 3 hours Warm and finally 105
C. for 2 hours to complete the polymerization. (The example of this temperature rise curve assumes a specific liquid composition for polymerization.)

After the polymerization, the polymer is released from the mold. The mold release is usually performed when the temperature is hot, but it is sometimes better to perform the release when the temperature is slightly lowered, and sometimes the mold is rapidly cooled with water or the like. First remove the gasket, then mechanically remove the polymer from the mold. In general, the polymer of the present invention can be released without using a special release agent. (The process from injecting the liquid composition composed of raw materials and monomers into the mold to the release is called casting polymerization.)

After the release, heat treatment is performed. Usually put in a heating furnace at a temperature 5 to 10 ° C. higher than the maximum polymerization temperature
Heat treatment is carried out at the same temperature for 0 minutes to 2 hours. (still,
The heat treatment also needs to be performed after roughening of the next semi-finished lens and subsequent polishing. )

The lens or the like obtained by the above operation can be put to practical use as a product as it is. However, a semi-finished lens is first produced by casting polymerization, and the rear surface thereof is roughened and polished to obtain a product having a desired power. It can also be a lens. It was recognized that the polymer molded product of the present invention is well suited for such roughening and polishing steps, and can be formed into an excellent product without melting or polishing surface being roughened.

The resin for lenses and the like according to the production method of the present invention can be dyed well in a dyeing bath at 80 to 95 ° C. using a disperse dye. It was confirmed that the film can be firmly adhered to the substrate, and that a strong vapor deposition of SiO ₂ and a metal oxide is basically possible in a vacuum vapor deposition device.

The present invention will be described more specifically and in detail with reference to the following examples. However, the present invention is not limited by these examples. In addition, the test method of various physical properties shown in an Example is as follows. 1) The refractive index N _D and Abbe number [nu _D: was measured at room temperature by Abbe refractometer. Α-monobromonaphthalene was used as the contact liquid. 2) Impact resistance: A steel flat plate having a thickness of 2 mm was subjected to a steel ball drop test conforming to the FDA standard, and ones that did not crack were evaluated as "good" and indicated in Table 1 by a circle. A broken one is indicated by a triangle. 3) Light resistance: An irradiation test was performed for 200 hours in an ultraviolet irradiation tester, and those having no coloring such as yellowing were evaluated as “good”. 4) Dyeability: Dipped in a disperse dye bath at 90 ° C. for 15 minutes,
A test was performed to determine whether or not dyeing was performed up to the medium concentration.

[0026]

[Examples 1-10] styrene as a liquid monomer the refractive index _{N D} is 1.55 or more when the homopolymer, 2,2
-Bis (acryloxy-poly <4.2> ethoxy-phenyl) propane [see lower column of Table 1] and / or 3-isopropenyl as a monomer having a polymerizable double bond and an NCO group using divinylbenzene BP-4.2E, BP4Br-2E, and BP-4.2E are used as raw material diols using -α, α-dimethylbenzyl isocyanate (hereinafter abbreviated as IPI) and having a structure of [Formula 1] that provides a high refractive index.
P4Br-4E (for explanations of these abbreviations, refer to the lower column of Table 1). Diethylene glycol and 1,4-bis (2
-Hydroxyethoxy) benzene, tricyclo (5.
2.1.0 ^2'6 ) The results when ^decane dimethanol and 1,4-cyclohexane dimethanol are used are listed as Examples 1 to 10 of the present invention.

Here, the liquid monomer such as styrene is IPI
And dissolves solid or highly viscous other diols with the liquid diol diethylene glycol.

The raw material monomer is placed in a heating vessel such as a beaker or a reaction vessel, and 0.1% by weight of di-n-butyltin dilaurate based on the weight of the raw material monomer is added as a catalyst for accelerating the urethanization reaction. Then, the mixture is heated to 60 to 80 ° C., and a urethanization reaction is caused to dissolve colorless and transparent. 50
After cooling to about ° C, 0.3% by weight of 2- [2-hydroxy-5- (1,1,3,3-tetramethylbutyl) phenyl] benzotriazole was added as an ultraviolet absorber and dissolved. 1.5% by weight of t-butyl peroxyisobutyrate (hydrocarbon solution,
74%, Nippon Oil & Fat K. K. ) And melt in a mold consisting of two tempered glass plates and a gasket.
C. and immediately put into the polymerization furnace and started heating.

The temperature is raised to 60 ° C. in the first two hours, to 70 ° C. in the next three hours, to 90 ° C. in the next nine hours, and to 105 ° C. in the next three hours. And finally 105
C. for 2 hours to complete the polymerization. After the polymerization,
Immediately released. Demolding is usually hot (90 to 90 here)
The mold was rapidly cooled with cold water and released. Whichever method was used to release the mold, the heat treatment described below had no effect on the polymer.

The heat treatment was performed by heating the polymer at 110 ° C. for 1 hour. Even when some distortion occurred at the time of release from the mold, it could be completely repaired. Each of the obtained resin plates was colorless and transparent, and their refractive indices N _D , Abbe number ν _D and impact resistance were measured, and the results are shown in [Table 1]. Light fastness and dyeing properties were measured at the same time.
Met. In addition, any of these resin plates can be easily roughed and polished without causing a melting accident, and when drilled with a drill of 1.5 and 2 mmφ with an electric drill, except for Example 4, , Beautifully perforated without chipping.

[0031]

According to the present invention, a resin for a lens or other optical material, which has a high refractive index, excellent impact resistance, and is easily polished and perforated, can be prepared by a conventional manufacturing equipment, It can be manufactured efficiently using a tank and casting polymerization equipment, and by selecting some of the raw materials appropriately, it is possible to increase the rigidity during heating or easily produce a product with a high Abbe number. The present invention provides a method for producing a resin for a high-refractive-index lens that can be used.

[Table 1]

Claims (5)

[Claims] 1. A compound represented by the general formula: ## STR1 ## (Wherein, X represents a bromine atom, a chlorine atom or a hydrogen atom, and m and n are m ≧ 1, n ≧ 1 and 2 ≧ m + n ≧ 6
Represents the number of ) And one or more diols selected from aliphatic, alicyclic, heterocyclic and aromatic for diluting the diols, if necessary. One or more diols and / or triols, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, and a homopolymer having a refractive index N
_A method for producing a resin for a high-refractive index lens, comprising reacting one or more radically polymerizable monomers having _D of 1.55 or more and copolymerizing them. 2. The method for producing a resin for a high refractive index lens according to claim 1, wherein in the general formula [X], X is a bromine atom. 3. The method for producing a resin for a high refractive index lens according to claim 2, wherein m = n = 1 in the general formula [1]. 4. The method according to claim 1, wherein the diol for dilution is 1,4-cyclohexanedimethanol. 5. The method according to claim 3, wherein the diol to be diluted is 1,4-cyclohexanedimethanol.