JPS5936105A - Manufacture of plastic lenz - Google Patents

Abstract

PURPOSE:To readily obtain titled lenz of high hardness and scratch resistance, capable of forming on it uniformly a transparent reflection-proof film by vacuum deposition, by using as an initiator, an organic peroxide in combination with a specific peroxy carbonate in the polymerization of diethylene glycol bisallyl carbonate. CONSTITUTION:A polymerization of (A) diethylene glycol bisallyl carbonate is carried out in a lenz mold, using (B) an initiator consisting of (i) an organic peroxide with a selected 10hr- half life temperature <=80 deg.C (pref. di-isopropyl peroxy-dicarbonate) and (ii) a peroxycarbonate of formula (R1 is H or 1-4C alkyl; R2 and R3 are each 1-4C alkyl; R4 is 1-12C alkyl or 3-12C cycloalkyl) radically-copolymerizable with the component (A) (e.g., t-butylperoxy iinyl carbonate), thus obtaining the objective lenz. EFFECT:Having excellent dyeability.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of polymerizing diethylene glycol bisallyl carbonate in a desired lens mold to easily increase hardness and produce a plastic lens with excellent scratch resistance.

Conventionally, plastic lenses manufactured by polymerizing diethylene glycol bisallyl carbonate using an organic peroxide with a selected 10-hour half-life temperature of 80'C or less, especially di-isopropyl peroxydicarbonate, as a polymerization initiator have been lightweight. Because it has many features that ordinary glass lenses do not have, such as being transparent and being dyeable, it has established an important position as a lens for spectacles in particular.

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However, compared to glass lenses, lenses have a major drawback in that they are easily scratched due to their low hardness. Therefore, as a solution to this drawback, recently, thermosetting resins such as silicone resin, polyester resin, melamine resin, or polyfunctional monomers such as allyl acrylate and allyl methacrylate, and diethylene glycol bisallyl carbonate have been used. Plastic lenses, which are coated on the surface of plastic lenses and cured under heat, have been developed and are commercially available, having surface hardness and scratch resistance equivalent to those of glass lenses.

However, although the surface hardness and scratch resistance of plastic lenses whose surfaces are coated with thermosetting resin have been greatly improved, they have lost their good dyeability, which is a major feature of plastic lenses. I was disappointed. In addition, there is an increase in the number of coating and curing processes for thermosetting resin, etc. Furthermore, it is difficult to uniformly apply thermosetting resin, etc. to the lens surface, resulting in a decrease in lens surface precision and difficulty in manufacturing lenses with complex shapes. A new drawback has arisen. Furthermore, unlike glass lenses, it is difficult for plastic lenses to uniformly form unpolymerized diethylene glycol bisallyl carbonate remaining inside the lens, regardless of whether or not the surface is processed.

The present inventors have solved the various drawbacks of the surface-treated plastic lenses, and have created a glass lens that has high hardness, excellent scratch resistance, and can have a transparent and uniform anti-reflection coating formed by vacuum deposition. As a result of repeated studies regarding the production of tic lenses, we selected a 10-hour half-life temperature (0.05% in benzene).
05 m01e/g) When diethylene glycol bisallyl carbonate is polymerized using an organic peroxide at 80°C or less as a polymerization initiator, the various drawbacks of the surface-treated plastic lens can be solved by using a specific peroxycarbonate in combination. In addition, we have found a method for manufacturing a plastic lens that has high hardness, excellent scratch resistance, and can have a transparent and uniform antireflection film formed by vacuum deposition, and have completed the present invention.

That is, the present invention provides a method for producing a plastic lens in which diethylene glycol bisallyl carbonate is polymerized in a desired lens mold, in which an organic peroxide having a 10-hour half-life temperature and degree of 80°C or less is selected as a polymerization initiator. General formula (I) 8 showing radical copolymerizability of one type or 2811 or more with diethylene glycol bisallyl carbonate (wherein R□ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, RfA and R8 are each carbon number 1 to 4
The alkyl group R6 represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 8 to 12 carbon atoms. This is a method for producing a plastic lens, characterized in that one or more peroxycarbonates represented by the following are used in combination:

Examples of the selected organic peroxides having a 10-hour half-life temperature of 80° C. or lower for use in the present invention include those listed in Table 1.

Table 1 The intermediate classification symbols in the table represent the following.

(()...Peroxyester (b)...Peroxydicarbonate (/1・self・
Diacyl peroxide These organic peroxides may be used singly or in combination of two or more. In particular, di-inoprobil peroxydicarbonate is preferably used alone or in combination with other organic peroxides.

Specific peroxycarbonates represented by general formula (1) that can be used in the present invention include, for example, tert-butyl peroxy vinyl carbonate, tert-hexyl peroxy vinyl carbonate, 1
, 1,8.13-tetramethylbutylperoxyvinyl carbonate, para-menthylperoxyvinyl carbonate, tert-butylperoxyisopropenyl carbonate, tert-hexylberoxyinglobenyl carbonate), 1,1,8. Examples include 3-tetramethylbutylperoxyisoprobenyl carbonate and para-menthylperoxybenyl carbonate.

The plastic lens of the present invention, which has high hardness and excellent scratch resistance, can be manufactured by a conventional method.

Dissolving a predetermined amount of diethylene glycol bisallyl carbonate, one or more organic peroxides with a half-life temperature of 80°C or less and a specific peroxycarbonate represented by general formula (I) for 10 hours, After mixing, as is or after prepolymerization,
The mixture is poured into a lens mold, the temperature is gradually raised from room temperature to 90°C, and polymerization is carried out for 10 to 80 hours. Thereafter, the lens is demolded and cleaned, and annealed in a nitrogen atmosphere or vacuum for 8 to 8 hours at 100 to 180°C to remove strain from the lens. It is also possible to shorten the annealing time by using ultraviolet light in combination.

The reason why a plastic lens with high hardness and excellent scratch resistance can be obtained by using the peroxycarbonate of general formula (1) in combination is considered to be as follows.

That is, until demolding, the organic peroxide having a selected 10-hour half-life temperature of 80° C. or lower is almost completely decomposed, and diethylene glycol bisallyl canibonate is combined.

On the other hand, the specific peroxycarbonate represented by general formula (I) has a high selected 10-hour half-life temperature, so it is hardly decomposed, and it also has good copolymerizability with diethylene glycol bisallyl carbonate, so it It is thought that it is copolymerized in the main chain of the bisallyl carbonate polymer. This is thought to be due to the fact that when this lens is annealed after demolding, the peroxycarbonate copolymerized in the main chain of this diethylene glycol bisallyl carbonate decomposes, promoting crosslinking between the main chains.

According to the present invention, the concentration of an organic peroxide with a selected 10-hour half-life temperature of 80°C or less in diethylene glycol bisallyl carbonate varies depending on its type, polymerization conditions, and the thickness and shape of the plastic lens, but generally 2
-5 weight percent, especially VC2.5-4 weight percent is preferred. If the concentration is lower than 2 weight percent, the polymerization time will increase and the hardness of the lens will decrease. Furthermore, if the amount exceeds 5% by weight, cracks will occur in the lens during polymerization, making it impossible to use it as a lens.

Specific peroxycarbonates represented by general formula (I) are also used singly or in mixtures of two or more.
In addition, the concentration for diethylene glycol bisallyl carbonate depends on its type, polymerization conditions, lens thickness,
Although it varies depending on the shape, it is generally preferably 0.05 to 5 weight percent, and preferably 3 to 1 weight percent. 0.
If the concentration is lower than 05% by weight, sufficient hardness cannot be obtained.

If the amount exceeds 5% by weight, the hardness of the lens will increase, but cracks may occur during annealing, and the lens will become brittle and break easily, losing one of its characteristics as a plastic lens.

On the other hand, selected organics, with a half-life temperature of 80℃ or less, 10 hours.

If you try to increase the hardness by increasing the concentration of peroxide alone, cracks will occur during polymerization.
It cannot be used as a plastic lens.

Furthermore, when a specific peroxycarbonate represented by general formula (I) is used alone, polymerization is extremely slow. Moreover, when the polymerization temperature is raised, cracking, foaming, and peeling from the mold occur, which is not preferable.

In other words, plastic lenses with high hardness and excellent scratch resistance can only be produced by using a selected organic peroxide with a 10-hour half-life temperature of 80°C or less and a specific beryloxycarbonate represented by general formula (1). is easily manufactured using conventional manufacturing processes.

Further, the hardness of the plastic lens is adjusted by the concentration of a specific peroxycarbonate represented by general formula (I).

The plastic lens manufactured in this way 5 has surface hardness and scratch resistance equivalent to that of a glass lens coated with a thermosetting resin without being coated with a thermosetting resin or the like.

Therefore, there is no need to apply a thermosetting resin or the like.

Therefore, all the drawbacks of plastic lenses caused by applying thermosetting resin or the like are solved. That is,
1. No complicated process required for applying thermosetting resin, etc. 2
．． There is no reduction in the surface precision of plastic lenses due to the application of thermosetting resin, etc., and it is possible to manufacture plastic lenses with complex shapes with high precision. 3. It is easy to dye, just like a low-hardness plastic lens that is not coated with thermosetting resin or the like. 4. Can be treated with anti-reflection treatment like glass lenses.

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

夾厘■-Yugo 1 A predetermined amount of diethylene glycol bisallyl carbonate (rcR-aJ manufactured by ppG Co., Ltd.,
Di-isopropyl peroxydicarbonate (manufactured by Perloil IPPJH Hon Yushi Co., Ltd.) and tertiary-butylberoxyvinyl carbonate were mixed and dissolved, and the mixture was heated at 80 to 4 centistokes until the solution viscosity reached 40 to 60 centistokes.
Polymerization was carried out at 0°C.

Next, pour the mixture into a lens mold and heat it at room temperature to 90°C.
After polymerization was carried out for 18 hours while gradually increasing the temperature until the temperature was increased, the cured polymer product was demolded. Thereafter, the cured polymer product was subjected to ultrasonic cleaning and then annealed in nitrogen gas at 120° C. for 8 hours to produce a plastic lens. However, Example 4
The samples thus obtained were annealed at 120° C. for 4 hours and irradiated with ultraviolet light for 2 hours. The samples thus obtained were subjected to a pencil hardness test, a Percoll hardness test, a dyeability test, and an antireflection finishing test.

The pencil hardness test was based on JIS-5400.

The Percoll hardness test was conducted in accordance with JIS-6911 using a Percoll hardness meter model 984-1.

The stainability test was conducted using a brown staining agent ("Nikon Orma 70").
Hard staining agent "7' Rau/H, J (manufactured by Nippon Kogaku Co., Ltd.)
was used. The staining method involves dissolving 90 cc of the staining agent in water and applying IgK. This staining solution was heated to 92° C., and the sample was immersed for 2 minutes. Thereafter, the sample was thoroughly washed with water and dried, and then the visual attenuation rate was measured.

For antireflection testing, samples were subjected to magnesium fluoride vapor deposition for 15 minutes at 100°C in 10' mmHg and argon. The surface condition at that time was visually observed. The results are shown in Table 2.

Comparative Examples 1 and 2 A predetermined amount of CR-
89, Perloil IPP, and annealing was performed according to Examples 1 to 8 to produce a plastic lens.

In Comparative Example 2, silicone resin (ix-12-92L
(manufactured by Shin-Etsu Silicon Co., Ltd.) was applied, and the coating film was cured at 100° C. for 80 minutes.

For Comparative Examples 1 and 2, a pencil hardness test, Percoll hardness test, and dyeability test 1. .

An anti-reflection treatment test was conducted.

The results are shown in Table 3.

Table 8 Using predetermined amounts of CR-39, Baroyl IPP, tertiary butyl peroxyisobutyrate (perbutyl IBJ, manufactured by Nippon Oil & Fats Co., Ltd.) and tertiary butyl peroxy vinyl carbonate in the blending parts shown in Table 4, Plastic lenses were prepared by performing annealing in accordance with Examples 1 to 8.

Using it, the same pencil hardness test, Percoll hardness test, dyeability test, and antireflection processing test as in Examples 1 to 4 were conducted. The results are shown in Table 4.

Table 4 A predetermined amount of CR-89 and Purloy p with the number of parts shown in Table 5.
yxpp, p-butylberoxypinyl carbonate and tert-hexylperoxyisopropenyl carbonate.

Plastic lenses were produced by performing annealing in accordance with Examples 1 to 8. Using it, the same pencil hardness test, Percoll hardness test, dyeability test, and antireflection processing test as in Examples 1 to 4 were conducted.

The results are shown in Table 5.

Table 5 Examples 9 and 10 Examples 1- Annealing was performed in accordance with 8 to produce a plastic lens. Using the same pencil hardness test and Percoll hardness test as in Examples 1 to 4,
Table 6 shows the results of a dyeability test and an anti-reflection finishing test.

Claims (1)

[Scope of Claims] 1. In a method for manufacturing a plastic lens in which diethylene glycol bisallyl carbonate is polymerized and formed in a desired lens mold, an organic peroxide having a 10-hour half-life temperature of 80°C or less is selected as a polymerization initiator. A general formula showing radical copolymerizability of one or more types with diethylene glycol bisallyl carbonate (wherein R□ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R8 and R3 each have 1 to 4 carbon atoms. and R1 represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 8 to 12 carbon atoms. Method of manufacturing plastic lenses.