JPS62235901A - Composition for synthetic resin lens and its production - Google Patents

Abstract

PURPOSE:To produce a lens having high refractive index and excellent durability by polymerizing a specific fumarate compd. and allyl compd. to a prescribed mol.wt., then further copolymerizing the same in a mold. CONSTITUTION:The compsn. for the lens consists essentially of (A) the fumarate expressed by formula I (e.g.: dibenzyl fumarate) and (B) the allyl compd. expressed by formula II (e.g.: triallyl trimellitate). X in the formulas denotes a halogen except fluorine and H and n denotes 2, 3. This lens is obtd. by dissolving the component A in the component B first and prepolymerizing the components until the average mol.wt. attains 2,000-8,000, then pouring the polymer into a mold and copolymerizing the same. The deposition of the component A in the subsequent stage is averted and the lens having the high refractive index and excellent durability is obtd. according to the above-mentioned method.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention is made of a synthetic leather resin that has a relatively high refractive index, excellent durability such as heat resistance, solvent resistance, and impact resistance, and is easy to mold. The present invention relates to a composition and manufacturing method for obtaining a lens. [Prior art] Synthetic resin lenses, especially diethylene glycol bis(allyl carbonate) resin lenses, are superior in terms of safety, ease of processing, and fashionability compared to glass lenses. With the development of anti-reflection technology, hard coats are rapidly becoming popular. The shift to plastic eye lenses has increased the demand for higher quality lenses, that is, thin plastic lenses made of high refractive index resin materials. The refractive index of diethylene glycol bis(acrylic carbonate) resin is 1.50, and several technical proposals have been made to improve this drawback. For example, an example of a copolymer of diethylene glycol bis(allyl carbonate) tohenzyl methacrylate disclosed in JP-A No. 54-41965 and 4-iodo Example of styrene copolymer, % 15515 1983
In the example of a copolymer of diallyl phthalate or diallyl terephthalate and methyl methacrylate prepolymer, the lens is formed by reacting an allyl group with a different reactivity with a (meth)acrylic group or a vinyl group. There is a manufacturing issue. If the (meth)acrylic group or vinyl group with a fast reaction rate polymerizes first, and the allyl group with a slow reaction rate polymerizes later, not only will they not copolymerize, but the allyl compound will completely polymerize. This will cause a decrease in solvent resistance. Another example is JP-A-55-15747. Examples of copolymers of bisphenol A dimethacrylate and phenyl methacrylate or benzyl methacrylate, JP-A-57-54901. Japanese Patent Publication No. 58-11360
Di(meth)acrylate having a halogen-substituted aromatic ring and an allyl compound or a di(
This is a reaction between a (meth)acrylic group and a vinyl group, which have similar reactivity, such as a copolymer with meth)acrylate, but there is a problem in that the control during lens production is extremely difficult. First, because the reaction is fast, it is difficult to control casting conditions, and distortion occurs inside and on the lens surface, which tends to cause mechanical defects.In addition, vinyl groups and (meth)acrylic groups are difficult to control on one reaction surface. The problem is that it is very sensitive and susceptible to external influences, making it extremely difficult to control conditions other than single polymerization conditions. Therefore, in terms of the efficiency of controlling one polymerization reaction and the completion of one polymerization reaction, the process inevitably becomes complicated. In addition, in the case of one or more examples in which a monofunctional monomer is used as the main component, it is impossible for the monomer to be completely polymerized and incorporated into the polymer chain, so the heat resistance and resistance due to unreacted monomers An adverse effect on solvent properties may also be considered. In addition, the next step is to improve the manufacturing defects and to create a diallyl compound having a halogen-substituted aromatic ring. Examples include diallyl phthalate or a copolymer of diallyl terephthalate and diallyl phthalate. The technology in this example is relatively easy to control reactions, and since all monomers are bifunctional, process control from solution mixing to polymerization is easy. A refractive index lens is obtained. However, because the specific gravity of the main component, a diallyl compound having a nuclear halogen 7Ilf-replaced aromatic ring, is high (about 1% as a polymer),
．． 7) It has the disadvantage that the lens becomes heavy and its merits as a high refractive index lens are lost. In addition, diallyl compounds having a nuclear halogen-substituted aromatic ring are expensive to synthesize and manufacture by pre-squeezing with diethylene glycol bis(allyl carbonate) and other synthetic resins for lenses, so consideration should be given to their high refractive index. However, it is inferior in terms of popularity. Furthermore, as a technical proposal for improving one or more drawbacks, a resin obtained by copolymerizing monomers A and B described in the claims of the present invention is considered. Since it is a solid, it is not only impossible to use A alone (and even after mixing with B, there was a manufacturing problem in that it was difficult to control the process from solution mixing to polymerization. PROBLEMS AND OBJECTIVES TO BE SOLVED 3 As mentioned above, the conventional technology has problems such as lens quality, manufacturing process, lens manufacturing control, and lens cost.The present invention solves the above problems. The objective is to have a relatively high refractive index, excellent durability such as heat resistance, solvent resistance, and impact resistance, excellent properties as a lens, and easy molding. The objective is to obtain a synthetic resin lens with a relatively slow reaction rate, which makes it easy to control one reaction, and a copolymerization of a fumarate compound, which has excellent durability and properties as a lens, and an allyl compound. ,
By pre-polymerizing the mixture of each compound until it reaches a predetermined molecular weight, operations and process control from mixing the solution to injection into the mold and polymerization are made easy and popular. The object of the present invention is to obtain a synthetic resin lens with high properties. [Means for Solving the Problems] The synthetic resin lens composition of the present invention is characterized in that its main components consist of the following A and B. 8. One or more monomers whose general formula is represented by [1]. □1. (In the formula or excluding fluorine) Represents rogene or hydrogen. ) B One or more monomers whose general formula is represented by [2].・Masu C-0-CH! −0H=(:!H,)n
[2] (In the formula, n represents 2 or 5.) Also, an uninvented method of manufacturing a synthetic resin lens f! :! /′
It is characterized in that comonomers containing iA and B as main components are prepolymerized with 1 having an average molecular weight of 2,000 to 8,000, and then injected into a mold and copolymerized. Next, the present invention will be explained in detail. In the synthetic resin lens composition of the present invention, component A, the monomer having the general formula [1], is often solid at room temperature, and is therefore used after being dissolved in component B. The composition ratio of A and B depends on the refractive index, heat resistance, heat resistance, impact resistance, solvent resistance, single-layer color dyeability of the synthetic resin lens to be obtained,
Alternatively, it is preferable to determine the temperature by considering the balance between the precipitation 111F of component A and the decomposition temperature of the polymerization initiator. % component A can exhibit the highest refractive index. The fumarate compound represented by the general formula
Although halogen other than fluorine or hydrogen can be used, chlorine is preferable from the viewpoint of increasing refractive index, coloring, and durability. The content of component A depends on its solubility with component B, but in terms of being a high refractive index resin and improving durability,
10 to 80 weight percent is preferred. Typical examples of component A include: dibenzyl fumarate, ortho-dichlorobenzyl fumarate, haladichlorobenzyl fumarate, ortho-sipromopenzyl fumarate, para-dibromobenzyl fumarate, ortho-short hensyl fumarate. Examples include rates. Component B is diallyl terephthalate, diallyl terephthalate, or diallyl terephthalate when n=2, and trimellitic triallyl or '*5e5-)allylbenzenetricarboxylate when n=5. Although it is possible to mold a lens by polymerizing only component B, it cannot be used as a lens material because the layering properties of the coating formed on the surface of the colored 1 are lost. There are three purposes for administering component B. The first purpose is to dissolve component A into a liquid that can be poured into the casting mold. The second purpose is that since it is a diallyl compound, it has a co-electromagnetic property and is relatively easy to control the reaction with the 7-maleto compound of component A. Therefore, there is less unreacted monomer that does not bond to the polymer chain. The third purpose is that component B alone exhibits a relatively high refractive index, so even if it is copolymerized with component A, the refractive index of component A will not be lowered much. The content tit of component B is 20 to 90 weight percent, and component B
When the amount increases, the durability of the coating formed on the surface tends to decrease due to coloring. An important point regarding the manufacturing method of the uninvented synthetic resin lens is that component A and component B are prepolymerized to an average molecular weight within a certain range before being injected into the mold. . Thereby. It becomes possible to copolymerize component A without precipitating it in the subsequent step. A specific example of prepolymerization will be shown. First, component A is dissolved in component B. Heat and stir as necessary. Next, a single layer initiation rule is added in a nitrogen atmosphere, and polymerization is carried out while controlling the temperature and viscosity. The polymerization initiator preferably has a decomposition temperature higher than the precipitation temperature by 10°C or more, and does not necessarily have to be the same as the one added immediately before injection into the mold. After polymerization to a predetermined molecular weight by prepolymerization, the polymerization initiator is added in the amount required as required in the atmosphere, and the mixture is poured into a mold. Thereafter, it is heated for 7IO to carry out thermal polymerization. The control point for prepolymerization is the average molecular weight υ. By controlling the average molecular weight within the range of 2,000 to 8,000, it is easy to mold a lens of a composition containing component A and component B as main components, and to satisfy various requirements for a highly popular synthetic resin lens. I can do it. When the average molecular weight is less than 2000, the precipitation temperature of component A is high, so the polymerization initiator must be selected from among those with a decomposition temperature of 1, making it difficult to select a polymerization initiator suitable for the monomer. occurs. In addition, all steps such as filtration, pouring, and weighing must be carried out at temperature #i, which is disadvantageous in terms of control of manufacturing conditions and production costs. Furthermore, since the volumetric shrinkage due to polymerization is relatively large, a defect in which the lens and the mold separate during the first polymerization is likely to occur. On the other hand, if the average molecular weight exceeds 8000, it may become difficult to prepare, filter, and inject the monomer. The polymerization initiator used in the present invention is not particularly limited, and any known radical polymerization initiator may be used. For example, hydroperoxides such as t-butylnohydroboroxide, dialkyl peroxides such as di-t-butyl peroxide. Diacyl oxides such as benzoyl peroxide, peroxydicarbohydrates such as diimbropyl peroxydicarbonate, peroxy esters and ketone peroxides such as °C-butyl peroxybiparate, Peroxides such as oxyketals,
Alternatively, there may be an azo compound 'f/llJ such as azobis(imbutyrilonitrile). The amount of radical polymerization initiator used depends on the monomer composition of the copolymerization component, precipitation temperature, and prepolymerization conditions. It varies depending on the thermal polymerization conditions in the mold, etc. - Although it cannot be generally limited, from 0.05 to [L
5% by weight, α5-5 during thermal polymerization in mold
．． It is preferable to use it in a range of 0% by weight. In the present invention, it is also possible to add components other than A and B in order to improve the durability such as impact resistance or the durability of the coating provided on the surface, or to change the balance of other lens properties. It is. For example, component A is 40
To the solution of 40% by weight of component B, 20% by weight of diethylene glycol bis(allyl carbonate) was mixed and prepolymerized.
When thermally polymerized in the mold, the refractive index of the obtained lens decreases, but the dyeability and the durability of the coating provided on the surface improve. Like this. It is easily possible to change the balance of performance by adding components other than A and B, but the monomer used in this case is preferably an acrylic compound or an acrylic compound, and at the same time, a polyfunctional monomer. is more suitable. When performing casting molding, it is used to impart various characteristics to lenses and to improve the process. Ultraviolet absorber and antioxidant are added to the monomer mixture. Additives 71D such as band 1 inhibitors, dyes, pigments, fluorescent agents, photochromic substances, various stabilizers and 1M type agents can be used as necessary. [Example] Hereinafter, the non-invention will be explained in more detail with reference to Examples.
The invention is not limited to these examples. In addition, all parts in the examples represent parts by weight. (Example 1) 70 parts of dibenzyl fumarate and 26 parts of triallyl limellitate were mixed and stirred at 60°C, and 2-hydroxy-4
- Added 02 parts of octoxybenzophenone. After 7, in a nitrogen atmosphere, t-butylperoxy(2-ethylhexanony)
100% and stirred at 60°C for 2 hours to perform prepolymerization.
The precipitation temperatures before and after prepolymerization and the average molecular weight after prepolymerization are shown in Table 1.Next, 56 parts of t-butylperoxy (2-ethylhexanoate) were added to the colander and mixed well. After filtering the insoluble matter of this mixture, -&00D(
The mixture was injected into a space formed by a glass mold designed to emit a diopter (D: diopter) and a gasket made of ethylene-vinyl acetate copolymer designed to have a center thickness of 2.0-. to 4 hours at 45°C, 4 hours at 49°C, 55 hours at 54°C, 5 hours at 59°C, 5 hours at 65°C, 2.5 hours at 69°C, 2 hours at 75°C, 2 Eil! l - 1 hour at 78°C, 1 hour at 85°C, 95
℃ for 1 hour. After that, the glass mold and gasket were separated from the lens.
. When a lens of -6,00 was cast using a glass mold, the incidence of dense layer defects was less than [L1%'). Next, post-curing was carried out at 100° C. for 5 hours to remove distortion inside the lens, and t0 was obtained. The optical surface condition of the nine lenses was good, and there was no internal distortion, making it satisfactory as an optical material. The refractive index was 1.575. (Example 2) 40 parts of di-orthochlorobenzyl fumarate and 56 parts of triallyl rimellitate were mixed and stirred at 600 °C.
12 parts of '-hydroxy-5'-methylphenyl)benzotriazole were added. After 70 years, in a nitrogen atmosphere,
1.1-Bis(t-butylperoxy) 6.5.5-trimethylcyclohexaquatate (NOF @ Perhexa 5M) (aerate 2 parts of L and stir at 65C for 4 hours,
Table 1 shows the precipitation temperatures before and after prepolymerization and the average molecular weight after prepolymerization. Next, further 1,1-bis(1,-butylperoxy)
After adding 56 parts of 5.5.5-) dimethylcyclohexanoate and mixing well, polymerization was carried out in a mold. The polymerization temperature was increased by an average of 8°C compared to Example 1. The following operations were performed in the same manner as in Example 1. (Example 5) 57 parts of dibenzyl fumarate and 59 parts of diallylisophthalate were mixed and stirred at 60°C, and ethyl-2-cyano-
Add 2 parts of 5,5-diphenylacrylate α, then add 2 parts of -butylperoxy(2-ethylhexanoate) [L] in a nitrogen atmosphere, and stir at 60°C for 2 hours to prepolymerize. went. The precipitation temperatures before and after prepolymerization and the average molecular weight after prepolymerization are shown in Table 1. Next, 1.1-bis(1-butylperoxy) 5.5.
5-) After mixing 56 parts of dimethylcyclohexanoate by mouth, polymerization was carried out in a mold. The following operations were performed in the same manner as in Example 1. (Implementation IT-21) 40 parts of di-orthochlorobenzyl fumarate and 56 parts of diallyl terephthalate were mixed and stirred at 60 te.
'-Hydroxy-5'-methylphenyl)benzotriazole (L2$ was added, then in a dynamic nitrogen atmosphere,
9. Add 12 parts of 1.1-bis(t-butylperoxy)5,5.5-trimethylcyclohexanoate and stir at 65°C for 4 hours to perform prepolymerization. Table 1 shows the precipitation temperatures before and after prepolymerization and the average molecular weight after prepolymerization. Next, further 1.1-bis(t-butylperoxy)
After adding 6 parts of S, S, , S-)limethylcyclohexanoate and mixing well, polymerization was carried out in a mold. Polymerization was carried out at an average temperature of 8° C. higher than in Example 1. The following operations are performed in the same manner as in implementation 1. (Example 5) 50i of diorthochlorobenzyl fumarate and 66 parts of diallyl terephthalate were mixed and stirred at 60°C, and 2 parts of 2-hydroxy-4-methoxybenzophenonoa was added. Then in a nitrogen atmosphere. 2 parts of penzoyl peroxidide (manufactured by Nippon γ Yuiji; Nibar B) was added, and the mixture was stirred at 60C for 1 hour to carry out prepolymerization. Table 1 shows the precipitation temperatures before and after pre-polymerization and the average molecular weight after pre-polymerization. Next, 4156 parts of benzoyl peroxa was further added, mixed well, and then polymerized in a mold. The polymerization temperature was raised to an average of 6°C higher than in Example 1. The following operations were performed in the same manner as in Example 1. (Comparative Example 1) Of the operations performed in Example 1, all operations were performed in the same manner as in Example 1, except for the operations related to prepolymerization. Specifically, 70 parts of dibenzyl fumarate and 261 g of triallyl trimellitate were mixed and stirred at 60°C, and 02 parts of 2-hydroxy-4-octoxybenzophenone was added. That (&1-)
゛Tyl-peroxy (2-ethylhexanoate) 58
After adding parts and mixing well, polymerization is carried out in a mold. The following operations were performed in the same manner as in Example 1. (Comparative Example 2) All of the operations performed in Example 1 were performed in the same manner as in Example 1, except for the prepolymerization and the operation related to the heavy content temperature condition of the trowel injected into the mold. Specifically, 40 parts of dibenzyl fumarate and 26 parts of triallyl trimellitate were mixed and stirred at 60°C, and 2 parts of 2-hydroxy-4-octoxybenzophenol (2 parts of 1L) was added to the PC- ) After adding 58 g of ethyl-peroxy(2-ethylhexanoate) and mixing well, polymerization was carried out in a mold. The polymerization temperature was raised to an average of 6°C higher than in Example 1. The following operations were performed in the same manner as in Example 1. For the synthetic resin lenses molded in Examples 1 to 5 and Comparative Examples 1 to 2, the refractive index, heat resistance (rusting in hot air at 150°C for 1 hour), appearance, dyeability (commercially available polyester) The results were shown in Table 2. Table 1 Example 1 47C42c 41JIJO25
5℃ 50 C4000 547℃ 4 2 Ci! 0LIO455
℃ 50 C4000 552℃ 47 C4000 Comparative example 1 47℃ -- 247℃ -- Table 2 Refractive index Heat resistance Appearance Dyeability (160℃) Example 11.570 0 Good Good 2 1.5
78 0 Good Good 5 1.570 Q
Good Good 4 1.578 0 Good
Good 5 1.575 0 Good Good ratio V row 1
(Test not possible due to precipitation) 21.570f type Poor distortion Uneven dyeing [Effects] As mentioned above, according to the present invention, a radical-capable fumarate compound and an allyl compound are mixed in advance until a predetermined molecular weight is reached. It is made of synthetic resin that has a high refractive index and has the properties necessary for a lens, as it is polymerized and then electrostatically charged in a mold, thereby avoiding the precipitation of solid components and simplifying the injection operation. You can get lenses. In addition, by being able to lower the degree of precipitation of the solid fraction, the range of selection of polymerization initiators has expanded, making it possible to change the balance of performance of the main component monomer in the present invention depending on the purpose. It is also one of the effects of the present invention that the temperature increases. that's all

Claims (2)

[Claims] (1) A composition for a synthetic resin lens, the main components of which are the following A and B. A One or more monomers whose general formula is represented by [1]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [1] (In the formula, X represents halogen or hydrogen excluding fluorine.) B One or more monomers whose general formula is represented by [2]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [2] (In the formula, n represents 2 or 3.) (2) A method for producing a synthetic resin lens, which comprises pre-polymerizing a comonomer containing A and B as main components until the average molecular weight reaches 2,000 to 8,000, and then injecting it into a mold and copolymerizing it.