JPS62235902A - Composition for synthetic resin lens - Google Patents

Abstract

PURPOSE:To increase the refractive index of a lens, to improve the durability thereof and to easily mold the lens by using a copolymer essentially consisting of a specific comonomer. CONSTITUTION:The compsn. for the lens consists essentially of the monomer expressed by formula I e.g.: diethylene glycol bis(benzyl fumarate) and the monomer expressed by formula II (e.g.: styrene) and is compounded with the other monomers and polymn. initiator, at need. In formulas, X denotes a halogen except fluorine and H, m denotes 1-5, R denotes -CH=CH2, -C(CH3)=CH2, etc.; n denotes 1-3. The high refractive index resin is obtd. from the monomer expressed by formula I alone. The heat resistance and solvent resistance are improved if the monomer expressed by formula II is copolymerized. Since this compsn. permits easy control of reaction, the operation and control in a production process are easy.

Description

[Detailed Description of the Invention] [Industrial Application] The present invention is a synthetic resin that has a relatively high refractive index, excellent durability such as heat resistance, solvent resistance, and impact resistance, and is easy to mold. Regarding manufactured lenses.

[Conventional ff technique]

Lenses made of cuticle resin, especially diethylene glycol bis(allyl carbonate) resin lenses, are inferior to glass lenses in terms of safety, erodibility, and fashionability, and in recent years, anti-reflection technology, hard coat technology, and no. With the development of docoat + anti-reflection technology, it is rapidly becoming popular. The use of plastic for eyeglass lenses is ok.
A grade lens.

That is, there is an increasing demand for thin plastic lenses made of high refractive index resin materials.

The refractive index of diethylene glycol bis resin is 1.50, and several technical proposals have been made to improve this drawback.

For example, a copolymer of 1% diethylene glycol bis(allyl carbonate)thenyl methacrylate is disclosed in JP-A-54-41965, and a copolymer of diethylene glycol bis(allyl carbonate) and 4-iodostyrene is disclosed in JP-A-54-77686. Examples of copolymers, JP-A-58-1551s
In cases such as the example of a copolymer of diallyl phthalate and diallyl phthalate and methyl methacrylate prepolymer, allyl groups with different reactivities are reacted with (meth)acrylic groups or vinyl groups, so it is difficult to manufacture lenses. There is the above problem @ that is, 1 reaction speed is very fast (meta)
The acrylic group or vinyl group polymerizes first, and the allyl group, which has a slow reaction rate, polymerizes later, so it is not an idiot that does not produce a co-electrostatic effect, but the allyl compound is not completely polymerized, which is the cause of reduced solvent resistance. becomes.

Examples of this include copolymers of bisphenol A dimethacrylate and phenyl methacrylate or benzyl methacrylate in JP-A-5S-15747, and JP-A-57-54901. The styrenic monomer fift of JP-A-58-18602 is composed of di(meth)acrylate and allyl compound or di(meth)acrylate having a substituted aromatic ring.
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 it is extremely difficult to control during lens manufacturing. 1. 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 optical defects. The problem is that it is sensitive to external influences, and it is very difficult to control conditions other than the polymerization conditions.Therefore, the difficulty in controlling the single polymerization reaction and the completeness of the single polymerization reaction are problematic. However, the process had to be complicated.

In addition, in the above two examples, in the case where only monofunctional monomers are used as the product, it is impossible for the monomers to completely polymerize and be incorporated into the polymer chain, and due to unreacted monomers. Adverse effects on heat resistance and bath agent resistance are also considered.

Ninth, the next step to improve the manufacturing defects is a diallyl compound having a halogen-substituted aromatic ring.

Examples include diallylinophthalate or diallyl terephthalate or copolymers with diallylinophthalate. This type of technology is relatively easy to control the reaction, and since all monomers are trifunctional, it is easy to control the process from solution mixing to polymerization. A high refractive index lens can be obtained. However, because the specific gravity of the diallyl compound having a nuclear aromatic ring, which is a product component, is high (approximately 1.7 as a polymer), the lens becomes heavy and has the disadvantage that the merits as a high refractive index lens are lost. ◎Also, diallyl compounds with a nuclear halogen-substituted aromatic ring are expensive to synthesize and purify compared to diethylene glycol bis(oryl carbide) and other lens resins, so they have a high refractive index. Even taking this into account, it is inferior in terms of popularity.

Furthermore, it is used in one or more examples. A common problem with bisphenol A dimethacrylate and di(meth)azilylates or diallyl compounds having a nuclear halogen-substituted aromatic ring is that they tend to precipitate. In many cases, these monomers are used after being dissolved in the monomer to be copolymerized, but if they are dissolved above a certain amount, they tend to precipitate even at room temperature, so the content is limited. It is necessary to keep the temperature above a foot.

There were manufacturing problems in that the selection of polymerization initiators was limited, and it was difficult to control the process from solution mixing to polymerization.

[Problems and Objectives to be Solved by the Invention As mentioned above, the conventional technology has problems such as lens quality, manufacturing process, lens manufacturing management, and lens cost.

The purpose of this invention is to solve the problems mentioned above, and its purpose is to provide a lens with a relatively high refractive index, durability such as heat resistance, solvent resistance, and impact resistance, and a long history as a lens. The object of the present invention is to obtain a sweet acid resin lens that is easy to mold due to its characteristics. More specifically, it is a liquid at room temperature and has a relatively slow reaction rate.

It is easy to control the reaction, and after polymerization, it has excellent durability and properties as a lens. By copolymerizing monomers represented by general formulas [1] and [2].

Solution 7u Injection into the mold 1. Easy operation and process control from the piece to the polymerization, to ensure general dissemination @
- To obtain a lens made of plastic.

[Mediator for solving problems]

In the synthetic resin lens composition of the present invention, the product components are 41 composed of the following A and B.

A, one or more monomers whose general formula is represented by [1].

(In the formula, or I-logen or hydrogen excluding fluorine, 1
几rn represents an integer from 1 to 5. )') B, one or more base bodies whose general formula is represented by [2].

@-Rn [2
] (In the formula, Rri, -CH=CH2, -C(OHa)=O
Ht − and n represents an integer from 1 to 3. )
5 Next, the present invention will be explained in detail. Typical examples of component A used in the invention are ethylene glycol bis(benzyl fumarate), diethylene glycol bis(benzyl fumarate), ) I7 ethylene glycol bis(benzyl fumarate), Recall bis (benzyl fumarate), tetraethylene glycol bis [benzyl fumarate], pentaethylene glycol bis (benzyl fumarate).

Examples include diethylene glycol bis(chlorobenzyl fumarate), )17 ethylene glycol bis(chlorobenzyl fumarate), diethylene glycol bis(promobenzyl fumarate), ) IJ ethylene glycol bis(bromobenzyl fumarate), and the like. In the present invention, although a high refractive index resin can be obtained by polymerizing component A alone, it is possible to obtain a high refractive index resin by polymerizing component A alone. Polymerize and use. The content of component A is preferably 20 to 80 percent.

Typical examples of component B include styrene,
Divinylbenzene, α-methylstyrene.

Allyl benzoate, methallyl benzoate, Schiff 1
J Ruinphthalate, diallyl terephthalate.

Dimetaglu phthalate. Trialiltrimerit x
-t, 1,5°5-triallylbenzenetricarboyacylate, and the like. Even if component B is polymerized alone, it can be molded into a lens, but it cannot be used as a lens material because it has poor impact resistance, discoloration, and durability of the coating formed on the surface. The purpose of using component B is to copolymerize it with component A to improve lens performance such as heat resistance and solvent resistance without reducing refractive index, impact resistance, film durability, etc. This is to improve the performance. Component B in the present invention shows a high refractive index even when polymerized alone, so even when it is copolymerized with component A, the refractive index does not decrease. In addition, component BFi is a liquid with relatively low viscosity, so it mixes with component A and is easy to handle even after cooling.
It also plays a role in facilitating reaction control.

In the invention, components other than A and B can be added in order to change the balance of properties as a lens, such as coloring with a refractive index of 1, impact resistance, or durability of a coating provided on the surface. For example, component A is 40% by weight,
Component B was mixed with 40% by weight, and 20'4 of diethylene glycol bis(carboxylic acid) was added to the solution.
When copolymerized with 41% mA@-, the resulting T-lens has a lower refraction 54, but has improved impact resistance and durability of the coating on the surface. As another example, ° is 40% by weight of component A and 301% of component B total.
Add chlorosteref3 to the mixed solution of m parts.
When mixed and copolymerized at 0 weight and t percent, the resulting lens is colored but exhibits a controlled refractive index. In this way, it is possible to change the balance of performance by adding components other than A and B, but vinyl compounds, acrylic compounds, or allyl compounds are preferable monomers to be used on the occasion. Yes.

As the polymerization initiator used in the present invention, #! ! The initiator is not limited to, and any known radical polymerization initiator may be used.

For example, hydroperoxides such as 1°C-butyl hydroperoxide, dialkyl peroxides such as di-t-butyl peroxide.

Diacyl peroxides such as benzoyl peroxide, peroxydicarbonates such as diimprovil peroxydicarbonate, peroxy esters and ketone peroxides such as monobutyl peroxybiparate, peroxy There are peroxides such as ketal, and azo compounds such as azobis (imbutyrilonitrile). Use of radical polymerization initiator
varies depending on the monomer composition, polymerization conditions, etc., and cannot be generally limited, but is preferably used in a range of 1.1 to 5.0 weight percent.

When performing casting molding, we provide lenses with various properties and improve the process.

Monomer mixture, ultraviolet absorber, l￥! f-hi preventive agent.

Additives such as anti-banding agents, dyes, pigments, fluorescent agents, photoclockwise substances, various stabilizers, and mold release agents can be used as necessary.

[Implementation row]

The invention will be explained in more detail with reference to the following, but the present invention is not limited to these embodiments.

In addition, all parts in the examples represent parts by weight.

(Example 1) Diethylene glycol bis(benzyl fumarate) 58
2-hydroxy-
2 parts of 4-octoxybenzophenone α were added. Thereafter, 1.8 parts of t-butyl peroxyneodecanoate (NOF: Half-Tyl ND) was added and mixed well. After filtering the insoluble matter of this mixture, at 1 degree -
The mixture was injected into a space formed by a glass mold designed to emit &00D (D; diopter) and a gasket made of an ethylene-vinyl acetate eutectic material designed to have a center thickness of 2.0. Polymerization was carried out in a constant temperature bath for 2
4 hours at 8℃, 3 hours at 50℃, 3 hours at 35℃, 3 hours at 45℃, 2.5 hours at 55℃, 65℃
for 2 hours, at 75°C for 1 hour, and at 85°C for 1 hour. Thereafter, the glass mold and gasket were separated from the lens. With this method, the diameter is 65-φ.

When a -6,00D lens was cast-polymerized, the incidence of poor adhesion between the glass mold and the lens was a. Next, post-cure was performed at 110°C for 2 hours to eliminate distortion inside the lens. The optical surface condition of the obtained lens is good, there is no internal distortion, and it is satisfactory as an optical material.

(Mikai Ushio 2) Diethylene glycol bis(benzyl fumarate) 58
59 parts of diallyl inphthalate were mixed and stirred, and 2
(2'-Hydroxy-5'-methylphenyl)pencitrianol α 2 parts ft, m-tip 〇 Then, 2.8 parts of diisopropyl peroxydicarbonate (manufactured by NOF@; Perloyle PP) was added and mixed well. . After filtering the insoluble matter of this mixed tooth, -&00D (D;
It was injected into a space created by a glass mold designed to emit 2.0 diopters and a gasket made of ethylene-vinyl acetate copolymer designed to have a center thickness of 2.0 Nl. Polymerization was carried out in a constant temperature bath at 40°C for 4 hours, at 45°C for 3 hours, at 50°C for 55 hours, at 55°C for 3 hours, at 60°C for 2.5 hours, and at 60°C for 2 hours.

It was carried out at 75°C for 1 hour and at 85°C for 1 hour. The glass mold and gasket were then separated from the lens. When a lens with a diameter of 65Wφ and -&OOD is cast-polymerized using this method, the incidence of poor adhesion between the glass mold and the lens is:
Q, less than 15% and t0 Next, post-curing was performed at 110° C. for 2 hours to remove distortion inside the lens. The optical surface condition of the obtained lens was good, with no distortion at 173 parts and 4, and was satisfactory as an optical material.

(Example 5) Diethylene glycol bis(benzyl fumarate) 58
30i of iaL styrene and 10 parts of α-methylstyrene were mixed and stirred, and 0.2 part of ethyl-2-cyano-3,3-diphenylacrylate was added. Then, 1.8 parts of t-butyl peroxybihalate (manufactured by NOF Corporation; Verbutyl PV) was added and mixed. After filtering the insoluble matter from this mixture, the same procedure as in Example 2 was performed to pour the mixture. Contains mold. '!' Bf between glass mold and lens
The incidence of defects was (less than 11%).
Clean the lens at 2:114°C to remove distortion inside the lens. The optical surface condition of the obtained lens was good.

There was no internal distortion, and the result was ″/f, which was satisfactory as an academic material.

(Implementation Ga 4) Diethylene glycol bis(benzyl fumarate) 58
and 40 parts of triallyl trimellitate were mixed and stirred,
12 parts of 2-hydroxy-4-octoxybenzophenone was added and then 1.8 parts of benzoyl peroxide (manufactured by Nihon Yutoji; Niper B) was added and mixed well. After filtering the insoluble matter from this mixture, -
&OOD will come out.''1 The glass mold is designed to have a center thickness of 2.0 mm, and the ethylene-vinyl acetate mixture is
It was injected into the space created by the gasket consisting of the r-body. Polymerization was carried out in a constant temperature bath at 50°C for 4 hours and at 55°C for 5 hours.
5.5 hours at 60℃, 5 hours at 65℃, 2.5 hours at 75℃
The temperature was 2 hours at 85°C and 2 hours at 90°C. After step 7, separate the glass mold and gasket from the lens.

The occurrence of poor adhesion between the glass mold and the lens when a lens with a diameter of 65mmφ and -&00D was cast and superimposed using this method was less than 11%.
The optical surface condition of the obtained t-lens, which was post-cured for a period of time to remove distortion inside the lens, was good and was satisfactory as an optical material.

(Example 5) Diethylene glycol bis(penzyl fumarais) 48
1 part, and 48 parts of dimethadyl inphthalate were mixed and stirred,
2 parts of 2(2'-hydroxy-5'-methylphenyl)benzotriazole α were added.

After that, 1. ．． 1-bis(1-butylbaroxy)3.
Add 5.8 parts of 3.5-trimethylcyclohexane (manufactured by Nippon Oil & Fats ■; Perhexa 3M), mix well, filter the insoluble matter from the mixture, and carefully remove It is injected into a space created by a designed glass mold and a gasket made of ethylene-vinyl acetate copolymer designed to have a center thickness of 2-0 mm. The heavy content is
In a constant temperature bath, 4 hours at 60℃, 3 hours at 65℃, 70C
for 55 hours, at 75°C for 3 hours, and at 85°C for 2.5 hours.

It was carried out at 4:14 at 90°C. Thereafter, the glass mold and gasket were separated from the lens. With this method, the diameter is 65m.
The amount of soil that caused poor adhesion between the glass mold and the lens when pouring a lens with φ, -6.0OD was less than 11%.Next, it was post-cured at 110℃ for 2 hours,
Removed distortion inside the lens. The obtained lens had a good optical surface condition and was satisfactory as an optical material.

(Example 6) Triethylene glycol bis(benzyl fumarate) 5
Mix 8 parts of styrene and 40 parts of styrene, stir, and add ethyl-2-
After adding 2 parts of cyano-3,3-diphenylacrylic L/-)Q, t-butyl peroxyneodecanoate (Nifu Yutsuki @B; filter the insoluble matter of the perbutyl mixture. After fC., casting was carried out in the same manner as in Example 1.The incidence of poor adhesion between the glass mold and the lens was less than 11%.Next, 1
Post-cure at 10°C for 2 hours.

Removed distortion inside the lens. The obtained lens had a good optical surface condition and was satisfactory as an optical material.

(Example 7) 8 parts of triethylene glycol bis(orthochloropendyl fumaley). 49 parts of diallyl inphthalate were mixed and stirred, and 12 parts of 2-hydroxy-4-octoxybenzophenone was added.

Thereafter, 2.8 parts of diimprovil peroxydicarpofluoride (Nippon Oil 1J PP) was thoroughly mixed with a knife. This /I45 method (filtrate the insoluble '1' and carry out casting overloading using the same method as in Example 2. Incidence of '!!! layer discoloration between the glass mold and the lens) The lens was post-cured for 2 hours at 110°C to eliminate distortion inside the lens.The optical surface condition of the obtained lens was good. I am glad that the material is satisfactory.

(Example 8) 58 parts of triethylene glycol bis(orthobromobenzyl fumarate), 30 parts of styrene, and 10 parts of α-methylstyrene were mixed and stirred.
-Methylphenyl) pen/) IJ azole (2 parts of L) was added. Then, 1.13 parts of t-butyl peroxypivalate (NOF ■ back; Perbutyl PV) was added and mixed well. After filtering out insoluble matter, cast polymerization was performed in the same manner as in Example 2. The incidence of poor adhesion between the glass mold and the lens was less than (L1%). The lens was post-cured for 2 hours to remove distortion inside the lens.The optical surface condition of the obtained lens was good and was satisfactory as an optical material.

(Implementation Ga 9) Tetraethylene glycol bis(benzyl fumarate)
48 parts; 50 parts of triallyl nitrimellitate were mixed and stirred, 12 parts of ethyl-2-thia/-1,3-diphenyl acrylate was added, and then penzoyl peroxide (NOF ■Committee) was added. ; 1.8 parts of Niper B) was added and mixed well. After filtering out insoluble matter from this mixture, cast polymerization was performed in the same manner as in Example 4. The incidence of poor adhesion between the glass mold and the lens was less than (114). Next, post-curing was performed at 110° C. for 2 hours.

Removed distortion inside the lens. The obtained lens had a good optical surface condition and was satisfactory as an optical material.

For the synthetic resin lenses molded by the methods of Examples 1 to 9, the refractive index, heat resistance (1 hour in hot air at 130°C!), impact resistance (FDA standard, lens center thickness 2
wa), dyeability (using a commercially available disperse dye for polyester) was tested and evaluated.

The results are shown in Table 1.

First refractive index Heat resistance Impact resistance Dyeability (130°C) Example 11.5780 0 Good 21.571 0 () Good 31.577 0 0 Good 41.572 0 0 Good 51.571 0 0 Good 61 .579Q ○ Good 71.580 0 0 Good 81.5900 0 Good 91.571 0 0 Good [Effect] As mentioned above, by using the composition of the invention, not only a high refractive index but also a high refractive index can be obtained. , Heat resistance and solvent resistance due to the cross-linked structure of the molecules.

It is possible to obtain lenses made of sweet acid resin that have good characteristics such as stability of the shot method, and excellent impact resistance and stainability.In addition, the product is liquid at room temperature, and the reaction rate is relatively slow. It is easy to control, and the polymerization initiator can be freely selected, making it easy to control the process.As a result, the manufacturing cost is low and the product is highly popular. This is also one of the effects of the present invention.

that's all

Claims (1)

[Scope of Claims] A synthetic resin composition for a lens, characterized in that the product consists of 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, and m represents an integer from 1 to 5.)B, the general formula is [2
] One or more monomers. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [2] (In the formula, R is -CH=CH_2・-C(CH_3)=C
H_2 Represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and n represents an integer from 1 to 3. )