JPS6392901A - Composition for synthetic resin lens - Google Patents

Abstract

PURPOSE:To improve the refractive index, impact resistance and weatherability of a lens by using a synthetic resin essentially consisting of specific bisphthalate. CONSTITUTION:The synthetic resin essentially consisting of the bisphthalate expressed by the formula is used for the compsn. for the lens. In the formula, R1 denotes H, methyl; R2 denotes -(CH2)n-, -(CH2CH2O)m-CH2CH2-, -[CH2CH(CH3) O]n-CH2CH(CH3) etc.; 2<=n<=10; 1<=m<=10. The other radical polymerizable compd., more particularly the compd. having the good alternating copolymerizability with the compd. expressed by the formula can be copolymerized with the compd. expressed by the formula. A UV absorbent, antioxidant, antistatic agent, dyes, etc., can be added at need to the liquid mixture composed of the monomers at the time of molding the lens by casting. The compsn. which permits easy molding is thereby obtd. and the lens having the excellent refractive index, impact resistance and weatherability is obtd.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is directed to a synthetic resin lens that is a novel composition, has a relatively high refractive index, and has excellent properties such as impact resistance and #temporality. Regarding the composition used.

[Conventional technology]

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, and in recent years, anti-reflection technology, hard coat technology,
With the development of anti-reflection technology, hard coats are rapidly becoming popular. Plastic eyeglass lenses are more high-quality lenses.

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(allyl carbonate) resin is 1.50, which is lower than the 1.53 of glass for lenses, and it has the disadvantage that it is thicker than glass lenses when compared with the same power.

Traditionally, synthetic resins with high refractive index include polystyrene,
There are polycarbonate, polyurethane, etc., but no material has been found that satisfies all of the properties of impact resistance, weather resistance, and transparency at the same time.

In order to increase the refractive index of K, it is generally effective to introduce a benzene ring into the molecular structure or add a herogen atom to the molecular structure, but the introduction of a benzene ring tends to make the resin brittle. %it@Causes a decrease in impact resistance. When halogen atoms are added, by irradiation with ultraviolet rays during weather resistance tests.

Since the bonds are broken and halogen atoms are liberated, the adhesion of the coating provided on the surface of the lens 91, which is colored, deteriorates.

In order to improve these drawbacks, several technical proposals have been made. In addition, the series of copolymers of bisphenol dimethacrylate and phenyl methacrylate or benzyl methacrylate of JP-A-55-13747, styrene yarn threads and nuclear halogens of JP-A-57-54901 and JP-A-58-18602 A series of copolymers of di(meth)acrylate and di(meth)acrylate having a substituted aromatic ring, and a series of salicylic acid (meth)acrylic ester derivatives of JP-A-60-146845, etc. There are methods that improve impact resistance and degree of polymerization by increasing the length of one molecule while introducing 10 gene atoms, or by copolymerizing with a monomer having a functional group with similar reactivity. However, these rows have a problem in that lens manufacturing control is extremely difficult. Tsuma p.

Since the reaction between (meth)acrylic and vinyl groups is far away, it is difficult to control casting conditions.

Distortion occurs inside and on the lens surface, which tends to cause optical defects.Also, (meth)acrylic and vinyl groups are very sensitive on the reaction surface and are susceptible to external influences.
The problem is that it is extremely difficult to control conditions other than polymerization conditions.

However, as a series that has improved the manufacturing disadvantages, diallyl compounds having a nuclear halogen-substituted aromatic ring.

Mention may be made of a series of copolymers with diallyl phthalate. However, the specific gravity of the diallyl compound having the nuclear halogen-substituted aroma fJ1 as the main component is large (1.7 or more J as poly1-
:,), the lens is heavy and its advantages as a high refractive index lens are lost.

Furthermore, di(meth)acrylate or diallyl compounds having a nuclear halogen-substituted aromatic ring used in one or more examples, or compounds listed in JP-A-60-137912 and JP-A-60-166307, etc. A common problem with methods that attempt to increase the refractive index by adding halogen atoms is the coloring of lenses. The cause may be heating during polymerization or
It is thought that irradiation with ultraviolet rays causes the release of nitrogen atoms. Therefore, it is difficult to control the polymerization reaction, and it is difficult to complete the polymerization reaction, and there is also a problem that unreacted monomers have an adverse effect on heat resistance and solvent resistance. Further, when a lens is subjected to a weather resistance test, there is a problem in that the -10 gen atoms are broken by ultraviolet energy and become liberated, resulting in an increase in coloration.

As a similar phenomenon, when the surface of a lens is subjected to plasma treatment, halogen atoms are liberated, which may cause an adverse effect during surface processing.

[Problem 3 to be solved by the invention As described above, the conventional technology has problems such as lens quality (performance) and lens manufacturing management problems.

The present invention is intended to solve the above-mentioned problems, and its purpose is to provide a material with a relatively high refractive index, impact resistance,
We are developing a synthetic resin lens composition that has excellent durability such as heat resistance, solvent resistance, and weather resistance, and satisfies the initial characteristics of lenses such as low specific gravity, and is easy to control and mold during production. It's about getting. [Means for Solving the Problems] The synthetic resin lens composition of the present invention is characterized in that its main component is represented by the following general formula [1].

(In the formula, R1 represents hydrogen or a methyl group, and R1 is.

-(CHz) -t η.

+ (CB2CH, O) -CH, CH, -.

m.

+ (CB, CH(CH,)O) -CHIC:H(
CH,)-.

Shi2S 3. represents, carries, 3. tn and J are each 2≦n≦10.

l≦Rage≦10.1≦! ), which represents an integer with ≦lO, then
The present invention will be described in detail.

Typical examples of the composition having the general formula (1) used in the present invention are as follows.

Ethylene glycol bis(allyl orthophthalate)
Ethylene glycol bis(methallyl ortho 7-thalerate)
, diethylene glycol bis (allyl ortho7thaleate), diethylene glycol bis (methallyl orthophthalate), triethylene glycol bis (allyl orthophthalate).

Triethylene glycol bis (methallyl ortho 7 tallate), polyethylene glycol bis (allyl orthophthalate), polyethylene glycol bis (methallyl ortho 7 tallate), propylene glycol bis (allyl ortho 7 tallate), propylene glycol bis (methallyl orthophthalate) s polypropylene glycol bis (allyl ortho phthalate), polypropylene glycol bis (methallyl ortho 7 talate), 2,2-bi x (
4μ(2'-7!J-ruoxycarbonylphenylcarbonyloxy)phenyl)prop7.2.2-bis(4'
-[2'-(2'''-allyloxycarbonylphenylcarbonyloxy)ethoxy)7enyl]propane, 2
．． 2-bis(4'-(4'-(21-(211-7
lyloxycarbonyl72'ylcarbonyloxy)furoboxy)phenyl]furopane, 2,2-his(4'
-(2'-'7')ruoxycarbonylphenylcarbonyloxy)phenyl)butane.

Used in the present invention. The bis-7talate compound represented by the general formula [1] can be synthesized by the following method.

[Method 1]

(shi) 10 Zl+2 2:: C'-i n! −
For example, in method 1, 2 moles of phthalic anhydride (A) and diethylene glycol (B, R, d, C:H, -CHz-
0-CM, -CHz) to produce diethylene glycol bis(7-talate) halfester (C) t-, and allyl alcohol CD) 'k non-1ai
i, for example, when reacted with para-toluenesulfonic acid in toluene, diethylene glycol bis(allyl orthophthalate) (1) is obtained.

According to method 2, triethylamine (
g) By reacting 2 moles.

Diethylene glycol bis(allyl orthophthalate) is obtained in the same manner as in method 1 by synthesizing the intermediate represented by the formula, reacting it with 2 moles of allyl chloride, and dehydrochlorinating it.

The compound of general formula (1) according to the present invention thus obtained can be liquid at room temperature or crystalline depending on the type of %R1 and R1. Those that are crystalline at room temperature are preferably dissolved in other radically polymerizable monomers, liquefied, and then copolymerized.1 Various properties as a synthetic resin lens.

In order to add a certain specific performance in addition to the performance, the compound of general formula (1) in the present invention can be mixed with other radically polymerizable monomers and copolymerized. In that case, the nanatsuma is used.

It does not significantly reduce the refractive index and does not have an adverse effect on the n-characteristics of the lens, and is expressed by the general formula [1] in the present invention.
It is preferable to use a monomer that exhibits good alternating copolymerizability with the compound described above.Moreover, it is more preferable to select a difunctional or higher functional monomer in order to form a crosslinked structure t.

The polymerization initiator used in the present invention is not particularly limited, and any known radical polymerization initiator may be used.

The list includes more hydrobars, oxides such as t-butyl hydroperoxide, dialkyl peroxides such as di-t-butyl peroxide, diacyl peroxides such as benzoyl peroxide, and diisopropyl peroxydicarbonate. peroxydicarbonate.

Examples include peroxy esters such as t-butyl peroxybivalate, peroxides such as ketone peroxide and peroxyketal, and azo compounds such as azobis (imptillonitrile). The amount of the radical polymerization initiator to be used varies depending on the monomer composition, polymerization conditions, etc., and cannot be generally limited, but it is preferably used in the range of 0.1 to 7.0 weight percent.

When performing casting molding, ultraviolet absorbers, antioxidants, antistatic agents, dyes, pigments, and fluorescent materials are added to the monomer mixture to impart various properties to the lens and improve the process. agents, photochromic substances, various stabilizers,
Additives such as a mold release agent can be used as necessary.

[Implementation row]

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples; all parts in the examples represent parts by weight.

(Implementation row 1) According to the above production method 1 as shown in the reaction formula below,
Diethylene glycol bis(allyl orthophthalate)
Rabbit) was produced.

(1) Gy) Feeding mouth (c) That is, 30 parts of phthalic anhydride α) was added to 11 parts of diethylene glycol (7), heated to ℃ while stirring, and kept for 2 hours to form diethylene glycol bis(
7 tallate) Hafestel (a) added part was obtained First, 6 parts of allyl alcohol was added to 20 parts of this compound (a), mixed with toluene, and stirred in the presence of para-toluene sulfonic acid. The mixture was refluxed for 2 hours at 0°C. Thereafter, toluene and unreacted substances were distilled off to obtain 15 parts of diethylene glycol bis(allyl ortho 7 tallate) (b). Yield: 62 cm.

437 parts of diethylene glycol bis(allyl orthophthalate) (!437 parts) obtained by grinding and 60 parts of diallyl iso7thalet were mixed and stirred, and 0.2 part of 2-hydroxy-4-octoxybenzophenone was added. 2.8 parts of oxycarbonate was added and mixed well. After filtering out insoluble matter from this mixture, a glass mold designed to produce -6.0 OD (D: diopter) and a center thickness of 2.8 parts was used. 1 Polymerization was injected into a space created by a gasket made of ethylene-vinyl acetate copolymer designed to be Ou.
The temperature was increased from 50°C to 100°C for 5 hours, and then at 100°C for 2 hours. The glass mold and gasket were then separated from the lens. When a lens with a diameter of 65 mm and -6,00 D was cast-polymerized using this method, the incidence of poor adhesion between the glass mold and the lens was less than 0.1%.
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, there was no internal distortion, and it was found to be satisfactory as an optical material.

(Example 2) According to the production method 2 as shown in the reaction formula below,
Triethylene glycol bis(methallyl ortho 7-thale) (S) was produced.

(X) to) Naka) Naka) + 2 N (CxHi)m) (E+) That is, 30 parts of phthalic anhydride (r) is added to 15 parts of triethylene glycol CM), and the mixture is stirred without stirring.
By heating and keeping for 2 hours, 36 parts of triethylene glycol bis(7talate) halfester e) was obtained.

By adding 10 parts of triethylamine to 24 parts of this compound p) and heating it at 60°C for 1 hour, the intermediate (I) and the intermediate (6
) was obtained. After adding 96 parts of toluene to this, it was cooled with ice water. Thereafter, 10 parts of methallyl chloride was added dropwise over 1 hour while stirring.
After stirring for an hour, toluene and unreacted substances were distilled off to obtain triethylene glycol bis(methallyl ortho 7 tallate) (13)18[-. Yield: 58 cm.

37 parts of the thus obtained triethylene glycol bis(methallyl ortho 7-thale) Q3) and 60 parts of diallyl infthale) were mixed and stirred.

2 Add 0.02 parts of (2'-hydroxy-5'-methylphenyl)benzotriazole, then add 0.00 parts, then add 1%
2.8 parts of butyl peroxyvivalate was added and mixed well. After filtering out insoluble matter from the mixture, cast polymerization was carried out in the same manner as in the actual process.

The incidence of poor adhesion between the glass mold and lens is 0.
．． Post-cure for 2 hours at IIO'C for less than 1 inch, and distortion inside the lens? I took it.

The optical surface condition of the obtained lens was good, there was no internal distortion, and it was satisfactory as an optical material.

(Example 3) As shown in the reaction formula below, according to the production method 2,
2,2-bis(41-(21-allyloxycarbonylphenylcarbonyloxy)phenyl(CI)+ 2
N(CaH2)1) (a) + 2 CM, == CH-CM, -CjQ Kamehachi (i) That is, add 30 parts of anhydrous 7 tal [(1) to 25 parts of bisphenol Aσ and stir. Heat to 90℃ while
By keeping the mixture for 2 hours, 45 parts of bisphenol A bis(phthalate)/1-7 ester (U) was obtained. By adding 12 parts of triethylamine (A) to 28 parts of this compound (B) and heating at 60°C for an hour, intermediate (A) was obtained.
I got it.

After adding 96 parts of toluene to this, it was cooled with ice water. Thereafter, 10 parts of allyl chloride was added dropwise over 1 hour while stirring. After 1 drop, the mixture was further stirred at room temperature for 2 hours, toluene and unreacted substances were distilled off, and 2,2-bis(
20 parts of 41-(27-allyloxycarbonylphenylcarbonyloxy)phenyl)propane were obtained. Yield: 62 cm.

2,2-bis(4'-(2-allyloxycarbonylphenylcarbonyloxy)phenyl) thus obtained
38 parts of propane and 60 parts of diallylisophthalate were mixed and stirred, and 0.2 part of ethyl-2-cyano-3,3-diphenylacrylate was added. Then, add 1.8 parts of benzoyl peroxide and mix. A glass mold designed to produce -6,00D per degree after filtering the insoluble matter of this mixture, and a center thickness of 2.
1 polymerization, which was injected into a space created by a gasket made of ethylene vinyl acetate copolymer, was carried out in a constant temperature bath at 50°C for 4 hours, from 55°C to 75°C for 9.5 hours, and from 75°C to 75°C for 9.5 hours. The temperature was raised to 90°C for 4.5 hours, and the temperature was heated to (a)°C for 2 hours. The glass mold and gasket were then separated from the lens. With this method, the diameter is 65uφ, -6,00
What is the incidence of poor adhesion between the glass mold and the lens when the lens D is cast-polymerized?

After the primary temperature was less than 0.11, post-curing was performed at 100° C. for 2 hours to remove distortion inside the lens. The obtained lens had a good optical surface condition and was satisfactory as an optical material.

(Execution row 4) Diethylene glycol bis (allyl ortho 7 tallate) produced using the experimental crab (hereinafter abbreviated as D Positive B7”A P)
Mix 47 parts and triallyl trimellitate part.
After stirring, 0.2 part of 2-hydroxy-4-methoxyhenzophenone was added. Thereafter, 2.8 parts of di-2-ethylhexylyloxycarbohydrate was added and mixed well. After filtering out insoluble matter from this mixture, cast polymerization and post-curing were performed in the same manner as in Example 1 to obtain lenses.

(Execution row 5) Triethylene glycol bis(methallyl orthophthalate) (hereinafter abbreviated as TEBMP) produced in Example 2 47
and 50 parts of triallyl trimellitate were mixed and stirred, and 0.2 part of 2-hydroxy-4-octoxybenzophenone was added.

Thereafter, 2.8 parts of similistilperoxydicarbonate was added and mixed well. After filtering out insoluble matter from this mixture, pour-cast polymerization and post-curing were performed in the same manner as in Example 1 to obtain a lens.

(Run 6) 48 parts of 2,2-bis(41(21++allyloxycarbonylphenylcarbonyloxy)phenyl)propane (hereinafter abbreviated as BAPPP) produced in Row 3 and 50 parts of triallyl trimellitate were mixed.・Stir, 2 (
0.2 part of 2'-hydroxy-51-methylphenyl)benzotriazole was added. Then, 1.8 parts of benzoyl peroxide was added and mixed well. After filtering out insoluble matter from this mixture, cast polymerization and post-curing were performed in the same manner as in Example 3 to obtain a lens.

(Run 7) 37 parts of D1iiBAP produced in Run 1, 48 parts of dimethallyl isophthalate, and 12 parts of allyl benzoate were mixed and stirred, and 0.2 part of ethyl-2-cyano-3,3-diphenylacrylate was added. Added. Thereafter, 2.8 parts of diimpropyl peroxydicarbonate was added and mixed well. After filtering out insoluble matter from this mixture, casting polymerization and post-curing were performed in the same manner as in Example 1 to obtain a lens.

(Example 8) TI! produced in Example 2! 37 parts of iBMI', 48 parts of dimethallyl isophthalate, and 812 parts of allylbenzony.
Department? The mixture was mixed and stirred, and 0.2 part of 2-hydroxy-4-methoxybenzophenone was added. Thereafter, 2.8 parts of 1-butyl peroxyvivalate was added and mixed well. After filtering out insoluble matter from this mixture, casting polymerization and post-curing were performed in the same manner as in Example 1 to obtain a lens.

(Run 9) 33 parts of BAI':PP produced in Run 3, 48 parts of dimethallyl isophthalate, and 12 parts of allyl benzoate were stirred, and 0.2 part of 2-hydroxy-4-octoxybenzophenone was added. . after that.

1.8 parts of benzoyl peroxide was added and mixed well. After filtering out insoluble matter from this mixture, a cast polymerization and post-curing were performed in the same manner as in Example 3 to obtain a lens.

(Example 10) 25 parts of DEBAP produced in Example 1, 62 parts of diallyl in 7 tallate, and 10 parts of diethylene glycol bisallyl carbonate were mixed and stirred, and 2(2'-hydroxy-51-methylphenyl)benzo) was mixed. IJ Azole 0
．． 2 parts were added. Thereafter, 2.8 parts of di-2-ethylhexyl peroxydicarbonate was added and mixed well. After filtering out insoluble matter from this mixture, cast polymerization and postcuring were performed in the same manner as in Example 1 to obtain lenses.

(Run U) 25 parts of TEBMP produced in Run 2, 62 parts of diallyl isophthalate, and 10 parts of diethylene glycol bisallyl carbonate were mixed and stirred, and 0.2 part of ethyl-2-cyano-3,3-diphenylacrylate was added. was added. Then, similistilperoxycarbonate 2.
8 parts were added and mixed well. After filtering out insoluble matter from this mixture, cast polymerization and post-curing were performed in the same manner as in Example 1 to obtain lenses.

(Example 12) 62 parts of lyli isophthalate and 10 parts of diethylene glycol bisallyl carbonate were mixed and stirred, and 0.2 part of 2-hydroxy-4-methoxybenzophenone was added. Thereafter, 1.8 parts of benzoyl peroxide was added and mixed. After filtering out insoluble matter from this mixture, cast polymerization and post-curing were performed in the same manner as in Example 3 to obtain lenses.

Regarding the synthetic resin lenses molded by the methods of the above implementation rows 1 to 12, the refractive index (20 ° C.), it thermal property (130 ° C.)
℃ warm air for 1 hour), fit impact 14 (FDA standard, center thickness of lens is 2M), and dyeability (using a commercially available disperse dye for polyester) were conducted and evaluated. The results are shown in Table 1.

Table 1 Refractive index Heat resistance Impact resistance Dyeability Example 11.5
72 0 0 Good 21.570 Q
Q Good 31.582 0 0
Good 41.574 0 0 Good 51°572 0 0 Good 61.586 0 0 Good 71.568 0 0 Good 81.566 0 0 Good 91.577
0 0 Good lυ1.564 0 0 Good 111.5
630 0 Good 121.571 0 0 Good [Effects of the Invention] As described above, by using the composition of the present invention, not only a high refractive index is obtained, but also heat resistance and heat resistance due to the crosslinked structure of the molecules. A synthetic resin lens having good properties such as solvent resistance and dimensional stability, as well as excellent impact resistance and stainability can be obtained. In addition, the composition of the present invention has a relatively slow reaction rate and is easy to control.
A wide range of polymerization initiators can be selected, and the 5-polymerization operation and process control can be facilitated. As a result, one of the effects of the present invention is that the manufacturing cost is low and the product is highly popular.

that's all

Claims (1)

[Scope of Claims] A composition for a synthetic resin lens, the main component of which is represented by the following general formula [1]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [1] (In the formula, R_1 represents hydrogen or a methyl group, and R_2
is -(CH_2)_n-, -(CH_2CH_2O)
_m-CH_2CH_2-, -[CH_2CH(CH_
3) O〕_m-CH_2CH(CH_3)-, ▲formula,
There are chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or, ▲Mathematical formulas, chemical formulas, tables, etc. There is ▼ which represents. However, n, m, l are respectively 2≦n≦10, 1≦
Represents an integer of m≦10, 1≦l10. )