JPH06294901A - Plastic lens material - Google Patents

Abstract

PURPOSE:To obtain a plastic lens excellent in impact resistance, low specific gravity and high refractive index by using a specified dithiol compd. for the plastic lens material. CONSTITUTION:This material is obtd. by effecting radical polymn. and hardening a compsn. comprising the following components A, B, C. A: 80-20 pts.wt. of sulfur-contg. urethane (meth)acrylate obtd. by the reaction of (meth)acrylate monomers having hydroxyl groups of formula I, Diisocyanate compd. of formula II and dithiol compd. of formula III, with II/III equiv. ratio satisfying II/III=N +1/N (N is an integer 1-3) and 1.0-1.5 equiv. ratio of (sum of hydroxyl groups of I and thiol groups of III)/(isocyanate groups of II). B: 20-80 pts.wt. of compd. having polymerizable unsatd. double bonds in the molecule. C: 0.005-5 pts.wt. of radical polymn. initiator. Further, to total 100 pts.wt. of the components A and B, 0.005-5 pts.wt. of the component C is compounded to prepare the compsn. The obtd, material has >1.58 refractive index and <1.30 specific gravity.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic lens material having high impact resistance, high refractive index and low specific gravity.

[0002]

2. Description of the Related Art Plastic lenses are widely used in optical products because of their features such as easy molding and light weight. Above all, transparent plastics used as eyeglass lenses require heat resistance and chemical resistance,
Instead of thermoplastics such as polymethylmethacrylate and polystyrene, thermosetting plastics such as polydiethylene glycol bisallyl carbonate (hereinafter referred to as CR-39) have been used. However, CR-
No. 39 has a drawback that it has a low refractive index of about 1.50.

A high refractive index plastic lens material has the advantage that when formed into a lens, the thickness can be reduced and the product can be made compact. In recent years, a new transparent high refractive index transparent material has been obtained. Many attempts have been made to develop plastics.

In order to obtain a transparent plastic having a high refractive index, as shown in JP-B-58-14449, introduction of a halogen atom other than fluorine into the molecular structure of a resin composition for a plastic lens, formation of an aromatic ring It is common to introduce. In particular, in order to obtain a high refractive index lens material having a refractive index of 1.58 or more, it is general to use a plastic lens resin having an aromatic ring substituted with a halogen group other than fluorine. However, the plastic lens resin having a halogen group-substituted aromatic ring in its molecular structure has a drawback that it tends to be brittle. In order to obtain a tough plastic lens resin, a method of introducing a urethane bond having excellent impact resistance into the molecular structure of the plastic lens resin is an effective method. In order to obtain a tough plastic lens resin with a high refractive index, a urethane bond is added to the molecular structure of the plastic lens resin,
Examples thereof include those having an aromatic ring substituted with a halogen group other than fluorine. Specifically, JP-A-60-5170
No. 6, Japanese Patent Laid-Open No. 63-193914, Japanese Patent Publication No. 4
No. 11570, for example.

However, in the technique for improving the refractive index by containing a halogen group in the molecular structure of the resin for a plastic lens as disclosed in the above publication, the resin for a plastic lens depends on the content of the halogen group. Since the specific gravity of the plastic lens also increases at the same time, even if the plastic lens resin cured product has a high refractive index and the plastic lens can be made thin, the effect of reducing the weight of the plastic lens is offset. The technique proposed in JP-A-1-242612 is effective as a solution to this drawback. This is a monomer having a radically polymerizable unsaturated group having a hydroxyl group in the molecule,
And a copolymer obtained from a diol compound having a sulfur atom in the molecule and a polyisocyanate, in which the urethane bond formed exhibits impact resistance, and since a sulfur atom is introduced, the specific gravity does not increase. It has a relatively high refractive index. That is, the copolymerization obtained by using a diol containing a sulfur atom is
It has a relatively high refractive index and has a smaller specific gravity than that containing a halogen group.

[0006]

However, the sulfur atom-containing diol compound used in JP-A-1-242612 has only one sulfur (II) atom having a high atomic refraction in the molecule. Therefore, the refractive index is not yet satisfactory, and the refractive index of the obtained copolymer is not satisfactory.

The present invention has been made against the above background, and an object thereof is to have a high refractive index of 1.58 or more, a low specific gravity of 1.30 or less, and an excellent impact resistance. It is to provide a material from which a plastic lens can be obtained.

[0008]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that a thiourethane bond structure has an effect of improving impact resistance equivalent to that of a urethane bond structure, It was found that the ratio was higher than that of the thiourethane bond structure, and when a specific dithiol compound was applied to the plastic lens material, it had excellent impact resistance,
It has been found that a high refractive index plastic lens having a low specific gravity of 1.30 or less and a refractive index of 1.58 or more can be obtained.

That is, the plastic lens material of the present invention comprises 80 to 20 parts by weight of the component (A) and 20 to 20 parts of the component (B).
80 parts by weight and 0.005 to 5 parts by weight of the component (C), and the total amount of the components (A) and (B) is 100.
The weight ratio of the component (C) is 0.005 to 5 parts by weight based on 100 parts by weight of the total amount of the resin composition for a plastic lens, and the refractive index is 1.
A plastic lens material having a specific gravity of 58 or more and a specific gravity of 1.30 or less. Each of the components (A), (B), and (C) here is shown below.

The component (A) comprises a hydroxyl group-containing (meth) acrylate monomer represented by the following general formula (I), a diisocyanate compound represented by the following general formula (II) and a dithiol compound represented by the following general formula (III). (II)
The equivalent ratio of / (III) is (II) / (III) = N + 1 / N (N
Is an integer of 1 to 3), and the equivalent ratio of the total of the hydroxyl group of (I) and the thiol group of (III) / the isocyanate group of (II) is 1.
80 to 20 parts by weight of sulfur-containing urethane (meth) acrylate obtained by reacting in the range of 0 to 1.5.

[Chemical 4] (In the formula, R ¹ represents hydrogen or a methyl group; R ² represents 2 to 5 carbon atoms.
Represents the integer. )

[Chemical 5] (In the formula, R ³ represents an aromatic hydrocarbon.)

[Chemical 6] (In the formula, R ⁴ and R ⁵ are each independently a hydrocarbon having 1 to 6 carbon atoms; m represents an integer of 0 to 3.)

The component (B) is 20 to 80 parts by weight of a compound having a polymerizable unsaturated double bond in the molecule, and the component (C) is 0.005 to 5 parts by weight of a radical polymerization initiator.

The present invention will be described in detail below.

The component (A) is a hydroxyl group-containing (meth) acrylate monomer represented by the general formula (I), a general formula (II).
And a diisocyanate compound represented by the general formula (III)
A dithiol compound represented by the formula (II) / (III) in an equivalent ratio of (II) / (III) = N + 1 / N (N is an integer of 1 to 3), a hydroxyl group of (I) and (III) Equivalent ratio of total thiol groups / (II) isocyanate groups is 1.0 to 1.5
It is a sulfur-containing urethane (meth) acrylate obtained by reacting within the range.

Specific examples of the hydroxyl group-containing (meth) acrylate monomer represented by the general formula (I) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate. , 4-hydroxybutyl (meth)
Acrylate, 5-hydroxypentyl (meth) acrylate, etc. are mentioned.

Specific examples of the diisocyanate compound represented by the general formula (II) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and m-xylylene diisocyanate containing an aromatic ring in the molecule. , P-xylylene diisocyanate, 1,3-bis (α, α-dimethylisocyanatomethyl) benzene,
Examples thereof include diphenylmethane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,5-diisocyanate, biphenyl diisocyanate and o-tolidine diisocyanate.

Among the diisocyanate compounds represented by the general formula (II), a diisocyanate compound having a structure in which two isocyanate groups are directly bonded to an aromatic ring is preferable from the viewpoint of the refractive index and the reactivity of urethane bond.

Specific examples of the dithiol compound represented by the general formula (III) include 1,2-ethanedithiol, 1,
4-butanedithiol, 1,6-hexanedithiol,
Dimercaptodiethyl sulfide, dimercaptodipropyl sulfide, dimercaptodibutyl sulfide,
2,2 '-(ethylenedithio) diethanethiol and the like can be mentioned.

In order to obtain the component (A), the general formula (I),
As a method for reacting each compound represented by the general formula (II) and the general formula (III), a known method can be used.

For example, in the presence of the diisocyanate compound (II) and the catalyst, the hydroxyl group-containing (meth) acrylate compound (I) and the dithiol compound (III) are gradually added under the condition of 50 to 70 ° C. and the reaction is carried out by stirring. It should be done by. As the catalyst for carrying out the above method, for example, di-n-butyltin dilaurate can be used.

As a particularly preferred method for producing the component (A), there are the following two methods. One of them is a reaction in which, in the presence of diisocyanate compound (II) and di-n-butyltin dilaurate, first, a hydroxyl group-containing (meth) acrylate compound (I) is gradually added dropwise at 50 to 90 ° C. Then, after a urethane bond is formed and the hydroxyl groups of the hydroxyl group-containing (meth) acrylate compound (I) almost disappear, the dithiol compound (II
This is a method in which I) is gradually added to promote the formation of a thiourethane bond to obtain a urethane (meth) acrylate.

As another method for producing the component (A), the dithiol compound (III) is first added in the presence of the diisocyanate compound (II) and di-n-butyltin dilaurate at 50 to 90 ° C. Is gradually added and reacted to form a thiourethane bond, and most of the hydroxyl groups of the dithiol compound (III) disappear, and then a hydroxyl group-containing (meth) acrylate compound (I) is gradually added dropwise to form a urethane bond. It is a method of advancing to obtain a sulfur-containing urethane (meth) acrylate.

The reaction for obtaining the component (A) is carried out by the hydroxyl group-containing (meth) acrylate monomer represented by the general formula (I), the diisocyanate compound represented by the general formula (II) and the dithiol represented by the general formula (III). And the compound
The equivalent ratio of (II) / (III) is (II) / (III) = N + 1 /
N (N is an integer of 1 to 3), the equivalent ratio of the hydroxyl group of (I) and the thiol group of (III) / isocyanate group of (II) is in the range of 1.0 to 1.5. . If the equivalent ratio of the total of the hydroxyl groups of (I) and the thiol groups of (III) / the isocyanate groups of (II) is less than 1, the unreacted isocyanate groups remain and the weather resistance of the cured product decreases, or the cured product Problems such as deterioration of physical properties such as elastic modulus and hardness occur.
On the other hand, if the corresponding amount ratio is 1.5 or more, the hydrophilicity of the cured product is improved due to unreacted hydroxyl groups and thiol groups, and the absorption deformation of the lens material increases, which is not preferable. It is preferably 1 to 1.2.

As the component (B), any compound having at least a polymerizable unsaturated double bond in the molecule can be used. Specific examples of the polymerizable unsaturated double bond include (meth) acryloyl group, (meth) allyl group and vinyl group.

The component (B) preferably has low viscosity from the viewpoint of solubility and dilutability, and preferably has an aromatic ring in the molecule from the viewpoint of refractive index.

Particularly, styrene derivatives such as styrene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, divinylstyrene, phenyl (meth) acrylate, benzyl (meth) acrylate, o-biphenyl (meth) acrylate and the like (meth ) Acrylic acid esters, diallyl phthalate, dimethallyl phthalate,
Allyl compounds such as diallylbiphenylate are preferred.

As the component (B), one type may be used alone, or several types may be used in combination.

The mixing ratio of the components (A) and (B) is
When the total amount of the component (A) and the component (B) is 100 parts by weight, the amount of the component (B) is 80 to 20 parts by weight with respect to 20 to 80 parts by weight of the component (A). Desirably, when the total amount of the components (A) and (B) is 100 parts by weight, (A)
(B) component 60 to 30 relative to component 40 to 70 parts by weight
It is preferable to use parts by weight.

When the amount of the component (A) exceeds 80 parts by weight, the viscosity of the composition becomes too high and the workability is deteriorated, and when it is less than 20 parts by weight, the object of the invention cannot be achieved.

The radical polymerization initiator as the component (C) is not particularly limited as long as it can generate an active radical by an active energy ray such as visible light, infrared ray, ultraviolet ray or heat.

Specific examples of radical polymerization initiators (thermal polymerization initiators) that generate active radicals by heat include diisopropyl peroxydicarbonate, t-butyl peroxyisobutyrate and 1,1,3,3-tetramethyl. Organic peroxides such as peroxy-2-ethylhexanoate,
Examples thereof include azo compounds such as 2,2-azobis (2,4-dimethylbarrelnitrile) and azobisisobutyronitrile.

Specific examples of radical polymerization initiators (photopolymerization initiators) that generate active radicals by active energy rays include 2-hydroxy-2-methyl-1-phenylpropan-1-one, hydroxycyclohexylphenyl ketone, Methylphenylglyoxylate, 2,4,6
-Trimethylbenzoyldiphenylphosphine oxide, benzyl dimethyl ketal, etc. can be used.

The radical polymerization initiator as the component (C) may be used alone or in combination of several kinds.

The component (C) is used in an amount of 0.005 to 5 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B). is there.
Further, it is preferably 0.001 to 3 parts by weight.

When the amount of the component (C) is less than 0.005 parts by weight based on 100 parts by weight of the total amount, sufficient polymerization and curing cannot be performed,
If it exceeds 5 parts by weight, the degree of yellowness of the cured plastic lens increases and the surface hardness decreases.

The plastic lens material of the present invention is
In order not to impair the object of the present invention, in order to improve the impact resistance and dyeability of the plastic lens, pentaethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, nonabutylene glycol di (meth) An appropriate amount of an aliphatic monomer such as acrylate or diethylene glycol bisallyl carbonate may be added.

Further, the plastic lens material of the present invention may contain additives such as an antioxidant, an anti-yellowing agent, an ultraviolet absorber, a bluing agent and a pigment, as long as the object of the present invention is not impaired. .

The method for curing the plastic lens material of the present invention is to combine two glass molds having a desired shape through a gasket made of polyvinyl chloride, ethylene-vinyl acetate copolymer, etc. Can be heated after being injected, irradiated with active energy rays, or a combination thereof.

[0038]

EXAMPLES The present invention will be specifically described below with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited thereto.

The various physical properties obtained in the examples and comparative examples were measured by the following test methods using a plastic lens material flat plate molded to a thickness of 2 mm for the test.

Visible light transmittance (%): ASTM D 1003-61
It was measured according to. Refractive index: The refractive index at 25 ° C. in the D line of 589.3 nm was measured with an Abbe refractometer. Rockwell hardness: Measured according to JIS K7202. -Tg (° C): The glass transition temperature (Tg) was measured by a thermomechanical analyzer (TMA). The load was 10 g. Chemical resistance: Absorbent cotton was impregnated with an organic solvent such as acetone or toluene, and the surface of a flat plate made of a plastic lens material for test was wiped 10 times or more, and the change of the surface was observed. Here, a sample in which no change in the surface was observed was rated as “good”. -Specific gravity: Measured according to JIS K7112. -Impact resistance: Weighs 16.3 g according to US FDA standards
The steel ball drop test was carried out by dropping the steel ball of No. 1 from a height of 127 cm onto a resin flat plate for a plastic lens for testing. Those that showed no damage at all were rated as “good”.

The abbreviations are as follows. UM1: Urethane methacrylate obtained in Synthesis Example 1 UM2: Urethane methacrylate obtained in Synthesis Example 2 UM3: Urethane methacrylate obtained in Synthesis Example 3 UM4: Urethane methacrylate obtained in Synthesis Example 4 UM5: Synthesis Example 5 Obtained Urethane Methacrylate UM6: Urethane Methacrylate Obtained in Synthesis Example 1

[Synthesis Example 1]: Synthesis of urethane methacrylate (UM1)

Tolylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Coronate T-100, molecular weight 174.16, hereinafter abbreviated as TDI) 348.32
g, di-n-butyltin dilaurate 0.64 g, 2,
6-di-tert-butyl-4-methylphenol
0.64 g was put into a 2 liter four-necked flask and stirred while heating to 70 ° C. to make a uniform solution. Next, while maintaining the temperature of this system at 70 ° C. and stirring, 260.3 g of 2-hydroxyethyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Acryester HO, molecular weight 130.15, hereinafter abbreviated as HEMA). Was gradually added dropwise over 5 hours. Furthermore, by keeping the temperature of this system at 70 ° C. and measuring IR spectrum and residual isocyanate equivalent, it was confirmed that the hydroxyl group of HEMA formed a urethane bond with the isocyanate group of TDI.

Thereafter, while maintaining the system at 70 ° C. and continuing stirring, dimercaptodiethyl sulfide (ratio H
SCH ₂ CH ₂ SCH ₂ CH ₂ SH, molecular weight 154.32,
154.32 g of a reagent manufactured by Aldrich) was gradually added over 3 hours. Thereafter, 191.06 g of benzyl methacrylate was added as a diluting monomer, and the system temperature was adjusted to 70
The reaction was continued for 14 hours while stirring while maintaining the temperature at 0 ° C. to terminate the thiourethane bond reaction to obtain a 20 wt% benzyl methacrylate solution of urethane methacrylate (UM1).

The end point of this reaction was confirmed by measuring the IR spectrum and the residual isocyanate equivalent.

[Synthesis Example 2]: Synthesis of urethane methacrylate (UM2)

Instead of TDI, xylylene diisocyanate (Takeda Pharmaceutical Co., Ltd., trade name: Takenate 5)
00 molecular weight 188.2, hereinafter abbreviated as XDI. ) 37
Using 6.4 g, except that styrene (198.08 g) was used as the diluting monomer instead of benzyl methacrylate, synthesis was carried out in the same manner as in Synthesis Example 1 to obtain a 20 wt% styrene solution of urethane methacrylate (UM2).

[Synthesis Example 3]: Synthesis of urethane methacrylate (UM3)

Instead of dimercaptodiethyl sulfide, 1,2-ethanedithiol (rational formula SHCH ₂ C
H ₂ SH, molecular weight 94.2, and Tokyo Chemical Industry Co., Ltd. reagent special grade 94.2 g were used, and styrene 1 was used as a diluting monomer.
Synthesis was carried out in the same manner as in Synthesis Example 1 except that 76.03 g was used to obtain a 20 wt% styrene solution of urethane methacrylate (UM3).

[Synthesis Example 4]: Synthesis of urethane methacrylate (UM4)

XDI 376.4 g, dilauric acid di-
0.64 g of n-butyltin and 0.64 g of 2,6-di-tert-butyl-4-methylphenol were placed in a 2-liter four-necked flask, and stirred to form a uniform solution while heating at 70 ° C. Next, while maintaining the temperature of this system at 70 ° C. and stirring, 2-hydroxypropyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Acryester HP, molecular weight 1
44.17, hereinafter abbreviated as HPMA) 288.34 g is 5
It was dripped gradually over time. Furthermore, the temperature of this system is set to 70
It was confirmed that the hydroxyl group of HPMA formed a urethane bond with the isocyanate group of XDI by measuring the IR spectrum and the residual isocyanate equivalent by keeping the temperature at ℃.

Thereafter, while maintaining the system at 70 ° C. and continuing stirring, 2,2-bis [3,5-dibromo-4 was further added.
(2-hydroxyethoxy) phenyl] propane (manufactured by Takemoto Yushi Co., Ltd., trade name: TBA-2, molecular weight 632.
0) 632 g was gradually added over 3 hours. 324.51 benzyl methacrylate as a diluting monomer
g and 1 while stirring while maintaining the system temperature at 70 ° C.
The reaction was continued for 4 hours to terminate the urethane bonding reaction, and a 20 wt% benzyl methacrylate solution of urethane acrylate (UM4) was obtained.

[Synthesis Example 5]: Synthesis of urethane methacrylate (UM5)

Instead of dimercaptodiethyl sulfide, 2,2'-thiodiethanol (rational formula HOCH ₂
CH ₂ SCH ₂ CH ₂ OH, molecular weight 122.19, Tokyo Chemical Industry Reagent Special Grade) 122.19 g was used, and benzyl methacrylate was used as the diluting monomer in the same manner as in Synthesis Example 1 except that 183.02 g was used. As a result, a 20 wt% benzyl methacrylate solution of urethane methacrylate (UM5) was obtained.

Synthesis Example 6: Synthesis of undiluted urethane methacrylate (UM1)

Synthesis was conducted in the same manner as in Synthesis Example 1 except that benzyl methacrylate, which was a diluting monomer, was not used,
An undiluted product of UM1 was obtained.

[Example 1] 87.5 g of a 20% by weight benzyl methacrylate solution of urethane methacrylate (UM1) obtained in Synthesis Example 1 as the component (A), and 12.5 g of benzyl methacrylate as the component (B). , 1,3,3-tetramethylperoxy-2-ethylhexanoate as a radical polymerization initiator which is the component (C).
2 g and t-butyl peroxyisobutyrate 0.1 g
50m after mixing and stirring at room temperature to make a uniform blend
The pressure was reduced to mHg and degassing was performed for 10 minutes.

Next, two pieces of tempered glass having a length of 100 mm, a width of 100 mm, and a thickness of 5 mm are made to face each other with a space of 2 mm, and the circumference is surrounded by a polyvinyl chloride tubular gasket. The above-mentioned formulation was injected, and the temperature was raised from 40 ° C. to 100 ° C. over 20 hours for curing. The cured product was removed from the mold, and heat-treated at 120 ° C. for 2 hours to remove the internal strain of the cured product to obtain a transparent plastic lens material flat plate.

This flat plate had a visible light transmittance of 91% and a high refractive index of 1.594. Furthermore, Tg is 94
The temperature was ℃, and the chemical resistance of acetone and toluene was also excellent. The Rockwell hardness was HRL 94 and the specific gravity was 1.25. When an impact resistance test was conducted on this flat plate, no damage was observed.

[Examples 2 to 5] (A), (B), (C)
Curing was carried out in the same manner as in Example 1 except that each component had the formulation shown in Table 1, and the same evaluation was performed. The evaluation results are shown in Table 1.
It was shown to.

Example 6 75 g of a 20 wt% benzyl methacrylate solution of the urethane methacrylate (UM1) obtained in Synthesis Example 1 as the component (A), 5 g of benzyl methacrylate as the component (B), 20 g of phenyl methacrylate, (C). As components, 0.1 g of methylphenylglyoxylate, 0.1 g of 1-hydroxycyclohexylphenyl ketone, and 0.1 g of t-butylperoxyisobutyrate were stirred at room temperature to form a uniform mixture,
The pressure was reduced to 50 mmHg and degassing was performed for 10 minutes.

Then, two pieces of tempered glass having a length of 100 mm, a width of 100 mm, and a thickness of 5 mm are made to face each other with a space of 2 mm, and the periphery is surrounded by a polyvinyl chloride tubular gasket into a mold. The above formulation was injected. Then, the mold was irradiated with ultraviolet rays for 5 minutes from a 120 W / cm high-pressure mercury lamp at a distance of 20 cm from both surfaces of the mold to polymerize and cure. Then, the cured product was removed from the mold and heat-treated at 120 ° C. for 2 hours to obtain a transparent flat plate.

When this flat plate was evaluated in the same manner as in Example 1, the visible light transmittance was 91% and the refractive index was 1.590. Furthermore, it had a Tg of 86 ° C. and was excellent in chemical resistance to acetone and toluene. The Rockwell hardness was HRL93 and the specific gravity was 1.25. When an impact resistance test was conducted on this flat plate, no damage was observed.

[Comparative Example 1] 100 g of diethylene glycol bisallyl carbonate (CR-39) and 2.5 g of diisopropyl peroxydicarbonate were well stirred at room temperature to form a uniform mixture, which was then depressurized to 50 mmHg for 10 minutes for removal. I noticed. Then, it was poured into the mold used in Example 1 and held at 40 ° C. for 10 hours, 60 ° C. for 5 hours, and 90 ° C. for 5 hours to be cured. After demolding, heat treatment was performed at 100 ° C. for 1 hour.

When this flat plate was evaluated in the same manner as in Example 1, the visible light transmittance was 92% and the refractive index was 1.499. Furthermore, Tg by TMA is 80
C., and the chemical resistance to acetone and toluene was also excellent. Rockwell hardness is HRL92, specific gravity is 1.
It was 32. When an impact resistance test was conducted on this flat plate, no damage was found.

Comparative Example 2 Instead of the component (A), 2,
Curing was performed in the same manner as in Example 1 except that 50 g of 2-bis (4-methacryloxyethoxy-3,5 dibromophenyl) propane and 50 g of styrene as the component (B) were used, and the same evaluation was performed. This flat plate had a visible light transmittance of 89% and a refractive index of 1.592. further,
It had a Tg of 108 ° C and was excellent in chemical resistance against acetone, toluene and the like. The Rockwell hardness was HRL 110, and the specific gravity was 1.35, which was high. When an impact resistance test was conducted on this flat plate, damage was found.

[Comparative Example 3] Example 3 was repeated except that 87.5 g of 20% by weight benzyl methacrylate of UM4 obtained in Synthesis Example 4 and 12.5 g of benzyl methacrylate as the component (B) were used in place of the component (A). It was cured in the same manner as in Example 1 and evaluated in the same manner.

This flat plate had a visible light transmittance of 89% and a refractive index of 1.585. Furthermore, Tg is 11
The temperature was 0 ° C, and the chemical resistance of acetone, toluene and the like was excellent. Rockwell hardness is HRL115, specific gravity is 1.3
It was as high as 8. When an impact resistance test was conducted on this flat plate, no damage was found.

[Comparative Example 4] Example 4 was repeated except that 87.5 g of 20% by weight benzyl methacrylate of UM5 obtained in Synthesis Example 5 and 12.5 g of benzyl methacrylate as the component (B) were used in place of the component (A). It was cured in the same manner as in Example 1 and evaluated in the same manner.

This flat plate had a visible light transmittance of 90% and a refractive index of 1.570, which were lower than those of Example 1. Further, it had a Tg of 99 ° C. and was excellent in chemical resistance against acetone, toluene and the like. Rockwell hardness is HR
L98, the specific gravity was 1.23. When an impact resistance test was conducted on this flat plate, no damage was found.

[Comparative Example 5] Synthesis Example 6 as the component (A)
100 g of the undiluted product of UM1 obtained in 1., and 1,1,3,3-tetramethylperoxy-2-ethylhexanoate 0.2 as the radical polymerization initiator which is the component (C)
g and t-butylperoxyisobutyrate (0.1 g) were tried to be mixed uniformly at room temperature, but the viscosity of UM1 was too high to stir, and a uniform blend could not be obtained. .

[0072]

[Table 1] Note) The abbreviations in the table are as follows. TBM; 2,2-bis (4-methacryloxyethoxy-3,5-dibromophenyl) propane St; styrene BzMA; benzyl methacrylate PhMA; phenyl methacrylate BiPhMA; o-biphenyl methacrylate CR-39; diethylene glycol bisallyl carbonate TMPEH; 1,1,3,3-tetramethylperoxy-
2-Ethylhexanoate TBP; t-Butylperoxyisobutyrate IPP; Diisopropylperoxydicarbonate MPG; Methylphenylglyoxylate HCPK; 1-Hydroxycyclohexylphenylketone UM1; Urethane methacrylate UM2 obtained in Synthesis Example 1 Urethane urethane UM3 obtained in Synthesis Example 2; urethane methacrylate UM4 obtained in Synthesis Example 3; urethane methacrylate UM5 obtained in Synthesis Example 4; urethane methacrylate UM6 obtained in Synthesis Example 5; obtained in Synthesis Example 1 Undiluted urethane methacrylate

EFFECTS OF THE INVENTION By using the plastic lens material of the present invention as demonstrated in the above examples, 1.5
It is possible to provide a plastic lens having a high refractive index of 8 or more, a low specific gravity of 1.30 or less, and excellent impact resistance.

[Procedure amendment]

[Submission date] January 18, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

[Chemical 1] (In the formula, R ¹ represents hydrogen or a methyl group; R ² represents 2 to 5 carbon atoms.
Represents a hydrocarbon group of. )

[Chemical 2] (In the formula, R ³ represents an aromatic hydrocarbon group .)

[Chemical 3] (In the formula, R ⁴ and R ⁵ are each independently a hydrocarbon having 1 to 6 carbon atoms; m represents an integer of 0 to 3.) Component (B): a polymerizable unsaturated double bond in the molecule. Compound having 20 to 80 parts by weight, component (C): radical polymerization initiator 0.005 to 5 parts by weight, and the total amount of component (A) and component (B) is 1
The amount of component (C) is 0.005 to 5 parts by weight based on 100 parts by weight of the total amount, and the resin composition for plastic lenses is radical-polymerized and cured. The refractive index is 1.58 or more. A plastic lens material having a specific gravity of 1.30 or less.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

The component (A) comprises a hydroxyl group-containing (meth) acrylate monomer represented by the following general formula (I), a diisocyanate compound represented by the following general formula (II) and a dithiol compound represented by the following general formula (III). (II)
The equivalent ratio of / (III) is (II) / (III) = N + 1 / N (N
Is an integer of 1 to 3), and the equivalent ratio of the total of the hydroxyl group of (I) and the thiol group of (III) / the isocyanate group of (II) is 1.
80 to 20 parts by weight of sulfur-containing urethane (meth) acrylate obtained by reacting in the range of 0 to 1.5.

[Chemical 4] (In the formula, R ¹ represents hydrogen or a methyl group; R ² represents 2 to 5 carbon atoms.
Represents a hydrocarbon group of. )

[Chemical 5] (In the formula, R ³ represents an aromatic hydrocarbon group .)

[Chemical 6] (In the formula, R ⁴ and R ⁵ are each independently a hydrocarbon having 1 to 6 carbon atoms; m represents an integer of 0 to 3.)

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0072

[Correction method] Change

[Correction content]

[0072]

[Table 1] Note) The abbreviations in the table are as follows. TBM; 2,2-bis (4-methacryloxyethoxy-3,5-dibromophenyl) propane St; styrene BzMA; benzyl methacrylate PhMA; phenyl methacrylate BiPhMA; o-biphenyl methacrylate CR-39; diethylene glycol bisallyl carbonate TMPEH; 1,1,3,3-tetramethylperoxy-
2-Ethylhexanoate TBP; t-Butylperoxyisobutyrate IPP; Diisopropylperoxydicarbonate MPG; Methylphenylglyoxylate HCPK; 1-Hydroxycyclohexylphenylketone UM1; Urethane methacrylate UM2 obtained in Synthesis Example 1 Urethane urethane UM3 obtained in Synthesis Example 2; urethane methacrylate UM4 obtained in Synthesis Example 3; urethane methacrylate UM5 obtained in Synthesis Example 4; urethane methacrylate UM6 obtained in Synthesis Example 5; obtained in Synthesis Example 1 Undiluted urethane methacrylate

Claims (1)

[Claims] 1. Component (A): a hydroxyl group-containing (meth) acrylate monomer represented by the following general formula (I), a diisocyanate compound represented by the following general formula (II), and a dithiol represented by the following general formula (III). The compound and (I
The equivalent ratio of (I) / (III) is (II) / (III) = N + 1 / N
(N is an integer of 1 to 3), which is obtained by reacting the hydroxyl group of (I) and the thiol group of (III) / isocyanate group of (II) in an equivalent ratio range of 1.0 to 1.5. Sulfur-containing urethane (meth) acrylate 80 to 20
Parts by weight, (In the formula, R ¹ represents hydrogen or a methyl group; R ² represents 2 to 5 carbon atoms.
Represents the integer. ) [Chemical 2] (In the formula, R ³ represents an aromatic hydrocarbon.) (In the formula, R ⁴ and R ⁵ are each independently a hydrocarbon having 1 to 6 carbon atoms; m represents an integer of 0 to 3.) Component (B): a polymerizable unsaturated double bond in the molecule. Compound having 20 to 80 parts by weight, component (C): radical polymerization initiator 0.005 to 5 parts by weight, and the total amount of component (A) and component (B) is 1
The amount of component (C) is 0.005 to 5 parts by weight based on 100 parts by weight of the total amount, and the resin composition for plastic lenses is radical-polymerized and cured. The refractive index is 1.58 or more. A plastic lens material having a specific gravity of 1.30 or less.