JPH0532735A - Composition for plastic lens and production of plastic lens - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent heatresistance, impact resistance, etc., and useful for plastic lens having high refractive index by compounding a urethane (meth)acrylate, a polybutylene glycol di(meth) acrylate, etc., at specific ratios. CONSTITUTION:The objective composition having a refractive index of >=1.55 can be produced by compounding (A) 30-80 pts.wt. of a urethane (meth)acrylate of formula I (R<1>, R<2> and R<4> are H or methyl; R<3> is aromatic hydrocarbon group; j, k, m and n are 1-5; X<1> to X<4> are H, methyl, Br, etc.; Y is group of formula II, formula III, etc.), (B) 10-60 pts.wt. of a polybutylene glycol di(meth)acrylate of formula IV (R<5> is H or methyl; p is 5=16), (C) 10-60 pts.wt. of a styrenic compound of formula V (X<5> is Br, Cl or I; q is 0-5) and (D) 0-50 pts.wt. of a compound having one or more polymerizable double bonds in the molecule [e.g. phenyl (meth)acrylate] (the sum of A to D is 100 pts.wt.) as main components.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a composition for a high refractive index plastic lens having a refractive index of 1.55 or more, which is excellent in heat resistance, impact resistance, low water absorption, and moldability, and such a composition. The present invention relates to a method for producing a high refractive index plastic lens having a refractive index of 1.55 or more.

[0002]

2. Description of the Related Art Plastic lenses have come to be widely used in optical products by taking advantage of their features such as easy molding and light weight. Above all, in eyeglass lenses, it is desired that the lens is light, so in recent years,
Diethylene glycol bisallyl carbonate (PPG
Resins made by the company, product name: CR-39) are the mainstream of plastic eyeglass lenses. Important properties required of such a plastic lens include a refractive index, moldability, heat resistance, impact resistance, low water absorption, surface accuracy of a molded product, and dyeability. And in recent years, further improvement of these characteristics has been demanded,
A method for producing a plastic lens using various monomers and oligomers instead of CR-39 has been proposed.

[0003]

The resin made of CR-39 has a low refractive index of 1.499, and therefore the conventional plastic lens has a drawback that it must be thicker than the inorganic glass lens. is there. In this regard, Japanese Patent Publication Sho 5
JP-A-8-14449 discloses a high refractive index resin obtained from a compound in which a halogen-substituted aromatic ring is bonded to a (meth) acryloyloxy group through an alkylene glycol group and a monofunctional monomer having an aromatic ring. Have been described. As described herein, for the purpose of obtaining a high refractive index resin, a method of introducing an aromatic ring structure or a halogen group (excluding fluorine) into the resin structure is common. However, this method has a problem in the impact resistance of the obtained resin and the dyeability with general disperse dyes.

On the other hand, JP-A-64-16813 describes a di (meth) acrylate of a polyalkylene glycol having an ether structure in the molecule as a component for improving the impact resistance of a lens. Moreover, since the di (meth) acrylate of these polyalkylene glycols has high hydrophilicity, the dyeability of the lens is also improved. In addition, typical examples of di (meth) acrylate include polyethylene glycol di (meth) acrylate,
There is polypropylene glycol di (meth) acrylate. When such a di (meth) acrylate is added to the above-mentioned monomer or oligomer having a halogen group other than fluorine and an aromatic ring, impact resistance and dyeability are improved. However, the more it is added, the lower the refractive index of the lens becomes, and further problems occur in terms of heat resistance and water absorption, so that a well-balanced performance cannot be achieved.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found a specific urethane (meth) acrylate capable of giving a cured product having a high refractive index, impact resistance and dyeability, and further When applied to a material for the production of plastic lenses together with a specific polybutylene glycol di (meth) acrylate that can give a cured product excellent in impact resistance, dyeability and low water absorption, it has a high refractive index and impact resistance. It has been found that a plastic lens having excellent dyeability and heat resistance and low water absorption can be manufactured. Furthermore, it was found that by combining this material with a styrene compound, it is possible to suppress the polymerization rate during polymerization and curing, to obtain a lens with no residual stress, and to improve the surface accuracy of the lens, and to complete the present invention. I arrived.

[0006]

Means for Solving the Problems That is, the present invention provides (A) a urethane (meth) represented by the following general formula (1).
30-80 parts by weight of acrylate,

[0007]

[Chemical 5] (In the formula, R ¹ , R ² and R ⁴ each independently represent hydrogen or a methyl group, R ³ represents an aromatic hydrocarbon, j, k,
m and n each independently represent an integer of 1 to 5, X ¹ ,
X ² , X ³ and X ⁴ are each independently hydrogen, a methyl group, bromine,
Represents chlorine or iodine, and Y is

[0008]

[Chemical 6] Represents ) (B) Polybutylene glycol di (meth) acrylate represented by the following general formula (2)
10 to 60 parts by weight,

[0009]

[Chemical 7] (In the formula, R ⁵ represents hydrogen or a methyl group, and p is 5 to 1
Represents an integer of 6. ) (C) 10 to 60 parts by weight of a styrene compound represented by the following general formula (3),

[0010]

[Chemical 8] (Wherein X ⁵ represents a methyl group, a bromine atom, a chlorine atom or an iodine atom, and q represents an integer of 0 to 5), and (D) has at least one polymerizable double bond in the molecule. Compound 0 to 50 parts by weight (however, (A) to (D)
The total amount of the components is 100 parts by weight. ) Is a main component for a plastic lens having a refractive index of 1.55 or more, and a method for producing a plastic lens having a refractive index of 1.55 or more, which comprises a step of polymerizing and curing the composition of the present invention.

The present invention will be described in detail below.

The urethane (meth) acrylate (A), which is the first component of the composition of the present invention, is a compound represented by the above general formula (1) and is a component which imparts a high refractive index to the plastic lens. . The method for synthesizing the component (A) is not particularly limited in the present invention, but the following three compounds (I) to (III) are preferably used in a molar equivalent ratio (I) /
(II) / (III) = 2 / N + 1 / N (N is an integer from 1 to 5)
It can be obtained by reacting within the range. That is, k in the general formula (1) is determined by this molar equivalent ratio, and since a mixture of compounds having different values of k is generally obtained, the value of k here means the median value (main component). .

(I) Hydroxyl group-containing (meth) acrylate compound represented by the following general formula (i)

[0014]

[Chemical 9] (In the formula, R ¹ and R ² represent hydrogen or a methyl group, and j is 1
Represents an integer of ~ 5. ) (II) Diisocyanate compound represented by the following general formula (ii)

[0015]

[Chemical 10] (In the formula, R ³ represents an aromatic hydrocarbon.) (III) A diol compound represented by the following general formula (iii)

[0016]

[Chemical 11] (In the formula, R ⁴ represents hydrogen or a methyl group, and m and n
Represents an integer of 1 to 5, X ¹ , X ² , X ³ and X ⁴ are hydrogen,
Represents a methyl group, bromine, chlorine or iodine, and Y is

[0017]

[Chemical 12] Represents ) Specific examples of the hydroxyl group-containing (meth) acrylate compound (I) represented by the general formula (i) are:
2-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, mono (meth) acrylic acid ester of polyethylene glycol (repeating units 2 to 5), polypropylene glycol (repeating unit 2 to 5) mono (meth) Examples thereof include acrylic acid ester.

Specific examples of the diisocyanate compound (II) represented by the general formula (ii) are those containing an aromatic ring in the molecule, such as 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate. Diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, 1,3-bis (α, α-dimethylisocyanatomethyl) benzene, diphenylmethane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,5 -Diisocyanate, biphenyl diisocyanate, o-tolidine diisocyanate and the like. In addition, 2 directly to the aromatic ring
One having a structure in which two isocyanate groups are bonded,
It is preferable in terms of refractive index and reactivity in urethane bond.

A diol compound represented by the general formula (iii) (I
As II), bisphenols obtained by adding several moles of ethylene oxide and propylene oxide can be used. As bisphenols, bisphenol A, bisphenol S, bisphenol F and derivatives thereof can be used. Of these, bisphenol A, bisphenol S and their derivatives are particularly preferable. When bisphenol F and its derivative are used, Tg, surface hardness and elastic modulus of the obtained plastic lens tend to be lower than those when bisphenol A, bisphenol S and their derivatives are used.

The above-mentioned reaction is carried out by a known method, for example, a diisocyanate compound (II) and a hydroxyl group-containing (meth) acrylate compound (I) and a diol compound (I
II) may be gradually added under the condition of 50 to 70 ° C., stirred and reacted, or the like. As the catalyst in this case, for example, di-n-butyltin dilaurate can be used. A particularly preferred method is the diisocyanate compound (I
In the presence of (I) and di-n-butyltin dilaurate, first, a hydroxyl group-containing (meth) acrylate compound (I) is added to 50
After gradually dropping and reacting under the condition of up to 90 ° C. to form urethane bond and almost disappearing the hydroxyl groups of the hydroxyl group-containing (meth) acrylate compound (I), the diol compound (III) is gradually added to the urethane. A method of promoting the formation of a bond to obtain a urethane (meth) acrylate can be mentioned. Further, in the presence of a diisocyanate compound (II) and di-n-butyltin dilaurate, first, a diol compound (III) is added in an amount of 50 to 90. It is added slowly under the condition of ℃ and reacted to form a urethane bond.
After almost all the hydroxyl groups of II) have disappeared, a hydroxyl group-containing (meth) acrylate compound (I) is gradually added dropwise to promote the formation of urethane bonds to obtain urethane (meth) acrylate. In the synthesis of the urethane (meth) acrylate (A), the component (C) and the component (D) that are not directly related to the urethane bonding reaction (the third component and the fourth component of the composition used in the present invention).
May coexist.

The polybutylene glycol di (meth) acrylate (B), which is the second component of the composition of the present invention, is a compound represented by the above general formula (2) and has a polymerization degree of 5 to 16
It is a polybutylene glycol obtained by sealing both ends with two (meth) acrylic acids. Where the degree of polymerization is the formula:
_{- (CH 2 CH 2 CH 2} CH 2 O) n - means the number of repeating units n represented by. If the degree of polymerization n is less than 5, sufficient flexibility cannot be obtained, while if it exceeds 16, the water absorption is increased and the crosslink density is lowered, the polymer hardness is lowered and the heat resistance is also lowered. Further, the viscosity of the monomer is increased, and thus the workability of casting is reduced. The preferred degree of polymerization is 7-12. However, since polybutylene glycol dimethacrylate is generally a mixture of polymer species having different degrees of polymerization in a normal distribution, the degree of polymerization n here means the median value.

This polybutylene glycol di (meth) acrylate (B) is, for example, a condensation reaction of polybutylene glycol obtained by ring-opening polymerization of tetrahydrofuran with acrylic acid or methacrylic acid, or polybutylene glycol with methyl acrylate or Although it can be easily produced by a transesterification reaction with methyl methacrylate, a method by a transesterification reaction is preferable because it gives a colorless and transparent monomer.

The styrenic compound (C) which is the third component of the composition of the present invention is styrene or a derivative thereof,
It is a component that lowers the viscosity of the compound without lowering the refractive index. Furthermore, by blending this styrene compound (C), the polymerization rate can be suppressed during the polymerization and curing of the blend by heating, and a lens free of residual stress due to resin shrinkage in cast polymerization can be obtained, and the lens Is a component that improves the surface accuracy of. The surface precision of the lens here means the precision with which the lens surface of the mold used for the lens superposition is obtained as designed. The residual stress means the stress remaining in the polymerized lens. A lens having residual stress may have poor surface accuracy as the stress is removed by leaving it naturally or by annealing.

Specific examples of the styrene compound (C) include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-chlorostyrene and 3-methylstyrene.
Chlorostyrene, 4-chlorostyrene, 2-bromostyrene, 3-bromostyrene, 4-bromostyrene, 2,
4-dibromostyrene, tribromostyrene, pentabromostyrene and the like can be mentioned. These may be used alone or in a mixture of two or more.

Compound (D) having at least one polymerizable double bond in the molecule which is the fourth component of the composition of the present invention
Is a component that imparts heat resistance, surface hardness, low viscosity, and the like. Particularly, in the present invention, urethane (meta) having a relatively high viscosity is used.
Since the acrylate (A) is used, it is preferable that the viscosity of the resin composition is lower in order to improve the casting workability.
Therefore, as the compound (D) having a polymerizable double bond, a low-viscosity ester monomer is particularly preferable.

Specific examples of the compound (D) include, for example, phenyl (meth) acrylate and benzyl (meth).
Acrylate, phenoxyethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth)
Acrylate, 2-phenylphenyl (meth) acrylate, 4-phenylphenyl (meth) acrylate, 3
-(2-phenylphenyl) -2-hydroxypropyl (meth) acrylate, 3- (4-phenylphenyl)
-2-Hydroxypropyl (meth) acrylate, 1-
Naphthyloxyethyl (meth) acrylate, 2-naphthyloxyethyl (meth) acrylate, 2,4,6-
Tribromophenyl (meth) acrylate, 2,4,6
-Tribromophenoxyethyl (meth) acrylate,
2,4,6-tribromophenyl-di (oxyethyl)
Aromatic ring-containing monofunctional (meth) acrylate compounds such as-(meth) acrylate and 2,4,6-tribromobenzyl (meth) acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth)
Aliphatic monofunctional (meth) acrylate compounds such as acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, alicyclic monofunctional (meth) acrylate compounds such as dicyclopentanyl (meth) acrylate; ethylene glycol di ( (Meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, and other poly ( Or mono) ethylene glycol di (meth) acrylate; propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di ( Poly (or mono) propylene glycol di (meth) acrylate such as acrylate, tetrapropylene glycol di (meth) acrylate, nonapropylene glycol di (meth) acrylate; 1,3-butylene glycol di (meth) acrylate, 1 , 4-butylene glycol di (meth) acrylate, 1,6-hexamethylene glycol di (meth) acrylate, 1,14-tetradecamethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalic acid Neopentyl glycol di (meth) acrylate, hydroxypivalic acid dipentaglycol caprolactone adduct di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, dicyclo Nteniruji (meth) acrylate, dicyclopentanyl di (meth)
Acrylate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1,
3-dioxane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, di (meth) acryloyloxyethyl isocyanurate, tris (meth) acryloyloxyethyl isocyanurate, 2,2-bis (4- (meth) acryloyloxyphenyl) -propane, 2 , 2-bis (4- (meth) acryloyloxyethoxyphenyl) -propane, 2,2-bis (4-
(Meth) acryloyloxydiethoxyphenyl) -propane, 2,2-bis (4- (meth) acryloyloxypentaethoxyphenyl) -propane, 2,2-bis (4- (meth) acryloyloxyethoxy-3,5 −
Dibromophenyl) -propane, 2,2-bis (4-
(Meth) acryloyloxydiethoxy-3,5-dibromophenyl) -propane, 2,2-bis (4- (meth) acryloyloxypentaethoxy-3,5-dibromophenyl) -propane, 2,2-bis ( 4- (meth) acryloyloxyethoxy-3,5-dimethylphenyl) -propane, 2,2-bis (4- (meth) acryloyloxyethoxy-3-phenylphenyl) -propane, bis (4- (meth) acryloyl Oxyphenyl) -sulfone, bis (4- (meth) acryloyloxyethoxyphenyl) -sulfone, bis (4- (meth) acryloyloxydiethoxyphenyl) -sulfone, bis (4- (meth) acryloyloxypentaethoxyphenyl) -Sulfone, bis (4- (meth) acryloyloxyeto Shi-3-phenyl-phenyl) -
Sulfone, bis (4- (meth) acryloyloxyethoxy-3,5-dimethylphenyl) -sulfone, bis (4- (meth) acryloyloxyphenyl) -sulfide, bis (4- (meth) acryloyloxyethoxyphenyl)- Sulfide, bis (4- (meth) acryloyloxypentaethoxyphenyl) -sulfide,
Bis (4- (meth) acryloyloxyethoxy-3-
Phenylphenyl) -sulfide, bis (4- (meth))
Examples thereof include polyfunctional (meth) acrylate compounds such as acryloyloxyethoxy-3,5-dimethylphenyl) -sulfide, di ((meth) acryloyloxyethoxy) phosphate, and tri ((meth) acryloyloxyethoxy) phosphate. . These can be used alone or in a mixture of two or more.

Regarding the blending ratio of the components (A) to (D) in the composition of the present invention, when the total amount of the components (A) to (D) is 100 parts by weight, 30 to 80 parts by weight of (A). ,
(B) 10 to 60 parts by weight, (C) 10 to 60 parts by weight,
(D) 0 to 50 parts by weight. If the amount of the component (A) is less than 30 parts by weight, sufficient heat resistance, surface hardness, elastic modulus and Young's modulus cannot be imparted to the lens, and if it exceeds 80 parts by weight, the viscosity of the composition becomes high and cast polymerization. Workability is reduced. A preferred blending amount is 30 to 60 parts by weight. Also,
If the amount of component (B) is less than 10 parts by weight, sufficient impact resistance cannot be imparted to the lens and dyeability cannot be imparted. On the other hand, if it exceeds 60 parts by weight, the heat resistance and surface hardness of the lens are lowered, which is not desirable. The preferred blending amount is 20 to 50 parts by weight. Further, if the amount of the component (C) is less than 10 parts by weight, the viscosity of the composition becomes high and the workability of cast polymerization is deteriorated. If it exceeds 60 parts by weight, the heat resistance and toughness of the lens are deteriorated, which is not desirable. The preferred blending amount is 10-4
0 parts by weight. The component (D) is not an essential component,
It is a component used for further improving the heat resistance and surface hardness of the lens, and also for lowering the viscosity of the composition and improving the workability of casting. The preferred blending amount is 5 to 30 parts by weight.

If desired, the composition of the present invention may contain various additives such as an antioxidant, an anti-yellowing agent, an ultraviolet absorber, a bluing agent and a pigment so as not to impair the effects of the present invention. You may mix | blend within the range.

The composition containing the components (A) to (D) of the present invention as described above in detail is not particularly limited in its preparation method. For example, the components (A) to (D) are mixed by a conventional method. It can be obtained by stirring and further adding various additives as required.

The manufacturing method of the present invention includes the above-mentioned (A) to
The method is characterized by having a step of polymerizing and curing a composition containing the component (D) as a main component, and by this polymerizing and curing, a good plastic lens having a refractive index of 1.55 or more can be obtained. This polymerization and curing may be performed by heating. In addition, a method may be used in which after the gelation by the active energy rays, the polymerization and curing are completed by heating.

A polymerization initiator may be used for this polymerization and curing. As the polymerization initiator, when it is polymerized and cured by heating, for example, benzoyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxyisobutyrate, t-butyl peroxy-2-ethylhexanoate, etc. Organic peroxide; 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-
A thermal polymerization initiator such as an azo compound such as dimethylvaleronitrile) can be used. In addition, when polymerization curing by active energy rays is also used, for example, 2-hydroxy-2
-Photopolymerization initiators such as methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, methylphenylglyoxylate, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (active energy ray-sensitive polymerization The initiator) can be used in combination with the thermal polymerization initiator. These can be used alone or in a mixture of two or more. The mixing ratio of the polymerization initiator is usually 0.05 to 5 parts by weight with respect to 100 parts by weight of the total of the components (A) to (D).

Various specific conditions for the polymerization and curing may be appropriately set so as to obtain a desired plastic lens. In the method of the present invention, the cast polymerization method is particularly preferable. For example, in two glass plate molds mirror-polished,
There is a mode in which the above-mentioned composition is injected through a gasket made of polyvinyl chloride, ethylene-vinyl acetate copolymer, ethylene-1-butene copolymer and the like and heated at an appropriate temperature. Further, the mold may be polymerized and cured by heating after irradiating the mold with active energy rays from one side or both sides. Regarding the polymerization temperature and time, the optimum value varies depending on the type of catalyst and the amount added, but it is generally from room temperature to 150 ° C.
Therefore, 0.5 to 30 hours is desirable. Furthermore, 30 ° C to 12
Preferred is 0 to 2 hours for 2 to 24 hours.

As the mold used here, various molds such as glass and glass, glass and plastic plate, glass and metal plate, metal plate and metal plate, or a combination of these can be used. In addition to the thermoplastic resin as described above, an adhesive tape made of polyester or the like may be used as the gasket. Electromagnetic waves such as electron rays, ultraviolet rays, and visible rays can be used as the active energy rays that are optionally used. It is desirable to use active energy rays having various types of low-pressure, high-pressure, and ultra-high-pressure mercury lamps, metal halide lamps, electrodeless lamps, xenon lamps, etc. as light sources.

[0034]

The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited thereto.

<Synthesis Example 1 (Urethane methacrylate (U
Synthesis of M1))> Tolylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Coronate T-100, molecular weight 174.16, hereinafter abbreviated as TDI).
g, di-n-butyltin dilaurate 0.64 g, 2,6
-Di-tert-butyl-4-methylphenol 0.
64 g was put in a glass container and stirred while heating to 70 ° C. to obtain a uniform solution. Then, 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 144.17, hereinafter abbreviated as HPMA) 288.3.
4 g was gradually added dropwise over 5 hours. Furthermore, by keeping the temperature of this system at 70 ° C. and measuring the IR spectrum and isocyanate equivalent weight, it was confirmed that the hydroxyl group of HPMA almost formed a urethane bond with the isocyanate group of TDI. Thereafter, while maintaining the system at 70 ° C. and continuing stirring, 2,2-bis [3,5-dibromo-4 (2-hydroxyethoxy) phenyl] propane (molecular weight 63
2.0, hereinafter abbreviated as TBA-2. ) 632 g was gradually added over 3 hours. After that, benzyl methacrylate, phenyl methacrylate, or
100-300 g of 1,6-hexamethylene glycol dimethacrylate was added, the reaction was continued for 14 hours while stirring while maintaining the system temperature at 70 ° C., and the urethane bond reaction was terminated to obtain a urethane methacrylate (UM1) monomer solution. . The end point of this reaction was confirmed by measuring the IR spectrum and isocyanate equivalent.

<Synthesis example 2 (urethane methacrylate (U
Synthesis of M2))> TDI 348.32 g, di-n-butyltin dilaurate 0.64 g, 2,6-di-tert-
0.64 g of butyl-4-methylphenol was placed in a glass container and stirred while heating to 70 ° C to form a uniform solution. 2-Hydroxyethyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Acryester HO, molecular weight 130.15, hereinafter H
260.30 g (abbreviated as EMA) was gradually added dropwise over 5 hours. Furthermore, by keeping the temperature of this system at 70 ° C. and measuring the IR spectrum and isocyanate equivalent weight, it was confirmed that the hydroxyl group of HEMA almost formed a urethane bond with the isocyanate group of TDI. Then, this system 7
While maintaining the temperature at 0 ° C and continuing stirring, add 632 more TBA-2.
g was added gradually over 3 hours. Then, 100-300 g of benzyl methacrylate was added, and the temperature of this system was 70 ° C.
The reaction is continued for 14 hours with stirring to maintain the urethane bond reaction, and the urethane methacrylate (UM
A benzyl methacrylate solution of 2) was obtained. The end point of this reaction was confirmed by measuring the IR spectrum and isocyanate equivalent.

<Synthesis Example 3 (urethane methacrylate (U
Synthesis of M3))> TDI 348.32 g, di-n-butyltin dilaurate 0.64 g, 2,6-di-tert-
0.64 g of butyl-4-methylphenol was placed in a glass container and stirred while heating to 70 ° C to form a uniform solution. Keep the temperature of this system at 70 ° C and stir it with HEMA.
260.30 g was gradually added dropwise over 5 hours. Furthermore, by keeping the temperature of this system at 70 ° C. and measuring the IR spectrum and isocyanate equivalent weight, it was confirmed that the hydroxyl group of HEMA almost formed a urethane bond with the isocyanate group of TDI. Thereafter, while maintaining the system at 70 ° C. and continuing stirring, 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane (molecular weight 316.
4, hereinafter abbreviated as BA-2. ) 316.4 g was gradually added over 3 hours. Then 1 benzyl methacrylate
00 to 300 g was added, and the reaction was continued for 14 hours while stirring while maintaining the temperature of this system at 70 ° C. to terminate the urethane bond reaction, to obtain a benzyl methacrylate solution of urethane methacrylate (UM3). The end point of the reaction is I
The measurement was performed by measuring the R spectrum and isocyanate equivalent weight.

<Synthesis Example 4 (urethane methacrylate (U
Synthesis of M4))> TDI 348.32 g, di-n-butyltin dilaurate 0.64 g, 2,6-di-tert-
0.64 g of butyl-4-methylphenol was placed in a glass container and stirred while heating to 70 ° C to form a uniform solution. Keep the temperature of this system at 70 ° C and stir it with HEMA.
260.30 g was gradually added dropwise over 5 hours. Furthermore, by keeping the temperature of this system at 70 ° C. and measuring the IR spectrum and isocyanate equivalent weight, it was confirmed that the hydroxyl group of HEMA almost formed a urethane bond with the isocyanate group of TDI. Then, while maintaining the system at 70 ° C. and continuing stirring, bis [3,5-dibromo-4 (2
-Hydroxyethoxy) phenyl] sulfone (molecular weight 6
54.0, hereafter abbreviated as TBS-2. ) 316.4 g was gradually added over 3 hours. Then, 100-300 g of phenyl methacrylate was added, and the temperature of this system was 70 ° C.
The reaction is continued for 14 hours with stirring while maintaining the temperature to end the urethane bonding reaction, and urethane methacrylate (UM4)
To obtain a phenyl methacrylate solution. The end point of the reaction was confirmed by measuring the IR spectrum and isocyanate equivalent.

<Synthesis Example 5 (Urethane methacrylate (U
Synthesis of M5))> Isophorone diisocyanate (manufactured by Daicel Hüls, molecular weight 218.3, hereinafter abbreviated as IPDI) 218.3 g, di-n-butyltin dilaurate 0.64 g, 2,6-di-tert. 0.64 g of -butyl-4-methylphenol was placed in a glass container and stirred while heating to 70 ° C to form a uniform solution. While maintaining the temperature of this system at 70 ° C., 260.30 g of HEMA was gradually added dropwise over 5 hours. Furthermore, the temperature of this system is set to 7
By keeping the temperature at 0 ° C. and measuring the IR spectrum and the isocyanate equivalent, it was confirmed that the hydroxyl group of HEMA formed almost a urethane bond with the isocyanate group of TDI.

<Synthesis Example 6 (Synthesis of Nonabutylene Glycol Dimethacrylate (9BGDM) by Transesterification Method)> Nonabutylene glycol (average molecular weight: 680, manufactured by Hodogaya Chemical Co., Ltd., trade name: PTG-650SN) 2.0 kg, MMA2.0
kg and hydroquinone monomethyl ether 0.5 g
Is charged, and titanium tetra-n-butoxide 5 is used as a catalyst.
Using 0 g, the produced methanol was azeotropically removed with MMA while stirring at 100 to 120 ° C., and the mixture was reacted for 3 hours. After the reaction, excess MMA was distilled off under reduced pressure, 1 kg of toluene was added to the residue, the mixture was washed with alkaline water, and toluene was distilled off under reduced pressure to obtain 9BGDM. The obtained 9BGDM was colorless and transparent, and the purity analysis by bromine addition was 100%.

<Example 1> 50g of UM1 and 9BGDM
25 g, styrene (hereinafter abbreviated as St) 25 g, diisopropyl peroxydicarbonate 0.2 g, t-
After thoroughly stirring 0.1 g of butyl peroxyisobutyrate and 0.05 g of 2-hydroxy-4-methoxybenzophenone at room temperature, the pressure was reduced to 50 mmHg and the pressure was reduced to 10
Deaerated for a minute. This composition has a mirror-finished outer diameter of 80.
mm with a curvature of 386 mm and an outer diameter of 80 mm, a curvature of 6
5 mm glass was combined so as to obtain a concave lens having a center thickness of 2.0 mm, and the mixture was poured into a mold surrounded by a polyvinyl chloride gasket.

Next, the mold in which the composition was injected was placed in a hot air drier, and the temperature inside the drier was heated from 30 ° C. to 50 ° C. over 10 hours and then from 50 ° C. to 80 ° C. over 5 hours. Then, the temperature was further heated from 80 ° C. to 100 ° C. over 4 hours, and finally maintained at 100 ° C. for 2 hours, then the lens was removed from the mold and heated at 120 ° C. for 1 hour for annealing treatment.

The lens thus manufactured was evaluated,
The results are shown in Table 1. The evaluation items other than the surface accuracy, the falling ball test, and the residual stress were measured by using a disc-shaped flat plate having a thickness of 2 mm or 5 mm and an outer diameter of 75 mm, which was prepared with the same formulation as the lens.

<Examples 2 to 6> Lenses were manufactured and evaluated in the same manner as in Example 1 except that the components (A) to (D) were used in the proportions shown in Table 1. The results are also shown in Table 1.

Comparative Example 1 Diethylene glycol bisallyl carbonate (manufactured by PPG, trade name: CR-39)
100 g and diisopropyl peroxydicarbonate 3 g were mixed and stirred well, and then poured into the same mold as that used in Example 1, and then at 45 ° C. for 10 hours at 60 ° C.
At 80 ° C. for 3 hours and at 95 ° C. for 6 hours for molding. The lens was removed from the mold, and heated at 120 ° C. for 1 hour to be annealed. The lenses and flat plates produced in this manner were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

<Comparative Examples 2 to 6> Lenses and flat plates were manufactured and evaluated in the same manner as in Example 1 except that the components (A) to (D) were used in the proportions shown in Table 2. The results are also shown in Table 2.

<Evaluation Method> The evaluation methods carried out in Examples and Comparative Examples are shown below. Visible light transmittance (%): Measured according to ASTM D 1003-61. Refractive index: A disk-shaped flat plate having a thickness of 2 mm was used, and it was measured by an Atsube refractometer at a D line of 589.3 nm. Saturated water absorption (% by weight): A disk-shaped flat plate having a thickness of 5 mm was used and left in a 100% saturated steam tank at 70 ° C for 3 days to measure the rate of weight increase. Falling ball test: A lens having a thickness of 2.0 mm was tested according to the FDA standard. However, the maximum weight of the steel ball when it was dropped from a height of 127 cm is shown. Rockwell hardness: Measured according to JIS K7202. Heat resistance: Using a disk-shaped flat plate having a thickness of 2 mm, Tg was measured at a load of 10 g with a TMA measuring machine. Surface accuracy: The curved state of the center of the lens was visually observed and classified into the following ranks.

A: There is no curvature at all. (The difference between the curvature at the time of design and the curvature of the molded lens is 0 to 1%) B: Slightly curved. (Difference 1-3%) C: Slightly curved. (Difference 3-5%) D: Curved. (Difference 5-10%) E: Remarkably curved. (10-20% difference) F: Cannot be used. (Difference of 20% or more) Dyeability: Using a disc-shaped flat plate having a thickness of 2 mm, 2 g of a dyeing agent (manufactured by Hattori Seiko Co., Ltd., product name: Seiko Plax Diamond Coat) was dispersed in 1 liter of water to obtain 90 ℃
It was dyed for 3 minutes, and the numerical value of visible light transmittance was measured. Residual stress: Toshiba Strain Inspector, SVP-100 was used to observe the residual stress of the lens. A black cross-shaped pattern or an entirely black pattern was designated as having no residual stress. The case where a rainbow-colored pattern was seen partially or concentrically was defined as having residual stress.

<Abbreviations in Table> UDM1-5: Urethane methacrylate 9BGDM obtained in Synthesis Examples 1-5: Nonabutylene glycol dimethacrylate St: Styrene HDDM: 1,6-hexamethylene glycol dimethacrylate 9EGDM: Nonaethylene glycol di Methacrylate IBX: Isobornyl Methacrylate BzMA: Benzyl Methacrylate

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

According to the present invention, heat resistance, impact resistance,
Low water absorption, excellent moldability, and appropriate suppression of polymerization rate,
It is possible to easily manufacture a plastic lens having a refractive index of 1.55 or more, which is excellent in terms of preventing residual stress.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical indication location G02B 1/04 7132-2K (72) Inventor Eriko Suda 4-chome, Sunadabashi, Higashi-ku, Nagoya, Aichi Prefecture 60 Issue Mitsubishi Rayon Co., Ltd. Product Development Laboratory (72) Inventor Mikito Nakajima 3-5 Yamato, Suwa City, Nagano Seiko Epson Corporation (72) Inventor Katsuyoshi Takeshita 3-5 Yamato, Suwa City, Nagano Prefecture Seiko In Epson Corporation (72) Inventor Yusuke Kakekake 3-5 Yamato 3-chome, Suwa City, Nagano Seiko Epson Corporation

Claims (2)

[Claims] 1. A urethane (meth) acrylate represented by the following general formula (1):
30 to 80 parts by weight, (In the formula, R ¹ , R ² and R ⁴ each independently represent hydrogen or a methyl group, R ³ represents an aromatic hydrocarbon, j, k,
m and n each independently represent an integer of 1 to 5, X ¹ ,
X ² , X ³ and X ⁴ are each independently hydrogen, a methyl group, bromine,
Represents chlorine or iodine, and Y is Represents ) (B) Polybutylene glycol di (meth) acrylate represented by the following general formula (2)
10 to 60 parts by weight, (In the formula, R ⁵ represents hydrogen or a methyl group, and p is 5 to 1
Represents an integer of 6. ) (C) 10 to 60 parts by weight of a styrenic compound represented by the following general formula (3): (Wherein X ⁵ represents a methyl group, a bromine atom, a chlorine atom or an iodine atom, and q represents an integer of 0 to 5), and (D) has at least one polymerizable double bond in the molecule. Compound 0 to 50 parts by weight (however, (A) to (D)
The total amount of the components is 100 parts by weight. ) A composition for a plastic lens, which has a refractive index of 1.55 or more and contains as a main component. 2. A method for producing a plastic lens having a refractive index of 1.55 or more, which has a step of polymerizing and curing the composition according to claim 1.