JPH05239154A - Optical material of high-refractive index - Google Patents

Abstract

PURPOSE:To provide the subject lightweight material having high Abbe number, excellent in surface characteristics in terms of surface accuracy, consisting of a resin produced by polymerizing and curing a composition comprising each specific three components. CONSTITUTION:The objective material consists of a resin which is produced by polymerizing and curing, through the action of heat, active energy rays and/or a radical generator, a composition comprising (A) 100 pts.wt. of a sulfur- contg. bis(meth)acrylate of formula I (R<1> is H or methyl; R<2> is 1-6C alkylene; Ar is 6-30C arylene, aralkylene, etc.; X is O or S; Y is S or SO2 when X is O, while being SO2, CO, etc., when X is S; (m) and (n) are each 1-5; (p) is 0-10), (B) 0.001-1 pt.wt. of a (meth)acrylate/phosphate of formula II (R<3> is the same as R<1>; R<4> is 1-12C alkylene, aralkylene, etc.; R<5> is H, 1-12C alkyl, etc.; (q) is 1-3), and (C) 1-99 pts.wt. of a compound copolymerizable with the component A and/or the component B, selected from styrene-based unsaturated monomers or mercapto compounds.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic lens resin, and more particularly to a lens resin having a high refractive index and excellent surface accuracy of a cured product.

[0002]

2. Description of the Related Art Conventionally, a diethylene glycol bisaryl carbonate resin has been widely used as a resin for plastic lenses. This resin has advantages such as excellent impact resistance, transparency, and good light-dispersion characteristics, but has a low refractive index of 1.50, and a lens is required to obtain the same refraction as glass. There was a drawback that it became thick.

On the other hand, it is known that various diacrylates or dimethacrylates are easily radically polymerized to give lenses having excellent transparency. For example, di (meth) acrylates having a bromine-containing bisphenol A skeleton (JP-A-59-184210 and JP-A-59-19).
3915), di (meth) acrylates having a sulfur-containing aromatic skeleton (JP-A-60-26010, JP-A-62-195357), lens resins obtained with a high refractive index. In addition, it is known that it exhibits excellent optical characteristics in the balance of high Abbe number.

However, in general, a cured resin having a high refractive index obtained by polymerizing various di (meth) acrylate compounds containing such an aromatic ring is separated from the mold of the cured resin produced during cast polymerization. Therefore, there is a problem in surface characteristics such as a decrease in surface accuracy when the cured resin is used as it is as a lens.

[Outline of Invention]

DISCLOSURE OF THE INVENTION The present invention aims to provide a resin for a lens which is improved in various drawbacks of the conventional resin for a lens, is lightweight, has a high refractive index, and is excellent in surface characteristics of surface accuracy. To do.

[0006]

<Summary> The high refractive index optical material according to the present invention comprises a composition containing the following compounds A, B and C, which are subjected to heat and / or active energy rays and / or ethylene. It is composed of a resin which is polymerized and cured by being subjected to the action of a radical generator on a polyunsaturated bond.

A: 100 parts by weight of sulfur-containing bis (meth) acrylate represented by the following general formula [I]

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents an alkylene group having 1 to 6 carbon atoms.
Ar represents an arylene group having 6 to 30 carbon atoms, an aralkylene group, or a group substituted with a halogen atom other than fluorine. X is -O- or-
Indicates S-. Y is -S- or-when X is -O-.
SO ₂ −, when X is —S—, —S—, —SO ₂ —,
It also represents -CO-, or has 1 to 1 carbon atoms.
12 is a group selected from the group consisting of an alkylene group, an aralkylene group, an alkylene ether group, an aralkylene ether group, an alkylene thioether group and an aralkylene thioether group. m and n each represent an integer of 1 to 5. p shows the number of 0-10. The plurality of groups may be the same or different. )

B: (meth) acrylate / phosphate represented by the following general formula [II]: 0.001 to 1 part by weight

(In the formula, R ³ represents a hydrogen atom or a methyl group. R ⁴ represents an alkylene group having 1 to 12 carbon atoms, an aralkylene group, an alkylene ether group, an aralkylene ether group or an alkylene thioether. And a group selected from a group and an aralkylene thioether group.
R ⁵ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an aralkyl group. q shows the integer of 1-3. The plurality of groups may be the same or different. )

C: a compound composed of at least one selected from a styrene unsaturated monomer or a mercapto compound, which is copolymerizable with the compound represented by the general formula [I] and / or the general formula [II] 1. ~ 99 parts by weight

<Effect> The resin for a high refractive index lens according to the present invention has not only a high refractive index but also a high Abbe's number, and moreover, peeling from a mold when a polymerized molding as a lens is obtained by cast polymerization. Nonetheless, the aforementioned problems of the prior art have been solved.

[Detailed Description of the Invention] [Chemical substance of cured product] The optical material according to the present invention comprises:
Polymerizing and curing a composition comprising compounds A, B and C by subjecting it to heat and / or an active energy ray and / or an exciting action consisting of the action of a radical generator on an ethylenically unsaturated bond. It will be.

Since some of the compounds A, B and C (styrene type monomer) have an ethylenically unsaturated bond,
It is considered that the above-mentioned excitation action causes the polymer to polymerize by polyaddition of ethylenically unsaturated bonds. It is not always clear how the mercapto compound C, which is a non-ethylenically unsaturated compound coexisting in such a place of polymerization, behaves, but the thiol group of the compound C is an ethylenic compound of the compounds A and / or B. The so-called Michael type addition to the unsaturated compound may possibly combine with the compounds A and / or B existing under the polymerization conditions.

The sulfur-containing (meth) acrylate represented by the above-mentioned general formula [I] can be polymerized by itself, but the surface accuracy of the cured product is lowered by peeling of the lens from the mold during polymerization molding. There are drawbacks. However, according to the present invention, a sulfur-containing (meth) acrylate [I] (compound A), a (meth) acrylate / phosphate (compound B) represented by the general formula [II] and another monomer (compound C) are used. By copolymerizing with, it is possible to improve the adhesion between the lens and the mold (for example, glass) and obtain a cured product having excellent surface accuracy.

[Monomer Component] The resin for optical materials according to the present invention is obtained by polymerizing and curing a composition containing three specific components.

Here, "comprising" the specific three components means that the monomer copolymerizable with the specific three components is specifically described, for example, as long as it does not impair the gist of the present invention. This means that up to about 10 parts by weight per 100 parts by weight of the specific three components may be used together. Also,
A plurality of each component may be used in combination between the components and / or within the components.

<Bis (meth) acrylate: Compound A> The basic monomer of the resin for lenses according to the present invention is sulfur-containing bis (meth) acrylate represented by the following formula [I]. In this specification, "(meth) acrylate" is a general term for acrylate and methacrylate.

[0019]

The symbols in the formula have the following meanings. R ¹ : a hydrogen atom or a methyl group. R ² : An alkylene group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms. Ar: all have 6 to 30 carbon atoms, preferably 6 to 1
5. An arylene group or an aralkylene group which is 5, or a halogen-substituted product thereof (however, halogen excludes fluorine). _{Preferably, -Ph '-, - CH 2} -P
_{h'-CH 2 -, - Ph} '(p) -S-Ph' (p)
_{-, - Ph '(p)} -SO 2 -Ph' (p) -, - P
_{h '(p) -C (CH} 3) 2 -Ph' (p) -, - P
h '(p) -CO-Ph (p) -, - CH 2 -Ph "
_{(Cl) 4 -CH 2 - (} - Ph '-: o-, m- or p- phenylene, -Ph' (p) -: phenylene, -P
h ″ (Cl) ₄ —: o—, m- or p-tetrachlorophenylene) X: —O— or —S—.

[0021] Y: when X is -O- is -S- or _-SO 2 -, when X is -S- is -S -, - SO ₂
-Or-CO-, or both are 1 to 12
A group selected from an alkylene group, an aralkylene group, an alkyl ether group, an aralkylene ether group, an alkylene thioether group and an aralkylene thioether group.

M and n: integers of 1 to 5, preferably 1 to 3, respectively. The number of p: 0-10, preferably 0-5. Multiple groups existing in the same molecule, for example R ¹ , may be the same or different.

As is apparent from the above formula, the sulfur-containing (meth) acrylate represented by the above general formula [I] used in the present invention has a structure in which acrylic acid or methacrylic acid is continuous with a chain containing sulfur and an aromatic ring. Is to have.

Specific examples of the (meth) acrylate [I] represented by the formula [I] include (i) p-bis (β-acryloyloxyethylthio) xylylene and p
-Bis (β-methacryloyloxyethylthio) xylylene, m-bis (β-acryloyloxyethylthio)
Xylylene, m-bis (β-methacryloyloxyethylthio) xylylene, α, α'-bis (β-acryloyloxyethylthio) -2,3,5,6-tetrachloro-p-xylylene, α, α'- Bis (β-methacryloyloxyethylthio) -2,3,5,6-tetrachloro-p-xylylene, 4,4′-bis (β-acryloyloxyethoxy) diphenyl sulfide, 4,4′-bis (β- Methacryloyloxyethoxy) diphenyl sulfide, 4,4'-bis (β-acryloyloxyethoxyethoxy) diphenyl sulfone, 4,4'-bis (β-methacryloyloxyethoxyethoxy) diphenyl sulfone, 4,4'-bis (β- Acryloyloxyethylthio) diphenyl sulfide, 4,4'-bis (β-methacryloyloxy) Ethylthio) diphenyl sulfide, 4,4'-bis (beta-acryloyloxy ethyl) diphenylsulfone, 4,4'-bis (beta-
Methacryloyloxydiethylthio) diphenyl sulfone, 4,4'-bis (β-methacryloyloxyethylthio) diphenyl ketone, and (b) the above formula [I]
When X in-is -S-, the formula -Ar-(-Y-Ar
-) _P- is a general formula

[0025]

[Chemical 1]

(In the formula, R ⁶ represents an alkylene group having 1 to 12 carbon atoms, preferably 1 to ⁶ carbon atoms, which may have an ether bond in the chain, and a represents an average degree of oligomerization 1 An oligomer represented by the formula:

[0027]

[Chemical 2]

An oligomer represented by the formula (wherein a is a number from 1 to 5 representing the average degree of oligomerization) is given.

Among the monomers represented by the above general formula [I], from the viewpoints of optical properties such as the refractive index of the polymer and handleability such as the viscosity of the monomer, particularly preferable monomers are ,
It is a bis (meth) acrylate represented by the general formula [I '].

[0030]

[Chemical 3]

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ⁷ and R ⁸ each represent a divalent hydrocarbon residue having 1 to 4 carbon atoms, and Z represents a halogen atom other than fluorine. , B represents 0 or an integer of 1 to 4.)

Specific examples of the monomer represented by the general formula [I '] include p-bis [β- (meth) acryloyloxyethylthio] xylylene and m-bis [β- (meth) acryloyl. Oxyethylthio] xylylene, p-bis [β- (meth) acryloyloxyisopropylthio] xylylene, m-bis [β- (meth) acryloyloxyethylthio] ethylphenylene, p-
There are bis [β- (meth) acryloyloxybutylthio] tetrachloroxylylene and the like, and more preferable monomers are p-bis [β- (meth) acryloyloxyethylthio] xylylene and m-bis [β- ( (Meth) acryloyloxyethylthio] xylylene.

<(Meth) acrylate / phosphate:
Compound B> The compound represented by the following general formula [II] used in the present invention is a phosphoric acid derivative and has a (meth) terminal
It is a (meth) acrylate / phosphate having 1 to 3 acrylic groups.

[0034]

The symbols in the formula have the following meanings. R ³ : a hydrogen atom or a methyl group. R ⁴ : an alkylene group having 1 to 12 carbon atoms,
A group selected from an aralkylene group, an alkylene ether group, an aralkylene ether group, an alkylene thioether group and an aralkylene thioether group. Preferably, an alkylene group having 2 to 4 carbon atoms.

R ⁵ : hydrogen atom or an alkyl group having 1 to 12 carbon atoms or an aralkyl group. Preferably, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. q: An integer of 1 to 3. The plural groups present in the same molecule may be the same or different.

Specific examples of the compound of the formula [II] include (meth) acryloyloxyethyl = phosphate (R ³ : -H or -CH ₃ , R ⁴ : -CH ₂ CH ₂
-, R ⁵ : H, q: 1), bis ((meth) acryloyloxyethyl) = phosphate, tris ((meth) acryloyloxyethyl) = phosphate, (meth) acryloyloxybutyl phosphate, bis ((meth))
Acryloyloxybutyl) = phosphate, tris ((meth) acryloyloxybutyl) = phosphate, ((meth) acryloyloxyoctyl) = phosphate, bis ((meth) acryloyloxyoctyl)
= Phosphate, 4-((meth) acryloyloxymethyl) benzyl = phosphate, bis [4-((meth))
Acryloyloxymethyl) benzyl] = phosphate, (meth) acryloyloxyethyloxyethyl =
Phosphate, bis ((meth) acryloyloxyethyloxyethyl) = phosphate, tris ((meth) acryloyloxyethyloxyethyl) = phosphate, (meth) acryloyloxyphenyloxyphenyl = phosphate, bis ((meth) acryloyloxyphenyl) = Phosphate, (meth) acryloyloxyethylthioethyl = phosphate, bis ((meth) acryloyloxyethylthioethyl) = phosphate,
Tris ((meth) acryloyloxyethylthioethyl) = phosphate, (meth) acryloyloxyphenylthiophenyl = phosphate, bis ((meth) acryloyloxyphenylthiophenyl) = phosphate, diethyl = (meth) acryloyloxyethyl = phosphate ( R ^3: H or ^{_{CH 3 -, R 4: -CH}} 2
_{^{CH 2 -, R 5: -C}} 2 H 5, q: 1), ethyl = di (meth) acryloyloxyethyl = phosphate, dibutyl = (meth) acryloyloxyethyl = phosphate, butyl (meth) acryloyloxyethyl = Phosphate, dioctyl = (meth) acryloyloxyethyl = phosphate, octyl = di (meth) acryloyloxyethyl = phosphate, (meth) acryloyloxyethyl = phenyl = phosphate, (meth) acryloyloxyethyl = diphenyl = phosphate,
Examples thereof include di (meth) acryloyloxyethyl = phenyl = phosphate.

Among the monomers represented by the above general formula [II], preferable in view of handling properties such as monomer viscosity, optical properties such as refractive index and transparency of the polymer, and heat resistance. The monomer is (meth) acrylate / phosphate represented by the general formula [II ′].

[0039]

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ⁶ represents an alkylene group having 1 to 4 carbon atoms, and c represents an integer of 1 to 3.)

Specific examples of the monomer represented by the general formula (II ') include, for example, bis (meth) acryloyloxyethyl phosphate, tris (meth) acryloyloxyethyl phosphate, and (meth) acryloyloxyethyl. = Phosphate, (meth) acryloyloxypropyl = phosphate, bis (meth) acryloyloxypropyl = phosphate, (meth) acryloyloxybutyl phosphate, bis (meth) acryloyloxybutyl) = phosphate, tris (meth)
Acryloyloxybutyl = phosphate, etc.,
Even more preferred monomers are bis (meth) acryloyloxyethyl = phosphate and tris (meth) acryloyloxyethyl = phosphate.

<Compound C> Compound C is a styrenic unsaturated monomer or a mercapto compound, both of which are copolymerized with compound A of general formula [I] and / or compound B of general formula [II]. It is possible.

While it is clear that the styrenic unsaturated monomer can be copolymerized with compounds A and / or B via a radical mechanism via cleavage of its ethylenically unsaturated bond,
It is not always clear how the mercapto compound "copolymerizes" with compounds A and / or B. However, as described above, it is understood that the mercapto compound is bound to the optical resin according to the present invention by some mechanism.

The styrenic unsaturated monomer, which is a group of compound C, is a styrene nucleus and / or side chain substitution product. The substituent is a lower alkyl (C ₆ or less),
Lower alkoxy (about C ₆ or less), halogen, trifluoromethyl, and others. A preferred specific example of the styrenic unsaturated monomer is represented by the following formula [III].

[0045]

[Chemical 4]

(In the formula, R ⁹ represents a hydrogen atom or a methyl group, X ² represents a halogen atom other than fluorine, z represents 0 or an integer of 1 to 5. A plurality of groups may be the same or different. Good too.)

Specific examples of such styrenic unsaturated monomers include, for example, styrene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene,
Examples thereof include tribromostyrene, pentabromostyrene, α-methylstyrene, p-methylstyrene, p-chloromethylstyrene.

Another group of compounds C are mercapto compounds, ie organic compounds containing --SH groups. −
At least one SH group, that is, a thiol group may be bonded.

There are various mercapto compounds which can be used as the compound C in the present invention, and the thiol compounds represented by the following formulas [IV], [V] or [VI] are typical.

[0050]

(In the formula, R ¹⁰ is —CH ₂ — or —CH
₂ CH ₂ - shows a. R ¹¹ has 2 to 15 carbon atoms
Represents a hydrocarbon residue or an alkyl ether residue. d
Represents an integer of 2 to 6. A plurality of groups may be the same or different. )

[0052]

[Chemical 5]

[0053] _{^{* - (- CH 2 -)}} g- ( wherein, e and g are each an integer of 1 to 8, f is an integer of 0 to 2.) Shows a. The plurality of groups may be the same or different. ]

[0054]

[Chemical 6]

(In the formula, R ¹² and R ¹³ each represent the same or different alkylene group having 1 to 3 carbon atoms. H and i each represent 0 or 1, and j represents 1 or 2.
The plurality of groups may be the same or different. )

These compounds can be used in combination within each group and / or between each group. (A) The compound represented by the general formula [IV] is thioglycolic acid (that is, α-mercaptoacetic acid) or β-mercaptopropionic acid ester of a divalent to hexavalent glycol.

Specific examples of the compound [IV] include, for example, pentaerythritol = tetrakis (β-mercaptopropionate), pentaerythritol = tetrakis (thioglycolate), trimethylolpropane =
Tris (β-mercaptopropionate), trimethylolpropane = tris (thioglycolate), diethylene glycol = bis (β-mercaptopropionate), diethylene glycol = bis (thioglycolate), triethylene glycol = bis (β- (Mercaptopropionate), triethylene glycol = bis (thioglycolate), dipentaerythritol = hexakis (β-mercaptopropionate), dipentaerythritol = hexakis (thioglycolate) and the like.

(B) Specific examples of the compound represented by the general formula [V] include, for example, tris [2- (β-thiopropionyloxy) ethyl] triisocyanurate and tris (2-thioglyconyloxyethyl). Isocyanurate, tris [2- (β-thiopropionyloxyethoxy) ethyl] triisocyanurate, tris (2-thioglyconyloxyethoxyethyl) triisocyanurate, tris [3- (β-thiopropionyloxy) propyl] tri Examples thereof include isocyanurate and tris (3-thioglyconyloxypropyl) triisocyanurate.

(C) Specific examples of the compound represented by the general formula [VI] include benzene dimercaptan, xylylene dimercaptan, and 4,4'-dimercaptodiphenyl sulfide.

Among these monomers of the compound C, styrene and dibromostyrene are used as the styrenic unsaturated monomer, and pentaerythryl-tetrakis (β-mercaptopropionate) is used as the mercapto compound.
And pentaerythritol tetrakis (thioglycolate), and mixtures thereof are preferred.

<Monomer Composition> The composition to be “polymerized and cured” according to the present invention comprises compounds A, B and C in the following ratios.

Compound B, ie (meth) acrylate /
If the proportion of phosphate is too small, the effect of improving the surface accuracy and coating adhesion of the cured resin cannot be obtained, and conversely if it is too large, the cured product after polymerization and molding can be released from the mold, particularly the glass mold. It will be impossible.

Also, if the proportion of other monomers that can be "copolymerized" with the sulfur (meth) acrylate or (meth) acrylate / phosphate of compound C, ie compounds A and / or B, is too low, the cured resin Impact resistance becomes low, and conversely, if this ratio is excessively high, the heat resistance of the cured resin becomes low. When two or more styrenic unsaturated monomers or mercapto compounds are used as the compound C, the total amount of these monomers is the above composition ratio. Further, when the styrene unsaturated monomer and the mercapto compound are used together, the composition ratio of both is 10 to 90 parts by weight of the former, 90 to 10 parts by weight of the latter, preferably 40 to 90 of the former. The latter 60 to the weight part
10 parts by weight.

This monomer composition comprises compounds A, B and C. As used herein, "comprising" means that the resulting polymerized cured product does not excessively impair the characteristics of the optical material of the present invention of high refractive index and high impact resistance.
A small amount of an ethylenically unsaturated monomer copolymerizable with the compounds A and B, for example, up to about 10 parts by weight per 100 parts by weight of the compound A + B + C, and a suitable auxiliary material,
It means that it may be included. Examples of such a monomer may include lower alkyl methacrylate, divinylbenzene, di (meth) acrylate and the like which belong to the above-mentioned known art. Such auxiliary materials include antioxidants, UV absorbers, dyes and pigments, and others.

<Polymerization and curing> A composition which may also contain a mercapto compound which is not an ethylenically unsaturated compound is added to the action of the radical generator on heat and / or active energy rays and / or ethylenically unsaturated bonds. And cured in multiple steps to produce an optical material according to the present invention.

The term "heat" as used herein as an exciting action for the polymerization and curing of the compounds A, B and C includes not only the mere application of heat but also the combined use of a thermal polymerization initiator (detailed later). , "Active energy rays" include not only the simple application of ultraviolet rays, ionizing radiation and other energy rays, but also the combined use of a photopolymerization initiator (detailed later), and the "radical generator" means the above-mentioned heat. It may overlap with the polymerization initiator and includes not only the use of the agent but also the case of forming a so-called redox system in which it is combined with a reducing agent when it is composed of an oxidizing agent such as a peroxide. is there.

The polymerization-curing step can be carried out by applying the above-mentioned exciting action to the monomer composition. Specifically, it can be carried out, for example, by a known radical polymerization in which an initiator that generates a free radical is added, but in order to improve its productivity, UV curing or a combination of UV curing and heat polymerization is used. Is desirable. For example, a composition obtained by adding a photopolymerization initiator and a thermal polymerization initiator is injected into a mold and cured by UV irradiation to an extent sufficient for demolding, and then, after demolding, heat polymerization is further performed in an oven. Let

Examples of the photopolymerization initiator used in this case include benzophenone, benzoin methyl ether,
Examples thereof include benzoin isopropyl ether, diethylthioxanthone, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Examples of the thermal polymerization initiator include benzoyl peroxide, diisopropyl peroxycarbonate, lauroyl peroxide, t-butylperoxy (2-ethylhexanoate) and azoisobutyronitrile.

The amount of photopolymerization initiator and thermal polymerization initiator used is in the range of about 0.01 to 5%, preferably 0.03 to 2%, based on the total weight of the composition. If the amount used is too small, the curing will be inadequate, and if it is too large, the cured resin will tend to turn yellow and it will be difficult to control polymerization.

As described above, in the present invention, an antioxidant, an ultraviolet absorber, etc. can be added to the composition before polymerization and curing to cure it.

The optical material obtained by the present invention comprises the above-mentioned polymerized and cured product. This polymerized cured product has a large refractive index, and its value is usually about 1.58 to 1.62. The Abbe number of this polymerized cured product is about 34 to 38. In addition, this polymerized cured product has high surface accuracy (see Examples below). Furthermore, this polymerized and cured product has good transparency (see Examples below).

The optical material made of such a polymerized and cured product can be used in the form of various optical elements. Typical optical elements include lenses (including Fresnel lenses, rod lenses, and other shapes), prisms, optical fibers, mirrors, and the like.

Such an optical element may be not only a molded product of the polymerized and cured product of the present invention, but also one whose surface is subjected to a surface treatment such as a hard coat or an antireflection coat. The polymerized and cured product of the present invention is advantageous in that the molded product itself is an optical element by taking advantage of the feature that the surface accuracy is good, but once a lump is made, it is processed. It goes without saying that an optical element can be manufactured by using this.

[0075]

EXAMPLES The following examples and comparative examples are intended to further illustrate the present invention. “Part” in these examples
Means parts by weight. The physical properties of the resins in these examples are measured by the following test methods.

Appearance Visual inspection. Refractive index A value measured at 25 ° C. with an Atsube refractometer. Surface accuracy When making 10 cured products, visually check the resin with the cured product separated from the glass mold during polymerization molding.
The resin that did not peel evenly was marked as ◯. Hardness Depends on pencil hardness.

Examples 1-10 and Comparative Examples 1-2 p-bis (β-methacryloyloxyethylthio) xylylene 85 parts, bis (methacryloyloxyethyl) =
0.003 parts phosphate, 15 parts styrene, 0.05 parts benzophenone, and t-butylperoxy-2-
0.3 parts of ethyl hexanoate (trade name "Perbutyl O" of NOF CORPORATION) was mixed. Degas the resulting mixture,
40mm diameter composed of glass plate and silicone rubber,
Injection into a cavity with a thickness of 2 mm, output 80 W / cm ²
The high pressure mercury lamp of No. 2 was used to irradiate the glass from one side of the glass at a height of 40 cm once for 3 minutes, for a total of 6 times. After removing the obtained cured product from the mold, it is heated in an oven at 80 ° C for 1 hour and then at 100 ° C.
After heating for 2 hours, a polymerized cured product was obtained.

These various components were changed as shown in the remarks column of Table 1 to obtain the same polymerized and cured product. The results of measuring the physical properties of these polymerized cured products were as shown in Table 1.

[0079]

[Table 1]

Remarks A: p-bis (β-methacryloyloxyethylthio)
Xylylene B: p-bis (β-methacryloyloxyethyloxyethylthio) xylylene C: α, α′-bis (β-methacryloyloxyethylthio) -2,3,5,6-tetrachloro-p-xylylene D: Bis (methacryloyloxyethyl) = phosphate E: tris (acryloyloxyethyl) = phosphate F: methacryloyloxyethyl = phosphate G: methacryloyloxyethyl = diphenyl = phosphate H: styrene I: dibromostyrene J: pentaerythritol = tetrakis (β-) Thiopropionate) K: Tris [2- (β-thiopropionyloxy) ethyl] = triisocyanurate L: Benzophenone M: t-Butylperoxy-2-ethylhexanoate

[0081]

As described above in the section of [Summary of the Invention], an optical material comprising a polymerized and cured product of a specific monomer composition according to the present invention has a high refractive index and high surface accuracy.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G02B 1/04 7132-2K

Claims (1)

[Claims] 1. A composition comprising the following compounds A, B and C is polymerized and cured by subjecting it to the action of a radical generator on heat and / or active energy rays and / or ethylenically unsaturated bonds. High refractive index optical material made of resin A: 100 parts by weight of sulfur-containing bis (meth) acrylate represented by the following general formula [I] (In the formula, R ¹ represents a hydrogen atom or a methyl group. R ²
Represents an alkylene group having 1 to 6 carbon atoms. Ar represents an arylene group having 6 to 30 carbon atoms, an aralkylene group, or a group substituted with a halogen atom other than fluorine. X represents -O- or -S-. Y
May, when X is -O- -S- or -SO ₂ - and, X
There is the case of _{-S- -S -, - SO 2 -} , also either shows a -CO-, or alkylene group having a carbon number of 1 to 12 both, aralkylene group, alkylene ether group, aralkylene ether group, A group selected from an alkylene thioether group and an aralkylene thioether group is shown.
m and n each represent an integer of 1 to 5. p is 0
Indicates the number from -10. The plurality of groups may be the same or different. ) B: 0.001 to 1 part by weight of (meth) acrylate / phosphate represented by the following general formula [II] (In the formula, R ³ represents a hydrogen atom or a methyl group. R ⁴
Represents a group selected from an alkylene group having 1 to 12 carbon atoms, an aralkylene group, an alkylene ether group, an aralkylene ether group, an alkylene thioether group and an aralkylene thioether group. R ⁵ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an aralkyl group. q shows the integer of 1-3. The plurality of groups may be the same or different. ) C: Compound 1 to 99 consisting of at least one selected from styrenic unsaturated monomers or mercapto compounds, which is copolymerizable with the compound represented by the general formula [I] and / or the general formula [II] Parts by weight