JP3270100B2 - High refractive index optical material - Google Patents

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 resin for plastic lenses, and more particularly to a resin for lenses having a high refractive index and excellent surface accuracy of a cured product.

[0002]

2. Description of the Related Art Conventionally, diethylene glycol bisaryl carbonate resins have been widely used as plastic lens resins. 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 requires a lens to obtain refraction equivalent to glass. However, there was a disadvantage that the thickness became thick.

[0003] On the other hand, it is known that various diacrylates or dimethacrylates easily undergo radical polymerization to give lenses having excellent transparency. For example, di (meth) acrylates having a bromine-containing bisphenol A skeleton (JP-A-59-184210, JP-A-59-19)
3915) and di (meth) acrylates having a sulfur-containing aromatic skeleton (JP-A-60-26010 and JP-A-62-195357) have high refractive indices. In addition, it is known that the composition exhibits excellent optical characteristics with a high balance of a high Abebe number.

However, in general, a cured resin having a high refractive index obtained by polymerization of various di (meth) acrylate compounds containing such an aromatic ring has a problem that the cured resin produced from the mold during casting polymerization molding is separated from the mold. Accordingly, 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.

[Summary of the Invention]

SUMMARY OF THE INVENTION An object of the present invention is to provide a lens resin which is improved in various disadvantages of the conventional lens resin, is lightweight, has a high refractive index, and is excellent in surface characteristics with surface accuracy. Is what you do.

[0006]

[Means for Solving the Problems]

<Summary> The high-refractive-index optical material according to the present invention comprises a composition comprising the following compounds A, B and C, and a radical generator for heat and / or active energy rays and / or ethylenically unsaturated bonds. It is made of a resin that is polymerized and cured by applying an action.

A: 100 parts by weight of sulfur-containing (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-
S- is shown. Y is -S- or-when X is -O-.
SO ₂ — represents, when X is —S—, —S—, —SO ₂ —, or —CO—;
12 represents an alkylene group or an aralkylene group, or a compound represented by the formula -Ar-(-Y-Ar-) _p-

Embedded image (In the formula, R ⁶ represents an alkylene group which may have an ether bond in a chain having 1 to 12 carbon atoms, and a is a number of 1 to 5 representing an average degree of oligomerization.) Oligomer or general formula

Embedded image (In the formula, a is a number of 1 to 5 representing the average degree of oligomerization.) m and n each represent an integer of 1 to 5. p shows the number of 0-10. A plurality of groups may be the same or different. Where p
Is 0, X represents -S-. )

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

(Wherein R ³ represents a hydrogen atom or a methyl group. R ⁴ represents an alkylene group, an aralkylene group, an alkylene ether group, an aralkylene ether group, an alkylenethioether each having 1 to 12 carbon atoms.) 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. A plurality of groups may be the same or different. )

C: a styrene-based unsaturated monomer represented by the general formula [III], which is copolymerizable with the compound represented by the general formula [I] and / or the general formula [II]; Or at least one compound selected from the group consisting of mercapto compounds represented by the general formula [VI] 1 to 99 parts by weight

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

Embedded image (Wherein, R ¹⁰ represents —CH ₂ — or —CH ₂ CH ₂ —. R ¹¹ represents a hydrocarbon residue or an alkyl ether residue having 2 to 15 carbon atoms. D is And an integer of 2 to 6. A plurality of groups may be the same or different.)

Embedded image

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

<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 number, and peels off from a mold when a polymer molded product as a lens is obtained by casting polymerization. Instead, the above-mentioned problems of the prior art have been solved.

[Specific description of the invention] [Chemical entity of the polymerized cured product]
Polymerizing and curing the composition comprising compounds A, B and C by subjecting them to an excitatory action consisting of the action of a radical generator on heat and / or active energy rays and / or ethylenically unsaturated bonds. It becomes.

Since some of the compounds A, B and C (styrene-based monomers) have an ethylenically unsaturated bond,
It is considered that the polymer is polymerized by polyaddition of an ethylenically unsaturated bond by the above-described excitation action. It is not always clear how the non-ethylenically unsaturated compound, mercapto compound C, coexisting in such a polymerization site behaves, but the thiol group of compound C is the ethylenically unsaturated compound of compound A and / or B. It is conceivable that the so-called Michael type addition to the unsaturated compound may bond to the compound A and / or B under the polymerization conditions.

The sulfur-containing (meth) acrylate represented by the above general formula (I) can be polymerized by itself, but the surface accuracy of the cured product is lowered by peeling off 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. Is copolymerized, the adhesion between the lens and the mold (for example, glass) is improved, and a cured product having excellent surface accuracy can be obtained.

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

Here, "comprising" a specific three component means that a monomer copolymerizable with the specific three component is specifically defined as, for example, this monomer unless the purpose of the present invention is impaired. It means that up to about 10 parts by weight per 100 parts by weight of the specific three components may be used in combination. Also,
Each of the components may be used in combination between and / or within the components.

<Bis (meth) acrylate: Compound A> The monomer which forms the basis of the resin for lenses according to the present invention is a sulfur-containing (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 is a} hydrogen atom or a methyl group. R ² : an alkylene group having 1 to 6, preferably 2 to 4 carbon atoms. Ar: each having 6 to 30 carbon atoms, preferably 6 to 1
5. An arylene group or an aralkylene group, or a halogen-substituted product thereof (wherein 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) -, - Ph '
(P) -CO-Ph (p ) -, - CH 2 -Ph "(C
_{l) 4 -CH 2 - (-} Ph '-: o-, m- or p- phenylene, -Ph' (p) -: phenylene, -Ph "
_{(Cl) 4 -: o-,} m- or p- tetrachloro-phenylene) X: -O- or -S-. However, when p is 0, X is-
S- is shown.

[0021] Y: X is an -S- or -SO ₂ when a -O- -, when X is -S- is -S -, - SO ₂ -
Or -CO-, or an alkylene group or an aralkylene group, each of which is 1 to 12, or a compound represented by the formula -Ar-(-Y-Ar-) p-

Embedded image (In the formula, R ⁶ represents an alkylene group which may have an ether bond in a chain having 1 to 12 carbon atoms, and a is a number of 1 to 5 representing an average degree of oligomerization.) Oligomer or general formula

Embedded image (In the formula, a is a number of 1 to 5 representing the average degree of oligomerization.)

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

As is clear from the above formula, the sulfur-containing (meth) acrylate represented by the 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. It has.

Specific examples of the (meth) acrylate [I] represented by the formula [I] include, for example, (a) p-bis (β-acryloyloxyethylthio) xylylene,
-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) diphenylsulfone, 4,4'-bis (β-methacryloyloxyethoxyethoxy) diphenylsulfone, 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) diphenylsulfone, 4,4'-bis (β-methacryloyloxyethylthio) diphenylketone, and (b) the above-mentioned formula [I]
Wherein X is -S-, the formula -Ar-(-Y-Ar
−) _P − is a general formula

[0025]

Embedded image

(Wherein, 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 1 which represents an average degree of oligomerization. Or an oligomer represented by the general formula:

[0027]

Embedded image

(Where a is a number from 1 to 5 representing the average degree of oligomerization).

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

[0030]

Embedded image

(Wherein, 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 except fluorine. , B represents 0 or an integer of 1 to 4.)

Specific examples of the monomer represented by the general formula [I '] include, for example, p-bis [β- (meth) acryloyloxyethylthio] xylylene, m-bis [β- (meth) acryloyl Oxyethylthio] xylylene, p-bis [β- (meth) acryloyloxyisopropylthio] xylylene, m-bis [β- (meth) acryloyloxyethylthio] ethylphenylene, p-
Bis [β- (meth) acryloyloxybutylthio] tetrachloroxylylene and the like, and more preferred 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)
(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 : a hydrogen atom or an alkyl or aralkyl group having 1 to 12 carbon atoms. Preferably, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms or a phenyl group. q: an integer of 1 to 3. A plurality of groups present in the same molecule may be the same or different.

Specific examples of the compound of the formula [II] include, for example, (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,
And di (meth) acryloyloxyethyl phenyl phosphate.

Among the monomers represented by the general formula [II], preferred are 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]

(Wherein, 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 and the like,
Even more preferred monomers are bis (meth) acryloyloxyethyl phosphate and tris (meth) acryloyloxyethyl phosphate.

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

It is clear that styrenic unsaturated monomers can be copolymerized with compounds A and / or B by radical mechanism via cleavage of their ethylenically unsaturated bonds,
It is not always clear how the mercapto compound “copolymerizes” with compounds A and / or B. However, as described above, the mercapto compound is understood to be bound to the optical resin according to the present invention by some mechanism.

The styrenic unsaturated monomer which is one group of the compound C is represented by the following formula [III].

[0045]

Embedded image

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

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

Another group of compounds C is a mercapto compound, that is, an organic compound having an --SH group is represented by the following formula [I
V], [V] or [VI].

[0049]

[0050]

(Wherein R ¹⁰ represents —CH ₂ — or —CH
₂ CH _2- . R ¹¹ has 2 to 15 carbon atoms each.
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]

Embedded image

[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. A plurality of groups may be the same or different. ]

[0054]

Embedded image

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

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

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 And isocyanurate and tris (3-thioglyconyloxypropyl) triisocyanurate.

(C) Specific examples of the compound represented by the general formula [VI] include, for example, benzenedimercaptan, xylylenedimercaptan, 4,4'-dimercaptodiphenylsulfide and the like.

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

<Monomer Composition> The composition to be "polymerized and cured" according to the present invention comprises Compounds A, B and C in the following proportions.

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

If the proportion of other monomers capable of “copolymerizing” with the sulfur (meth) acrylate or (meth) acrylate / phosphate of the compound C, ie, the compounds A and / or B, is too small, the cured resin may not be cured. When the ratio is excessively large, the heat resistance of the cured resin decreases. When two or more styrenic unsaturated monomers or mercapto compounds are used as the compound C, the total amount of these monomers is used as the above composition ratio. When the styrenic unsaturated monomer and the mercapto compound are used together, the composition ratio of both is 90 to 10 parts by weight of the former to 10 to 90 parts by weight, preferably 40 to 90 parts by weight of the former. The latter 60 to weight parts
10 parts by weight.

This monomer composition comprises compounds A, B and C. Here, `` comprising '' means that the resulting polymer cured product does not excessively impair the characteristics of the optical material of the present invention such as high refractive index and high impact resistance,
A small amount of the ethylenically unsaturated monomer copolymerizable with the compounds A and B, for example, up to about 10 parts by weight based on 100 parts by weight of the total of the compounds A + B + C, and a suitable auxiliary material,
Means that it may be included. Examples of such a monomer include lower alkyl methacrylate, divinylbenzene, and di (meth) acrylate belonging to the above-mentioned known art. Such auxiliary materials include antioxidants, UV absorbers, dyes and pigments, and the like.

<Polymerization Curing> The composition which may contain a mercapto compound which is not an ethylenically unsaturated compound is further reduced by the action of a radical generator on heat and / or active energy rays and / or ethylenically unsaturated bonds. Or multi-stage application to polymerize and cure to produce the optical material according to the invention.

Here, the term “heat” in the excitation action on the polymerization and curing of the compounds A, B and C includes not only the application of heat but also the combined use of a thermal polymerization initiator (detailed later). The "active energy ray" includes not only the simple application of ultraviolet rays, ionizing radiation and other energy rays but also the use of a photopolymerization initiator (described in detail below), and the "radical generator" It may overlap with the polymerization initiator, and in addition to the mere use of the polymerization initiator, includes a case where the polymerization initiator forms a so-called redox system in combination with a reducing agent when it comprises an oxidizing agent such as a peroxide. is there.

The polymerization curing step can be carried out by applying the above-mentioned excitation to the monomer composition. Specifically, for example, the polymerization can be carried out by a known radical polymerization in which an initiator generating free radicals is added. In order to improve the productivity, ultraviolet curing or a combination of ultraviolet curing and heat polymerization is used. Is desirable. For example, a composition obtained by adding a photopolymerization initiator and a thermal polymerization initiator to a composition is injected into a mold, cured by irradiation with ultraviolet rays to a degree sufficient to remove the mold, and then heated again in an oven after the mold is removed. Let it.

The photopolymerization initiator used at this time includes, for example, benzophenone, benzoin methyl ether,
Benzoin isopropyl ether, diethylthioxanthone, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like can be mentioned.

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

The amount of the photopolymerization initiator and the 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 is too small, the curing will be insufficient, and if it is too large, the cured resin will be easily yellowed and the polymerization control will be difficult.

As described above, in the present invention, the composition before polymerization and curing can be cured by adding an antioxidant, an ultraviolet absorber and the like.

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

The optical material made of such a polymerized and cured product can be used in the form of various optical elements. Representative optical elements include lenses (including Fresnel lenses, bar 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 may also be one whose surface is subjected to a surface treatment such as a hard coat or an antireflection coat. In addition, it is advantageous to make the molded product itself an optical element, taking advantage of the fact that the polymer cured product according to the present invention has good surface accuracy.However, once a lump is formed, it is processed. Needless to say, an optical element can be manufactured.

[0075]

The following examples and comparative examples are provided to further illustrate the present invention. "Department" in these examples
Means parts by weight. The physical properties of the resins in these examples were measured by the following test methods.

Appearance Visual observation. Refractive index It is a value measured at 25 ° C with an Atsube refractometer. Surface Accuracy When 10 cured products were produced, the resin whose cured product was peeled off from the glass mold during polymerization molding was visually evaluated as × 1,
Resins which did not peel off any of the sheets were marked with ○. Hardness Depends on pencil hardness.

Examples 1-10 and Comparative Examples 1-2 85 parts of p-bis (β-methacryloyloxyethylthio) xylylene, bis (methacryloyloxyethyl) =
0.003 part of phosphate, 15 parts of styrene, 0.05 part of benzophenone, and t-butylperoxy-2-
0.3 parts of ethyl hexanoate (trade name "Perbutyl O", manufactured by NOF CORPORATION) was mixed. Degas the resulting mixture,
40mm diameter composed of glass plate and silicone rubber,
Injected into a 2mm thick cavity, output 80W / cm ²
Irradiation was carried out from one side of the glass from a height of 40 cm once for 3 minutes each for a total of 6 times using a high pressure mercury lamp. After the obtained cured product is released from the mold, it is placed in an oven at 80 ° C for 1 hour, and then at 100 ° C
For 2 hours to obtain a polymer cured product.

These components were changed as shown in the remarks column of Table 1 to obtain a similar polymerized cured product. The measurement results of the physical properties of these polymer 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- Thiopionate) K: Tris [2- (β-thiopropionyloxy) ethyl] = triisocyanurate L: Benzophenone M: t-Butylperoxy-2-ethylhexanoate

[0081]

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

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI G02B 1/04 G02B 1/04 (56) References JP-A-4-202309 (JP, A) JP-A 4-371901 (JP) JP-A-4-300886 (JP, A) JP-A-5-320181 (JP, A) JP-A-61-225161 (JP, A) JP-A-62-195357 (JP, A) 57-113434 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 220/00-220/70 C08F 230/02-230/10

Claims (1)

(57) [Claims] 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 Embedded image A: 100 parts by weight of sulfur-containing (meth) acrylate represented by the following general formula [I] (wherein, R ¹ represents a hydrogen atom or a methyl group.
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 is, when X is -O- -S- or -SO ₂ - and
When X is _{-S- -S -, - SO 2 -} , or -CO
Represents an alkylene group or an aralkylene group having 1 to 12 carbon atoms ,
Formula -Ar - (- Y-Ar-) p - is the general formula ## STR2 ## (Wherein, R ⁶ represents an ether bond in a chain having 1 to 12 carbon atoms)
A represents an alkylene group which may have
It is a number from 1 to 5 representing the degree of merification. Oligomer represented by) or general formula 3], Wherein a is a number from 1 to 5 representing the average degree of oligomerization
is there. ) Is shown . m and n each represent an integer of 1 to 5. p shows the number of 0-10. A plurality of groups may be the same or different. Where p
Is 0, X represents -S-. B) 0.001 to 1 part by weight of a (meth) acrylate / phosphate represented by the following general formula [II]: (Wherein, R ³ represents a hydrogen atom or a methyl group.
⁴ is an alkylene group having 1 to 12 carbon atoms,
And a group selected from an aralkylene group, an alkylene ether group, an aralkylene ether group, an alkylenethioether group and an aralkylenethioether group. R ⁵ is a hydrogen atom or a carbon atoms an alkyl group or an aralkyl group having from 1 to 12. q shows the integer of 1-3. A plurality of groups may be the same or different. ) C: Formula (I) and (or) a compound represented by the general formula [II] and can be copolymerized, to styrene-based unsaturated monomer and the general formula represented by the general formula [III] [IV] no 1 to 99 parts by weight of at least one compound selected from the group consisting of mercapto compounds represented by the general formula [VI] (Wherein, R ⁹ represents a hydrogen atom or a methyl group, and X ¹ represents
Represents a halogen atom excluding nitrogen, and z represents an integer of 0 to 5
You. A plurality of groups may be the same or different. ) (Wherein, R ¹⁰ represents —CH ₂ — or —CH ₂ CH ₂ —
You. R ¹¹ is a hydrocarbon residue having 2 to 15 carbon atoms.
Or an alkyl ether residue. d is an integer of 2 to 6
Indicates a number. Multiple groups may be the same or different
No. ) Embedded image Wherein R ¹² and R ¹³ are the same or different
It represents an alkylene group having 1 to 3 carbon atoms. h and i are it
0 or 1 and j each represent 1 or 2. Multiple exists
Groups may be the same or different. )