WO2010073613A1 - Optical resin composition, optical lens, and eyeglass plastic lens - Google Patents

Abstract

Provided is an eyeglass plastic lens obtained by curing an optical resin composition wherein bending failure strain as evaluated by the "bending characteristics test method" is 6.5% or greater. This optical resin composition comprises a compound having two or more epithio groups; inorganic sulphur; and a compound having an aromatic skeleton and two or more mercapto groups.

Description

Optical resin composition, optical lens, and plastic lens for spectacles

The present invention relates to an optical resin composition, an optical lens, and a plastic lens for spectacles.
This application claims priority based on Japanese Patent Application No. 2008-328208 filed in Japan on December 24, 2008, the contents of which are incorporated herein by reference.

In recent years, rimless spectacles have been provided and used in which a plastic lens for spectacles is perforated and a frame is fixed to the hole with screws or the like. The frameless glasses are formed by setting a two-point frame on a frameless frame lens (a so-called two-point frame lens).

Whether or not a plastic lens for spectacles can be used as a frameless frame lens (two-point frame lens) is, for example, a conventional general lens, such as a lens strength evaluation method such as impact resistance or the hardness of the lens itself. This evaluation method could not be determined.
For this reason, the “oriori test” (two-point lens durability), in which the lens is actually glazed and drilled, set in a two-point frame, and evaluated in a form close to the final form sold by a retail store. Test and test method) are employed as evaluation methods (see, for example, Patent Document 1).

However, even if an evaluation is performed in the final form in this way, if the strength (durability) is obtained from the evaluation result, the lens cracks in the state that the user is using after processing at an actual retail store. Or, a clear standard could not be obtained whether lens breakage occurred.
Furthermore, since the evaluation apparatus and evaluation method in this final form are different for each spectacle lens manufacturer, there is no unified clear standard (for example, JIS) to prevent problems such as damage after processing. The only criterion is whether or not problems will occur for several years in the market after launch.

By the way, as a plastic lens for eyeglasses, allyl carbonate having a refractive index of about 1.5 has been mainly used in the past, but polythiourethane having a refractive index of about 1.60 to 1.70 is provided. It is suitably used as a two-point frame lens. This is because polythiourethane has high strength and can be processed in various ways, and therefore has sufficient resistance to processing for two-point frames. When the refractive index of the lens material is high, the edge portion of the lens can be particularly thinly formed, so that it is excellent in functionality and design, so that it is more preferable as a lens for a two-point frame. Become.
In recent years, episulfide resins having a refractive index of about 1.74 to 1.76 have been provided.

Japanese Unexamined Patent Publication No. 2008-90078

However, this episulfide resin has a lower strength than the above polythiourethane, and cannot be said to have sufficient resistance to processing for two-point frames and subsequent use.
Therefore, when a two-point frame is selected as a spectacle frame at a retail store or a user side, only a conventional lens having a refractive index of 1.70 or less has been used as a lens. It was not possible to select the most advanced lens having a refractive index of 1.74 or more.
That is, conventionally, a lens for a two-point frame has a refractive index of 1.70 or less, and the type of lens is selected based on the refractive index, and the most advanced lens having a refractive index of 1.74 or more. However, the current situation is that it cannot be supplied to users even if it has the strength required for two-point frames.

An object according to an aspect of the present invention is to clarify the criteria that can be used as a lens for a two-point frame, and thereby, for a state-of-the-art lens having a refractive index of 1.74 or more that has not been used in the past, An object of the present invention is to provide a plastic lens for spectacles for such a two-point frame by making it usable as a lens for a frame. Another object of the present invention is to provide an optical resin composition and an optical lens suitable for the plastic lens for spectacles.

One aspect of the optical resin composition illustrating the present invention includes (A) a compound having two or more epithio groups, (B) inorganic sulfur, (C) an aromatic ring skeleton, and two or more mercapto groups. An optical resin composition comprising:
When the total amount of the compound (A), the inorganic sulfur (B) and the compound (C) is 100% by weight, the compounding ratio of the compound (C) is 3 to 18% by weight. To do.

An aspect of the optical lens that exemplifies the present invention is obtained by curing the optical resin composition.

One aspect of the plastic lens for spectacles illustrating the present invention is a plastic lens for spectacles obtained by curing an optical resin composition, and has a bending fracture strain evaluated by the “bending characteristic test method” shown below. 6.5% or more, and the optical resin composition includes a compound having two or more epithio groups, inorganic sulfur, and a compound having an aromatic ring skeleton and two or more mercapto groups. It is an optical resin composition.
"Bending characteristic test method"
The optical resin composition is polymerized and cured into a flat plate shape, and cut out to prepare a test piece of 60 (mm) × 25 (mm) × 2.4 (mm). This test piece was set in a bending tester with a fulcrum distance of 38 mm, a support base radius of 2 mm, and an indenter radius of 5 mm, and in an atmosphere of a temperature of 23 ± 1 ° C. and humidity of 50 ± 5% RH, a test speed of 1.0 mm / A bending test is performed at min, and the bending strain (bending fracture strain) when the test piece breaks is measured.

As will be described later, the present inventor has confirmed that a good correlation can be obtained between the bending fracture strain and the result of the “tilting test” (two-point lens durability test and test method; Patent Document 1). did. In particular, based on the results of the “tilting test” of lenses that have been recognized as being usable as lenses for two-point frames in the market, the bending fracture strain corresponding to this criterion is 6.5% or more. I found something.

Therefore, a compound satisfying the criteria that can be used as a lens for a two-point frame in this way, and having two or more epithio groups, inorganic sulfur, an aromatic ring skeleton, and a compound having two or more mercapto groups, By using a novel optical resin composition containing as a thermosetting optical resin composition, it is possible to provide a two-point frame lens having a particularly high refractive index of 1.74 or more.

Therefore, according to the plastic lens for spectacles of this aspect, it has sufficient strength as a lens for a two-point frame, that is, resistance to processing and resistance to use, and furthermore, the edge portion of the lens can be formed thinly. Excellent functionality and design.

The plastic lens for spectacles of the present invention has sufficient strength as a lens for a two-point frame, that is, resistance to processing and use, and further, the edge portion of the lens can be formed thinly. Excellent in design and design.
Moreover, the optical resin composition and the optical lens of the present invention are suitable for the plastic lens for spectacles.

It is a side view for demonstrating the bending characteristic test method which concerns on this embodiment. It is a figure which shows the dimension data of the processing test piece used for a tension test and a tilt test. It is a figure for demonstrating the state of the processing test piece at the time of performing a tension test. It is a graph which shows the relationship between bending fracture strain and tilt test resistance.

Hereinafter, the present invention will be described in more detail.
The plastic lens for spectacles of this embodiment is obtained by polymerizing and curing a thermosetting optical resin composition. And in this embodiment, this thermosetting optical resin composition has a compound (A) having two or more epithio groups, an inorganic sulfur (B), an aromatic ring skeleton, and two or more mercapto groups. An optical resin composition comprising a compound (C). The optical resin composition and the optical lens obtained by curing the optical resin composition are also products of this embodiment.

"Compound (A) having two or more epithio groups"
Specifically, the compound (A) having two or more epithio groups is preferably a compound having two or more episulfide groups in the molecule. That is, the epithio group (—S—) is preferably (—S—) constituting the episulfide group. The compound having two or more episulfide groups in the molecule is preferably a compound having one or more partial structures represented by the following formula (1), and all known bifunctional or more episulfide compounds are all compounds. It becomes a target.

（式中、Ｒ_１は炭素数１～１０の炭化水素基、Ｒ_２、Ｒ_３、Ｒ_４はそれぞれ炭素数１～１０の炭化水素基または水素原子を示す。すなわち、Ｒ_１は炭素数１～１０の二価の炭化水素基を表し、具体的には、直鎖、分岐または環状の炭素数１～１０のアルキレン基、フェニレン、アルキル置換フェニレン及びナフタレン等の炭素数６～１０のアリーレン基、またはアルキレン基及びアリーレン基の組み合わせからなる炭素数７～１０のアラルキレン基が挙げられる。その中、Ｒ_１として炭素数１～１０のアルキレン基が好ましい。メチレンやエチレンであれば、より好ましい。メチレンであれば、更に好ましい。Ｒ_２、Ｒ_３、Ｒ_４はそれぞれ独立に水素原子、炭素数１～１０の一価の炭化水素基を表す。炭素数１～１０の一価の炭化水素基としては、直鎖、分岐または環状の炭素数１～１０のアルキル基、炭素数６～１０のアリール基、炭素数７～１０のアラルキル基が挙げられる。その中、Ｒ_２、Ｒ_３、Ｒ_４として、水素原子または炭素数１～１０のアルキレン基が好ましい。水素原子やメチル基であれば、より好ましい。水素原子であれば、更に好ましい。）

(Wherein R ₁ represents a hydrocarbon group having 1 to 10 carbon atoms, and R ₂ , R ₃ and R ₄ each represents a hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms. That is, R ₁ represents ₁ carbon atom. Represents a divalent hydrocarbon group of ˜10, specifically, a linear, branched or cyclic alkylene group of 1 to 10 carbon atoms, an arylene group of 6 to 10 carbon atoms such as phenylene, alkyl-substituted phenylene, and naphthalene. Or an aralkylene group having 7 to 10 carbon atoms, which is a combination of an alkylene group and an arylene group, of which an alkylene group having 1 to 10 carbon atoms is preferred as R ₁ , and methylene or ethylene is more preferred. R ₂ , R ₃ and R ₄ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a monovalent hydrocarbon having 1 to 10 carbon atoms. Examples of the elementary group include linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms, among which R ₂ , R ₃ R ₄ is preferably a hydrogen atom or an alkylene group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.)

In addition, the compound having two or more episulfide groups in the molecule is more preferably a compound having a structure represented by the following formula (2).

（式中、Ｒ_５～Ｒ_１０はそれぞれ炭素数１～１０の炭化水素基または水素原子を示す。Ｙは置換または未置換の直鎖、分岐または環状の炭素数１～１０の炭化水素基、置換または未置換の１，４－ジチアン基、アリーレン基、アラルキレン基を表す。ｍは０～２の整数を表し、ｎは０～４の整数を表す。）

(Wherein R ₅ to R ₁₀ each represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. Y represents a substituted or unsubstituted linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms, A substituted or unsubstituted 1,4-dithiane group, an arylene group or an aralkylene group, m represents an integer of 0 to 2, and n represents an integer of 0 to 4)

Here, R ₅ to R ₁₀ each have the same meaning as R ₂ to R _4, and particularly preferably a hydrogen atom. Y represents a substituted or unsubstituted linear, branched or cyclic divalent aliphatic hydrocarbon group having 1 to 10 hydrocarbons, a substituted or unsubstituted 1,4-dithian group, an arylene group or an aralkylene group. Among them, the divalent aliphatic hydrocarbon group having 1 to 10 hydrocarbons is preferably a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, particularly a linear alkylene group.
As the arylene group and the aralkylene group, the same groups as those described above for R ₁ can be exemplified. Further, Y may have a substituent, as long as it does not adversely affect the physical properties (for example, transparency, uniformity, refractive index, heat resistance, etc.) of the resin produced using this compound. Although it does not restrict | limit in particular, you may have a reactive group. In particular, it may be a trifunctional or higher functional compound having a structure represented by the formula (2), in particular, a 2,3-epithiopropylthio group as a substituent, but a bifunctional compound is preferred. Further, a compound where n = 0 is most preferable. In addition, these compounds may include polyether oligomers or polysulfide oligomers such as dimers, trimers, and tetramers of these compounds.

Specific examples of preferable compounds having two or more episulfide groups in the molecule include bis (2,3-epithiopropyl) sulfide, bis (2,3-epithiopropyl) disulfide, bis (2 , 3-epithiopropylthio) methane, 1,2-bis (2,3-epithiopropylthio) ethane, 1,2-bis (2,3-epithiopropylthio) propane, 1,3-bis ( 2,3-epithiopropylthio) propane, 1,3-bis (2,3-epithiopropylthio) -2-methylpropane, 1,4-bis (2,3-epithiopropylthio) butane, , 4-bis (2,3-epithiopropylthio) -2-methylbutane, 1,3-bis (2,3-epithiopropylthio) butane, 1,5-bis (2,3-epithiopropylthio) ) Bae 1,5-bis (2,3-epithiopropylthio) -2-methylpentane, 1,5-bis (2,3-epithiopropylthio) -3-thiapentane, 1,6-bis (2 , 3-epithiopropylthio) hexane, 1,6-bis (2,3-epithiopropylthio) -2-methylhexane, 3,8-bis (2,3-epithiopropylthio) -3,6 -Trithia octane, 1,2,3-tris (2,3-epithiopropylthio) propane, 2,2-bis (2,3-epithiopropylthio) -1,3-bis (2,3- Epithiopropylthiomethyl) propane, 2,2-bis (2,3-epithiopropylthiomethyl) -1- (2,3-epithiopropylthio) butane, 1,5-bis (2,3-epi Thiopropylthio) -2- (2,3-epithiopropipropyl Thiomethyl) -3-thiapentane, 1,5-bis (2,3-epithiopropylthio) -2,4-bis (2,3-epithiopropylthiomethyl) -3-thiapentane, 1- (2,3 -Epithiopropylthio) -2,2-bis (2,3-epithiopropylthiomethyl) -4-thiahexane, 1,5,6-tris (2,3-epithiopropylthio) -4- (2 , 3-epithiopropylthiomethyl) -3-thiahexane, 1,8-bis (2,3-epithiopropylthio) -4- (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -4,5-bis (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epi Thiopropylthio) -4,4-bis ( 2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -2,5-bis (2,3-epithiopropylthiomethyl)- 3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -2,4,5-tris (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,1 , 1-tris [[2- (2,3-epithiopropylthio) ethyl] thiomethyl] -2- (2,3-epithiopropylthio) ethane, 1,1,2,2-tetrakis [[2- (2,3-epithiopropylthio) ethyl] thiomethyl] ethane, 1,11-bis (2,3-epithiopropylthio) -4,8-bis (2,3-epithiopropylthiomethyl) -3 , 6,9-trithiaundecane, 1, 1-bis (2,3-epithiopropylthio) -4,7-bis (2,3-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3 A chain aliphatic 2,3-epithiopropylthio compound such as -epithiopropylthio) -5,7-bis (2,3-epithiopropylthiomethyl) -3,6,9-trithiaundecane, as well as,

1,3-bis (2,3-epithiopropylthio) cyclohexane, 1,4-bis (2,3-epithiopropylthio) cyclohexane, 1,3-bis (2,3-epithiopropylthiomethyl) Cyclohexane, 1,4-bis (2,3-epithiopropylthiomethyl) cyclohexane, 2,5-bis (2,3-epithiopropylthiomethyl) -1,4-dithiane, 2,5-bis [[ 2- (2,3-epithiopropylthio) ethyl] thiomethyl] -1,4-dithiane, 2,5-bis (2,3-epithiopropylthiomethyl) -2,5-dimethyl-1,4- Cycloaliphatic 2,3-epithiopropylthio compounds such as dithiane, and

1,2-bis (2,3-epithiopropylthio) benzene, 1,3-bis (2,3-epithiopropylthio) benzene, 1,4-bis (2,3-epithiopropylthio) benzene 1,2-bis (2,3-epithiopropylthiomethyl) benzene, 1,3-bis (2,3-epithiopropylthiomethyl) benzene, 1,4-bis (2,3-epithiopropyl) Thiomethyl) benzene, bis [4- (2,3-epithiopropylthio) phenyl] methane, 2,2-bis [4- (2,3-epithiopropylthio) phenyl] propane, bis [4- ( 2,3-epithiopropylthio) phenyl] sulfide, bis [4- (2,3-epithiopropylthio) phenyl] sulfone, 4,4′-bis (2,3-epithiopropylthio) biphenyl, etc. Aroma And the like 2,3-epithiopropylthio compounds.

Further, compounds obtained by replacing the epithiopropylthio group of the episulfide compound with an epithiopropyloxy group can also be mentioned. However, the preferred compound of the present embodiment is a compound having an epithiopropylthio group, and is not limited to the above exemplified compounds. These may be used alone or in combination of two or more.

Among these exemplified compounds, more preferable compounds include bis (2,3-epithiopropyl) sulfide, bis (2,3-epithiopropyl) disulfide, bis (2,3-epithiopropylthio) methane, , 2-bis (2,3-epithiopropylthio) ethane, 1,2,3-tris (2,3-epithiopropylthio) propane, 2,5-bis (2,3-epithiopropylthiomethyl) And at least one compound selected from the group consisting of 1,4-dithiane and bis [4- (2,3-epithiopropylthio) phenyl] sulfide. The most preferred compound is one of bis (2,3-epithiopropyl) sulfide and bis (2,3-epithiopropyl) disulfide or a mixture thereof.

"Inorganic sulfur (B)"
Inorganic sulfur (B) serves as a refractive index adjusting component, and its purity is preferably 98% or more. If the purity is less than 98%, the lens tends to be fogged due to impurities, but if it is 98% or more, the fogging is eliminated. Preferably it is 99.0% or more, More preferably, it is 99.5% or more, Most preferably, it is 99.9% or more. Among the sulfur impurities, there are oils, acidic components, moisture, ash components, arsenic, chlorides, sulfides, and metals. Therefore, such oil, acid content, moisture, and ash content are preferably 1% by weight or less in the inorganic sulfur (B). Oil, acid content, and ash content do not copolymerize with other monomers, and therefore remain in the lens after polymerization and curing, causing fogging. Moisture reacts with other monomers to form oligomers, causing fogging. Therefore, these are more preferably 0.1% by weight or less.
The sulfur purity, oil, acid content, water content, ash content, and arsenic are measured according to JIS K6222-1 standard, and chloride and sulfide are measured with a standard solution according to JIS K8088 standard. Apply the comparison. The main components of metals detected by atomic absorption analysis are copper, lead, iron, nickel and the like.

Moreover, as such inorganic sulfur (B), it is preferable to use fine powder finer than 10 mesh. In the case of grains larger than 10 mesh, it is difficult to completely dissolve the sulfur, so that it is difficult to produce a lens. More preferably, it is fine powder finer than 30 mesh, and most preferably fine powder finer than 60 mesh.

Regarding the production method of inorganic sulfur (B), sublimation purification method from natural sulfur ore, extraction by sulfur melting method buried underground, recovery method using hydrogen sulfide obtained from petroleum and natural gas desulfurization process, etc. as raw materials Etc. The inorganic sulfur (B) used in the present embodiment may be any method as long as a purity of 98% or more is ensured.
Generally available inorganic sulfur includes finely divided sulfur, colloidal sulfur, precipitated sulfur, crystalline sulfur, sublimated sulfur and the like depending on the shape and purification method. In this embodiment, any sulfur may be used as long as a purity of 98% or more is ensured, but fine sulfur with fine particles is preferable.

"Compound (C) having an aromatic ring skeleton and two or more mercapto groups"
The compound (C) having an aromatic ring skeleton and two or more mercapto groups serves as a compound strength improving component, and a compound represented by the following formula (3) is particularly preferably used.

（ただし、ｎ、ｍ、ｌは０又は１以上の整数である。）

(However, n, m, and l are 0 or an integer of 1 or more.)

Here, n, m, and l are preferably 0 or 1, and more preferably 0. That is, most preferred is xylylene thiol in which n, m, and l in Formula (3) are all 0. In addition, as xylylene dithiol, any of o-xylylene dithiol, m-xylylene dithiol, and p-xylylene dithiol may be sufficient.
In addition, even when n, m, and l in Formula (3) are all 1 or more, the functional group having a thiol group (mercapto group) is o- with respect to the benzene ring (aromatic ring). , M-, and p-.
Furthermore, the functional group which has a thiol group (mercapto group) may have three or more with respect to a benzene ring (aromatic ring) instead of two. That is, this compound (C) may have three or more mercapto groups.

In such a compound (C), if the molecular chain is too long, the glass transition temperature (Tg) decreases, and if there are too many benzene rings, the Abbe number decreases. Is also preferably 0 or 1.

In an optical resin composition comprising such a compound (A) having two or more epithio groups, inorganic sulfur (B), and a compound (C) having an aromatic ring skeleton and two or more mercapto groups Is preferably in the following range.
When the total amount of the compound (A), the inorganic sulfur (B) and the compound (C) is 100% by weight, the refractive index is 1. for the blending ratio of the inorganic sulfur (B) as the refractive index adjusting component. If it becomes 74, the addition amount is not particularly limited, but it is preferably 5 to 30% by weight, more preferably 10 to 17% by weight. If the amount of addition (formulation) of inorganic sulfur (B) increases (for example, more than 30% by weight), problems such as increased yellowing after heating, decreased light resistance, and increased appearance defects such as cloudiness may occur. Because there is. Moreover, it is because the refractive index of the plastic lens obtained will be less than 1.74, for example, when there are too few compounding quantities (for example, less than 5 weight%).

Further, the compound (C) having an aromatic ring skeleton and two or more mercapto groups is a compound strength improving component, so it is desirable to add as much as possible. However, if added too much, the Abbe number decreases due to the effect of the aromatic ring, and the heat resistance (Tg) also decreases. Therefore, the content is preferably 3 to 18% by weight, and more preferably 5 to 10% by weight.
In addition, about the compound (A) which has two or more epithio groups, the preferable compounding ratio of the said inorganic sulfur (B) and the compound (C) which has the said aromatic ring skeleton and two or more mercapto groups The compounding ratio after subtracting the preferable compounding ratio, that is, (A) compounding ratio = 100 wt%-((B) compounding ratio + (C) compounding ratio)
Is a preferable blending ratio.

"Additive"
However, in addition to the compound (A), the inorganic sulfur (B), and the compound (C), various additions are made for the optical resin composition to be the thermosetting optical resin composition according to the present embodiment. An agent is blended.
For example, in order to reduce yellowing caused by the inorganic sulfur (B), the compound (D) having one or more disulfide bonds, which is not the compound (A) or the compound (C), is effectively blended. The compound (D) is preferably added in an amount of 0.3 to 20 parts by weight when the total amount of the compound (A), inorganic sulfur (B) and compound (C) is 100 parts by weight. . However, since the compound (D) is not a component that crosslinks with other monomers, the glass transition temperature (Tg) decreases when added in a large amount, and further, the Abbe number decreases when a compound containing an aromatic ring is selected. Therefore, it is more preferable to use 0.5 to 5 parts by weight.

Moreover, it turned out that what has a specific structure is preferable among this compound (D) when the high refractive index of the plastic lens obtained, low yellow, and handling of the compound (D) are considered.
That is, the compound (D) preferably has an aromatic ring in order to maintain the high refractive index of the optical material, and the molecular weight thereof is preferably less than 300 in order to realize a low yellow color of the optical material. From the viewpoint of being easy to do, those having a molecular weight of 150 or more are preferred as those that are liquid or solid and have a weak odor.

Specific examples of such a compound (D) include dimethyl disulfide, diethyl disulfide, di n-propyl disulfide, di n-butyl disulfide, di n-hexyl disulfide, di n-octyl disulfide, di n-decyl disulfide, di n-dodecyl disulfide, di-propyl disulfide, di-t-butyl disulfide, diallyl disulfide, bis (2-hydroxyethyl) disulfide, bis (3-carboxypropyl) disulfide, dicyclohexyl disulfide, diphenyl disulfide, di-p-toluyl disulfide, Dichlorodiphenyl disulfide, bis (2,4,5-trichlorodiphenyl) disulfide, dinaphthyl disulfide, bis (6-hydroxy-2-naphthyl) disulfide, difurfuryl Sulfide, dipyridyl disulfide, dithio dimorpholine, tetra n- butyl disulfide and the like. These compounds may be used alone or in combination of two or more. Among them, preferred examples include diphenyl disulfide, di p-toluyl disulfide, dichlorodiphenyl disulfide, dinaphthyl disulfide, difurfuryl disulfide, dipyridyl disulfide and the like. Moreover, as a most preferable thing, diphenyl disulfide can be mentioned.

In addition, with respect to the optical resin composition to be the thermosetting optical resin composition according to the present embodiment, as other additives, conventionally known general additives such as ultraviolet absorbers and pre-reaction catalysts Various additives such as a reaction rate adjusting agent and a curing catalyst are appropriately mixed.

Such an optical resin composition can be polymerized and cured by the following method to form a plastic lens for spectacles. In this method, when the compound (A) having two or more epithio groups is polymerized to obtain a resin, among the compounds constituting the resin, compounds other than the compound (A), for example, an aromatic ring skeleton and two compounds A curing catalyst is dissolved or dispersed in advance in the above compound (C) having a mercapto group, and other resin additives, in particular, an ultraviolet absorber is dissolved in advance in the compound (A), for example, and finally cured. A method of mixing a solution containing a catalyst and a solution containing the compound (A), or a resin additive other than a curing catalyst is dissolved in the compound (A) or the compound (C) in advance, and finally And a method of mixing a curing catalyst.

By such a method, it is possible to minimize the time during which the compound (A) and the curing catalyst are in contact with each other, and a large exotherm is generated due to the polymerization of the compound (A) in a preparation stage with a large charge amount. This makes it possible to prepare without having to do so. Therefore, it is possible to prevent the danger that the prepared liquid will cause a runaway reaction, and also to suppress the occurrence of optical distortion of the resin resulting from an increase in the viscosity of the prepared liquid and a decrease in yield. Is possible.

However, the plastic lens for spectacles of the present embodiment is required to have a bending fracture strain of 6.5% or more evaluated by the following method as its physical characteristics. This method is the following “bending property test method” based on “plastic-bending property determination method” of “JIS K 7171”.
"Bending characteristic test method"
The thermosetting optical resin composition is polymerized and cured into a flat plate shape, and a test piece of 60 (mm) × 25 (mm) × 2.4 (mm) is produced by cutting. This test piece was set in a bending tester with a fulcrum distance of 38 mm, a support base radius of 2 mm, and an indenter radius of 5 mm, and in an atmosphere of a temperature of 23 ± 1 ° C. and humidity of 50 ± 5% RH, a test speed of 1.0 mm / A bending test is performed at min, and the bending strain (bending fracture strain) when the test piece breaks is measured.

Here, this “bending characteristic test method” is the same as the principle of the method defined in “JIS-7171” “Plastics-Determination of bending characteristics”. Apply a force at a constant speed to bend until the specimen breaks. And the force added to the test piece at that time is measured. However, in this “bending property test method”, a test piece with a size not recommended (not specified) in “JIS K 7171” is used, and the distance between fulcrums on the support base is changed accordingly. This is different from the “JIS” method.

That is, in the “bending characteristic test method” in the present embodiment, first, five sheets of the thermosetting optical resin composition obtained by polymerization and curing in a flat plate shape are produced, and the length is 60 (mm) by cutting. Five test pieces of width: 25 (mm) × thickness: 2.4 (mm) are prepared.
Next, as shown in FIG. 1, this test piece 1 is set in an Instron 5582 type testing machine. Specifically, as the pair of support bases 2 and 2, those having a radius of 2 mm at the corner of the support portion 2 a that is a place for supporting the test piece 1 are used, and the distance between these support points (between the support portions 2 a and 2 a The distance is set to 38 mm, and the test piece 1 is placed on the support bases 2 and 2 (support portions 2a and 2a). Further, as the indenter 3, one having a tip 3a radius of 5 mm is used.
Then, a bending test is performed at a test speed of 1.0 mm / min in an atmosphere with a temperature of 23 ± 1 ° C. and a humidity of 50 ± 5% RH, and the bending strain (bending fracture strain) when the specimen 1 breaks is measured. To do. Moreover, such a measurement is performed about all the five test pieces, and let the average value of five test pieces be a measured value.
At the same time as the measurement of the bending fracture strain, the bending stress and the flexural modulus were also measured for reference.

For reference, a tensile test of the thermosetting optical resin composition comprising the optical resin composition according to the present embodiment is performed according to “JIS K 7113” “Plastic tensile test method”. It carried out as follows.
Five sheets of the above-mentioned thermosetting optical resin composition obtained by polymerization and curing in a flat plate shape were produced, and processed specimens 4 having the dimension data shown in FIG. It was processed into.

Then, the processed test piece 4 was further sandwiched between a pair of jigs 5 and 5 arranged vertically as shown in FIG. That is, by inserting the pin 5a of the jig 5 shown in FIG. 3 into the pair of holes 4a and 4a of the machining test piece 4 shown in FIG. Held.
Thereafter, the pair of upper and lower jigs 5 and 5 are sandwiched and fixed by an Instron 5582 type 100 kN capacity chuck, and the test speed is 1.0 mm / mm in an atmosphere of temperature 23 ± 1 ° C. and humidity 50 ± 5% RH. A tensile test was performed at min, and tensile strength (maximum load) [N] and displacement at the time of tensile failure [mm] were measured. Moreover, such a measurement was performed about all the five test pieces, and the average value of five test pieces was made into the measured value.

Further, the present inventor has confirmed that a good correlation can be obtained between the bending fracture strain and the result of the “tilting test” (two-point lens durability test and test method). The two-point durability test method (aori test) will be described below.

"Two-point durability test method (Aori test)"
Ten S-0.00 lenses having a thickness of 2.0 mm are manufactured using two spherical masters having a radius of curvature of 120 mm from the thermosetting optical resin composition. These lenses are tumbled and punched using the same apparatus with the same dimensional data as the tensile test piece (processed test piece 4) shown in FIG. 2 to obtain a two-point durability test lens sample.

In addition, for each sample after processing, carefully observe the hole state after drilling with a magnifying glass, and confirm that all samples do not have defects that affect the tilt test results, such as fine cracks and scratches. Further, a polycarbonate sleeve is fitted from both sides of each hole of the two lens samples so that the screw and the lens come into contact with each other and no cracks or the like are generated when the lens sample is set on the frame.
The two lenses are screwed and set to a Yohki frame having the shape described in Japanese Patent Application Laid-Open No. 2008-90078 (Patent Document 1) using a torque screwdriver under a uniform condition of 0.14 Nm.

Subsequently, the frame on which the lens is set is set in an evaluation apparatus (see JIS B7285) also described in Japanese Patent Laid-Open No. 2008-90078 (patent document 1), the stroke is 66 mm, and the frame opening degree is in the range of +15 to +40 mm. Adjust so that the load cell load when the frame is fully open is in the range of 86 to 88 gf.
Thereafter, the opening / closing motion is repeated at a speed of 120 rpm (120 reciprocations per minute), and the number of times until the lens is cracked or broken is defined as two-point resistance (tilting test resistance).

At this time, it is checked every 1000 times whether the generation of fine cracks due to opening and closing movements and the load cell load when the frame is fully open have changed, and if the load load changes, the load applied to the lens by adjusting the frame opening degree Was made constant. In addition, tightening was performed with the torque driver every 5000 times so that the screw did not loosen. This test was repeated 5 times to obtain an average value.

Further, the refractive index of the plastic lens for spectacles according to the present embodiment was measured by the “refractive index measuring method” shown below.
"Refractive index measurement method"
The refractive index at the e-line of the polymerized cured product of the thermosetting optical resin composition was measured with KPR-20 manufactured by Kalnew.

Moreover, the plastic lens for spectacles was produced as follows with the thermosetting optical resin composition which concerns on this embodiment mentioned above.
[Example]
Bis (β-epithiopropyl) sulfide “Mitsubishi Gas Chemical Co., Ltd .: IU-11A” as compound (A) having two or more epithio groups is added to 750 parts by weight of sulfur powder as inorganic sulfur (B) “purity” 150 parts by weight of “a reagent of 98% or more” and 10 parts by weight of 2- (2-hydroxy-5-t-octylphenyl) benzotriazole “Sipro Kasei Co., Ltd .: Seesorb 709” as an ultraviolet absorber were added, Stir until dissolved at ° C. Subsequently, 5 parts by weight of 2-mercapto-1-methylimidazole “reagent” was added as a pre-reaction catalyst, reacted at 60 ° C. for 60 minutes, and then cooled to 20 ° C. At this time, no reprecipitation of sulfur was observed in the reaction product, and the 20 ° C. refractive index nD of the reaction solution after cooling was 1.6640.

Next, 70 parts by weight of xylylene thiol as a compound (C) having an aromatic ring skeleton and two or more mercapto groups, 2 parts by weight of dibutyltin dichloride as a reaction rate adjusting agent, and triethylbenzylammonium as a curing catalyst Chloride “reagent” (0.3 parts by weight) was mixed and dissolved. Next, this mixture was added to the pre-reacted material, and vacuum deaeration was performed under a reduced pressure of 20 ° C. and 20 torr until the 20 ° C. refractive index nD of the mixture became 1.6640.
After defoaming, the solution was poured into a predetermined flat plate and S-0.00 lens mold while being filtered with a PTFE 1.0 μm filter. After the injection, it was cured in a pattern of 20 hours at 20 ° C., then 10 hours at 30 ° C., 10 hours to 100 ° C., and 5 hours at 100 ° C. After curing, the mother mold was released, and the obtained lens was washed, and then annealed at 105 ° C. for 1 hour to obtain an evaluation lens.

The above-mentioned “two-point durability test (tilting test)” and “refractive index measurement” were performed on the obtained evaluation lens, and the tilting test resistance and the refractive index (ne) according to the number of occurrences of cracks were measured. The obtained results are shown in Table 1. Also, using a test piece obtained by polymerizing and curing the same thermosetting optical resin composition by the same polymerization curing method, based on the above “bending property test method”, “bending fracture strain”, “bending stress” ”And“ flexural modulus ”were also measured. Furthermore, “tensile strength” and “displacement at the time of tensile failure” were also measured based on the above “tensile test method”. The obtained results are also shown in Table 1.

Next, for comparison, a plastic lens for spectacles was produced as follows using a thermosetting optical resin composition (Comparative Examples 1 to 3) different from the present embodiment.
[Comparative Example 1 (standard)]
Bis (β-epithiopropyl) sulfide “Mitsubishi Gas Chemical Co., Ltd .: IU-10A” as compound (A) having two or more epithio groups is added to 477 parts by weight of 2- (2-hydroxy-) as an ultraviolet absorber. 5.4 parts by weight of 5-methylphenyl) -2H-benzotriazole “Cipro Kasei Co., Ltd .: Seesorb 701”, 0.3 parts by weight of catechol as a stabilizer, sulfur powder as inorganic sulfur (B) “purity of 98% or more 3 parts by weight of the reagent was added and stirred well until dissolved, and the liquid temperature was cooled to 5 ° C.

Next, as a compound having two or more mercapto groups, 37.2 parts by weight of bis (2-mercaptoethyl) sulfide “Mitsubishi Gas Chemical Co., Ltd .: IU-10B” and pentaerythritol tetrakis (3-mercaptopropionate) To the mixture of 39.6 parts by weight, 0.45 parts by weight of tetrabutylphosphonium bromide and 0.06 parts by weight of dibutyltin dichloride were added as a curing catalyst, and dissolved by stirring. Subsequently, this mixture was added to the above-mentioned mixture cooled to 5 ° C. with stirring, and further cooled to 5 ° C. with stirring for 15 minutes after the completion of the addition.

Next, 0.06 part by weight of an acid phosphate ester “Zerek UN manufactured by stepan” was added as a mold release agent to 43.2 parts by weight of m-xylylene diisocyanate as a compound having two or more isocyanate groups, and the pressure was reduced to 5 torr. The mixture was stirred for 30 minutes and then added to the mixture cooled to 5 ° C. in 5 portions so that the liquid temperature did not exceed 13 ° C. After completion of the addition, the mixture was stirred and degassed for 1 hour under a reduced pressure of 5 torr while being cooled to 5 ° C. After defoaming, the solution was filtered through a PTFE 1.0 μm filter and poured into a predetermined flat plate and S-0.00 lens mold. did. After the injection, it was cured in a pattern of 30 ° C. for 10 hours, 100 ° C. for 10 hours, and 100 ° C. for 1 hour. After completion of curing, the mother mold was released, and the obtained lens was washed and then annealed at 120 ° C. for 1 hour to obtain an evaluation lens.
The obtained lens was measured and evaluated in the same manner as in Example 1. Moreover, it measured similarly to the said Example 1 using the test piece obtained by carrying out polymerization hardening of the same thermosetting optical resin composition by the same polymerization hardening method. The obtained results are shown in Table 1.

[Comparative Example 2]
Bis (β-epithiopropyl) sulfide “Mitsubishi Gas Chemical Co., Ltd .: IU-11A” as compound (A) having two or more epithio groups is added to 750 parts by weight of sulfur powder as inorganic sulfur (B) “purity” 150 parts by weight of “a reagent of 98% or more” and 10 parts by weight of 2- (2-hydroxy-5-t-octylphenyl) benzotriazole “Sipro Kasei Co., Ltd .: Seesorb 709” as an ultraviolet absorber were added, Stir until dissolved at ° C. Subsequently, 5 parts by weight of 2-mercapto-1-methylimidazole “reagent” was added as a pre-reaction catalyst, reacted at 60 ° C. for 60 minutes, and then cooled to 20 ° C. At this time, no reprecipitation of sulfur was observed in the reaction product, and the 20 ° C. refractive index nD of the reaction solution after cooling was 1.6641.

Next, 70 parts by weight of bis (2-mercaptoethyl) sulfide “Mitsubishi Gas Co., Ltd .: IU-11B” as a compound having two or more mercapto groups, 2 parts by weight of dibutyltin dichloride as a reaction rate adjusting agent, Triethylbenzylammonium chloride “reagent” (0.3 parts by weight) as a curing catalyst was mixed and dissolved. This mixed and dissolved product was added to the pre-reacted material and vacuum deaerated under a reduced pressure of 20 ° C. and 20 torr until the 20 ° C. refractive index nD of the mixture became 1.6641.
After defoaming, the solution was poured into a predetermined flat plate and S-0.00 lens mold while being filtered with a PTFE 1.0 μm filter. After the injection, it was cured in a pattern of 20 hours at 20 ° C., then 10 hours at 30 ° C., 10 hours to 100 ° C., and 5 hours at 100 ° C. After curing, the mother mold was released, and the obtained lens was washed, and then annealed at 105 ° C. for 1 hour to obtain an evaluation lens.
The obtained lens was measured and evaluated in the same manner as in Example 1. Moreover, it measured similarly to the said Example 1 using the test piece obtained by carrying out polymerization hardening of the same thermosetting optical resin composition by the same polymerization hardening method. The obtained results are shown in Table 1.

[Comparative Example 3]
As an isocyanate compound having two or more isocyanate groups, 506 parts by weight of norbornane diisocyanate “Mitsui Chemical Co., Ltd .: MR-8A” and 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole as an ultraviolet absorber 15 parts by weight of “Sipro Kasei Co., Ltd .: Seesorb 701”, 0.9 parts by weight of dibutyltin dichloride as a curing catalyst, and 0.6 parts by weight of acidic phosphate ester “Zelec UN from stepan” as a release agent The mixture was added and dissolved by stirring for 1 h under a reduced pressure of 5 torr.

Next, this mixed solution was cooled to 10 ° C., and 239 parts by weight of pentaerythritol tetrakis (3-mercaptopropionate) “Mitsui Chemical Co., Ltd .: MR-8B1” as a compound having two or more mercapto groups, Mercaptomethyl-3,6-dithia-1,8-octanedithiol “Mitsui Chemicals Co., Ltd .: MR-8B2” (255 parts by weight) was added, and the mixture was stirred and degassed for 1 hour under reduced pressure of 5 torr while cooling to 10 ° C. It was.
After defoaming, the solution was poured into a predetermined flat plate and S-0.00 lens mold while being filtered with a PTFE 1.0 μm filter. After the injection, the temperature was gradually raised from 10 ° C. to 120 ° C. over 15 hours, and then cured at 120 ° C. for 3 hours in a pattern. After completion of curing, the mother mold was released, and the obtained lens was washed and then annealed at 130 ° C. for 1 hour to obtain an evaluation lens.
The obtained lens was measured and evaluated in the same manner as in Example 1. Moreover, it measured similarly to the said Example 1 using the test piece obtained by carrying out polymerization hardening of the same thermosetting optical resin composition by the same polymerization hardening method. The obtained results are shown in Table 1.

In the above Examples and Comparative Examples 1 to 3, especially Comparative Example 1 has been used as a two-point lens conventionally, and there is no problem in the market and it has been recognized that it can be used. . Therefore, the thermosetting optical resin composition of Comparative Example 1 was used as a criterion for determining that it can be used as a two-point lens in this embodiment. That is, if the result of the “Ari test resistance” in Comparative Example 1 is equal to or higher, it is determined that the thermosetting optical resin composition can basically be used as a two-point lens.

In addition, as shown in Table 1, with respect to the examples and comparative examples 1 to 3, in particular, “tilting test resistance”, “bending stress”, “bending elastic modulus”, “bending fracture strain”, “tensile strength” Then, the relationship between each characteristic value of “displacement at the time of tensile fracture” was examined, and the presence or absence of correlation was determined. As a result, there was a correlation between the “tilting test resistance” and “bending stress”, “flexural modulus”, “bending fracture strain”, “tensile strength”, and “displacement at tensile fracture”. However, there was a high correlation between “tilting test resistance” and “bending fracture strain”. FIG. 4 shows the relationship between the “bending fracture strain” and the “tilting test resistance”.

As shown in FIG. 4, “bending fracture strain” (%) and “tilting test resistance” (number of occurrence of cracks) have a high correlation approximated by the expression “y = 4766x-11536”. I understood.
Accordingly, as described above, the “tilting test resistance” (number of occurrence of cracks) of Comparative Example 1, which is a criterion for determining that the lens can be used as a two-point lens, is 19600 times, and corresponds to the “tilting test resistance”. Since the “bending fracture strain” on the formula “y = 4766x−11536” is 6.5%, in this embodiment, if the “bending fracture strain” is 6.5% or more, it is for a two-point frame. Judgment is made that the lens can be used as a lens.

In particular, the product of the example uses the novel optical resin composition as the thermosetting optical resin composition as described above, and thereby the bending fracture strain becomes 7.8%, and the refractive index is 1 as well. It has a high refractive index of .74. Therefore, the plastic lens for eyeglasses of this embodiment represented by such an example product has sufficient strength as a lens for a two-point frame, that is, resistance to processing and use, and has a high refractive index. By having it, the edge portion of the lens can be formed thin, so that it is excellent in functionality and design.

In addition, since the bending fracture strain is used as a criterion in this way, the time required for measurement of this bending fracture strain is about one day, and the conventional “tilting test” takes a long time of about one week. Compared with what is required, the time required for determination can be remarkably shortened. Therefore, in the novel optical resin composition described above, a two-point frame can be used for trial manufacture and production of lenses having excellent characteristics corresponding to needs by changing the compounding ratio, additive types, polymerization conditions, and the like. It can be determined in a short time whether or not it can be used as a lens for use, thereby enabling efficient product development. Furthermore, since the plastic lens for spectacles of the present embodiment can be supplied to the market based on the judgment standard corresponding to the “tilting test” in this way, it is a good lens with no risk of lens cracking or lens breakage as a two-point frame lens. Can be supplied quickly and safely without waiting for a long-term market decision.

In Comparative Example 2, the bending fracture strain is 4.9% and does not satisfy the standard that can be used as a two-point frame lens. It was determined to be inappropriate.
Moreover, the thing of the comparative example 3 has been used as a two-point lens conventionally, and there is no problem in the market and it has been recognized that it can be used. And also in this comparative example 3, bending fracture strain is 6.5% or more, and it was confirmed that the recognition in the market in the past corresponds with the judgment by the standard in the present embodiment.

Further, in the plastic lens for eyeglasses of this embodiment, after being processed into the lens, at least one primer layer for imparting impact strength may be provided on one side or both sides thereof. . Further, a hard coat layer and an antireflection layer may be sequentially laminated on the surface. In that case, the hard coat layer preferably contains composite oxide particles mainly composed of titanium oxide and an organosilicon compound as main components. The antireflection layer is preferably composed of a multilayer inorganic oxide layer.
In addition to the primer layer, the hard coat layer, and the antireflection layer, a conventionally known top coat layer such as a top coat layer for preventing fogging, a top coat layer for preventing dirt, and a top coat layer for preventing static electricity is used. You may have.

The optical resin composition and the optical lens of the present invention are applied to a two-point frame lens requiring sufficient strength, and also applied to a two-point frame lens requiring functionality and design.

DESCRIPTION OF SYMBOLS 1 Test piece 2 Support stand 3 Indenter 4 Processing test piece 5 Hole

Claims (17)

In an optical resin composition comprising (A) a compound having two or more epithio groups, (B) inorganic sulfur, and (C) a compound having an aromatic ring skeleton and two or more mercapto groups,
When the total amount of the compound (A), inorganic sulfur (B) and the compound (C) is 100% by weight, the compounding ratio of the compound (C) is 3 to 18% by weight. Optical resin composition. The optical resin composition according to claim 1, wherein the compounding ratio of the inorganic sulfur (B) is 5 to 30% by weight. The optical resin composition according to claim 1 or 2, wherein the compound (C) is represented by the following formula (1).

(However, n, m, and l are 0 or an integer of 1 or more.) The optical resin composition according to claim 3, wherein the compound (C) is xylylene thiol in which n, m, and l in the formula (1) are all 0. An optical lens obtained by curing the optical resin composition according to any one of claims 1 to 4. 6. The optical lens according to claim 5, wherein the bending fracture strain evaluated by the following "bending characteristic test method" is 6.5% or more.
"Bending characteristic test method"
The optical resin composition is polymerized and cured into a flat plate shape, and cut out to produce a test piece of 60 (mm) × 25 (mm) × 2.4 (mm); Set in a bending tester with a radius of 2 mm and an indenter radius of 5 mm, and perform a bending test at a test speed of 1.0 mm / min in an atmosphere of a temperature of 23 ± 1 ° C. and a humidity of 50 ± 5% RH. Measure the bending strain at the time (bending fracture strain). The optical lens according to claim 5 or 6, wherein at least one primer layer for imparting impact strength is provided on one side or both sides of the optical lens. The optical lens according to any one of claims 5 to 7, wherein a hard coat layer and an antireflection layer are sequentially laminated on the surface of the optical lens. The optical lens according to claim 8, wherein the hard coat layer contains composite oxide particles containing titanium oxide as a main component and an organosilicon compound as main components. The optical lens according to claim 8 or 9, wherein the antireflection layer comprises a multilayer inorganic oxide layer. A plastic lens for spectacles obtained by curing an optical resin composition,
The bending fracture strain evaluated by the “bending property test method” shown below is 6.5% or more, and the optical resin composition includes a compound having two or more epithio groups, inorganic sulfur, and aroma. A plastic lens for spectacles, which is an optical resin composition comprising a compound having a ring skeleton and two or more mercapto groups.
"Bending characteristic test method"
The optical resin composition is polymerized and cured into a flat plate shape, and cut out to produce a test piece of 60 (mm) × 25 (mm) × 2.4 (mm); Set in a bending tester with a radius of 2 mm and an indenter radius of 5 mm, and perform a bending test at a test speed of 1.0 mm / min in an atmosphere of a temperature of 23 ± 1 ° C. and a humidity of 50 ± 5% RH. Measure the bending strain at the time (bending fracture strain). The plastic lens for spectacles according to claim 11, wherein the compound having an aromatic ring skeleton and two or more mercapto groups is represented by the following formula (2).

(However, n, m, and l are 0 or an integer of 1 or more.) 13. The glasses according to claim 12, wherein the compound having an aromatic ring skeleton and two or more mercapto groups is xylylene dithiol in which n, m, and l in the formula (2) are all 0. Plastic lens. The plastic lens for spectacles according to any one of claims 11 to 13, wherein at least one primer layer for imparting impact strength is provided on one side or both sides of the plastic lens for spectacles. 15. The plastic lens for spectacles according to claim 11, wherein a hard coat layer and an antireflection layer are sequentially laminated on the surface of the plastic lens for spectacles. 16. The plastic lens for spectacles according to claim 15, wherein the hard coat layer contains composite oxide particles mainly composed of titanium oxide and an organosilicon compound as main components. The plastic lens for spectacles according to claim 15 or 16, wherein the antireflection layer comprises a multilayer inorganic oxide layer.

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