JPH1120036A - Sulfur-bearing urethane resin lens and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce and disappear the offensive smell and malodor peculiar to sulfur atom-containing substance at working such as cutting, polishing or the like by a method wherein the specified mixing ratio of a specified perfume composition is mixed with a monomer mixture. SOLUTION: In a high refractive index sulfur-bearing urethane resin lens, which is obtained by cast-polymerizing a monomer mixture consisting of a two or mor function-containing polyisocyanate compound such as hexamethylene diisocyanate or the like and a two or more function-containing polythiol compound and which has the refractive index of 1.55 or more, 40 wt.% or more of β-damaskon 1-(2,6,6-trimethyl-1-cyclohexenil-2-butene-ion} or the like as a perfume composition is included. The usage of the perfume composition depends on the kinds of the compound and of the surfur-bearing urethane resin lens to be used and is normally 0.005-0.5 wt.% of the whole monomer mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-refractive-index sulfur-containing urethane resin lens used for glasses, optical materials and the like. More specifically, a refractive index of 1.5 obtained by cast polymerization of a monomer mixture comprising a bifunctional or higher polyisocyanate compound and a bifunctional or higher polythiol compound.
5 or more high refractive index sulfur-containing urethane resin lens,
The present invention relates to a plastic lens that hardly emits an off-odor and an offensive odor peculiar to a sulfur atom-containing substance at the time of cutting and polishing the molded body, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, plastic lenses are rapidly becoming popular as optical materials such as spectacle lenses and camera lenses because plastic lenses are lighter, harder to break, and can be dyed compared to inorganic lenses. At present, examples of resins most widely used for these purposes include those obtained by radical polymerization of diethylene glycol bis (allyl carbonate) (hereinafter, referred to as DAC). This resin has various characteristics such as being excellent in impact resistance, being lightweight, being excellent in dyeing properties, being excellent in workability such as cutting property and polishing property, and the like. .

[0003] However, this DAC lens is
The refractive index is nd compared to the inorganic lens (nd = 1.52).
In order to obtain optical properties equivalent to that of a glass lens, it is necessary to increase the center thickness, edge thickness, and curvature of the lens, and it is inevitable that the lens becomes thicker as a whole. Therefore, a lens resin having a higher refractive index is widely desired.

Attempts have been made to introduce sulfur atoms in order to increase the refractive index of the resin, and sulfur-containing urethane-based resins composed of polyisocyanate and polythiol having excellent impact resistance (Japanese Patent Application Laid-Open Nos. 60-199016 and 62/1990). -267316, 63
No. 46213) has been proposed and commercialized, and has become the mainstream of high refractive index resin lenses.

[0005] However, since this resin contains a sulfur atom, an off-flavor and a bad smell of the sulfur atom-containing substance are generated during cutting and polishing of the lens, which may give a strong discomfort to the worker. Improvement was strongly desired.

The present inventors have already proposed a processing method for reducing or eliminating off-flavors and odors generated during cutting and polishing of a sulfur-containing urethane resin lens. For example, a technique for adding a specific fragrance imparting compound (Japanese Unexamined Patent Publication No. 5-27)
3401 and 5-297201).

[0007] However, although the addition of these specific fragrance imparting compounds exhibits a tentative effect, it is not possible to improve the odor until all workers no longer feel uncomfortable, and further improvement is desired. Was.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a lens made of a sulfur-containing urethane resin, which does not have the above-mentioned problems, by eliminating the odor and odor peculiar to a sulfur atom-containing substance during processing such as cutting and polishing. An object of the present invention is to provide a lens made of a sulfur-containing urethane resin having a high refractive index and containing a specific amount of a specific fragrance composition to be reduced or eliminated, and a method for producing the lens.

[0009]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, by using a certain specific compound, a sulfur atom-containing substance peculiar to a lens generated during lens processing has been developed. The present inventors have found that off-flavors and odors can be reduced or eliminated, and completed the present invention.

That is, the present invention relates to a high refractive index sulfur-containing urethane resin lens having a refractive index of 1.55 or more, comprising β-damascon, α-isomethylionone, acetylcedrene, 2-tert-butylcyclohexyl acetate, 4
-tert-butylcyclohexyl acetate, dimethylbenzylcarbinyl acetate, isocampylcyclohexanol, dimethyloctanol, tetrahydromyrcenol, tetrahydrolinalool, p-tert-butyl-α-methylhydrocinnamic aldehyde, β-phenylethyl alcohol A sulfur-containing urethane resin lens containing a perfume composition containing one or more selected from the group in an amount of 40% by weight or more in a range of 0.005 to 0.5% by weight. Is disclosed.

Further, in the method for producing a lens made of a high-refractive-index sulfur-containing urethane resin having a refractive index of 1.55 or more, β-damascon, α-isomethylionone, acetylsedrene, 2-tert. -Butylcyclohexyl acetate, 4-tert-butylcyclohexyl acetate, dimethylbenzylcarbinyl acetate, isocampylcyclohexanol, dimethyloctanol, tetrahydromyrcenol, tetrahydrolinalool, p-tert-butyl-α-methylhydrocinnamic aldehyde, adding a fragrance composition containing one or more selected from the group consisting of β-phenylethyl alcohol in a range of 40% by weight or more in a range of 0.005 to 0.5% by weight and polymerizing by heating; For manufacturing sulfur-containing urethane resin lenses It also discloses the law.

More specifically, a high-refractive-index sulfur-containing urethane resin having a refractive index of 1.55 or more obtained by casting polymerization of a monomer mixture comprising a polyfunctional polyisocyanate compound having two or more functions and a polythiol compound having two or more functions. The present invention relates to a plastic lens and a method for producing the plastic lens, which do not generate an off-odor or a bad odor of a sulfur atom-containing substance during cutting and polishing of the molded body.

According to the present invention, it is possible to reduce or eliminate off-flavors and offensive odors of a sulfur atom-containing substance generated during cutting and polishing of a lens, and to perform processing of a sulfur-containing urethane resin lens without feeling unpleasant odors by an operator. It becomes possible.

In the present invention, the compound used as the fragrance composition is β-damascon {1- (2,6,6-trimethyl-1-cyclohexenyl) -2-buten-1-one}, α
-Isomethylionone {γ-methylionone, 4- (2,
6,6-trimethyl-2-cyclohexen-1-yl) -3-
Methyl-3-buten-2-one {Acetylcedrene} Me
thyl cedrylone, Cedar keton
e, Cedry methyl ketone, Verto
fix, Woodyflor, Lignofix, Lix
etone, 9-acetyl-2,6,6,8-tetramethyltricyclo [5.3.1 ^{1 ,} 7.0 ^1,5 ] -8-undecene デ, 2-
tert-butylcyclohexyl acetate @ Verd
ox, Agrumex, Ylanat-ortho｝, 4-
tert-butylcyclohexyl acetate @Verv
etone, Vertenex, Oryclon, Ver
topol, Ylanate, Vester, Dor
isyl, dimethylbenzylcarbinyl acetate, α, α-dimethylphenylethyl acetate, DMBC
A, Meltol acetate, Isocampyl cyclohexanol Santalex T, Sande
la, Indian, Sandiff, Sandeol,
Santalydol, 3- (5, 5, 6-Trimeth
ylbiccyclo [2.2.1] hept-2-yl) c
Cyclohexanol｝, dimethyloctanol ｛T
Etrahydrogeraniol, Dihydro
citronellol, 3,7-dimethyl
tanol, Perargol, Rosidol, Ros
orcol, DMO｝, tetrahydromyrcenol ｛2,
6-Dimethyl-2-octanol｝, tetrahydrolinalool ｛3,7-Dimethyloctano
l}, p-tert-butyl-α-methylhydrocinnamic aldehyde {3- (4-tert-Butylphen)
yl) propanal, Bourgeonal｝, β-
Phenylethyl alcohol @ Rose p, Mello
1, a perfume composition containing one or more selected from the group consisting of Gallicol and Phenrose in a range of 40% by weight or more, and the amount of the perfume composition depends on the type of the compound and the sulfur-containing urethane resin used. Depending on the lens, it is usually 0.00
It is in the range of 5 to 0.5% by weight. These compounds are commercially available and can be easily obtained.

The sulfur-containing urethane resin used in the present invention is, for example, a resin obtained by reacting polyisocyanate with polythiol. Specifically, as the polyisocyanate, for example, hexamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate,
Aliphatic polyisocyanates such as 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, isophorone diisocyanate, bis (isocyanate (Natomethyl) cyclohexane, dicyclohexylmethanediisocyanate, cyclohexanediisocyanate, dicyclohexyldimethylmethanediisocyanate, 2,5-bis (isocyanatomethyl) bicyclo [2,
2,1] heptane, 2,6-bis (isocyanatomethyl)
Alicyclic polyisocyanate such as bicyclo [2,2,1] heptane, aromatic polyisocyanate such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, thiodiethyl diisocyanate, bis (isocyanate Methylthio) methane, bis (4-isocyanatomethylbenzene) sulfide, diphenyldisulfide-4,
Sulfur-containing isocyanates such as 4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, 1,4-dithiane-2,5-diisocyanate, thiophene-2,5-diisocyanate, etc. No.

Further, as the polythiol, for example,
1,2-ethanedithiol, 1,2-propanedithiol,
1,2,3-propanetrithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, bicyclo [2.2.1] pepta-exo-cis-2,
3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 2,2-bis (mercaptomethyl) -1,3-propane Dithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropanebis (2-mercaptoacetate), trimethylolpropanebis (3 -Mercaptopropionate), aliphatic polythiols such as pentaerythritol tetrakis (2-mercaptoacetate) and pentaerythritol tetrakis (3-mercaptopropionate), dimercaptobenzene, bis (mercaptomethyl) ) Benzene, bis (mercaptoethyl) benzene, bis (mercaptomethyleneoxy) benzene, bis (mercaptoethyleneoxy) benzene, trimercaptobenzene, tris (mercaptomethyl) benzene, tris (mercaptoethyl) benzene, tris (mercaptomethyleneoxy) Aromatic polythiols such as benzene, tetramercaptobenzene, tetrakis (mercaptomethyl) benzene, tetrakis (mercaptoethyl) benzene, tetrakis (mercaptomethyleneoxy) benzene, tetrakis (mercaptoethyleneoxy) benzene, dimercaptobiphenyl and naphthalenedithiol; Morpholino-4,
Heterocyclic-containing polythiols such as 6-dithiol-sym-triazine, bis (mercaptomethylthio) benzene, bis (mercaptoethylthio) benzene, tris (mercaptomethylthio) benzene, tris (mercaptoethylthio) benzene, tetrakis (mercaptomethylthio) ) Benzene, tetrakis (mercaptoethylthio) benzene, etc., and aromatic polythiols containing a sulfur atom in addition to mercapto groups such as alkylated nuclei thereof, bis (mercaptomethyl) ether, bis (mercaptomethyl) sulfide, bis (mercapto) Ethyl) ether, bis (mercaptoethyl) sulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-merca Topuropiruchio) methane, 1,2-bis (mercaptomethyl) ethane, 1,
2-bis (2-mercaptoethylthio) ethane, 1,2-bis (3-mercaptopropylthio) ethane, 1,3-bis (mercaptomethylthio) propane, 1,3-bis (2-mercaptoethylthio) propane, 1,2-bis (2-mercaptoethylthio) 3-mercaptopropane, 1,2,3-tris (mercaptomethylthio) propane, 1,2,3-tris (2-mercaptoethylthio) propane, tetrakis (mercaptomethylthio) Methyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, bis (2,
3-dimercaptopropyl) sulfide, 2,5-dimercapto-1,4-dithiane, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide,
Bis (mercaptopropyl) disulfide, 5,7-bis (mercaptoethylthio) -3,6,9-trithiaundecane-1,11-dithiol and the like, and esters of thioglycolic acid and mercaptopropionic acid, hydroxymethyl Sulfidobis (2-mercaptoacetate), hydroxymethylsulfidebis (3-mercaptopropionate), hydroxyethylsulfidebis (2-mercaptoacetate), hydroxyethylsulfidebis (3-mercaptopropionate), hydroxymethyldisulfidebis (3-mercaptopropionate), hydroxyethyl disulfide bis (2-mercaptoacetate), 1,4-dithiane-2,5-diolbis (3-mercaptopropionate), bis (2-mercaptoethyl) thiodipropionate Esters), bis (2-mercaptomethyl ester) dithiodipropionate, bis (2,3-dimercaptopropyl ester) thiodiglycolate, etc., aliphatic polythiols containing sulfur atoms in addition to mercapto groups, 3,4 And heterocyclic compounds containing a sulfur atom in addition to a mercapto group such as -thiophenedithiol, 2,5-dimercapto-1,3,4-thiadiazole.

Furthermore, halogen-substituted polythiols such as chlorine-substituted and bromine-substituted products may be used.
These can be used alone or in combination of two or more.

The sulfur-containing urethane resin lens of the present invention is usually obtained by cast polymerization. Specifically, the monomer mixture and the above-mentioned compound used in the present invention are thoroughly mixed, and if necessary, the mixture is defoamed by an appropriate method.
It is poured into a mold and heated to polymerize. At this time, a known release treatment may be applied to the mold in order to facilitate release after polymerization. Further, in order to adjust the reaction rate to a desired one, a known catalyst may be appropriately added.

The polymerization temperature and the polymerization time are appropriately determined depending on the combination of the monomers to be used and the kind of the compound to be added. For example, the polymerization can be carried out at 20 to 200 ° C. for 0.5 to 100 hours.

When the compound used in the present invention is a compound having active hydrogen, the lens made of a sulfur-containing urethane resin of the present invention can be reacted with an isocyanate compound in advance.

If necessary, an internal release agent, a chain extender, a crosslinking agent, a light stabilizer,
Various additives such as ultraviolet absorbers, antioxidants, oil-soluble dyes, and fillers may be added. Further, the sulfur-containing urethane resin lens of the present invention, if necessary, to improve the anti-reflection, impart high hardness, improve abrasion resistance, improve chemical resistance, impart anti-fogging property or impart fashionability, etc., Physical or chemical treatment such as surface polishing, antistatic treatment, hard coat treatment, anti-reflection coat treatment, dyeing treatment, light control treatment and the like can be performed.

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below.

[0023]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Hereinafter, percentages are by weight unless otherwise specified.

Example 1 46.5 parts by weight of m-xylylene diisocyanate, 53.5 parts by weight of pentaerythritol tetrakis (thioglycolate), 0.1% of dibutyltin dilaurate, After thoroughly mixing and degassing the mixture, the mixture was poured into a mold subjected to a release treatment. 12 over 15 hours
After the temperature was raised to 0 ° C., the mixture was heated at 120 ° C. for 5 hours to carry out polymerization. After the completion of the polymerization, the mixture was gradually cooled, and the polymer was taken out of the mold. The obtained lens was colorless and transparent, and no odor was felt even when approached to the nose.

[0025]

[Table 1] When this was cut and polished with an edger for processing eyeglass lenses, the malodor inherent to the sulfur atom-containing substance originally disappeared almost completely, and the operator did not feel unpleasant odor.

[Example 2] In Example 1, instead of 0.05% of the compounded fragrance A, compounded fragrance B0.05 shown in Table 2 was used.
%, And a lens was obtained in the same manner as in Example 1. When the obtained lens was cut and polished in the same manner as in Example 1,
The inherent malodor inherent in the sulfur atom-containing substance almost disappeared, and the operator did not feel any unpleasant odor.

[0027]

[Table 2]

Example 3 35.0 parts by weight of m-xylylene diisocyanate, 32.3 parts by weight of 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, 0.01% of dibutyltin dichloride, After mixing 0.05% of the prepared perfume A and 0.1% of an acidic phosphoric acid ester-based internal release agent ZELECAN (manufactured by DuPont), the mixture was sufficiently defoamed, and the mixture was poured into a mold. 120 over 15 hours
After the temperature was raised to 120 ° C., polymerization was carried out by heating at 120 ° C. for 5 hours. After the completion of the polymerization, the mixture was gradually cooled, and the polymer was taken out of the mold. The obtained lens was colorless and transparent, and no odor was felt even when approached to the nose.

When this was cut and polished by an edger for processing eyeglass lenses, the bad smell inherent to the sulfur atom-containing substance, which had originally been slight, had completely disappeared.

Comparative Example 1 A lens was obtained in the same manner as in Example 1 except that the compounded flavoring A was not used. When the obtained lens was cut and polished in the same manner as in Example 1, an odor peculiar to the sulfur atom-containing substance was strongly generated,
The worker was very discomforted.

[Comparative Example 2] Compounded fragrance A used in Example 1
A lens was obtained in the same manner as in Example 1, except that 0.1% of benzyldimethylcarbinol, which is an aroma imparting compound disclosed in JP-A-5-273401, was used in place of the above. When the obtained lens was cut and polished in the same manner as in Example 1, the odor peculiar to the sulfur atom-containing substance was slightly generated, and the operator felt discomfort.

[0032]

The lens made of the sulfur-containing urethane resin of the present invention comprises:
At the time of processing such as cutting and polishing of the resin lens, almost no or no odor peculiar to the sulfur atom-containing substance is generated. Therefore, it becomes possible for an operator to process a sulfur atom-containing lens without feeling uncomfortable, and since there is no odor at the time of normal wearing of a spectacle lens or the like, a low refraction lens containing no sulfur atom can be used. It has excellent effects such as being able to be handled similarly.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Hideaki Ota 1-1-5 Nishi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Takasago International Corporation

Claims (2)

[Claims] 1. A high refractive index sulfur-containing resin lens having a refractive index of 1.55 or more obtained by polymerizing a monomer mixture comprising a bifunctional or higher polyisocyanate compound and a bifunctional or higher polythiol compound. In the monomer mixture, as a fragrance composition, β-damascon, α-isomethylionone, acetylcedrene, 2-tert-butylcyclohexyl acetate, 4-tert-butylcyclohexyl acetate, dimethylbenzylcarbinyl acetate, isocampyl 40 or more of one or more selected from the group consisting of cyclohexanol, dimethyloctanol, tetrahydromyrcenol, tetrahydrolinalool, p-tert-butyl-α-methylhydrocinnamic aldehyde, and β-phenylethyl alcohol
A composition containing 0.005 to 0.005% by weight or more.
A sulfur-containing urethane resin lens, which is contained in an amount of 5% by weight. 2. A method for producing a high-refractive-index sulfur-containing resin lens having a refractive index of 1.55 or more obtained by polymerizing a monomer mixture comprising a bifunctional or higher polyisocyanate compound and a bifunctional or higher polythiol compound. In the production method, the monomer mixture, as a fragrance composition, β-
Damascon, α-isomethylionone, acetylcedrene, 2-tert-butylcyclohexyl acetate, 4
-tert-butylcyclohexyl acetate, dimethylbenzylcarbinyl acetate, isocampylcyclohexanol, dimethyloctanol, tetrahydromyrcenol, tetrahydrolinalool, p-tert-butyl-α-methylhydrocinnamic aldehyde, β-phenylethyl alcohol A sulfur-containing urethane resin lens, wherein a composition containing one or more selected from the group consisting of 40% by weight or more is added in an amount of 0.005 to 0.5% by weight and polymerized by heating. Manufacturing method.