JP2871398B2 - Method for producing transparent polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a transparent polymer preferably used for optical applications represented by plastic lenses such as a correction lens, a sunglass lens, a fashion lens, a camera lens, a lens for an optical device and a prism. It is about.

[0002] The present invention also relates to a method for producing a transparent polymer useful as an adhesive used for bonding optical articles.

[0003]

2. Description of the Related Art An olefin-based thermosetting resin is generally excellent in heat resistance and chemical resistance.

[0004] Although diethylene glycol bisallyl carbonate is widely used for optical applications such as spectacle lenses, a low refractive index poses a problem in reducing the thickness and weight of lenses.

In order to solve this problem, a resin containing a sulfur atom (JP-A-63-316766 and JP-A-63-316766) has been proposed.
Japanese Patent Application Laid-Open No. 162671/1994 and Japanese Patent Application Laid-Open No. 63-188660) have been proposed.

[0006] Japanese Patent Application Laid-Open No. 2-158612 proposes a resin having a refractive index of 1.62 to 1.64.

[0007]

However, when a resin is produced by radical polymerization of a monomer containing a sulfur atom, the resulting resin is colored or has internal strain due to radicals generated during polymerization and heat generated by polymerization. In some cases, it becomes a fatal defect when used for optical applications.

The present invention relates to a method for producing one or more thiols in a molecule.
As a result of intensive studies on a method for obtaining a transparent polymer using a monomer having a (meth) acrylate group, there was little coloring during polymerization (that is, the hue was improved), yellowing was unlikely to occur under use conditions, and visible The present inventors have found a method for producing a light sulfur-containing transparent polymer having a high light transmittance, a high refractive index, and have completed the present invention.

[0009]

Means for Solving the Problems The present invention relates to a method for producing one molecule in a molecule.
In the method for producing a transparent polymer for polymerizing a composition containing a monomer having a thiol (meth) acrylate group, the compound having a mercapto group and the phenolic O
With a compound having an H group, a composition comprising the total composition 0.1 to 7.0 wt%, it characterized by radical polymerization
Relating to the method of manufacturing the transparency polymer.

[0010] In the molecule used in the present invention, one or more molecules may be used.
Monomers having an all (meth) acrylate group include compounds containing a sulfur atom and a hydroxy group, compounds containing a mercapto group, and (meth) acrylic acid, (meth) acrylic acid esters, and (meth) acrylic halides as alkali acids or acids. By reacting in the presence of

[0011] One or more switch in the molecule used in the present invention
Specific examples of the monomer having an all (meth) acrylate group include the following compounds.

First, examples of compounds having one thiol (meth) acrylate group will be described below.

Methyl mercaptan, ethyl mercaptan, thiophenol, mercaptoethyleneoxybenzene, mercaptopropyleneoxybenzene, mercaptoethylenethiomethylenebenzene, mercaptopropylenethiomethylenebenzene, hydroxyethylenethiobenzene, hydroxypropylenethiobenzene, hydroxyethylenethiomethylenebenzene, (Meth) acrylates such as hydroxypropylenethiomethylenebenzene, and those obtained by substituting a naphthalene ring or a diphenyl ring for these compounds in place of the benzene ring.

The thiol ( meth) used in the present invention is
(T) Examples of compounds having two or more thiol (meth) acrylate groups among monomers having an acrylate group are shown below.

1,2-dimercaptoethane, 1,3-dimercaptopropane, 1,4-dimercaptobutane, 2-mercaptoethanol, mercaptoethyl sulfide, mercaptoethyl ether, hydroxyethyl sulfide, pentaerythritol tetrakisthioglycolate , Pentaerythritol tetrakisthiopropionate, 4,4'-hydroxyphenyl sulfide, 1,4-bis (hydroxyethylenethio) benzene, 1,4-benzenedithiol, 1,3-
Benzenedithiol, 1,2-benzenedithiol, 4-t-butyl-1,2-benzenedithiol, 1,2-bis (mercaptomethylene) benzene, 1,3-bis (mercaptomethylene)
Benzene, 1,4-bis (mercaptomethylene) benzene,
1,2-bis (mercaptoethylene) benzene, 1,3-bis (mercaptoethylene) benzene, 1,4-bis (mercaptoethylene) benzene, 1,2-bis (mercaptomethylenethio) benzene, 1,3-bis (Mercaptomethylenethio)
Benzene, 1,4-bis (mercaptomethylenethio) benzene, 1,2-bis (2-mercaptoethylenethio) benzene,
1,3-bis (2-mercaptoethylenethio) benzene, 1,4-
Bis (2-mercaptoethylenethio) benzene, 1,2-bis (2-mercaptoethylenethiomethylene) benzene, 1,3-
Bis (2-mercaptoethylenethiomethylene) benzene,
1,4-bis (2-mercaptoethylenethiomethylene) benzene, 4,4′-thiodithiophenol, 4,4′-biphenyldithiol, 1,2-bis (mercaptomethyleneoxy) benzene, 1,3-bis ( Mercaptomethyleneoxy) benzene, 1,4-bis (mercaptomethyleneoxy) benzene,
1,2-bis (mercaptoethyleneoxy) benzene, 1,3-
Bis (mercaptoethyleneoxy) benzene, 1,4-bis (mercaptoethyleneoxy) benzene, 1,4-bis (hydroxyethylenethio) benzene, 1,4-bis (2-hydroxyethylenethiomethylene) benzene, 1,4 -(Meth) acrylate compounds such as bis (2-mercaptoethyleneoxymethylene) benzene and 1,3,5-trimercaptobenzene.

The (meth) acrylate compound used in the present invention is preferably a compound having a thiol (meth) acrylate group from the viewpoint that a resin having a high refractive index can be obtained. Further, in order to obtain a polymer having high hardness and being hard to be softened by heat, a compound having two or more (meth) acrylate groups is preferable.

In the course of studying the present invention, one of the above
Monomers having two or more thiol (meth) acrylate groups are more likely to become yellowish or reddish when polymerized by ordinary radical polymerization, and to stabilize a uniform hue. It was found that it was difficult to manufacture.

Therefore, in the present invention, it has been found that the color of a polymer after polymerization can be stably improved by a method of adding one or more compounds selected from a chain transfer compound and a radical scavenging compound to a monomer.

Examples of the chain transfer compound and the radical scavenging compound used in the present invention are described below.

Ethyl mercaptan, hexyl mercaptan, octyl mercaptan, dodecyl mercaptan, stearyl mercaptan, mercaptoethanol, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexanedithiol, 1,12-dodecanedithiol, mercapto Methyl sulfide, 2-mercaptoethyl sulfide, 3-
Mercaptopropyl sulfide, 6-mercaptohexyl sulfide, 1,2-bis-2-mercaptoethylthioethane, 1,2-bis-3-mercaptopropylthioethane, 1,3-
Bis-2-mercaptoethylthiopropane, 1,4-bis-2-
Mercaptoethylthiobutane, 1,6-bis-2-mercaptoethylthiohexane, bis-2- (2-mercaptoethylthio) ethylsulfide, 2-mercaptoethylether, 3-mercaptopropylether, 6-mercaptohexylether, 1,4-cyclohexanedithiol, bis-2
-Mercaptoethoxymethane, 1,2-bis-2-mercaptoethoxyethane, bis-2- (2-mercaptoethoxy) ethyl ether, 1,4-benzenedithiol, 1,3-benzenedithiol, 1,2-benzenedithiol , 4-t-butyl-1,2
-Benzenedithiol, 1,2-bis (mercaptomethylene) benzene, 1,3-bis (mercaptomethylene) benzene, 1,4-bis (mercaptomethylene) benzene, 1,2-bis (mercaptoethylene) benzene, 3-bis (mercaptoethylene) benzene, 1,4-bis (mercaptoethylene) benzene, 1,2-bis (mercaptomethylenethio) benzene, 1,3-bis (mercaptomethylenethio) benzene, 1,4-bis ( Mercaptomethylenethio) benzene, 1,
2-bis (2-mercaptoethylenethio) benzene, 1,3-bis (2-mercaptoethylenethio) benzene, 1,4-bis (2-mercaptoethylenethio) benzene, 1,2-bis (2-
Mercaptoethylenethiomethylene) benzene, 1,3-bis (2-mercaptoethylenethiomethylene) benzene, 1,4-
Bis (2-mercaptoethylenethiomethylene) benzene,
1,2-bis (mercaptomethyleneoxy) benzene, 1,3-
Bis (mercaptomethyleneoxy) benzene, 1,4-bis (mercaptomethyleneoxy) benzene, 1,2-bis (2-
Mercaptoethyleneoxy) benzene, 1,3-bis (2-mercaptoethyleneoxy) benzene, 1,4-bis (2-mercaptoethyleneoxy) benzene, 4,4'-thiodithiophenol, 4,4'-biphenyldithiol , 1,3,5-trimercaptobenzene, trimercaptoethyl isocyanurate, pentaerythritol tetrathioglycolate,
Pentaerythritol trithioglycolate, pentaerythritol dithioglycolate, pentaerythritol tetramercaptopropionate, pentaerythritol trimercaptopropionate, pentaerythritol dimercaptopropionate, trimethylolpropanetrithioglycolate, trimethylolpropanedithioglycolate And mercaptan-based compounds such as trimethylolpropane trimercaptopropionate, trimethylolpropanedimercaptopropionate, and mercaptopropyl isocyanurate.

[0021]

[0022]

2,6-di-t-butyl-4-methylphenol,
It is a so-called polymerization inhibitor or antioxidant having a phenolic OH group such as 4-methoxyphenol, 4-t-butylcatechol and hydroquinone.

[0024]

[0025]

[0026]

[0027]

Among these compounds, those particularly preferably used in the present invention are mercaptan compounds.

It was also found that the use of a mercaptan compound and a compound having a phenolic OH group in combination further improved the transparency of the resin.

The amount of the chain transfer compound and the radical scavenging compound that can be used in the present invention is preferably 0.1% by weight or more in total of one or more compounds selected from the group. Furthermore, 1.0% by weight
It is preferable that it is above. When the amount is less than 0.1% by weight, it becomes difficult to improve the hue of the polymer after polymerization. Further, the chain transfer compound and the radical-scavenging compound that can be used in the present invention, if the amount used is large, may reduce the mechanical properties of the polymer after polymerization or bleed out during use.
It is preferably 7.0% by weight or less, and at this time, the mercapto group of the compound to be added and the phenolic OH
It is more preferable that the total number of moles of the group is the following ratio with respect to the number of moles of the (meth) acrylate group.

[0031]

(Equation 1) The mercaptan compound used in this case is 1.0 to 5.
0% by weight of the compound having a phenolic OH group is
It is preferable to use 0.1 to 1.0% by weight.

Further, one or more thiol (me
(T) It is also possible to copolymerize by adding another radically polymerizable monomer to the monomer having an acrylate group . The monomer to be added is not particularly limited as long as it is an olefinic compound, and preferably includes (meth) acrylic compounds, styrene compounds, acrylonitrile, N-phenylmaleimide, and the like. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth)
Examples include acrylate, cyclohexylmethylene (meth) acrylate, styrene, vinylnaphthalene, halogen-substituted styrene, and α-methylstyrene.

When used in applications requiring a polishing step or a surface coating step, a monomer having two or more radically polymerizable functional groups in the molecule is copolymerized to provide heat resistance. A resin having an excellent crosslinked structure can be obtained. The monomer having two or more radically polymerizable functional groups in the molecule is not particularly limited. Examples thereof include divinylbenzene, diallyl phthalate, ethylene glycol di (meth) acrylate, and diethylene glycol di (meth). Acrylate, triethylene glycol di (meth) acrylate, bisphenol A-di (meth) acrylate, bisphenol A-dihydroxyethyl (meth) acrylate, tetrabromo-bisphenol A-di (meth) acrylate, tetrabromo-
Bisphenol A-dihydroxyethyl (meth) acrylate, triallyl isocyanurate, pentaerythritol tetrakis (meth) acrylate, pentaerythritol tris (meth) acrylate, diethylene glycol bisallyl carbonate and the like.

However, due to the optical properties of the obtained resin, these monomers for copolymerization are 5% of the entire monomer composition.
The content is preferably 0% by weight or less.

By adding a stabilizer such as an ultraviolet absorber or an antioxidant to the adjusted monomer thus obtained, light and heat yellowing that occur under the usage condition of the polymer after polymerization are further increased. Can be prevented.

Further, a photopolymerization initiator such as a benzophenone type and a thermal polymerization initiator such as a peroxide type or an azo type are added to facilitate the polymerization in the next polymerization step. General.

Various known polymerization initiators can be used, and a desired reaction temperature is selected and used. For example, benzoyl peroxide, di-iso-
Propyl peroxy carbonate, di-iso-propyl peroxy dicarbonate, di-2-ethylhexyl peroxy dicarbonate, di-n-propyl peroxy dicarbonate, t-butyl peroxy-2-hexyl hexanate, azobisiso Butyronitrile and the like.

The transparent polymer of the present invention can be produced by polymerizing the obtained adjustment monomer. For example, the case of polymerizing using a mold will be described below.

The obtained adjustment monomer is filled in the space between two molds having a predetermined shape. Then, light or thermal polymerization is performed to shape the mold. The mold is made of glass, ceramics, metal, or the like, and glass, particularly glass with a reinforced surface, is usually used.

When manufacturing a plastic lens,
In many cases, the cavity of the mold is formed by two opposing glass molds and a gasket having the purpose of providing a certain thickness to the plastic lens and preventing liquid leakage of the filled adjustment monomer. A needle such as an injection needle is inserted between the gasket and the glass mold, and the adjustment monomer can be filled into the cavity of the mold by a method of injecting the adjustment monomer.

The mold filled with the conditioning monomer is then irradiated with an actinic ray such as ultraviolet rays, or is heated in an oven or a liquid tank and polymerized. There may be a method in which heat polymerization is performed after photopolymerization, or conversely, both methods in which photopolymerization is performed after heat polymerization are used. In the case of photopolymerization, it is common to irradiate light containing a large amount of ultraviolet light using a mercury lamp as a light source. When performing thermal polymerization, the condition for gradually increasing the temperature from around room temperature and raising the temperature to about 100 ° C. over several hours to several tens of hours is the optical uniformity of the polymerized product (such as a plastic lens). , For maintaining quality and improving reproducibility.

Through the above steps, a sulfur-containing transparent polymer containing sulfur in the polymer molecule can be produced. When the obtained polymer is used as a plastic lens, various coating techniques such as providing a hard coat layer on the surface to improve the damage resistance of the lens and further providing a multi-coat layer to increase the light transmittance of the lens are used. In combination, the value as a plastic lens can be further enhanced.

The optical resin obtained by the present invention is suitably used for spectacle lenses, camera lenses, compact disk big-up lenses, lenses for other optical devices, and the like.

[0044]

The present invention will be described more specifically with reference to the following examples. The present invention is not limited to the embodiment.

The yellowness in the examples was measured with a color computer SM-3 manufactured by Suga Test Instruments Co., Ltd. YI is an index given by the following equation and indicates the degree of yellowness of the transmitted light of the sample. The larger the value, the stronger the yellowishness of the sample.

YI = {100 (1.28X-1.06Z)} / Y X, Y, Z: tristimulus values of color The total light transmittance is measured by a fully automatic direct-reading haze computer manufactured by Suga Test Instruments Co., Ltd. did. Assuming that the amount of incident light and the amount of transmitted light captured by the integrating sphere are T1 and T2, the total light transmittance Tt is given by the following equation.

Tt = 100T2 / T1 The light resistance was determined by measuring the yellowness (YI) 2 after irradiating the sample with carbon arc light for 60 hours using an ultraviolet regular life fade meter FA-3 manufactured by Suga Test Instruments Co., Ltd. and the value before irradiation. The difference from the yellowness (YI) 1 was determined by the difference ΔYI (the following equation).

ΔYI = (YI) 2 − (YI) 1 The refractive index was measured using a Pulfrich refractometer.

Example 1 55.0% by weight of a compound having a structure represented by the following formula 1:
And styrene 40.0% by weight, mercaptoethyl sulfide 3.5% by weight, t-butylhydroxytoluene 1.
After adding 0.5% by weight of benzoyl peroxide to a monomer composition of 0% by weight and filling a mold composed of two glass plates and a polyester tape, the mixture is heated at 40 ° C to 110 ° C over 14 hours. Heated to ° C.

After that, when the mold was removed,
A transparent resin having a thickness of 3 mm was obtained. Table 1 shows the results of evaluation of yellowness, total light transmittance, light resistance, and refractive index using this resin.

[0051]

Embedded image Example 2 90.0% by weight of a compound having a structure represented by the following formula 2:
Then, 0.5% by weight of benzoyl peroxide was added to a monomer composition composed of 5% by weight of divinylbenzene, 4.0% by weight of mercaptoethyl sulfide, and 0.5% by weight of t-butylhydroxytoluene. Table 1 shows the results of manufacturing and evaluating the resin plate in the same manner as in Example 1.

[0052]

Embedded image Example 3 90.0% by weight of a compound having a structure represented by the following formula 3:
And 0.5% by weight of benzoyl peroxide in a monomer composition consisting of 5.0% by weight of styrene, 3.5% by weight of pentaerythritol tetrakisthiopropionate and 1.0% by weight of t-butylhydroxytoluene. After the addition, the results of manufacturing and evaluating a resin plate in the same manner as in Example 1 are shown in Table 1.

[0053]

Embedded image Example 4 89.7% by weight of a compound having the structure shown in Formula 3 and α
0.1% by weight of benzoyl peroxide is added to a monomer composition consisting of 7.5% by weight of methylstyrene, 2.5% by weight of pentaerythritol tetrakisthioglycolate and 0.2% by weight of t-butylhydroxytoluene. After that, the results of manufacturing and evaluating a resin plate in the same manner as in Example 1 are shown in Table 1.

Comparative Example 1 59.5% by weight of a compound having the structure shown in Formula 1, 40.0% by weight of styrene, 0.0% of p-methoxyphenol
After adding 0.49% by weight of benzoyl peroxide to the monomer composition of 1% by weight, the results of manufacturing and evaluating a resin plate in the same manner as in Example 1 are shown in Table 1.

Comparative Example 2 A monomer composition comprising 90.0% by weight of a compound having the structure shown in Formula 2, 9.48% by weight of divinylbenzene, and 0.02% by weight of t-butylhydroxytoluene was added to a monomer composition of 0.02% by weight. 5
After adding benzoyl peroxide in an amount of 1% by weight, the results of manufacturing and evaluating a resin plate in the same manner as in Example 1 are shown in Table 1.
Shown in

Comparative Example 3 94.49% by weight of a compound having the structure shown in Formula 3
After adding 0.5% by weight of benzoyl peroxide to a monomer composition comprising 5.0% by weight of styrene and 0.01% by weight of t-butylhydroxytoluene, a resin plate was prepared in the same manner as in Example 1. Table 1 shows the results of the manufacture and evaluation.
Comparative Example 4 91.39% by weight of a compound having a structure represented by Formula 3;
A monomer composition consisting of 8.5% by weight of α-methylstyrene and 0.01% by weight of t-butylhydroxytoluene is added with 0.1% by weight.
After adding 1% by weight of benzoyl peroxide, the results of manufacturing and evaluating a resin plate in the same manner as in Example 1 are shown in Table 1.

[0057]

[Table 1]

[0058]

EFFECTS OF THE INVENTION The polymer after polymerization is less colored, has a high total light transmittance, is hardly yellowed during use, has a high refractive index,
Lightweight polymers can be provided.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-113027 (JP, A) JP-A-63-193826 (JP, A) JP-A-2-160809 (JP, A) JP-A-3-3 217412 (JP, A) JP-A-63-57613 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 2 / 38,20 / 38 C08F 120 / 38,220 / 38 G02B 1 / 04,5 / 04 G02C 7/02

Claims (1)

(57) [Claims] 1. The method according to claim 1, wherein one or more thiol (meth)
In a method for producing a transparent polymer for polymerizing a composition containing a monomer having a relevant group, a method having a mercapto group
Compound, a compound having a phenolic OH group, the composition comprising the total composition of 0.1 to 7.0 wt%, the production method of transparency polymeric you characterized by radical polymerization.