JPH0892322A - Cross-linked resin - Google Patents

Abstract

PURPOSE: To obtain the subject transparent crosslinked resin, having a high refractive index without clouding suitable for optical uses, etc., and readily available according to a cast polymerization method by using a cross-linking agent consisting essentially of a specific divinylbiphenyl. CONSTITUTION: This crosslinked resin comprises a copolymer obtained by copolymerizing (A) 4,4'-divinylbiphenyl as a crosslinking agent with (B) a radically polymerizable monomer alone or plural kinds thereof. Furthermore, the component (A) and (C) any of vinylbenzene purified to >80wt.% purity, especially 3,3'-divinylbiphenyl, 3,4'-divinylbiphenyl, m-divinylbenzene and p- divinylbenzene are preferably used in combination as the crosslinking agent and a monomer of the formula R is H or a 1-2C alkyl; R' is H, a 1-2C alkyl or a halogen-substituted phenyl; X is a halogen other than F; (p) is the number of halogen substitutions and 1-5; (k) is 0-1: (m) is 0-4; [(p)+(m)]<5; A is CH2 CH2 , etc.} is preferably used as the component (B).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin crosslinked product which is effective for vinyl-based high refractive index resins for optical materials, and more specifically, 4,4'-divinylbiphenyl is incorporated into a vinyl-based resin main chain. Therefore, it is to provide a crosslinked resin having a high refractive index, which is effective for an optical material and the like in terms of product quality.

[0002]

2. Description of the Related Art Vinyl resins are widely used in home appliances, sundries, automobiles, etc., and are one of the essential materials in our daily lives. In the field of optical materials, vinyl-based high refractive index resins are widely used for plastic lenses and prisms. Among them, especially polymethylmethacrylate resin (PMMA resin) has its transparency, surface hardness, heat resistance,
Due to its refractive index, it is used for optical applications and as a transparent molding material.

Due to the demands in the fields of application of these vinyl resins, it is desired to further improve the heat resistance and the refractive index. Therefore, a methyl methacrylate-styrene copolymer resin (MS resin) obtained by copolymerizing styrene with methyl methacrylate is used. Although MS resin is cheaper than PMMA resin and has a high refractive index and excellent moldability, it has poor heat resistance and surface hardness, and there is no end to the demand for improvements in the field of large optical molding materials. The biggest points in lens design are the large, thin, lightweight molding material and the suppression and elimination of aberrations.
For this purpose, a material having a high refractive index is required. Also, temperature stability of refractive index is required, and glass transition temperature (heat resistance)
A material having a high linear expansion coefficient and a small linear expansion coefficient is desired.

In order to improve surface hardness and heat resistance, optical resins are three-dimensionally crosslinked with polyfunctional monomers such as divinylbenzene and diallyl phthalate. For example, in JP-A-61-130901, divinylbenzene having a purity of 80% by weight or more and non-polymerizable impurities of 2% by weight or less and a radical-polymerizable vinyl-based monomer which gives a polymer having a refractive index of 1.55 or more Copolymerization methods using the body have been proposed.

[0005]

The three-dimensional cross-linking method of the above method is a polymerization method for reducing the fogging of the lens caused by the influence of non-polymerizable impurities contained in divinylbenzene. If the amount is increased, the degree of cross-linking will be excessively advanced, resulting in a very brittle material, so that the divinylbenzene content is limited to an appropriate range. Therefore, in order to improve the refractive index without generating haze, it is necessary to dramatically improve the purity of divinylbenzene or use a crosslinking agent other than divinylbenzene. On the other hand, although diallyl phthalate has a relatively high refractive index of 1.57, the reactivity of the allyl group as a polymerizable functional group is poor and the cross-linking performance of divinylbenzene is inferior. As the high refractive index monomer radically copolymerized with the crosslinking agent, in addition to the above-mentioned JP-A-61-130901, JP-A-61-86701 and JP-A-61-73101 include halogen elements other than fluorine. Incorporated (meth) acrylic monomer compounds and the like are shown. However, these known high-refractive-index resins use only divinylbenzene as a cross-linking agent and have not solved the fundamental problem.

[0006]

[Means for Solving the Problems] In view of the above situation, the present inventors have conducted a search for a novel cross-linking agent that gives a high refractive index, and as a result, 4,4'-divinylbiphenyl is a radically polymerizable monomer. They have found that they have an excellent crosslinking effect on the body and have completed the present invention. That is, the present invention is characterized in that it comprises a copolymer obtained by copolymerizing 4,4'-divinylbiphenyl as a crosslinking agent, and a homopolymer or a plurality of radical-polymerizable monomers thereof. It is a cross-linked resin. In addition, 4,4'-divinylbiphenyl and purity 80% by weight
Resin cross-linking characterized by comprising a divinylbenzene purified in the above as a cross-linking agent, and a copolymer obtained by copolymerizing this with a single or a plurality of radical-polymerizable monomers. It is the body. And again 4,4'-
In addition to divinylbiphenyl as an essential ingredient, 3,3 '
-A combination of at least one selected from divinylbiphenyl, 3,4'-divinylbiphenyl, metadivinylbenzene and 1,1'-diphenylethylene as a cross-linking agent, and a radically polymerizable monomer alone Alternatively, it is a cross-linked resin characterized by comprising a copolymer obtained by copolymerizing a plurality of types.

Further, the copolymer is a resin crosslinked product described above obtained by a cast polymerization method, and the most preferred monomer capable of radical polymerization with 4,4'-divinylbiphenyl is It is a cross-linked resin as described above, which is a monomer represented by the general formula [1].

[Chemical 2] (In the formula, R is hydrogen or a C1-C2 alkyl group, R'is hydrogen or a C1-C2 alkyl group or a halogen-substituted phenyl group, X
Is a halogen element except fluorine, p is the number of halogen substitutions, is an integer of 1 to 5, k is an integer of 0 to 1, m is an integer of 0 to 4, and p + m is 5 or less. A is -CH2-CH2-,-CH2-CH (OH) -CH2-,-CH (CH2OH)
It represents a group selected from -CH2-, -CH2-CH2-CH2-, -CH2-CH (CH3)-. ) Further, a radical-polymerizable monomer using 4,4'-divinylbiphenyl as a cross-linking agent is a unit amount of at least one selected from 2-vinylnaphthalene, 4-vinylbiphenyl, or 1,1'-diphenylethylene. It is a crosslinked resin as described above, which is a body. The present invention will be described in detail below.

4,4'-as a novel cross-linking agent in the present invention
Since divinylbiphenyl is a powder crystal with a melting point of 153 ° C and a recrystallization method can be used in the purification process, it does not require purification by a heating distillation method unlike liquid divinylbenzene, and a high-purity crosslinking agent can be easily obtained. Obtainable. Since excessive purification leads to an increase in the cost of the cross-linking agent, it must be used separately from those for special optical applications. Some impurities of 4,4'-divinylbiphenyl include alkyl biphenyl impurities such as 4-ethyl-4'-vinylbiphenyl, 4,4'-dimethylbiphenyl, 4-ethylbiphenyl, 4-methylbiphenyl, and biphenyl. However, the amount of these impurities is preferably 10 parts by weight or less, and particularly preferably 5 parts by weight or less. These impurities elute over time after forming a molded article such as a lens, and become a factor that obstructs the lens surface, stains, or weather resistance. Further, in the surface treatment of the lens, the uniformity of hard coating or multi-coating is lacked, which causes the phenomenon of peeling of the treatment layer, so it is preferable that the amount is as small as possible. In order to suppress the impurities to 10 parts by weight or less, recrystallization may be carried out twice with a solvent such as toluene, benzene, hexane, cyclohexane, etc., and a high-purity 4,4'-divinylbiphenyl crosslinking agent can be easily obtained. Also 3,3 '
-Compared to divinylbiphenyl, 3,4'-divinylbiphenyl, metadivinylbenzene, 1,1'-diphenylethylene, paradivinylbenzene, etc., it is the only solid at room temperature and has a high boiling point, which is high in polymerization and crosslinking processes. It is a cross-linking agent that hardly causes a phenomenon such as evaporation even at temperature, and is also a very effective cross-linking agent in fields other than optical applications, for example, fields such as foam moldings and ion exchange resins.

In the present invention, the above-mentioned 4,4'-divinylbiphenyl may be used alone as a cross-linking agent, but it is preferably used in combination with a known high-purity divinylbenzene in view of compatibility with monomers. Further, the cross-linking effect is improved, and a synergistic effect of increasing the refractive index is observed without adverse effects such as clouding of the obtained molded product. The amount of 4,4'-divinylbiphenyl added as a crosslinking agent is within the range of 0.06 to 10% by weight based on the total amount of raw material monomers. If it is less than 0.06% by weight, the crosslinking effect is poor and it is impossible to impart solvent resistance and a high refractive index. When it is 10% by weight or more, it is not preferable in terms of solubility. In this case, a polymerization monomer, a polymerization initiator, a polymerization aid such as a molecular weight modifier, etc. and a predetermined amount of 4,4′-divinylbiphenyl cross-linking agent are added at the same time and the mixture is heated and polymerized after injection into the lens mold. In the case of 4,4'- at the polymerization temperature
It is preferable to add it in consideration of the solubility limit of vinylbiphenyl. The amount of high-purity divinylbenzene used together with 4,4'-divinylbiphenyl is within the range of 0.05 to 90% by weight based on the total amount of raw material monomers. If it is less than 0.05% by weight, it is not preferable in terms of synergistic effect. On the other hand, when it is 90% by weight or more, a hard lens having a high refractive index can be obtained, but it becomes a brittle lens, which is not preferable. It is desirable that divinylbenzene have a high purity of 80% or more in order to avoid adverse effects such as clouding of the molded body.

The radical-polymerizable monomer copolymerized with 4,4'-divinylbiphenyl as a crosslinking agent is a side chain alkyl-substituted styrene such as styrene or α-methylstyrene.
Nuclear alkyl-substituted styrene such as vinyltoluene, bromostyrene, halogenated styrene such as chlorostyrene, 2-vinylnaphthalene, 4-vinylbiphenyl, aromatic vinyl monomers such as 1,1′diphenylethylene, acrylonitrile,
Methacrylonitrile, fumaronitrile, maleonitrile,
Vinyl cyanide monomers such as α-chloroacrylonitrile, methyl methacrylate, ethyl methacrylate, propylene methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, phenyl methacrylate, methyl acrylate, ethyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, (Meth) acrylic acid alkyl esters such as 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, phenyl acrylate, and benzyl acrylate, and others are represented by the following general formula
Various polymerizable monomers such as (meth) acrylate compounds, maleic acid, maleic acid esters, itaconic acid and itaconic acid esters, N-alkylmaleimides, N-phenylmaleimides (PMI) can be used. Derivatives obtained by introducing halogen groups other than fluorine, such as chlorine, bromine, and iodine, and sulfur into these polymerized monomers are effective as means for improving the refractive index.

Of these, the dyes having high dyeability, high refractive index and low dispersibility are particularly preferred, and the following general formula [1] is preferred.
It is represented by.

[Chemical 3] (In the formula, R is hydrogen or a C1-C2 alkyl group, R'is hydrogen or C1
~ C2 alkyl group or halogen-substituted phenyl group, X is a halogen element other than fluorine, p is the number of halogen substitution 1 ~
An integer of 5 and k represent an integer of 0 to 1. m represents an integer of 0 to 4. p + m must be 5 or less. A is -CH2-CH2-,-CH2-CH (OH)
-CH2-,-CH (CH2OH) -CH2-,-CH2-CH2-CH2-,-CH2-CH (CH3)-
Represents a kind of group selected from ) As such a monomer, for example, 2,4,6-tribromophenyl (meth) acrylate, p-chlorophenyl (meth)
Acrylate, 1- (meth) acryloxyethoxydibromobenzene, 1- (meth) acryloxyethoxy-2,4,6-tribromobenzene, 1- (meth) acryloxyethoxydiethoxy-2,4,6- Tribromobenzene, 1- (meth) acryloxyethoxy-4-bromobenzene, 1- (meth) acryloxyethoxy-2,4,6-trichlorobenzene, 1- (meth) acryloxyethoxypentabromobenzene, etc. .

Further, 2,3,4,5,6-pentabromophenyl (meth) acrylate, 3- (2,3,4,5,6-pentabromophenoxy-2-hydroxypropyl (meth) acrylate, 2 , 3,4,
5,6-Pentabromphenoxyethyl acrylate, 3-
(2,4,6-tribromophenoxy) -2-hydroxypropyl
(Meth) acrylate, 3- (2,4,6-tribromo-3-methylphenoxy) -2-hydroxypropyl (meth) acrylate,
2- (2,4,6-tribromo-3-methylphenoxy) -1-hydroxymethylethyl acrylate, 2,4-dibromophenyl
(Meth) acrylate, 2,4-dibromophenoxyethyl acrylate, 3- (2,4-dibromophenoxy) -2-hydroxypropyl (meth) acrylate, 3- (2,4-dibromo-3-methylphenoxy) 2-hydroxypropyl (meth) acrylate, 3- (2,3,4,5,6-pentachlorophenoxy-2-hydroxypropyl (meth) acrylate and the like.

Furthermore, 3- [2- (2,4,6-tribromophenyl) -4,6-dibromophenoxy] -2-hydroxypropyl
(Meth) acrylate, 3- [2- (2,4,6-tribromophenyl) -4,6-dibromophenoxy] -2-hydroxyethyl
(Meth) acrylate, 2- (2,4,6-tribromophenyl)-
4,6-dibromophenyl (meth) acrylate, 3- 〔2- (2,4
-Dibromophenyl) -4,6-dibromophenoxy] -2-hydroxypropyl (meth) acrylate, 2- (2,4-dibromophenyl) -4,6-dibromophenoxyethyl (meth) acrylate, 2- (2, 4-dibromophenyl) -4,6-dibromophenyl (meth) acrylate, 3- [2- (4-bromophenyl)-
4,6-Dibromophenoxy] -2-hydroxypropyl (meth) acrylate, 2- (4-bromophenyl) -4,6-dibromophenoxyethyl (meth) acrylate, 2- (4-bromophenyl) -4, 6-dibromophenyl (meth) acrylate, 2-
Phenyl-4-bromophenyl (meth) acrylate, 3- [2
-(2,4,6-Trichlorophenyl) -4,6-dichlorophenoxy] -2-hydroxypropyl (meth) acrylate, 2- (2,
4,6-Trichlorophenyl) -4,6-dichlorophenyl (meth)
A variety of acrylates, 3- [2- (4-chlorophenyl) -4,6-dichlorophenoxy] -2-hydroxypropyl (meth) acrylate, 2- (4-chlorophenyl) -4,6-dichlorophenyl (meth) acrylate, etc. A compound can be mentioned. Also, a mixture of these may be used. As used herein, the terms “(meth) acryloxy” and “(meth) acrylate” include any group or structure derived from acrylic acid or methacrylic acid.

In addition to the above-mentioned monomers, preferable radical polymerizable monomers in the present invention are 2-vinylnaphthalene, 4-vinylbiphenyl, 1,1'-diphenylethylene and the like. These will be described below. First 2-
Vinyl naphthalene is a powder crystal, and some
Contains alkylnaphthalene impurities such as methylnaphthalene and 2-ethylnaphthalene, but these are 10 parts by weight of the total.
It is preferably (%) or less, and particularly preferably 1 part by weight (%) or less. Since these impurities cause optical characteristics, especially birefringence, it is preferable that the impurities be as small as possible. A recrystallization method is generally used as a method for purifying 2-vinylnaphthalene, but a method in which it is dissolved in a solvent such as cyclohexane and then adsorbed on silica gel for purification is also effective.

Further, 4-vinylbiphenyl preferably used as a radically polymerizable monomer in the present invention is a powder crystal and contains a slight amount of alkylbiphenyl impurities such as 4-ethylbiphenyl and 4-methylbiphenyl at the time of production. These are preferably 10 parts by weight (%) or less, and particularly preferably 5 parts by weight (%) or less.
These impurities elute with time when formed into a molded article such as a lens, and become a factor that obstructs the surface of the lens such as clouding, dirt, or weather resistance. Further, in the surface treatment of the lens, the uniformity of hard coating and multi-coating is lacked, which causes the phenomenon of peeling of the treatment layer, so it is preferable that the amount is as small as possible. A recrystallization method is generally used as a method for purifying 4-vinylbiphenyl, but a method in which it is purified by dissolving it in a solvent and then adsorbing treatment to silica gel or the like is also effective.

Further, 1,1′-diphenylethylene, which is preferably used as a radically polymerizable monomer in the present invention, contributes to adjusting the crosslinking rate. It is possible to reduce the number and time of operations for removing and adding various polymerization inhibitors that are frequently used in the crosslinking step. Further, since it is an aromatic monomer that also has the effect of improving transparency, it has a great effect of being compounded. 1,1'-diphenylethylene contains some impurities such as 1,1'-diphenylethane at the time of production, but these are preferably not more than 20 parts by weight (%) and preferably not more than 10 parts by weight (%). Is particularly preferable. Distillation separation is generally used as a method for purifying 1,1′-diphenylethylene.

In the production of the copolymer of the present invention, the radical-polymerizable monomer as described above is added to 4,4'-, simultaneously with a polymerization initiator such as a polymerization initiator and a molecular weight modifier, if necessary. Polymerization is carried out by adding a predetermined amount of a divinylbiphenyl crosslinking agent. At this time, 4,4′-divinylbiphenyl may be melt fed to the polymerization system at a temperature equal to or higher than the melting point, or may be dissolved in a polymerization monomer or the like to be fed to the polymerization system, and the application range to the process is wide. In addition, 4,4'-divinylbiphenyl is an essential cross-linking agent component, and when used in combination with it, 3,3'-divinylbiphenyl, 3,4'-divinylbiphenyl, metadivinylbenzene, paradivinylbenzene, etc. are liquids. , 4,4′-divinylbiphenyl have good solubility, and can be used as a cross-linking agent individually or in combination of two or more in consideration of the cross-linking speed, the optical properties of the cross-linked product, the mechanical strength and the like. Further, it is preferable to use high-purity divinylbenzene as the divinylbenzene.

When one or more of the radically polymerizable monomers described above are polymerized using a crosslinking agent alone or in a mixture, the polymerization initiation method may be either thermal initiation or initiator initiation. When the initiator is initiated, the polymerization initiator may be either an organic peroxide or an azo compound. Examples of the organic peroxide here include t-hexyl peroxyisopropyl monocarbonate, peroxy esters such as t-hexyl peroxy-2-ethylhexanoate, 1,1-bis
Examples thereof include peroxyketals such as (t-hexylperoxy) 3,3,5-trimethylcyclohexane and diacyl peroxides such as lauroyl peroxide.

Examples of the azo compound initiator include 2,2'-azobisisobutyronitrile and 2,2'-azobis.
Azonitriles such as (2-methylbutyronitrile) and 1,1′-azobis (cyclohexane-1-carbonitri) can be mentioned. The half-life temperature of the initiator is T ₁ (1 hour half-life temperature)
80 ℃ to 120 ℃ is preferable, and the polymerization temperature is T ₁ + 5 ℃ to 20 ℃.
C. is preferable. The crosslinking efficiency of the initiator needs to be selected in consideration of the specificity of the process and the case of using it in combination with other crosslinking agents and additives. In any case, there is no particular limitation.

Further, molecular weight regulators to be appropriately blended when obtaining these resins are mercaptans such as t-dodecyl mercaptan, n-dodecyl mercaptan and n-octyl mercaptan, and monoterpenoids such as 1-methyl-4-isopropylidenecyclohexene. Examples thereof include styrene dimers such as 2,4-diphenyl-4-methyl-1-pentene. However, mercaptans have a drawback of odor, and monoterpenoids are natural products and may contain a large amount of impurities, which may cause deterioration of hue. 2,4-diphenyl-4-methyl-1-pentene and the like undergo degenerative chain transfer depending on the polymerization temperature, and thus the conversion rate does not increase and may cause deterioration of productivity.
It is necessary to select any molecular weight regulator after grasping these characteristics. In either case, there is no particular limitation.

The polymerization method is not limited,
It can also be used in a solution batch system, a continuous polymerization system, a suspension polymerization system or an emulsion polymerization system. However, since it is crosslinked, it is difficult to perform bulk polymerization treatment accompanied by melting or dissolution. In this respect, particularly when obtaining a high-refractive-index resin molding for an optical material, a casting polymerization method (cast polymerization method) of directly casting into an optical molding die such as a lens is desirable. The shape of the mold for casting polymerization is arbitrary, and may be plate-shaped, lens-shaped, cylindrical, prismatic, conical,
A mold having a spherical shape or a mold designed according to the purpose, a mold, or the like can be used. Polymerization proceeds with a mixture of a monomer containing a crosslinking agent and a polymerization initiator charged in such a mold under heating. Alternatively, the reaction is preliminarily advanced (preliminary polymerization) in another container in advance, and the dissolved gas such as air is degassed in vacuum, and then injected into a mold and heated to polymerize. The heating temperature varies depending on the kind of the monomer used, but it is preferable to carry out the polymerization while gradually gradually raising the temperature to 40 to 130 ° C. The total amount of the monomer, the crosslinking agent, the polymerization initiator and the like may be mixed at once, or may be separately mixed in stages.

This mixture also has the properties of n-octadecyl-3- (3,3,3), depending on its intended use as a molding polymer for optical materials.
5-di-t-butyl-4-hydroxyphenyl) propionate,
Hindered phenols such as 2,6-di-t-butyl-4-methylphenol, trisnonylphenyl phosphite,
Phosphorus compounds such as tris (2,4-di-t-butylphenyl) phosphite, sulfur compounds such as pentaerythrityl tetrakis (3-laurylthiopropionate), 2- [1- (2-hydroxy-3,
5-Di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate and other phenol acrylate-based antioxidants may be added. Further, an ultraviolet absorber, an anti-coloring agent, an antistatic agent, a fluorescent paint, a release agent, and other stabilizers may be added and used.

[0023]

EXAMPLES In order to describe the present invention more specifically, examples and comparative examples corresponding thereto are shown below. The refractive index of the vinyl resin composition obtained in Examples and Comparative Examples is
It was measured at 25 ° C. using an Abbe refractometer manufactured by Atago Co., Ltd. Explaining an embodiment for obtaining a vinyl resin, a raw material charging liquid composed of a polymerized monomer and an initiator is mixed and dissolved and then subjected to a vacuum devolatilization treatment. The devolatilized raw material charging solution was gently poured into a lens mold composed of a glass mold and a polypropylene gasket. Polymerization was performed by using an oven with a temperature control program and applying heat of an arbitrary heating pattern to the mold. After the completion of the polymerization, the mixture was gradually cooled to room temperature, and the resin composition was released from the glass mold and the polypropylene gasket. The released vinyl resin molding was left in a constant temperature and humidity room at 25 ° C for 30 days, and then the degree of haze of the molding was visually observed. 4,4'-divinylbiphenyl (DVBP) used in Examples and Comparative Examples has a purity of 94% (manufactured by Nippon Steel Chemical Co., Ltd.), high-purity divinylbenzene (pu-DVB) has a purity of 9%.
5% (Nippon Steel Chemical Co., Ltd .: DVB-960) product and divinylbenzene (DVB) are 60% pure (Nippon Steel Chemical Co., Ltd .: DVB-570) products.

Example 1 Styrene (St) and 4,4'-divinylbiphenyl (DVBP) were copolymerized. Regarding the composition ratio (parts by weight) of the raw materials, St / DVBP is 95/5, respectively. 0.1 parts by weight of t-butylperoxy-3.5.5-trimethylhexanoate (Trigonox 42: manufactured by Kayaku Akzo Co., Ltd.) was added as a polymerization initiator to the total amount of monomer raw materials, and the temperature was from 65 ° C to 125 ° C. The temperature was gradually raised over 35 hours to apply heat in a heating pattern to polymerize. The conditions after the completion of the polymerization were as described above, and the refractive index of the cast polymer resin thus obtained was measured to visually observe the degree of haze of the molded body. The resin composition is shown in Table 1 and the optical characteristics are shown in Table 2.

Comparative Example 1-1 Styrene (St) and high-purity divinylbenzene (pu-DVB: purity 9
5%) was copolymerized. Cast polymerization was performed under the same conditions as in Example 1 except that 4,4′-divinylbiphenyl was not added and the composition ratio (parts by weight) of the raw materials was 95/5 for each St / pu-DVB. The resin composition is shown in Table 1 and the optical characteristics are shown in Table 2. Comparative Example 1-2 Cast polymerization was carried out under the same conditions as in Comparative Example 1-1 except that high-purity divinylbenzene (pu-DVB) was changed to low-purity divinylbenzene (DVB: purity 60%). The resin composition is shown in Table 1 and the optical characteristics are shown in Table 2.

Example 2 Styrene (St), 4,4'-divinylbiphenyl (DVBP) and high-purity divinylbenzene (pu-DVB) were copolymerized. The composition ratio (parts by weight) of the raw materials is 65/5/30 for St / DVBP / pu-DVB, respectively.
Cast polymerization was carried out under the same conditions as in Example 1 except that The resin composition is shown in Table 1 and the optical characteristics are shown in Table 2.

Comparative Example 2-1 Styrene (St) and high-purity divinylbenzene (pu-DVB) were copolymerized. Cast polymerization was carried out under the same conditions as in Example 1 except that 4,4′-divinylbiphenyl was not added and the composition ratio (parts by weight) of the raw materials was St / DVB of 65/35. The resin composition is shown in Table 1 and the optical characteristics are shown in Table 2. Comparative Example 2-2 Cast polymerization was carried out under the same conditions as in Comparative Example 2-1 except that high-purity divinylbenzene (pu-DVB) was changed to low-purity divinylbenzene (DVB). The resin composition is shown in Table 1 and the optical characteristics are shown in Table 2.

Example 3 Styrene (St), methyl methacrylate (MMA), 4,4'-divinylbiphenyl (DVBP) and high-purity divinylbenzene (pu-DV)
B) was copolymerized. Raw material composition ratio (parts by weight) is St / MM
Cast polymerization was carried out under the same conditions as in Example 1 except that A / DVBP / pu-DVB was 20/40/5/35, respectively. The resin composition is shown in Table 1 and the optical characteristics are shown in Table 2.

Comparative Example 3-1 Styrene (St), methyl methacrylate (MMA) and high-purity divinylbenzene (pu-DVB) were copolymerized. Composition ratio of raw materials without adding 4,4'-divinylbiphenyl (parts by weight)
Was cast-polymerized under the same conditions as in Example 1 except that St / MMA / pu-DVB was 20/40/40, respectively. The resin composition is shown in Table 1 and the optical characteristics are shown in Table 2. Comparative Example 3-2 Cast polymerization was carried out under the same conditions as in Comparative Example 3-1, except that high-purity divinylbenzene (pu-DVB) was changed to low-purity divinylbenzene (DVB). The resin composition is shown in Table 1 and the optical characteristics are shown in Table 2.

Example 4 α-methylstyrene (αMS), methylmethacrylate (MM
A), 4,4'-Divinylbiphenyl (DVBP) and high-purity divinylbenzene (pu-DVB) were copolymerized. Composition ratio of raw materials
(Parts by weight) is αMS / MMA / DVBP / pu-DVB 10/60/5/25 respectively
Is. t-butyl peroxyisopropyl carbonate
(Perbutyl I: manufactured by NOF CORPORATION) was added to the total amount of monomer raw materials in 0.1
Part by weight was added, and the temperature was gradually raised from 65 ° C to 125 ° C over 35 hours. The conditions after completion of the polymerization are as described above. The resin composition is shown in Table 1 and the optical characteristics are shown in Table 2.

Comparative Example 4 α-methylstyrene (αMS), methylmethacrylate (MMA)
And divinylbenzene (DVB) were copolymerized. Composition ratio of raw materials without adding 4,4'-divinylbiphenyl (parts by weight)
Was cast-polymerized under the same conditions as in Example 4 except that the αMS / MMA / DVB were respectively set to 10/60/30. The resin composition is shown in Table 1 and the optical characteristics are shown in Table 2.

Example 5 N-phenylmaleimide (PMI), styrene (St), 4,4'-divinylbiphenyl (DVBP) and high-purity divinylbenzene (pu-DV)
B) was copolymerized. Raw material composition ratio (parts by weight) is PMI / St
Cast polymerization was carried out under the same conditions as in Example 4 except that / DVBP / pu-DVB was 5/30/5/60, respectively. The resin composition is shown in Table 1 and the optical characteristics are shown in Table 2.

Comparative Example 5 N-phenylmaleimide (PMI) styrene (St) and divinylbenzene (DVB) were copolymerized. The composition ratio (parts by weight) of the raw material was PMI / St / DVB without adding 4,4'-divinylbiphenyl.
Were cast-polymerized under the same conditions as in Example 4, except that each was 5/30/65. The resin composition is shown in Table 1 and the optical characteristics are shown in Table 2.

Example 6 2,4,6-tribromophenyl methacrylate (TBPM), 4,4 '
-Divinylbiphenyl (DVBP) and high-purity divinylbenzene
Copolymerization of (pu-DVB) was performed. The composition ratio (parts by weight) of the raw materials is
Cast polymerization was carried out under the same conditions as in Example 4 except that TBPM / DVBP / pu-DVB were 75/6/19, respectively. The resin composition is shown in Table 1 and the optical characteristics are shown in Table 2.

Comparative Example 6 2,4,6-Tribromophenyl methacrylate (TBPM) and divinylbenzene (DVB) were copolymerized. The composition ratio (parts by weight) of the raw material was TBPM without adding 4,4'-divinylbiphenyl.
Cast polymerization was carried out under the same conditions as in Example 4 except that / DVB was 75/25, respectively. The resin composition is shown in Table 1 and the optical characteristics are shown in Table 2.

Example 7 Acryloxydiethoxy-2,4,6-tribromobenzene (AO
DETBB), 4,4'-divinylbiphenyl (DVBP) and high-purity divinylbenzene (pu-DVB) were copolymerized. The composition ratio (parts by weight) of the raw materials was cast-polymerized under the same conditions as in Example 4 except that AODETBB / DVBP / pu-DVB were 75/6/19, respectively. The resin composition is shown in Table 1 and the optical characteristics are shown in Table 2.

Comparative Example 7 Acryloxydiethoxy-2,4,6-tribromobenzene (AO
Copolymerization of DETBB) and divinylbenzene (DVB) was performed. Four,
Composition ratio of raw material without adding 4'-divinylbiphenyl
(Parts by weight) was cast-polymerized under the same conditions as in Example 4 except that AODETBB / DVB was 75/25, respectively. The resin composition is shown in Table 1.
The optical characteristics are shown in Table 2.

Example 8 2,4,6-tribromophenyl methacrylate (TBPM), methacryloxydiethoxy-2,4,6-tribromobenzene (MAOD
ETBB), 4,4'-divinylbiphenyl (DVBP) and high-purity divinylbenzene (pu-DVB) were copolymerized. Composition ratio of raw materials
(Weight part) TBPM / MAODETBB / DVBP / pu-DVB is 30/40 respectively
Cast polymerization was carried out under the same conditions as in Example 4 except that the ratio was / 6/24. The resin composition is shown in Table 1 and the optical characteristics are shown in Table 2.

Comparative Example 8 2,4,6-tribromophenyl methacrylate (TBPM), methacryloxydiethoxy-2,4,6-tribromobenzene (MAOD
Copolymerization of ETBB) and divinylbenzene (DVB) was performed. 4,4 '
-Catalyst polymerization was carried out under the same conditions as in Example 4 except that divinylbiphenyl was not added and the composition ratio (parts by weight) of the raw materials was TBPM / MAODETBB / DVB 30/40/30, respectively. The resin composition is shown in Table 1 and the optical characteristics are shown in Table 2.

Example 9 Acryloxyethoxy-2,4,6-tribromobenzene (AOEO
TBB), methacryloxydiethoxy-2,4,6-tribromobenzene (MAODETBB), and styrene (St) were copolymerized with 4,4′-divinylbiphenyl (DVBP). AOEOTBB / MAODETBB / St / DVBP are 30/35/30/5 respectively for the composition ratio (parts by weight) of raw materials
Cast polymerization was carried out under the same conditions as in Example 4 except that The resin composition is shown in Table 1 and the optical characteristics are shown in Table 2.

Comparative Example 9 Acryloxyethoxy-2,4,6-tribromobenzene (AOEO
TBB), methacryloxydiethoxy-2,4,6-tribromobenzene (MAODETBB), styrene (St) and divinylbenzene (D
VB) was copolymerized. Without adding 4,4'-divinylbiphenyl, the composition ratio (parts by weight) of the raw material was AOEOTBB / MAODETBB / S.
Cast polymerization was carried out under the same conditions as in Example 4 except that t / DVB was set to 30/35/30/5, respectively. The resin composition is shown in Table 1 and the optical characteristics are shown in Table 2.

Example 10 2,3,4,5,6-pentabromophenyl acrylate (PBPA),
Copolymerization of 4,4'-divinylbiphenyl (DVBP) and high-purity divinylbenzene (pu-DVB) was performed. The composition ratio (parts by weight) of the raw materials was cast-polymerized under the same conditions as in Example 4 except that PBPA / DVBP / pu-DVB were 80/5/15, respectively. Table 1 shows the resin composition
Table 2 shows the optical characteristics.

Comparative Example 10 2,3,4,5,6-pentabromophenyl acrylate (PBPA) and divinylbenzene (DVB) were copolymerized. Without adding 4,4'-divinylbiphenyl, the composition ratio (parts by weight) of the raw materials was
Cast polymerization was carried out under the same conditions as in Example 4 except that PBPA / DVB was set to 80/20. The resin composition is shown in Table 1 and the optical characteristics are shown in Table 2.

Example 11 3- (2,4,6-tribromo-3-methylphenoxy) -2-hydroxypropyl acrylate (TBMPHA), styrene (St), 4,4 '
-Divinylbiphenyl (DVBP) and high-purity divinylbenzene
Copolymerization of (pu-DVB) was performed. The composition ratio (parts by weight) of the raw materials is
Cast polymerization was carried out under the same conditions as in Example 4 except that TBMPHA / St / DVBP / pu-DVB were 60/20/5/15, respectively. The resin composition is shown in Table 1 and the optical characteristics are shown in Table 2.

Comparative Example 11 3- (2,4,6-tribromo-3-methylphenoxy) -2-hydroxypropyl acrylate (TBMPHA), styrene (St) and divinylbenzene (DVB) were copolymerized. The composition ratio (parts by weight) of the raw material was TBMP without adding 4,4'-divinylbiphenyl.
Cast polymerization was carried out under the same conditions as in Example 4 except that HA / St / DVB was set to 60/20/20 respectively. The resin composition is shown in Table 1 and the optical characteristics are shown in Table 2.

Example 12 3- [2- (2,4-Dibromophenyl) -4,6-dibromophenoxy] -2-hydroxypropyl acrylate (Br ₂ PBr ₂ PH
A), bromostyrene (Br-St), 4,4'-divinylbiphenyl
(DVBP) and high-purity divinylbenzene (pu-DVB) were copolymerized. The composition ratio (parts by weight) of the raw materials is Br ₂ PBr ₂ PHA / Br-St / DVB
Cast polymerization was carried out under the same conditions as in Example 4 except that P / pu-DVB was 70/10/5/15, respectively. The resin composition is shown in Table 1 and the optical characteristics are shown in Table 2.

Comparative Example 12 3- [2- (2,4-Dibromophenyl) -4,6-dibromophenoxy] -2-hydroxypropyl acrylate (Br ₂ PBr ₂ PH
A), bromstyrene (Br-St) and divinylbenzene (DVB) were copolymerized. The composition ratio (parts by weight) of the raw materials is Br ₂ PBr ₂ PHA
Cast polymerization was carried out under the same conditions as in Example 4 except that / Br-St / DVB was set to 70/10/20, respectively. The resin composition is shown in Table 1 and the optical characteristics are shown in Table 2.

[Table 1]

[0048]

[Table 2]

Example 13 Copolymerization of 2-vinylnaphthalene (VN), styrene (St) and 4,4'-divinylbiphenyl (DVBP) was carried out. Composition ratio of raw materials
VN / St / DVBP (weight part) is 35/60/5 respectively. 0.1 parts by weight of t-butylperoxy-3.5.5-trimethylhexanoate (Triconox 42: manufactured by Kayaku Akzo) was added to the total amount of the monomer raw materials, and the temperature was gradually increased from 65 ° C to 125 ° C over 35 hours. The temperature was raised to. The resin composition is shown in Table 3 and the optical characteristics are shown in Table 4.

Example 14 4-Vinylbiphenyl (VBP), styrene (St) and 4,4'-divinylbiphenyl (DVBP) were copolymerized. Composition ratio of raw materials
(Parts by weight) VBP / St / DVBP is 35/60/5, respectively. T-Butylperoxy-3.5.5-trimethylhexanoate (Trigonox 42: manufactured by Kayaku Akzo) was added to the total amount of monomer raw materials.
0.1 part by weight was added, and the temperature was gradually raised from 65 ° C to 125 ° C over 35 hours. The resin composition is shown in Table 3 and the optical characteristics are shown in Table 4.

Example 15 2-Vinylnaphthalene (VN), Styrene (St), 4,4'-Divinylbiphenyl (DVBP), High-purity divinylbenzene (pu-DVB)
Was copolymerized. Raw material composition ratio (parts by weight) is VN / St / DV
BP / pu-DVB are 35/55/5/5 respectively. 0.1 parts by weight of t-butylperoxy-3.5.5-trimethylhexanoate (Trigonox 42: manufactured by Kayaku Akzo) was added to the total amount of the monomer raw materials, and gradually increased from 65 ° C to 125 ° C over 35 hours. The temperature was raised to. The resin composition is shown in Table 3 and the optical characteristics are shown in Table 4.

Comparative Example 13 Styrene (St) and divinylbenzene (DVB) were copolymerized. No 4,4'-divinylbiphenyl was added. The composition ratio (parts by weight) of the raw materials is 90/10 for St / DVB, respectively.
0.1 parts by weight of t-butylperoxy-3.5.5-trimethylhexanoate (Trigonox 42: manufactured by Kayaku Akzo) was added to the total amount of the monomer raw materials, and gradually increased from 65 ° C to 125 ° C over 35 hours. The temperature was raised to. The resin composition is shown in Table 3 and the optical characteristics are shown in Table 4.

Example 16 2-Vinylnaphthalene (VN), styrene (St), methylmethacrylate (MMA), 4,4'-divinylbiphenyl (DVBP) and 3,3 '
-Divinylbiphenyl (3,3'-DVBP) and 3,4'-divinylbiphenyl (3,4'-DVBP) were copolymerized. Composition ratio of raw materials
(Parts by weight) are VN / St / MMA / DVBP / 3, 3'-DVBP / 3, 4'-DVBP 20/10/10/10/25/25, respectively. T for the total amount of monomer raw materials
-Butylperoxy-3.5.5-trimethylhexanoate
(Trigonox 42: manufactured by Kayaku Akzo) was added 0.1 part by weight,
The temperature was gradually raised from 65 ° C to 125 ° C over 35 hours. The resin composition is shown in Table 3 and the optical characteristics are shown in Table 4.

Example 17 Styrene (St), methyl methacrylate (MMA), 1,1-diphenylethylene (DPE), 4,4'-divinylbiphenyl (DVBP)
And high-purity divinylbenzene (pu-DVB) were copolymerized.
The composition ratio (parts by weight) of the raw materials is 39/20/1/5/35 for St / MMA / DPE / DVBP / DVB, respectively. 0.1 parts by weight of t-butylperoxy-3.5.5-trimethylhexanoate (Trigonox 42: manufactured by Kayaku Akzo) was added to the total amount of the monomer raw materials, and gradually increased from 65 ° C to 125 ° C over 35 hours. The temperature was raised to. The resin composition is shown in Table 3 and the optical characteristics are shown in Table 4.

Reference Example 1 Styrene (St), methyl methacrylate (MMA), 4,4'-divinylbiphenyl (DVBP) and divinylbenzene (DVB) were copolymerized. Raw material composition ratio (parts by weight) is St / MMA / DVBP / DV
B is 40/20/5/35 respectively. T for the total amount of monomer raw materials
-Butylperoxy-3.5.5-trimethylhexanoate
(Trigonox 42: manufactured by Kayaku Akzo) was added 0.1 part by weight,
The temperature was gradually raised from 65 ° C to 125 ° C over 35 hours. The resin composition is shown in Table 3 and the optical characteristics are shown in Table 4.

Example 18 2-Vinylnaphthalene (VN), 4-Vinylbiphenyl (VBP),
Copolymerization of styrene (St) and 4,4'-divinylbiphenyl (DVBP) was performed. Raw material composition ratio (parts by weight) is VN / VBP / St / DVBP
Are 35/15/45/5 respectively. T-
Butyl peroxy-3.5.5-trimethylhexanoate (Trigonox 42: manufactured by Kayaku Akzo) was added in an amount of 0.1 part by weight to obtain 65.
The temperature was gradually raised from ° C to 125 ° C over 35 hours. The resin composition is shown in Table 3 and the optical characteristics are shown in Table 4.

Example 19 2-Vinylnaphthalene (VN), 2,4,6-tribromophenyl methacrylate (TBPM), 4,4'-divinylbiphenyl (DVBP)
And high-purity divinylbenzene (pu-DVB) were copolymerized.
The composition ratio (parts by weight) of the raw materials is 10/65/6/19 for VN / TBPM / DVBP / pu-DVB, respectively. Add 0.1 parts by weight of t-hexyl peroxyisopropyl carbonate (Perhexyl I: made by NOF Corporation) to the total amount of monomer raw materials, and from 65 ° C to 125 ° C
The temperature was gradually raised over 35 hours. The resin composition is shown in Table 3 and the optical characteristics are shown in Table 4.

Example 20 2-Vinylnaphthalene (VN), acryloxydiethoxy-2,
Copolymerization of 4,6-tribromobenzene (AODETBB), 4,4'-divinylbiphenyl (DVBP) and high-purity divinylbenzene (pu-DVB) was performed. Raw material composition ratio (parts by weight) is VN / AODETBB / DVB
P / pu-DVB are 10/65/6/19 respectively. 0.1 parts by weight of t-hexyl peroxyisopropyl carbonate (Perhexyl I: manufactured by NOF CORPORATION) was added to the total amount of the monomer raw materials, and the mixture was heated to 65 °
The temperature was gradually raised from C to 125 ° C over 35 hours. The resin composition is shown in Table 3 and the optical characteristics are shown in Table 4.

Example 21 2-Vinylnaphthalene (VN), 2,4,6-tribromophenyl methacrylate (TBPM), methacryloxydiethoxy-2,4,6
-Tribromobenzene (MAODETBB), 4,4'-divinylbiphenyl (DVBP) and high-purity divinylbenzene (pu-DVB) were copolymerized. Raw material composition ratio (parts by weight) is VN / TBPM / MAODETBB
/ DVBP / pu-DVB are 10/20/40/6/24 respectively. 0.1 parts by weight of t-hexyl peroxyisopropyl carbonate (Perhexyl I: manufactured by NOF CORPORATION) was added to the total amount of monomer raw materials, and the temperature was gradually raised from 65 ° C to 125 ° C over 35 hours. The resin composition is shown in Table 3 and the optical characteristics are shown in Table 4.

Example 22 2-Vinylnaphthalene (VN), 3- (2,4,6-tribromo-3-methylphenoxy) -2-hydroxypropyl acrylate (TBM
PHA), styrene (St), 4,4'-divinylbiphenyl (DVBP)
And high-purity divinylbenzene (pu-DVB) were copolymerized.
The composition ratio (parts by weight) of the raw materials is 10/50/20/5/15 for VN / TBMPHA / St / DVBP / pu-DVB, respectively. t-hexyl peroxyisopropyl carbonate (Perhexyl I: NOF Corporation)
0.1 parts by weight with respect to the total amount of the monomer raw material, from 65 ° C. 12
The temperature was gradually raised to 5 ° C over 35 hours. Table 3 shows the resin composition
Table 4 shows the optical characteristics.

Example 23 2-Vinylnaphthalene (VN), 3- [2- (2,4-dibromophenyl) -4,6-dibromophenoxy] -2-hydroxypropyl acrylate (Br ₂ PBr _2P HA), bromstyrene ( Br-St), 4,
Copolymerization of 4'-divinylbiphenyl (DVBP) and high-purity divinylbenzene (pu-DVB) was performed. Composition ratio of raw materials (parts by weight)
Is VN / Br2PBr _2P HA / Br-St / DVBP / pu-DVB respectively 10/60/1
It is 0/5/15. 0.1 parts by weight of t-hexyl peroxyisopropyl carbonate (Perhexyl I: manufactured by NOF CORPORATION) was added to the total amount of monomer raw materials, and the temperature was gradually raised from 65 ° C to 125 ° C over 35 hours. The resin composition is shown in Table 3 and the optical characteristics are shown in Table 4.

Example 24 2-Vinylnaphthalene (VN), 1,1-diphenylethylene (DP
E), 3- [2- (2,4-dibromophenyl) -4,6-dibromophenoxy] -2-hydroxypropyl acrylate (Br ₂ PBr ₂ PH
A), bromstyrene (Br-St), 4,4'-divinylbiphenyl
(DVBP) and high-purity divinylbenzene (pu-DVB) were copolymerized. The composition ratio (parts by weight) of the raw materials is VN / DPE / Br ₂ PBr ₂ PHA / Br
-St / DVBP / pu-DVB are 10/1/59/10/5/15 respectively. t-
Hexyl peroxyisopropyl carbonate (Perhexyl I: manufactured by NOF CORPORATION) was added in an amount of 0.1 part by weight with respect to the total amount of monomer raw materials, and the temperature was gradually raised from 65 ° C to 125 ° C over 35 hours. The refractive index of the obtained resin composition was measured and the results are shown in Table 1.
Summarized in.

[0063]

[Table 3]

[0064]

[Table 4]

[0065]

As described above, according to the present invention,
By using as a crosslinking agent having 4'-divinylbiphenyl (DVBP) as a main component, it is possible to easily obtain a transparent high-refractive-index resin crosslinked body suitable for optical use without clouding, especially by a cast polymerization method. I can. Further, when used in combination with high-purity divinylbenzene as a crosslinking agent, it is possible to improve the conventional defects such as exerting an excellent synergistic effect.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takeharu Akishima 4-6-14 Nakai, Nakai, Kokurakita-ku, Kitakyushu, Fukuoka

Claims (6)

[Claims] 1. A copolymer obtained by copolymerizing 4,4′-divinylbiphenyl as a cross-linking agent with a radical-polymerizable monomer alone or in combination. Crosslinked resin. 2. A cross-linking agent comprising 4,4'-divinyl biphenyl and divinyl benzene purified to a purity of 80% by weight or more as a cross-linking agent, which is copolymerized with a single or a plurality of radical-polymerizable monomers. A crosslinked resin, characterized by comprising the copolymer obtained by the above. 3. A type selected from 4,3'-divinylbiphenyl as an essential component and 3,3'-divinylbiphenyl, 3,4'-divinylbiphenyl, metadivinylbenzene, paradivinylbenzene. A resin cross-linked product comprising the above-mentioned combination as a cross-linking agent, and a copolymer obtained by copolymerizing this with a single or a plurality of radical-polymerizable monomers. 4. The resin crosslinked product according to claim 1, wherein the copolymer is obtained by a cast polymerization method. 5. The resin according to claim 1, wherein the monomer capable of radical polymerization with 4,4′-divinylbiphenyl is a monomer represented by the following general formula [1]. Crosslinked body. [Chemical 1] (In the formula, R is hydrogen or a C1-C2 alkyl group, R'is hydrogen or a C1-C2 alkyl group or a halogen-substituted phenyl group, X
Is a halogen element excluding fluorine, p is an integer of 1 to 5 showing the number of halogen substitutions, k is an integer of 0 to 1, m is an integer of 0 to 4,
p + m is 5 or less. A is -CH2-CH2-,-CH2-CH (OH) -CH2-,-C
It represents one kind of group selected from H (CH2OH) -CH2-, -CH2-CH2-CH2-, -CH2-CH (CH3)-. ) 6. A cross-linking agent of 4,4′-divinylbiphenyl, and a radically polymerizable monomer thereof is selected from at least 2-vinylnaphthalene, 4-vinylbiphenyl or 1,1′-diphenylethylene. The cross-linked resin according to any one of claims 1 to 3, which comprises one or more kinds of selected monomers.