JPS63170401A - Resin composition having high refractive index - Google Patents

Abstract

PURPOSE:To obtain the titled composition having long-period preservation stability and heat stability, not inhibiting initiator activity of polymerization initiator, free from problem of bad smell, by adding a specific polymerization initiator to a radically polymerizable polyfunctional vinyl monomer. CONSTITUTION:An aromatic ring-containing radically polymerizable polyfunctional vinyl monomer is blended with usually 0.01-1,000ppm N- nitrosophenylhydroxylamine salt compound shown by formula I (n is 1-4; X is metal or 1-4 valance or NH4). A di(meth)acrylate shown by formula II (R is H or CH3; X is Cl, Br or F; n is 0-4; m is 0-6; A is -SO2-, etc.) or an isocyanate modified monomer shown shown by formula III (R1 and R2 are CH3 or H; X is Cl, Br or F; Z is polyfunctional isocyanate residue; A is SO2; m and n are 0-4 and m+n=0-4; p is 0-4; q is 2 or 3) is preferable as the monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a high refractive index resin composition with excellent storage stability.

[Prior art] Generally, in order to obtain a resin with a high refractive index, monomers (
It is effective to 1) contain an aromatic ring, and (2) contain a halogen element other than fluorine. Therefore, it is common practice to use the aromatic vinyl monomer (1) or a nuclear halogen-substituted aromatic vinyl monomer using a combination of (1) and (2).

For example, as an example of (1), JP-A-59-19170
As examples of using (1) and (2) in combination, Japanese Patent Publication No. 58-14449 and Japanese Unexamined Patent Application Publication No. 59-8709 describe that Japanese Patent Publication No. 8709 provides a high refractive index.

[Problems to be solved by the invention] However, these high refractive index monomers containing an aromatic ring and a vinyl group have radical polymerizability in common, and all of them cannot be stored for a long period of time or heated. If this happens, polymerization progresses, resulting in increased viscosity and gelation. As a countermeasure against this, various polymerization inhibitors are mixed and added for the purpose of capturing radicals and suppressing the polymerization of Nanatsuma. For example, tri-nitrophenylmethyl, diphenylpicrylhydrazyl (DPPH), and tri-nitrophenyl hydrazyl are used as radicals that are themselves stable. On the other hand, those that react with radicals to become stable radicals include quinones such as benzoquinone and hydroquinone, polyoxy compounds such as pt-butylcatechol, nitro compounds such as nitrobenzene and todinitrobenzene, and p-7 enyldiamine. Organic sulfur compounds such as 7mino compounds, dimethylthiocarbamic acid, and sulfur are used. However, it was not sufficient to suppress the increase in viscosity and the occurrence of gelation. Also, depending on the polymerization inhibitor,
Even when an initiator is added, there are problems such as a polymerization inhibiting effect, a decrease in initiator efficiency, and a bad odor.

The present invention has focused on this problem, and by adding and mixing a specific polymerization inhibitor, even if it is a monomer for high refractive index resin made of a polyfunctional vinyl monomer containing an aromatic ring and capable of radical polymerization, it can be used for a long period of time. It is an object of the present invention to provide a composition for a high refractive index resin that is stable even when stored or heated, does not inhibit the initiator efficacy of a polymerization initiator, and does not have the problem of bad odor.

Means for Solving Problem E] The present invention has the following configuration to achieve the above object.

That is, the present invention is characterized in that a polyfunctional vinyl monomer containing an aromatic ring and capable of radical polymerization contains an N-nitrosophenylhydroxylamine salt compound represented by the general formula [I]. Integer X of ~4: relates to a metal selected from monovalent to tetravalent metals and NH4.

In the present invention, such a high refractive index resin composition is a polyfunctional vinyl monomer containing an aromatic ring and capable of radical polymerization, in particular a di(meth)acrylate monomer represented by the general formula [II].
or general formula II] is effective.

Specific examples of the general formula [I[] include the following.

2.2-bis(4-acryloxyphenyl)propane,
2.2-bis(4-methacryloxyphenyl)propane, 2.2-bis(4-acryloxyethoxyphenyl)
Propane, 2,2-bis(4-methacryloxyethoxyphenyl)propane, 2,2-bis(4-methacryloxyethoxyphenyl)sulfone, 2,2-bis(4-methacryloxyethoxyphenyl)sulfone, and these compounds 2,2-bis(4-
Chryloxyethoxy-3,5-dibromophenyl)propane, 2,2-bis(4-methacryloxyethoxy-3)
,5-dibromophenyl)propane, 2,2-bis(4
-acryloxyethoxy-3,5-dibromophenyl)
Examples include sulfone, 2,2-bis(4-methacryloxyethoxy-3,5-dibromophenyl)sulfone, and the like. These monomer compounds can be used not only alone but also in combination of two or more.

Specific examples of general formula [III] include the following.

These monomer compounds can be used not only alone but also in combination of two or more.

Specific examples of general formula [III] include the following.

Addition reaction product of reacting 2 moles of bisphenol A monoacrylate with 1 mole of xylylene diisocyanate, addition reaction product of reacting 2 moles of tetrabromo bisphenol A jetoxy monoacrylate with 1 mole of hexamethylene diisocyanate, 2 moles of bisphenol S monoacrylate and 1 mole of diphenylmethane diisocyanate, and an addition reaction product in which 2 moles of tetrabromo bisphenol S jetoxy monomethacrylate are reacted with 1 mole of xylylene diisocyanate. These monomer compounds can be used not only singly but also with the general formula [
It is also possible to use a mixture of two or more of [n] and [I[[].

In the present invention, depending on the degree of various physical properties desired depending on the intended use of the high refractive index resin, an Ichinomiya functional monomer having a radically polymerizable double bond may be used in addition to the crosslinking polyfunctional monomer. It is also possible to add and/or blend a polyfunctional monomer.

Such monomers include styrene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, phenyl (meth)acrylate, monochlorophenyl' (meth)acrylate, dichlorophenyl (meth)acrylate, trichlorophenyl (meth)acrylate. , Monobromophenyl (meth)acrylate, Dibromophenyl (meth)acrylate, Tribromophenyl (meth)acrylate, Pentabromophenyl (meth)acrylate, Monochlorophenoxyethyl (meth)acrylate, Dichlorophenoxyethyl (meth)acrylate, Lichlorof Enoxyethyl (meth)acrylate, monobromophenoxyethyl (meth)acrylate, dibromonoenoxyethyl (meth)acrylate, tribromophenoxyethyl (meth)acrylate,
pentabromophenoxyethyl (meth)acrylate,
Benzyl (meth)acrylate, bromobenzyl acrylate, dibromobenzyl acrylate, α-naphthyl 7-acrylate, α-naphthyl methacrylate, ethyl acrylate, ethyl methacrylate, tribromopentyl methacrylate, 2゜3-dibromopropyl acrylate, or phenylallyl carbonate, benzyl Allyl carbonate, allyl benzoate, allyl naphthalenecarboxylate and its halogen derivatives, bisallyl terephthalate, bisallyl isophthalate,
Trimellitic acid triallyl ester, 1,3-benzene bisallyl carbonate, 1,4-benzene bisallyl carbonate, 1,5-naphthalene bisallyl carbonate, 1,6-naphthalene bisallyl carbonate, 2
, 6-naphthalene bisallyl carbonate, 4,4'-
diphenylpropane allyl carbonate, 4.4-
Diphenylsulfone bisallyl carbonate, 1,4-
Di(meth)acryloxybenzene, 1,4-di(meth)
Examples include acryloxyethoxybenzene, divinylbenzene, divinylnaphthalene, and aromatic polyvalent vinyl compounds in which the aromatic ring of these compounds is substituted with a nuclear halogen.

The composition ratio of the crosslinking polyfunctional monomer, which is an essential component in the present invention, and the above-mentioned -functional monomer varies in thermal properties, mechanical properties, optical properties, etc. depending on the use of the high refractive index resin. Therefore, it cannot be limited uniformly, but for example, when considering eyeglass lenses, the crosslinking polyfunctional monomer, which is an essential component in the present invention, is 5% by weight or more, preferably 10% by weight or more. It is preferable to do so. If the amount is less than 5% by weight, crosslinking will be insufficient, resulting in poor cutting and polishing processability, heat softening resistance, and impact resistance.

On the other hand, the composition ratio of the crosslinking polyfunctional monomer, which is an essential component in the present invention, and the polyfunctional monomer cannot be uniformly limited depending on the use of the high refractive index resin. It is preferable that the amount of the crosslinking polyfunctional monomer as an essential component is 5% by weight or more, preferably 10% by weight or more.

If the amount is less than 5%, the stabilizing effect against long-term storage and heating as shown in the present invention decreases.

The component of the general formula [I] of the present invention includes an ammonium salt of N-nitrosophenylhydroxylamine, a monovalent metal salt such as Na, and CU.

Divalent metal salts such as Ni, Co, Mn, ln, MQ, and Ti; trivalent metal salts such as AI, 3i, and Fe.

Examples include 4frJ metal salts such as sn and v. Among these, N-nitrosophenylhydroxylamine 〇 salt is particularly preferably used.

The amount of addition of the component of general formula [I] is O,0OIJX'to
, ooo ppm or less, preferably in the range of 0.01 or more and i, ooo ppm or less. 0.0'+
If it is less than ppm, the effect of improving the thermal stability and storage stability of the high refractive index resin composition, which is the object of the present invention, is poor, and i, o
When it exceeds ooppm, the high refractive index resin composition becomes colored, and the coloration tends to increase due to heating or long-term storage.

In producing the high refractive index resin with excellent thermal stability of the present invention, in addition to the above-mentioned essential ingredients, antistatic agents, anticoloring agents, surface smoothing agents, ultraviolet absorbers, antioxidants, etc. Practicality can be improved by incorporating additives such as: For example, antistatic agents include nonionic surfactants and quaternary ammonium salts; anticoloring agents include triphenylphosphine, triphenylantimony, and triphenyl arsenic; and surface smoothing agents include silicone compounds. , fluorine surfactants, organic surfactants, etc., as ultraviolet absorbers, 2-(hydroxy-5-methylphenyl)benzotriazole, 2-(hydroxy-5-tert-butylphenyl)benzotriazole, 2-(3 °, 5-di-tert-butyl-2-hydroxyphenyl)-benzotriazole, 2-hydroxy-4-n-octoxybenzophenone, etc. As antioxidants, hindered phenol, hindered amine, etc. can be added. .

For the production of the high refractive index resin with excellent thermal stability of the present invention, known radical polymerization methods, photopolymerization methods, etc. can be employed. That is, after using the above monomers alone or after mixing the above various monomers, a polymerization initiator such as diisopropyl peroxydicarbonate, similystyl peroxydicarbonate, tert-butyl peroxypivalate, lauroyl peroxide is added. , tert-butylperoxyisobutyrate, tert-butylperoxyisopropyl carbonate, di-tert-butyl peroxide, benzoyl peroxide, azodiisobutyronitrile, azobis-tert-octane, etc. per 100 parts of the monomer, Mix approximately 0.01 to 10 parts by weight.

The resulting mixture is poured into a mold prepared in advance and heated gradually to complete polymerization.

In this case, even if the component of general formula [I], which has the role of suppressing polymerization due to heating, is present, if the amount added is within the above range, polymerization will proceed sufficiently by adding the above polymerization initiator, and for practical use. It is possible to obtain a high refractive index resin with excellent performance. Note that the polymerization temperature and polymerization time cannot be uniformly limited because they vary depending on the type of monomers used, the composition ratio, and the selection of the polymerization initiator, but they are generally 1 to 1 at 40 to 150 °C.
It is preferable to complete the polymerization over 00 hours.

Further, the resin of the present invention can also be produced using a photopolymerization method. That is, photosensitizers using the above monomers alone or in combination with various monomers, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzophenone, 2-hydroxy-2-methyl-propiophenone, 0.01 to 10 parts by weight of benzyl dimethyl ketal, benzoin isopropyl ether, acetophenone, dimethoxyacetophenone, 1-chloroanthraquinone, 1,4-naphthoquinone, etc. are mixed with 100 parts by weight of the monomer, and the mixture is heated under an ultraviolet lamp. Polymerization is carried out by irradiation with a mercury lamp, etc. In this case, it is also possible to partially use a polymerization initiator.

[Examples] In order to explain the present invention in more detail, Examples are given below, but the present invention is not limited to these Examples.

Example 1 2.2-bis(4-methacryloxyethoxy-3,5-
dibromophenyl) propane 50% by weight, styrene 50%
N-nitrosophenylhydroxylamine Aα in weight%
10 pDm of salt was added and mixed well. This mixed solution was placed in a glass ampoule and heated to 60°C. When the contents of the ampoule were examined 24 hours after the start of heating, no increase in viscosity or gelation was observed, and the ampoule remained liquid with the same properties as before heating.

Next, 0.1% by weight of diisopropyl peroxydicarbonate was added to this mixed solution, and the mixture was poured into a mold consisting of a polyethylene gasket and a glass lens mold.
The temperature was gradually raised from 40°C to 110°C over 30 hours to carry out a polymerization reaction.

The polymerization was monitored by a gel fraction method, and showed a polymerization efficiency of about 48% in 5 hours after the start of heating and 99% or more in 30 hours.

The obtained resin exhibited a refractive index of 1.59, and an extremely excellent colorless and transparent lens was obtained.

Comparative Example 1 In Example 1, when the same Motsuma composition was heated at 60°C except that no salt was used for N-nitrosophenylhydroxylamine, corrosion, viscosity increase, and gelation occurred after 6 hours. . Furthermore, 0.1% by weight of diisopropyl peroxydicarbonate was added to the above mixed solution, and heating polymerization was carried out in a mold in the same manner as in Example 1. The polymerization reaction rate was approximately 50% after 5 hours and 30% after 30 hours. The polymerization behavior was 99% or more, which was the same as in Example 1.

Example 2 2.2-bis(4-methacryloxyethoxy-3,5-
60 parts by weight of propane (dibromophenyl) was mixed with divinylbenzene (manufactured by Dow Chemical Company, trade name: "DVB-55")
5 pmm of N-nitrosophenylhydroxylamine salt was added to 20 parts by weight of purity 60% and 20 parts by weight of chlorstyrene (ortho/para=65/35) and mixed well. This mixed solution was heated at 70° C., but no increase in viscosity or gelation was observed even after 15 hours had passed, and the mixture remained in the same liquid state as the initial state.

Next, 0.1% by weight of tert-butylperoxyisobutyrate and te
The mixture was poured into a mold consisting of rt-butylperoxyisopropyl carbonate and a glass lens mold, and the temperature was raised stepwise from 40°C to start L/120°C to carry out a polymerization reaction over 24 hours.

After the start of polymerization, the polymerization reaction rate was 38% in 4 hours and 99% or more in 24 hours. The obtained resin has a refractive index of 1.62
A colorless and transparent lens was obtained.

Comparative Example 2 When the same Motsuma composition as in Example 2 was heated at 70° C. except that N-nitrosophenylhydroxylamine Aα salt was not used, an increase in viscosity and gelation occurred after 3 hours. Also, add te to the above mixture.
rt-butyl peroxyisobutyrate 0.1% by weight,
and tert-butylperoxyisopropyl carbonate (0.1%) and heated polymerization in a mold in the same manner as in Example 2. The polymerization reaction rate was 38% in 4 hours and over 99% in 24 hours. The polymerization behavior was the same as in Example 2.

Comparative Example 3 In Example 2, 5 oppm of hydroquinone monomethyl ether was added instead of N-nitrosophenylhydroxylamine Al11 salt and the same Motsuma composition was heated at 70°C. After 5 hours, no increase in viscosity was observed. Admitted.

In addition, tert-butylperoxyisobutyrate 0.1% by weight and te
When 0.1% by weight of rt-peroxyisopropyl carbonate was added and heat polymerization was carried out in a mold in the same manner as in Example 2, the polymerization reaction rate was 40% in 4 hours and 99% or more in 24 hours after the start of polymerization. showed that.

Example 3 5.0 parts by weight of hexamethylene diisocyanate, 2-(
45.0 parts by weight of 4-acryloxyethoxy-3,5-dibromophenyl)2-(,i-hydroxyethoxy-3,5-dibromophenyl)propane, and divinylbenzene (manufactured by Dow Chemical Company, trade name DV B-5
NGO-
0.01% by weight of dibutyltin dilaurate as an OH reaction catalyst and 51) pm of 〇 salt were added to N-nitrosophenylhydroxylamine and mixed well. This mixed solution was heated at 70° C., but no increase in viscosity or gelation was observed even after 24 hours had passed, and the mixture remained liquid with the same properties as the initial state.

Next, g-tert-
Add 0.1% by weight of butyl peroxide and 0.05% by weight of diisopropyl peroxydicarbonate,
Polymerization was performed by injecting it into a mold consisting of a polyethylene gasket and a glass lens mold. Polymerization was first heated at 50°C for 5 hours, followed by heating at 90°C for 11 hours.
The mixture was heated at 00°C for 5 hours and at 120°C for 5 hours. The polymerization reaction rate was approximately 45% after 5 hours from the start of heating and 99% or more after 5 hours at 120°C. The obtained lens has a refractive index of 1.
61, it was colorless and transparent and had strong properties.

Comparative Example 4 The same Motsuma composition as in Example 3 except that N-nitrosophenylhydroxylamine Aα salt was not used was heated at 70°C.
Viscosity increase and gelation occurred. In addition, the above mixture
When 0.05% by weight of ert-butyl peroxydicarbonate was added and heat polymerization was carried out in the mold in the same manner as in Example 3, the polymerization reaction rate was approximately 45% after 5 hours.
After 5 hours at 0°C, it was 99% or more, which was the same behavior as in Example 3.

Comparative Example 5 In Example 3, 500 ppm of 2,6-tert-butyl-p-cresol was added instead of N-nitrosophenylhydroxylamine 80, salt, and heating was performed at 70°C with the same Motsuma composition. However, after 4 hours had passed, viscosity increased and gelation occurred. Next, 0.1% by weight of di-tert-butyl peroxide and 0.05% by weight of diisopropyl peroxydicarbonate were added as polymerization initiators to this mixed solution, and heating polymerization was carried out in a mold in the same manner as in Example 3. However, Example 3
It showed similar polymerization behavior and refractive index.

[Effects of the Invention] The high refractive index resin composition of the present invention has the following effects.

1. It is stable even after long-term storage and heating, and its storage stability is significantly improved.

2. The opening and opening horns of the polymerization initiator are not inhibited, and the polymerization behavior is the same as when no polymerization inhibitor is added.

3. High refractive index resin can be obtained without any bad odor.

4. Furthermore, by limiting the proportion of polymerization inhibitor,
It is possible to obtain a colorless and transparent product without any coloring.

Claims (6)

[Claims] (1) A high refractive index resin composition characterized by containing an N-nitrosophenylhydroxylamine salt compound represented by the general formula [I] in a radically polymerizable polyfunctional vinyl monomer containing an aromatic ring. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] n: An integer from 1 to 4 X: A metal selected from NH_4, a metal with a valence of 1 to 4 (2) A diacrylate in which the radically polymerizable polyfunctional vinyl monomer containing an aromatic ring is represented by the following general formula [II],
The high refractive index resin composition according to claim 1, which is at least one selected from dimethacrylates. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II] (However, R is H or CH_3, X is Cl, Br or F, n is an integer from 0 to 4, m is an integer from 0 to 6, A is ▲Mathematical formula , chemical formulas, tables, etc. ▼ or -SO_2-
represents. ) (3) The radically polymerizable polyfunctional vinyl monomer containing an aromatic ring is an isocyanate-modified monomer represented by the following general formula [III].
The high refractive index resin composition described in item 1). ▲There are mathematical formulas, chemical formulas, tables, etc.▼[III] (However, R_1 and R_2 are CH_3 or H,
X is Cl, Br or F, Z is a residue of a polyfunctional isocyanate, A is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or -SO_
2-, m and n are each integers from 0 to 4,
And the sum of m and n is an integer value from 0 to 4, and p is from 0 to 4.
q represents an integer from 2 to 3. ) (4) The high refractive index resin composition according to claim (1), wherein X in the N-nitrosophenylhydroxylamine salt compound represented by the general formula [I] is Al. (5) The N-nitrosophenylhydroxylamine salt compound represented by the general formula [I] is 0.001 or more 10,
The high refractive index resin composition according to claim (1), characterized in that the content is in a range of 000 ppm or less. (6) The N-nitrosophenylhydroxylamine salt compound represented by the general formula [I] is 0.01 or more and 1,000
The high refractive index resin composition according to claim (1), characterized in that the content is in a range of 0 ppm or less.