JPH072806B2 - Polymerizable composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polymerizable composition suitable for producing a transparent resin, and more specifically, it is particularly excellent in scratch resistance, heat resistance, colorless transparency, hardness and the like. Another object of the present invention is to provide a polymerizable composition suitable for producing a transparent resin.

[Problems to be Solved by Prior Art and Invention]

The transparent resin is excellent in its lightness and stability in breakage, and is attracting attention as a material replacing the inorganic glass.
For example, it is expected to be used for optical lenses such as microscopes, cameras, and glasses, or for windows of houses, automobiles, airplanes, and the like. The properties of the transparent resin required for such applications include optical properties such as colorless transparency and light refraction; heat resistance,
It has mechanical properties such as scratch resistance, impact resistance, machinability, polishability, and moldability. Regarding transparent resin instead of inorganic glass,
Various studies have been made and proposed. For example, resins obtained by polymerizing methyl methacrylate, allyl glycol carbonate and the like are known. These transparent resins are
Although it has the advantages of being lighter in weight and superior in impact resistance than inorganic glass, it is not sufficiently satisfactory as a substitute for inorganic glass because it has the drawback of being inferior in scratch resistance. Therefore, as a resin having excellent scratch resistance, a resin obtained by polymerizing monomers having 3 or more polymerizable functional groups in one molecule has been proposed. For example, JP-A-54-6624 discloses that a general formula A resin obtained by polymerizing the monomer shown by is proposed. The present inventors have tried to produce these resins, for example, a resin obtained from a monomer in which x is 0 in the above general formula, and the resin is excellent in scratch resistance, but is colored. Therefore, it was unsuitable for use as an inorganic glass.

[Means for solving problems]

As a result of intensive studies to solve the above problems, the present inventors have found that an allyl carbonate compound having 3 or more allyl carbonate groups in one molecule, an antioxidant, and / or
Alternatively, a resin obtained by polymerizing a polymerizable composition composed of a phosphorus compound in which at least one hydroxyl group is directly bonded to a phosphorus atom,
They have found that they are colorless and transparent, have excellent mechanical properties such as scratch resistance and heat resistance, and have extremely excellent properties that can substitute for inorganic glass, and have provided the present invention.

That is, the present invention comprises (a) an allyl carbonate compound having three or more allyl carbonate groups in one molecule, and (b) an antioxidant and / or a phosphorus compound in which at least one hydroxyl group is directly bonded to a phosphorus atom. It is a polymerizable composition characterized by the above.

The allyl carbonate compound used in the present invention, in one molecule Any known compound may be used without limitation as long as it has three or more allyl carbonate groups represented by.

The allyl carbonate compound preferably used in the present invention is as follows.

General formula [I] An allyl carbonate compound represented by.

Here, the alkyl group and the alkoxy group have no limitation on the number of carbon atoms, but the number of carbon atoms is preferably in the range of 1 to 10 in consideration of the surface hardness of the resin obtained by polymerization. Examples of the aryl group include phenyl group, tolyl group, xylyl group, naphthyl group, anthryl group, phenanthryl group, benzyl group and the like. Substituents for these alkyl and aryl groups include halogen atoms,
A hydroxyl group, an alkoxy group, an epoxy group, etc. can be mentioned. Further, in the above general formula [I], m may be an integer of 0 or more, but from the viewpoint of the hardness of the obtained resin, m is 0.
It is preferably an integer of -30. Further, l may be an integer of 1 or more, but is preferably an integer of 1 to 20.

General formula (II) An allyl carbonate compound represented by.

In the above general formula [II], as the halogen atom represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ , fluorine, chlorine, bromine and iodine atoms are adopted. Further, k may be an integer of 1 or more, but in order to make the viscosity of the allyl carbonate compound represented by the general formula [II] an appropriate value and facilitate handling, k is an integer of 1 to 3. Preferably there is.

General formula (III) An allyl carbonate compound represented by.

An allyl carbonate compound in which three or more hydroxyl groups of carbohydrate are substituted with allyl carbonate groups.

Carbohydrates include glycerin, glucose, fructose, mannose, galactose, glucopyranose,
Examples thereof include xylopyranose, arabinose, fructopyranose, xylulose, xylulose 5-phosphate, sorbitol, maltose, cellobiose, isomaltose, lactose, sucrose, amylose and the like.

The allyl carbonate compound of the polymerizable composition of the present invention includes the transparency of a resin obtained by polymerizing the polymerizable composition,
From the viewpoint of scratch resistance and the like, the allyl carbonate compounds represented by the general formulas [I] and [II] are preferable, and the allyl carbonate compound represented by the general formula [I] is most preferable.

Specific examples of allyl carbonate compounds preferably used in the present invention include, for example, Etc. can be mentioned.

Next, as the antioxidant which is the other component of the polymerizable composition of the present invention, for example, Yoshinaga Abe, Makoto Sudo, "New Edition Plastics Compounding Agent-Basic and Application" (Taiseisha) and Motoyama In addition to the antioxidants listed in "Handbook Rubber / Plastic Blended Chemicals" (Rubber Digest), edited by Tokihiko,
Any known compound can be adopted as an antioxidant for plastics without any limitation. Examples of the antioxidant preferably used in the present invention include a thio compound containing a divalent sulfur atom, a phosphite compound and a phosphine compound.

As the thio compound containing a divalent sulfur atom, the following compounds can be preferably used.

B general formulas [IV], [V] and [VI] SR ₁ COOR ₂ ) ₂ [IV] XR ₁ OOCR ₃ SR ₂ ) j [V] R ₄ SR ₁ COOR ₂ [VI] A carbonyloxy compound represented by.

In the above general formulas [IV], [V] and [VI], the number of carbon atoms of the alkyl group is not particularly limited, but generally the compatibility with the above-mentioned allyl carbonate compound is improved and the obtained resin In order to prevent the elution of the carbonyloxy compound from the above, the carbon number is 1 to 30, and further 5 to
It is preferably in the range of 25. Suitable alkyl groups include pentyl group, octyl group, nonyl group, decyl group,
Undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group, eicosyl group and the like can be mentioned.

Further, in the above general formulas [IV], [V] and [VI], the number of carbon atoms of the alkylene group is not particularly limited, but from the viewpoint of transparency of the obtained resin, the number of carbon atoms is preferably 1 to 20. . Suitable alkylene groups include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group and the like. Further, as the arylene group, phenylene group, tolylene group, xylylene group, 2-
Examples thereof include methyl-5-t-butylorphenylene group and naphthylene group.

B general formula [VII] and [VIII] R ₅ -SH (VII) HS-R ₆ -SH (VIII) A thiol compound represented by.

In the general formulas [VII] and [VIII], the carbon number of the alkyl group and the alkylene group is not particularly limited,
It is preferable that the number of carbon atoms in the alkyl group and the alkylene group described for the carbonyloxy compound in the item (a) is the same. Further, the number of carbon atoms of the alkenyl group is not particularly limited, but compatibility with an allyl carbonate compound,
Considering prevention of elution from the resulting resin, the carbon number is 2
It is preferably in the range of -30, more preferably in the range of 3-20. The cycloalkyl group preferably has 5 to 7 carbon atoms. As the aryl group, a phenyl group, a tolyl group,
Xylyl group, para-t-butylphenyl group, naphthyl group,
Examples thereof include a phenanthryl group, anthryl group, and a benzyl group. Examples of the arylene group include a phenylene group,
Examples thereof include a tolylene group, a xylylene group and a naphthylene group.

C General formulas [IX] and [X] R ₇ -S-R ₈ [IX] R ₇ -S-S-R ₈ [X] The sulfide compound represented by.

In the general formulas [IX] and [X], as the alkyl group, the alkenyl group and the aryl group, the groups described in the above item (b) are preferable.

D General formula [XI] A thio compound containing phosphorus.

In the general formula [XI], as the alkyl group and the aryl group, the groups described in the above item (b) are preferable.

Further, as the phosphite compound that can be used as the antioxidant of the polymerizable composition of the present invention, the following compounds are suitable.

E General formulas [XII], [XIII] and [XIV] The phosphite compound represented by.

In the above general formulas [XII], [XIII] and [XIV], R ₁₂ ,
As the alkyl group and aryl group represented by R ₁₃ , R ₁₄ , R ₁₅ , R ₂₃ and R ₂₄ , the groups described in the above item b can be preferably used. The alkyl group represented by R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₆ and R ₂₇ is not particularly limited in the number of carbon atoms, but is generally in the range of 1 to 5 carbon atoms. Is preferred. Further, the alkylene group represented by R ₂₅ preferably has 1 to 5 carbon atoms.

Furthermore, the following compounds are suitable as the phosphine compound that can be used in the present invention as an antioxidant.

F General formula [XV] A phosphine compound represented by.

In the general formula [XV], as the alkyl group and the aryl group, the groups described in the above item B can be preferably used.

The compounds that can be particularly preferably used as the above-mentioned antioxidant used in the present invention are specifically illustrated as follows.

_{S (CH 2 COOC 12 H 25} ) 2, S (CH 2 CH 2 COOC 12 H 25) 2, S (CH 2 COOC 13 H 27) 2, S (CH 2 CH 2 COOC 13 H 27) 2, S ( CH ₂ CH ₂ COOC ₁₄ H ₂₉ ) ₂ , S (CH ₂ CH ₂ COOC ₁₈ H ₃₇ ) ₂ , S (CH ₂ CH ₂ COOC ₂₂ H ₄₅ ) ₂ , C (CH ₂ OOCCH ₂ CH ₂ SC ₁₂ H ₂₅ ) ₄ , C (CH ₂ OOCCH ₂ CH ₂ SC ₁₃ H ₂₇ ) ₄ , C (CH ₂ OOCCH ₂ CH ₂ SC ₁₈ H ₃₇ ) ₄ , C (CH ₂ CH ₂ OOCCH ₂ CH ₂ SC ₁₄ H ₂₉ ) ₄ , Carbonyloxy compounds such as S (CH ₂ CH ₂ OOCCH ₂ CH ₂ SC ₁₃ H ₂₇ ) ₂ , C ₁₂ H ₂₅ SCH ₂ CH ₂ COOH, C ₁₂ H ₂₅ SCH ₂ CH ₂ COOCH ₃ ; butyl mercaptan, amyl mercaptan, heptyl Mercaptan, decyl mercaptan, dodecyl mercaptan, tetradecyl mercaptan, pentadecyl mercaptan, hexadecyl mercaptan, octadecyl mercaptan, allyl mercaptan, cyclopentathiol, cyclohexathiol,
Thiol compounds such as thiophenol, thiocresol, para-t-butylphenol, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, butanedithiol, hexanedithiol, decandithiol, dithiophenol; isopropyl sulphide, dibutyl sulphide, Dihexyl sulfide, dinonyl sulfide, didecyl sulfide, dioctadecyl sulfide, thioanisole, benzylmethyl sulfide, diphenyl sulfide, α-phenylethyl sulfide, thiobis (β-naphthol), Tetramethylthiuram monosulfide, Tetrabutylthiuram sulfide, Diallyldisulfide, Dipropyldisulfide, Dibutyldisulfide,
Dioctyl disulphide, di-t-dodecyl disulphide, ditetradecyl disulphide, diphenyl disulphide, dibenzyl disulphide, tetraethyl thiuram disulphide, N, N'-dimethyl-N, N'- Sulfide compounds such as diphenylthiuram disulfide; (C ₁₀ H ₂₁ S) ₃ P, (C ₁₂ H ₂₅ S) ₃ P and other thio compounds containing phosphorus; And phosphite compounds such as triphenylphosphine, diethylphenylphosphine, tributylphosphine, trioctylphosphine, and tris (4-methoxyphenyl) phosphine.

The thio compound containing a divalent sulfur atom is not limited to a low molecular weight organic compound and may be a polymer or an oligomer containing a divalent sulfur atom. Examples thereof include polyhexamethylene thioether, polyhexamethylene tetramethylene thioether, polyethylene tetrasulfide and the like.

Among the antioxidants described above, a thio compound containing a divalent sulfur atom is preferably used in consideration of the transparency, scratch resistance, impact resistance and the like of the resin obtained. Among them, the carbonyloxy compounds represented by the general formulas [IV], [V] and [VI], the thiol compounds represented by the general formulas [VII] and [VIII], and the general formulas [IX] and [X]. ] The sulfide compound shown by these is preferable, and especially a carbonyloxy compound is used most preferably.

Next, as the phosphorus compound which is another component of the polymerizable composition of the present invention, any known phosphorus compound may be used without any limitation as long as it is a phosphorus compound in which at least one hydroxyl group is directly bonded to a phosphorus atom. Among such phosphorus compounds, the compounds that can be preferably used in the present invention are as follows.

General formula [XVI] The phosphoric acid compound shown by.

In the general formula [XVI], the alkyl group represented by R ₁ and R ₂ is not particularly limited in the number of carbon atoms, but has good compatibility with the above-mentioned allyl carbonate compound, and the above-mentioned from the resin obtained. In order to prevent the elution of phosphate compounds,
The number of carbon atoms is preferably in the range of 1 to 30, more preferably 3 to 25. Suitable alkyl groups include pentyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group,
Examples thereof include octadecyl group and eicosyl group.

Further, in the above general formula [XVI], the aryl group represented by R ₁ and R ₂ includes a phenyl group, a tolyl group, a xylyl group, 2
-Methyl-5-t-butylorthophenyl group, naphthyl group,
Examples thereof include anthryl group, phenanthryl group, biphenyl group and the like.

H general formula [XVII] The phosphite compound represented by.

The alkyl group and aryl group in the above general formula [XVII] are
The groups described in the above item g are preferred.

General formula [XVIII] The phosphonic acid compound represented by.

In the general formula [XVIII], the alkyl group and the aryl group are preferably the groups described in the above item g.

Nu general formula [XIX] The phosphonous acid compound shown by.

In the above general formula [XIX], the alkyl group or the aryl group is
The groups described in the above section g are preferred.

General formula [XX] A pyrophosphate compound represented by.

As the alkyl group and the aryl group in the general formula [XX], the groups described in the above item g are suitable.

General formula [XXI] The phosphinic acid compound represented by.

As the alkyl group and the aryl group in the general formula [XXI], the groups described in the above section g are suitable.

Specific examples of the phosphorus compound preferably used in the present invention are as follows. Phosphoric acid, monomethyl phosphate, monooctyl phosphate, monododecyl phosphate, monooctadecyl phosphate, monobenzyl phosphate, monocyclohexyl phosphate, mono (phenoxyethyl) phosphate, mono (2-
Phosphoric acid compounds such as chloroethyl), monophenyl phosphate, diethyl phosphate, di (2-ethoxyhexyl) phosphate, didodecyl phosphate, diphenyl phosphate, di (nonylphenyl) phosphate; monomethyl phosphite, phosphorus phosphite Acid monoisopropyl, phosphorous acid mono (2-ethylhexyl), phosphorous acid mono (dodecyl), phosphorous acid mono (octadecyl), phosphorous acid monobenzyl, phosphorous acid phenyl, phosphorous acid mono (pt-butylphenyl) ), Dimethyl phosphite,
Diisopropyl phosphite, dibutyl phosphite, di (2-ethylhexyl) phosphite, dilauryl phosphite, ditridecyl phosphite, dioleyl phosphite, distearyl phosphite, dinonyl phosphite, diphenyl phosphite , Phosphite compounds such as di (p-biphenyl) phosphite, di (pt-butylphenyl) phosphite, di (2-bromoethyl) phosphite; n-butylphosphonic acid, octadecylphosphonic acid, benzylphosphone Phosphonic compounds such as acid, phenylphosphonic acid and 4-ethylphenylphosphonic acid; phosphonous compounds such as isobutylphosphonous acid, dodecylphosphonous acid, phenylphosphonous acid, ethyl phenylphosphonous acid, and phenylpropylphosphonous acid phenyl ester; Dimethylpyrophosphate, dibutylpyrophosphate, di (2-ethylhexyl) pyrophosphate, dilauryl Pyrophosphate, diphenyl pyrophosphate, pyrophosphate compounds such as pyrophosphates; dimethyl phosphinate, ethyl methyl phosphinate, methyl phenyl phosphinic acid, dibenzyl phosphinic acid, and phosphinic acid compounds such as diphenyl phosphinic acid.

Further, the phosphorus compound in which at least one hydroxyl group is directly bonded to the phosphorus atom is not limited to a low molecular weight organic compound,
It may be an oligomer or polymer containing an atom to which a hydroxyl group is directly bonded, or a polymerizable compound.

Among the above-mentioned phosphorus compounds in which at least one hydroxyl group is directly bonded to the phosphorus atom, the phosphoric acid compound is most preferably used in consideration of the transparency, scratch resistance, impact resistance and the like of the obtained resin.

Furthermore, by using the above-mentioned antioxidant and the above-mentioned phosphorus compound in combination, it is possible to more effectively prevent the coloring of the obtained resin.

In the polymerizable composition of the present invention, the amount of the antioxidant and / or the phosphorus compound added cannot be unconditionally limited depending on the type of the antioxidant or the phosphorus compound, the polymerization conditions, etc., but generally 3 or more in one molecule. To 100 parts by weight of the allyl carbonate compound having an allyl carbonate group of
It is preferable to use 0.01 to 5 parts by weight, and more preferably 0.01 to 3 parts by weight, respectively. At this time, if an antioxidant or a phosphorus compound is used more than necessary, the polymerization may be hindered when the polymerizable composition is polymerized, and the inherent properties of the resin obtained from the allyl carbonate compound may be impaired.

In addition, the polymerizable composition of the present invention can be mixed with an allyl carbonate compound and a copolymerizable monomer, if necessary. This monomer is selected according to the purpose and can be used without particular limitation. Examples of such monomers include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, and fumaric acid; methyl acrylate, methyl methacrylate, benzyl methacrylate, phenyl methacrylate, 2-hydroxyethyl. Methacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A dimethacrylate, 2,2-bis (4-methacryloxyethoxyphenyl) propane, 2,2-bis (3,5-dibromo-4) -Acrylic acid and methacrylic acid ester compounds such as methacryloxyethoxyphenyl) propane and trifluoromethylmethacrylate; Fumarate ester compounds such as monomethyl fumarate, diethyl fumarate, and diphenyl fumarate; diallyl phthalate, Allyl compounds such as allyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl epoxysuccinate, diallyl malate, allyl cinnamate, allyl isocyanate, diallyl chlorendate, diallyl hexaphthalate, diallyl carbonate; styrene, chlorostyrene, methylstyrene, vinyl Aromatic vinyl compounds such as naphthalene and isopropenylnaphthalene. These monomers can be used alone or in combination of two or more.

For the purpose of improving the refractive index of the polymer of the polymerizable composition of the present invention, a monomer having a refractive index of 1.5 or more, particularly a homopolymer among the monomers copolymerizable with the above allyl carbonate compound, Addition to the polymerizable composition of the present invention can also be performed as necessary. Examples of these monomers include acrylic acid and methacrylic acid ester compounds such as benzyl methacrylate, phenyl acrylate, bisphenol A dimethacrylate, and bromophenyl methacrylate; allyl compounds such as diallyl phthalate and diallyl chlorendate; styrene, Aromatic vinyl compounds such as chlorostyrene and vinylnaphthalene, and mixtures thereof.

Further, the polymerizable composition of the present invention may be mixed with additives such as an ultraviolet absorber, an anti-coloring agent, an antistatic agent, a fluorescent dye, a dye and an inorganic filler, if necessary.

As a method for obtaining a colorless and transparent synthetic resin using the polymerizable composition of the present invention, a usual casting polymerization method is used as it is.
That is, the above-mentioned polymerizable composition or a mixture of the polymerizable composition and another copolymerizable monomer is polymerized by a usual polymerization initiation means. The polymerization can be initiated by using radical polymerization initiators such as various peroxides and azo compounds, irradiation with ultraviolet rays, α rays, β rays, γ rays, roentgen rays, or the like, or a combination of both. As the radical polymerization initiator, known compounds such as benzoyl peroxide and p-chlorobenzoyl percaxide can be used.

The polymerizable composition of the present invention has a gas chromatography, a liquid chromatography, an infrared absorption spectrum,
It is possible to determine the identification and the composition ratio, etc. by the usual separation of organic substances such as nuclear magnetic resonance spectrum and elemental analysis, and analysis means.
Further, also for the polymer after the polymerization of the polymerizable composition, the type and amount of the antioxidant and the phosphorus compound present in the polymer, after the operations such as extraction and concentration, the usual method for analyzing resin additives. Can be used for identification and quantification.

〔effect〕

As described above, the polymerizable composition of the present invention is a composition comprising an allyl carbonate compound having 3 or more allyl carbonate groups in one molecule, an antioxidant and / or a specific phosphorus compound. By adding an antioxidant and / or a specific phosphorus compound, the resin obtained from an allyl carbonate compound having three or more allyl carbonate groups in one molecule has excellent properties such as scratch resistance and impact resistance originally possessed. Coloring of the resin can be prevented without lowering.

Therefore, the resin obtained by polymerizing the polymerizable composition of the present invention has excellent scratch resistance, impact resistance, and colorless transparency, and is used as an alternative to inorganic glass as an optical lens or window glass. It is a useful material that can be suitably used for applications such as.

〔Example〕

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

The resins obtained in the examples were measured for various physical properties by the following test methods.

(1) Using a yellowness color meter (SM-4 type manufactured by Suga Test Instruments Co., Ltd.),
The yellowness of the test piece having a thickness of 2 mm was measured.

(2) Hardness Using a Rockwell hardness tester, L for a 2 mm thick test piece
-Measured values on the scale.

(3) Scratch resistance A # 0000 steel wool was attached to a scratch resistance tester manufactured by Fukuda Machine Industry Co., Ltd.
After visually reciprocating the degree of scratches on the surface after reciprocating, the state in which no scratches were found was A, and the degree of scratches of the methyl methacrylate polymer was E, and 5 of A to E
The grade was evaluated.

(4) Refractive index The refractive index at 20 ° C was measured using an Atsube refractometer. Bromonaphthalene was used as the contact liquid.

Example 1 Structural formula Trimethylolpropane triallyl carbonate
2.2 parts by weight of diisopropyl peroxydicarbonate (hereinafter abbreviated as IPP) was added to a polymerizable composition of 100 parts by weight and 0.2 part by weight of dilauryl thiodipropionate and mixed well. Then mix this mixture with two glass plates and ethylene-
It was poured into a mold composed of a gasket made of vinyl acetate copolymer, and cast polymerization was performed. Polymerization was initially started at 40 ° C using an air oven and gradually increased to 90 ° C for 18 hours. Then, after holding at 90 ℃ for 1 hour, remove the mold from the air furnace, remove the gasket,
The polymer was removed from the glass plate. Further, the polymer was heated at 120 ° C. for 2 hours for post-curing. The obtained polymer is
It was colorless and transparent, the yellowness was 1.2, the hardness was 121, the scratch resistance was B, and the refractive index was 1.502.

Example 2 A polymer was obtained in the same manner as in Example 1 except that the compounds shown in Table 1 were used as the allyl carbonate compound and the amount of IPP used was changed to the amount shown in Table 1. The result is first
Shown in the table.

Regarding the allyl carbonate compound used in No. 1 in Table 1, a polymer was obtained in the same manner as in No. 1 above, except that dilauryl thiodipropionate was not used as an antioxidant. The result is No. 1 in Table 1 as a comparative example.
Also listed as 1.

Example 3 100 parts by weight of trimethylolpropane triallyl carbonate as an allyl carbonate compound and a thio compound containing a divalent sulfur atom shown in Table 2 as an antioxidant.
A polymerizable composition consisting of 0.2 parts by weight was polymerized in the same manner as in Example 1. In each case, a colorless transparent polymer was obtained.
The physical properties of this polymer are shown in Table 2.

Example 4 As an allyl carbonate compound, the structural formula is Is trimethylolethane triallyl carbonate 10
Similar to Example 1 except that 0.2 parts by weight of the phosphite compound or phosphine compound shown in Table 3 was added as an antioxidant to 0 parts by weight, using 1.7 parts by weight of IPP as an initiator. Polymerization was carried out by the method. In each case, a colorless transparent polymer was obtained. The physical properties of this polymer are shown in Table 3.

Example 5 As an allyl carbonate compound, a structural formula Pentaerythritol triallyl carbonate 10
A polymerizable composition comprising 0 parts by weight and dilauryl thiodipropionate in an amount shown in Table 4 as an antioxidant,
Polymerization was carried out in the same manner as in Example 1 using the initiators shown in Table 4. The properties of the obtained polymer are shown in Table 4.

Example 6 A mixture obtained by thoroughly mixing 3 parts by weight of monomers shown in Table 5 with a polymerizable composition consisting of 100 parts by weight of trimethylolpropane triallyl carbonate and 0.3 parts by weight of distyryl thiodipropionate. IPP 2.2 for 100 parts by weight
Polymerization was carried out in the same manner as in Example 1 by adding parts by weight. The physical properties of the obtained polymer are shown in Table 5.

Example 7 0.3 parts by weight of distyryl thiodipropionate and 2.2 parts by weight of IPP were added to 100 parts by weight of a mixture obtained by mixing predetermined amounts of the monomers shown in Table 6 with trimethylolpropane triallyl carbonate. Then, polymerization was carried out in the same manner as in Example 1. The physical properties of the obtained polymer are shown in Table 6.

Example 8 100 parts by weight of trimethylolpropane triallyl carbonate and 0.4 parts by weight of dibutyl phosphate were added to a polymerizable composition by IPP.
2.2 parts by weight were added and mixed well. Then, using this mixed solution, a polymer was obtained in the same manner as in Example 1. The obtained polymer is colorless and transparent, has a yellowness of 2.8, a hardness of 122, and a scratch resistance of B,
The refractive index was 1.502.

Example 9 A polymer was obtained in the same manner as in Example 8 except that the compounds shown in Table 7 were used as the allyl carbonate compound and the amount of IPP used was changed to the amount shown in Table 7. The result is No. 7
Shown in the table.

Example 10 A polymerizable composition comprising 100 parts by weight of trimethylolpropane triallyl carbonate as an allyl carbonate compound and 0.2 polymerized part of the compound shown in Table 8 as a phosphorus compound in which at least one hydroxyl group is directly bonded to a phosphorus atom was carried out. Polymerization was carried out as in Example 9. In each case, a colorless transparent polymer was obtained. The physical properties of this polymer are shown in Table 8.

Example 11 To a polymerizable composition of 100 parts by weight of trimethylolpropane triallyl carbonate, 0.2 parts by weight of dibutyl phosphate and 0.2 parts by weight of dilaurylthiodipropionate, 2.2 parts by weight of IPP was added and mixed well. Then, using this mixed solution, a polymer was obtained in the same manner as in Example 1. The obtained polymer is colorless and transparent, has a yellowness of 0.7, a hardness of 121, a scratch resistance of B, and a refractive index of
It was 1,502.

Example 12 A polymer was obtained in the same manner as in Example 11 except that the compounds shown in Table 9 were used as the allyl carbonate compound. The results are shown in Table 9.

Example 13 As an allyl carbonate compound, 100 parts by weight of trimethylolpropane triallyl carbonate, 0.2 part by weight of dilaurylthiodipropionate, and a phosphorus compound in which at least one hydroxyl group was directly bonded to a phosphorus atom were used as a phosphorus compound.
Polymerization was carried out in the same manner as in Example 11 except that 0.2 parts by weight of the compound shown in the table was added to 2.2 parts by weight of IPP as an initiator. In each case, a colorless transparent polymer was obtained. The physical properties of this polymer are shown in Table 10.

Example 14 With respect to 100 parts by weight of trimethylolpropane triallyl carbonate as an allyl carbonate compound, 0.2 parts by weight of dibutyl phosphate and 0.2 parts by weight of the compound shown in Table 11 as an antioxidant were added to the polymerizable composition, and the start was started. Polymerization was carried out in the same manner as in Example 11 using 2.2 parts by weight of IPP as the agent. In each case, a colorless transparent polymer was obtained. The physical properties of this polymer are shown in Table 11.

Example 15 Based on a polymerizable composition consisting of 100 parts by weight of trimethylolpropane triallyl carbonate, 0.3 parts by weight of distyryl thiodipropionate, and 0.2 parts by weight of dibutyl phosphate, 3% by weight of the monomer shown in Table 12 was used. 2.2 parts by weight of IPP was added to 100 parts by weight of a mixture in which the monomers were thoroughly mixed, and Example 11
Polymerized in the same manner as. The physical properties of the obtained polymer are shown in Table 12.

Claims (1)

[Claims] 1. An (a) allyl carbonate compound having three or more allyl carbonate groups in one molecule, and (b) an antioxidant and / or a phosphorus compound in which at least one hydroxyl group is directly bonded to a phosphorus atom. A polymerizable composition comprising: