JP2001226438A - Polymerizable composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymerizable composition giving a hardened material excellent in optical properties (a high transparency, high refractive index, high Abbe number), thermal properties, mechanical properties and having high productivity and useful for various optical parts. SOLUTION: This polymerizable composition using polymerizable compounds and a polymerization initiator as the essential components, includes a (meth) acrylate compound expressed by formula (I) and a (meth)acrylate compound having at least one hydroxyl in the molecule as the polymerizable compounds. (R1-R4 are each H, an alkyl, an alkoxy, nitro or a halogen, R5 is H or an alkyl, R6 is a substituent having a sulfur atom and R7 is H or methyl).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polymerizable composition. Further, the present invention relates to a cured product obtained by polymerizing the polymerizable composition, and an optical component comprising the cured product. More specifically, the present invention relates to a polymerizable composition which is characterized in that a (meth) acrylate compound having a specific structure is used in combination as a polymerizable compound, and which can be polymerized and cured by light, heat, or the like.

[0002]

2. Description of the Related Art Inorganic glass is used in a wide range of fields as a transparent optical material because of its excellent properties such as excellent transparency and small optical anisotropy. However, there are problems such as being heavy and easily damaged and poor productivity. In recent years, development of optical resins in place of inorganic glass has been actively carried out.

A fundamentally important property as an optical material is transparency. Up to the present, polymethyl methacrylate (PMMA), bisphenol A polycarbonate (BPA-PC), polystyrene (PS), methyl methacrylate-styrene copolymer (MS), styrene-acrylonitrile Polymerized polymer (SAN), poly (4-methylpentene-1)
(TPX), polycycloolefin (COP), polydiethylene glycol bisallyl carbonate (EGA)
C), polythiourethane (PTU) and the like are known.

[0004] PMMA has excellent transparency and weather resistance, and also has good moldability. However, refractive index (n _d) of as small as 1.49, there is a disadvantage that a large water absorption.
BPA-PC is excellent in transparency, heat resistance, impact resistance and high refraction, but has large chromatic aberration and its application field is limited. PS and MS are excellent in moldability, transparency, low water absorption and high refractive index, but are inferior in impact resistance, weather resistance and heat resistance and are hardly practically used as optical resins. SAN is considered to have a relatively high refractive index and a good balance of mechanical properties, but has some difficulty in heat resistance (heat deformation temperature: 80 to 90 ° C.) and is hardly used as an optical resin. .

[0005] TPX and COP are transparent, have low water absorption,
Although excellent heat resistance, a low refractive index (n _d = 1.47~
1.53), there is a problem that the impact resistance, gas barrier properties and dyeability are poor. EGAC is a thermosetting resin containing diethylene glycol bisallyl carbonate as a monomer, and is most often used for general-purpose spectacle lenses. Although it is excellent in transparency and heat resistance and has extremely small chromatic aberration, it has a defect that it has a low refractive index ( _nd = 1.50) and is inferior in impact resistance. PTU is a thermosetting resin obtained by a reaction between a diisocyanate compound and a polythiol compound, and is most frequently used for an ultra-high refractive index spectacle lens. This material is particularly excellent in transparency, impact resistance, and high refractive index, and has a small chromatic aberration, and is extremely excellent. However, it has a drawback that the heat polymerization molding time is long (1 to 3 days).
The problem remains in terms of productivity.

For the purpose of polymerizing and curing in a short time in order to enhance the productivity described above, a method of obtaining an optical lens by photopolymerization using an acrylic acid ester containing a bromine atom or a sulfur atom has been proposed. (For example,
JP-A-4-161410, JP-A-3-21741
No. 2 publication). However, according to this method, although polymerization can be performed in a short time, the obtained resin is not always satisfactory as an optical component. That is, for example, when used as a spectacle lens, a high-refractive-index lens has problems such as being brittle and fragile and having a large specific gravity. Therefore, development of a material that overcomes these problems has been strongly desired.

As described above, the conventional optical resins have excellent characteristics, but at present, each has its own disadvantages to be overcome. Under these circumstances,
At present, there is an urgent need to develop a high-refractive-index optical resin having excellent optical properties, mechanical properties, and thermal properties and good productivity.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve the drawbacks of conventional optical resins, to have excellent optical characteristics (high transparency, high refractive index, high Abbe number), thermal characteristics, and mechanical characteristics. An object of the present invention is to provide a high-productivity optical resin which has good (impact resistance) and can be polymerized and molded and cured in a short time.

[0009]

Means for Solving the Problems The present inventors have made intensive studies in order to solve the above problems, and as a result, have reached the present invention. That is, the present invention relates to a polymerizable composition containing a polymerizable compound and a polymerization initiator as essential components, wherein the polymerizable compound is a sulfur-containing (meta-type) represented by the following formula (1) The present invention relates to a polymerizable composition containing an acrylate compound and a (meth) acrylate compound having at least one hydroxyl group in a molecule.

[0010]

Embedded image (Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a nitro group or a halogen atom, and R ₅ each independently represent a hydrogen atom or an alkyl group; R ₆ each independently represents a substituent containing a sulfur atom, and R ₇ each independently represents a hydrogen atom or a methyl group.) In addition, the present invention relates to a (meth) acrylic acid having at least one hydroxyl group in the molecule. The present invention relates to the polymerizable composition, wherein the ester compound is a (meth) acrylate compound represented by the following formula (2) (Chemical Formula 5).

[0011]

Embedded image (Wherein, R ₈ each independently represents a hydrogen atom or an alkyl group, and R ₉ each independently represents a hydrogen atom or a methyl group.) Further, the present invention provides a polymerizable compound,
The polymerizable composition according to any one of the above or the above, further comprising at least one kind of a (meth) acrylate compound represented by the following formula (3) or (4) (Formula 6). The present invention relates to a cured product obtained by polymerizing such a polymerizable composition, and an optical component and an optical lens made of the cured product.

[0012]

Embedded image (In the above formula, R ₁₀ , R ₁₁ and R ₁₂ each independently represent a hydrogen atom or a methyl group, and m represents an integer of 1 to 10.)

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The polymerizable composition of the present invention is a polymerizable composition comprising a polymerizable compound and a polymerization initiator as essential components, wherein the polymerizable compound is a sulfur-containing (meth) compound represented by the formula (1). It is characterized by containing an acrylate compound and a (meth) acrylate compound having at least one hydroxyl group in a molecule.
The sulfur-containing (meth) acrylate compound represented by the formula (1) according to the present invention has a substituent having a sulfur atom in the molecule and has a hydroxyl group bonded to a secondary or tertiary carbon. It is a novel compound characterized in that it is a (meth) acrylate ester group.

In the sulfur-containing (meth) acrylate compound represented by the general formula (1) of the present invention, R ₁ , R ₂ ,
R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a nitro group or a halogen atom, preferably a hydrogen atom, a linear, branched or cyclic alkyl which may have a substituent; Represents a linear, branched or cyclic alkoxy group, a nitro group or a halogen atom which may have a substituent, more preferably a hydrogen atom or a carbon atom having 1 to 20 carbon atoms which may have a substituent. Straight chain,
It represents a branched or cyclic alkyl group, a linear or branched or cyclic alkoxy group having 1 to 20 carbon atoms which may have a substituent, a nitro group, or a halogen atom.

Specific examples of the substituents R ₁ , R ₂ , R ₃ and R ₄ include, for example, hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group,
Isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n- Octadecyl group, cyclopentyl group, cyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclohexylmethyl group, cyclohexylethyl group, tetrahydrofurfuryl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-butoxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-n-propoxypropyl group, 3-n-butoxypropyl group, 3-n-hexyloxypropyl group, 2-
Methoxyethoxyethyl group, 2-ethoxyethoxyethyl group, phenoxymethyl group, 2-phenoxyethoxyethyl group, chloromethyl group, 2-chloroethyl group, 3-chloropropyl group, 2,2,2-trichloroethyl group,

Methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, n-pentyloxy, n-
Hexyloxy group, 2-ethylhexyloxyl group, n-
Octyloxy group, n-decyloxy group, n-dodecyloxy group, n-tetradecyloxy group, n-octadecyloxy group, cyclopentyloxy group, cyclohexyloxy group, 4-tert-butylcyclohexyloxy group, cycloheptyloxy group, Cyclooctyloxy group, cyclohexylmethyloxy group, cyclohexylethyloxy group, 2-methoxyethyloxy group, 2-ethoxyethyloxy group, 2-n-butoxyethyloxy group, 3-methoxypropyloxy group, 3-ethoxypropyloxy A 3-n-propoxypropyloxy group,
3-n-butoxypropyloxy group, 3-n-hexyloxypropyloxy group, 2-methoxyethoxyethyloxy group, phenoxymethyloxy group, 2-phenoxyethoxyethyloxy group, chloromethyloxy group, 2-
Chloroethyloxy group, 3-chloropropyloxy group,
Examples thereof include a 2,2,2-trichloroethyloxy group, a nitro group, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The substituents R ₁ , R ₂ , R ₃ and R ₄ are even more preferably a hydrogen atom, a carbon atom having 1 to 10 carbon atoms.
Unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms
Unsubstituted linear or branched alkoxy group, a fluorine atom or a chlorine atom, and among them, a hydrogen atom,
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, te
It is an rt-butoxy group, a fluorine atom or a chlorine atom.
A hydrogen atom is particularly preferred as the substituent R ₁ .

In the formula (1), the substituents R ₅ each independently represent a hydrogen atom or an alkyl group.
It is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom. Further, in the formula (1), the substituents R ₆ each independently represent a substituent containing a sulfur atom, and the structure of the substituent is characterized by containing at least one sulfur atom. Specific examples of the substituent R ₆ include a substituent represented by the following formula (a) or (b). R ₁₃ -O- (a) R ₁₄ -S- (b) (wherein, R ₁₃ represents a monovalent organic group containing at least one sulfur atom, and R ₁₄ contains a sulfur atom. Represents a monovalent organic group which may be present)

The substituent R ₁₃ is preferably at least one
Represents an alkyl group, an aralkyl group, an aryl group, or an acyl group which may have a substituent and contains at least one sulfur atom. The substituent R ₁₃ also includes a heterocyclic-containing group. Further, the substituent R ₁₄ preferably represents an alkyl group, an aralkyl group, an aryl group or an acyl group which may have a substituent. Further, in order to obtain a high refractive index, it is more preferable that the substituent R ₁₄ contains a sulfur atom.

In the formula (1), the substituent R ₆ is preferably a chain or cyclic alkoxy group containing a sulfur atom, an aralkyloxy group containing a sulfur atom, or a sulfur atom. Aryloxy group, sulfur atom-containing acyloxy group, sulfur atom-containing chain or cyclic alkylthio group, sulfur atom-containing aralkylthio group, sulfur atom-containing And an arylthio group which may contain a sulfur atom.

Examples of the substituent R ₆ include a methylthioethoxy group, an ethylthioethoxy group, a propylthioethoxy group, a butylthioethoxy group, a methylthioethylthioethoxy group, a methylthioethylthioethylthioethoxy group, and a 2,2- Dimethylthioethyloxy group, 2,2-
Diethylthioethyloxy group, 2,2-dipropylthioethyloxy group, 2,2-dibutylthioethyloxy group, 3,3-dimethylthiopropyloxy group, 3,3-
Diethylthiopropyloxy group, 2,2-dipropylthioethyloxy group, 2,2-dibutylthioethyloxy group, (1,3-dithiolan-2-yl) methoxy group, 2
-(1,3-dithiolan-2-yl) ethoxy group, 3-
(1,3-dithiolan-2-yl) propyloxy group,
(1,3-dithiolan-4-yl) methoxy group, 2-
(1,3-dithiolan-4-yl) ethoxy group, 3-
A (1,3-dithiolan-4-yl) propyloxy group,
(1,4-dithian-2-yl) methoxy group, 2-
(1,4-dithian-2-yl) ethoxy group, 3-
(1,4-dithian-2-yl) propyloxy group,
(1,3,5-trithian-2-yl) methoxy group, 2
A-(1,3,5-trithian-2-yl) ethoxy group,
3- (1,3,5-trithian-2-yl) propyloxy group,

A 4-methylthiobenzyloxy group, a 3-methylthiobenzyloxy group, a 2-methylthiobenzyloxy group, a 2,4-dimethylthiobenzyloxy group,
4-dimethylthiobenzyloxy group, 2,4,6-trimethylthiobenzyloxy group, 4-methylthiophenylethyloxy group, 3-methylthiophenylethyloxy group, 2-methylthiophenylethyloxy group, 2,4-
Dimethylthiophenylethyloxy group, 3,4-dimethylthiophenylethyloxy group, 2,4,6-trimethylthiophenylethyloxy group, 4-methylthiophenyloxy group, 3-methylthiophenyloxy group, 2-methylthiophenyloxy Group, 2,4-dimethylthiophenyloxy group, 2,5-dimethylthiophenyloxy group, 2,6-dimethylthiophenyloxy group, 3,4-
Dimethylthiophenyloxy group, 3,5-dimethylthiophenyloxy group, 2,4,6-trimethylthiophenyloxy group, 2,3,4,5,6-pentamethylthiophenyloxy group,

Methylthio, ethylthio, propylthio, butylthio, methoxyethylthio, butoxyethylthio, methoxypropylthio, cyclohexylthio, 2-methylthioethylthio, 2-ethylthioethylthio, 2 -Propylthioethylthio group, 2-
Butylthioethylthio, methylthioethylthioethylthio, methylthioethylthioethylthioethylthio, 2,2-dimethylthioethylthio, 2,2-diethylthioethylthio, 2,2-dipropylthioethyl Thio group, 2,2-dibutylthioethylthio group, 3,3-
Dimethylthiopropylthio group, 3,3-diethylthiopropylthio group, 2,2-dipropylthioethylthio group,
2,2-dibutylthioethylthio group, (1,3-dithiolan-2-yl) methylthio group, 2- (1,3-dithiolan-2-yl) ethylthio group, 3- (1,3-dithiolan-2 -Yl) propylthio group, (1,3-dithiolan-4-yl) methylthio group, 2- (1,3-dithiolan-4-yl) ethylthio group, 3- (1,3-dithiolan-4-yl) propylthio Group, (1,3-dithiane-
2-yl) methylthio group, 2- (1,3-dithiane-2)
-Yl) ethylthio group, 3- (1,3-dithiane-2-
Yl) propylthio group, (1,4-dithian-2-yl) methylthio group, 2- (1,4-dithian-2-yl) ethylthio group, 3- (1,4-dithian-2-yl) propylthio group , (1,3,5-trithiane-2-
Yl) methylthio group, 2- (1,3,5-trithiane-
2-yl) ethylthio group, 3- (1,3,5-trithian-2-yl) propylthio group,

Benzylthio, 4-methylbenzylthio, 4-methoxybenzylthio, 4-methylthiobenzylthio, 3-methylthiobenzylthio, 2-methylthiobenzylthio, 2,4-dimethylthiobenzylthio A 3,4-dimethylthiobenzylthio group, 2,
4,6-trimethylthiobenzylthio, 4-methylthiophenylethylthio, 3-methylthiophenylethylthio, 2-methylthiophenylethylthio, 2,
4-dimethylthiophenylethylthio group, 3,4-dimethylthiophenylethylthio group, 2,4,6-trimethylthiophenylethylthio group, phenylthio group, 4-methylphenyl group, 4-methoxyphenylthio group, -Methylthiophenylthio, 3-methylthiophenylthio, 2-methylthiophenylthio, 2,4-dimethylthiophenylthio, 2,5-dimethylthiophenylthio, 2,6-dimethylphenylthio, 3, 2,4-dimethylthiophenyl group, 3,5-dimethylthiophenylthio group, 2,4,6-trimethylphenylthio group, 2,3
4,5,6-pentamethionylthiophenylthio group, thiazolin-2-ylthio group,

A methylthiomethylcarbonyloxy group, a methylthioethylcarbonyloxy group, a (1,3-dithiolan-2-yl) carbonyloxy group, a (1,3-dithiolan-4-yl) carbonyloxy group, a (1,3- (Dithian-2-yl) carbonyloxy group, (1,4-dithian-2-yl) carbonyloxy group, (1,3,5
-Trithian-2-yl) carbonyloxy group, 4-methylthiobenzoyloxy group, thiophen-2-carbonyloxy group, thiazole-2-carbonyloxy group,
Methylthiomethylcarbonylthio group, methylthioethylcarbonylthio group, (1,3-dithiolan-2-yl)
Carbonylthio group, (1,3-dithiolan-4-yl)
Carbonylthio group, (1,3-dithian-2-yl) carbonylthio group, (1,4-dithian-2-yl) carbonylthio group, (1,3,5-trithian-2-yl)
Examples include a carbonylthio group, a benzoylthio group, a 4-methylthiobenzoylthio group, a thiophen-2-carbonylthio group, and a thiazole-2-carbonylthio group, but are not limited thereto. In the formula (1), R ₇ is each independently a hydrogen atom or a methyl group.

As the sulfur-containing (meth) acrylate compound represented by the formula (1), the following formulas (1-A) and (1-
B) or a structure represented by (1-C) (Formula 7),
Preferably, it has a structure represented by the formula (1-A) or the formula (1-B), and the sulfur-containing (meth) acrylate compound represented by the formula (1-B) is particularly preferable.

[0027]

Embedded image (Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are the same as above) The sulfur-containing (meth) acrylate represented by the formula (1) according to the present invention As specific examples of the compounds, the following Table 1 (Tables 1 to
The compounds shown in Table 20) are exemplified, but the present invention is not limited thereto.

[0028]

[Table 1]

[0029]

[Table 2]

[0030]

[Table 3]

[0031]

[Table 4]

[0032]

[Table 5]

[0033]

[Table 6]

[0034]

[Table 7]

[0035]

[Table 8]

[0036]

[Table 9]

[0037]

[Table 10]

[0038]

[Table 11]

[0039]

[Table 12]

[0040]

[Table 13]

[0041]

[Table 14]

[0042]

[Table 15]

[0043]

[Table 16]

[0044]

[Table 17]

[0045]

[Table 18]

[0046]

[Table 19]

[0047]

[Table 20]

The sulfur-containing (meth) acrylate compound represented by the formula (1) according to the present invention is produced according to a synthetic chemistry technique known per se. That is,
Typically, it is preferably produced by a route represented by the following scheme (c) (Chem. 8) (for example, Japanese Patent Application No. 11-16 / 1990).
9511).

[0049]

Embedded image

That is, more specifically, a compound containing a sulfur atom represented by R ₆ —H [a sulfur-containing compound, more specifically, a compound represented by the following formula (6) -A) or (6-b)] to produce a dihydroxy compound represented by the formula (7) as a synthetic intermediate. _{R 13 -OH (6-a)} R 14 -SH (6-b) ( In the above formula, R _13, R ₁₄ are as defined above)

A method of reacting the dihydroxy compound represented by the formula (7) with, for example, (meth) acrylic acid (eg, (meth) acrylic acid or an acid halide derivative thereof), or a halopropionic acid (eg, , 3-chloropropionic acid, 3-bromopropionic acid, 3-chloro-2-methylpropionic acid, 3-bromo-2-methylpropionic acid) or an acid halide thereof to give a halopropionate compound. After that, a sulfur-containing (meth) acrylic ester compound represented by the formula (1) is obtained by various known esterification methods such as a method of dehydrohalogenating and (meth) acrylic esterification. Is preferably manufactured.

The polymerizable composition of the present invention comprises, as a polymerizable compound, a sulfur-containing (meth) acrylate compound represented by the above formula (1) and a (meth) compound having at least one hydroxyl group in the molecule. It is characterized by containing an acrylate compound. The (meth) acrylate compound having at least one hydroxyl group in the molecule is not particularly limited to a chemical structure, but is preferably a monovalent, divalent or higher (polyvalent) glycidyl ether compound. On the other hand, it is an epoxy acrylate compound obtained by reacting a (meth) acrylic ester, and more preferably obtained by reacting a (meth) acrylic ester compound on a divalent or polyvalent glycidyl ether compound. It is a divalent or polyvalent epoxy acrylate compound.

Specific examples of the epoxy acrylate compound include, for example, phenol glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, resorcin diglycidyl ether, bis (4-hydroxyphenyl) methane (commonly called bisphenol F) , 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A) diglycidyl ether, 4,4'-bishydroxyphenyl sulfide diglycidyl ether, 4,4'-bishydroxyphenyl sulfone (commonly known as bisphenol S) ) Diglycidyl ether, 4,4'-biphenol diglycidyl ether, 3,3 ', 5,5'-tetramethyl-
(Meth) acrylic acid esters are allowed to act on various known monovalent or divalent or higher-valent epoxy compounds such as 4,4'-biphenol diglycidyl ether and tris (2,3-epoxypropyl) isocyanurate. Epoxy (meth) acrylate compound obtained; (meth) acrylic acid is allowed to act on various known epoxy resins such as phenol novolak type epoxy resin, cresol novolak type epoxy resin, phenol ziloc type epoxy resin and bisphenol type epoxy resin. (Meth) acrylate compounds obtained by the above method. Among these, as the (meth) acrylate compound having at least one hydroxyl group in the molecule, a (meth) acrylate compound represented by Formula (2) (Formula 9) is particularly preferable.

[0054]

Embedded image (Wherein R ₈ and R ₉ are as defined above)

The content of the sulfur-containing (meth) acrylate represented by the formula (1) in the entire weight of the polymerizable compound contained as an essential component in the polymerizable composition of the present invention is not particularly limited. Is usually 1 to 99% by weight, preferably 5 to 95% by weight, more preferably 10 to 90% by weight, and further preferably 20% by weight.
To 80% by weight, and a content of 25 to 75% by weight is particularly preferable. Further, the content of the (meth) acrylic acid ester containing at least one hydroxyl group in the molecule in the entire weight of the polymerizable compound contained as an essential component in the polymerizable composition is not particularly limited, but usually, 5
To 99% by weight, preferably 10 to 90% by weight, more preferably 20 to 80% by weight, and still more preferably 25 to 75% by weight. However, the sum of the sulfur-containing (meth) acrylate represented by the formula (1) and the (meth) acrylate containing at least one hydroxyl group in the molecule does not exceed 100%.

As the polymerizable compound in the polymerizable composition of the present invention, a sulfur-containing (meth) acrylate compound represented by the formula (1) and (meth) acrylic acid having at least one hydroxyl group in the molecule The ester compounds may be used alone, or a plurality of different (meth) acrylate compounds may be used in combination.

Further, the polymerizable composition of the present invention may contain, if necessary, a sulfur-containing (meth) acrylate compound represented by the formula (1) as a polymerizable compound, as long as the desired effects are not impaired. In addition to the (meth) acrylate compound having at least one hydroxyl group in the molecule, it may contain various known polymerizable compounds (polymerizable monomers or oligomers).

Known polymerizable compounds that may be contained in the polymerizable composition of the present invention include, for example, methyl (meth) acrylate, butyl (meth) acrylate,
Ethylhexyl (meth) acrylate, ethyl carbitol (meth) acrylate, lauryl (meth) acrylate, tetracyclododecyl (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate , Isobornyl (meth) acrylate, Nn-butyl-O- (meth) acryloyloxyethyl carbamate, acryloylmorpholine, trifluoroethyl (meth) acrylate, tribromobenzyl (meth) acrylate, perfluorooctylethyl (meth) acrylate , Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexyl Njioruji (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate,
Polypropylene glycol di (meth) acrylate,

2,2-bis (4-acryloyloxyphenyl) propane, 2,2-bis (4-methacryloyloxyphenyl) propane, bis (4-acryloyloxyphenyl) methane, bis (4-meta) Acroyloxyphenyl) methane, 4,4'-bis (2-acryloyloxy) phenyl sulfide, 4,4'-bis (2-methacroyloxy) phenyl sulfide, 2,2-bis (4-acroyl Oxyethoxyphenyl) propane,
2,2-bis (4-methacroyloxyethoxyphenyl) propane, 2,2-bis [4- (2-acryloyloxypropoxy) phenyl] propane, 2,2-bis [4- (2-methacro Yloxypropoxy) phenyl] propane, bis (4-acryloyloxyethoxyphenyl) methane, bis (4-methacroyloxyethoxyphenyl) methane, bis [4- (2-acryloyloxypropoxy) phenyl] methane, [ 4- (2-methacroyloxypropoxy) phenyl] methane, 4,
4'-bis (2-acroyloxyethoxy) phenyl sulfide, 4,4'-bis (2-methacroyloxyethoxy) phenyl sulfide, 4,4'-bis (2
-Acroyloxypropoxy) phenyl sulfide,
4,4'-bis (2-methacroyloxypropoxy) phenyl sulfide, 4,4'-bis (2-acryloyloxyethoxy) phenyl sulphone, 4,4'-
Bis (2-methacroyloxyethoxy) phenylsulfone, 4,4′-bis (2-acryloyloxypropoxy) phenylsulfone, 4,4′-bis (2-methacroyloxypropoxy) phenylsulfone,
Di (meth) acrylate of ethylene oxide or propylene oxide adduct of 2,2-bis (4-hydroxyphenyl) propane, di (meth) acrylate of ethylene oxide or propylene oxide of bis (4-hydroxyphenyl) methane, 4,4 ′ Di (meth) acrylate of ethylene oxide or propylene oxide adduct of dihydroxyphenyl sulfide,

Trimethylolpropane tri (meth) acrylate, dipentaerythritol pentaacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylol tetraacrylate, dipentaerythritol hexaacrylate, 2- (meth) acryloyloxyethyl tris isocyanate Monofunctional or polyfunctional (meth) such as nurate, (meth) acryloxypropyltris (methoxy) silane
Acrylates: vinylbenzene, divinylbenzene,
Trivinylbenzene, isopropenylbenzene, diisopropenylbenzene, triisopropenylbenzene, N
-Various known polymerizable monomers such as vinyl compounds such as vinylpyrrolidone and N-vinylcaprolactam; and allyl group-containing compounds such as ethylene glycol diallyl carbonate, triallylic acid triallyl ester and triallyl isocyanurate; ) Various known polymerizable oligomers such as acrylates, epoxy (meth) acrylates, polyester (meth) acrylates, and polyether (meth) acrylates are exemplified.

In the polymerizable composition of the present invention, other than the sulfur-containing (meth) acrylate compound represented by the formula (1) and the (meth) acrylate compound having at least one hydroxyl group in the molecule. It is preferable that the polymerizable compound contains at least one (meth) acrylate compound represented by the following formula (3) or (4).

[0062]

Embedded image (Wherein R ₁₀ , R ₁₁ , R ₁₂ and m are the same as above)

In the formulas (3) and (4), R ₁₀ and R ₁₁
And R ₁₂ each independently represent a hydrogen atom or a methyl group. In the formula (4), m represents an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 4, and further preferably an integer of 1 to 3. And the integer 1 is particularly preferred. The amount of the polymerizable compound to be used other than the (meth) acrylate compound represented by the formula (1) or (2) is not particularly limited, but in order to further achieve the effects of the present invention, It is usually at most 80% by weight, preferably at most 70% by weight, more preferably at most 60% by weight, even more preferably at most 50% by weight, based on the total weight of the polymerizable compound.

The polymerization initiator contained as an essential component in the polymerizable composition of the present invention is not particularly limited, and a known photopolymerization initiator or thermal polymerization initiator can be used. Examples of such a photopolymerization initiator include benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, -Hydroxy-2-
Methyl-1-phenylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinolpropan-1-one, N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethyl Anthraquinone, 2-tert-butylanthraquinone,
1-chloroanthraquinone, 2-amylanthraquinone, 2-isopropylthioxatone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone,
2,4-diisopropylthioxanthone, acetophenone dimethyl ketal, benzophenone, 4-methylbenzophenone, 4,4′-dichlorobenzophenone, 4,
Examples thereof include 4'-bisdiethylaminobenzophenone, Michler's ketone, and the like. These can be used alone or in combination of two or more. The amount of the photopolymerization initiator used is 0.001 to 50 parts by weight, preferably 0.01 to 30 parts by weight, more preferably 0.01 to 30 parts by weight, based on 100 parts by weight of the polymerizable compound.
0.1 to 10 parts by weight, more preferably 0.2 to 10 parts by weight.
-5 parts by weight.

Examples of the thermal polymerization initiator include, for example, benzoyl peroxide, p-chlorobenzoyl peroxide, diisopropyl peroxycarbonate, di-2-
Examples include peroxides such as ethylhexyl peroxycarbonate and tert-butyl peroxypivalate, and azo compounds such as azobisisobutyronitrile. The amount of the thermal polymerization initiator to be used is generally 0.001 to 50 parts by weight, preferably 0.01 to 30 parts by weight, more preferably 0 to 30 parts by weight, based on 100 parts by weight of the polymerizable compound. 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight.

Specifically, the polymerizable composition of the present invention has, as a polymerizable compound, a (meth) acrylate compound represented by the formula (1) and one or more hydroxyl groups in the molecule. It can be obtained by using a compound as an essential component, optionally using the above-mentioned known various polymerizable compounds in combination, further adding the polymerization initiator, and then mixing and dissolving. The polymerizable composition is used for polymerization and curing after removing insoluble matters and foreign substances by filtration before polymerization as required, and further sufficiently defoaming under reduced pressure.

In producing the polymerizable composition, if necessary, an internal release agent, a light stabilizer, an ultraviolet absorber, an antioxidant, a coloring pigment (for example, cyanine green, cyanine blue, etc.) It is also possible to add various known additives such as dyes, flow regulators, inorganic fillers (for example, talc, silica, alumina, barium sulfate, magnesium oxide, etc.).

The cured product of the present invention and the optical component comprising the cured product are obtained by polymerizing and curing the above polymerizable composition. As these methods, conventionally known various methods are adopted and suitably performed, but typically, the polymerizable composition obtained as described above is injected into a mold and started by heat or light. Cast polymerization using a radical polymerization reaction to be performed. The mold is composed of two mirror-polished molds via a gasket made of, for example, polyethylene, ethylene-vinyl acetate copolymer, polyvinyl chloride, or the like. Examples of the mold include a combination of glass and glass, glass and a plastic plate, and glass and a metal plate. As the gasket, in addition to using the above-mentioned soft thermoplastic resin (polyethylene, ethylene-vinyl acetate copolymer, polyvinyl chloride, etc.), two molds may be fixed with a polyester adhesive tape or the like. Further, a known treatment method such as a mold release treatment may be performed on the mold.

As described above, as the radical polymerization reaction, a polymerization reaction using heat (thermal polymerization), a polymerization reaction using light such as ultraviolet rays (photopolymerization), a polymerization reaction using gamma rays, or the like, Are exemplified. Among these methods, thermal polymerization requires several hours to several tens of hours, whereas photopolymerization using ultraviolet light or the like can be cured in a matter of seconds to several minutes. This is a preferable method in consideration of enhancing the properties. When performing thermal polymerization, the polymerization temperature is affected by polymerization conditions such as the type of polymerization initiator, and is not limited.
° C, preferably 50 to 170 ° C.

As a method of molding an optical lens, as described above, for example, a method of obtaining a lens by performing cast polymerization with light or / and heat (for example, Japanese Patent Application Laid-Open No.
0-135901, JP-A-10-67736, JP-A-10-130250, etc.). That is, the polymerizable composition containing the acrylate compound of the present invention produced by the above-described method is, if necessary, defoamed by an appropriate method, and then injected into a mold. It is preferably carried out by a method of irradiating and polymerizing. Further, the polymerization by heat is suitably performed by a method of performing polymerization by gradually heating from a low temperature to a high temperature.

The obtained optical lens may be subjected to surface polishing, antistatic treatment, hard coat treatment, or the like for the purpose of providing antireflection, imparting high hardness, improving abrasion resistance, imparting antifogging property or giving fashionability, if necessary. Non-reflective coating treatment, dyeing treatment,
Various known physical or chemical treatments such as a light control treatment (for example, a photochromic lens formation treatment) may be performed.

As a method for forming a substrate for an optical information recording medium such as an optical disk or a magneto-optical disk, for example, a polymerizable composition containing an acrylate compound represented by the general formula (1) obtained by the above method is used. Is injected into a disk substrate mold cavity, polymerized by a radical polymerization method or the like, and post-heat treated as required (Japanese Patent Application Laid-Open No. 58-1).
Nos. 30450, 58-137150, 6
No. 2-280008), a method of photopolymerizing in a double-sided glass mold (Japanese Patent Application Laid-Open No. 60-202557), a method of thermally polymerizing a liquid resin by applying pressure after completion of vacuum casting or liquid injection (Japanese Patent Application Laid-Open No. No. 60-203414) and conventionally known methods.

The cured product obtained by photopolymerizing the polymerizable composition of the present invention, and the optical component comprising the cured product, require several minutes to several hours for polymerization and curing, and use the existing polydiethylene glycol diallyl carbonate. One of the features is that it can be polymerized and molded in a shorter time and has higher productivity than a thermosetting optical resin represented by polythiourethane.

Further, the cured product and the optical component of the present invention are characterized by having excellent optical properties, mechanical properties, and thermal properties and having a high refractive index. Specific examples of the optical component include various plastic lenses typified by corrective spectacle lenses, optical information recording medium substrates, plastic substrates for liquid crystal cells, and optical fiber coating materials.

[0075]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Production Examples and Examples, but the present invention is not limited to these Examples. The evaluation of the physical properties of the polymerizable composition produced in each of the following examples, the cured product obtained by curing the polymerizable composition, and the optical component (lens) was performed by the following methods. Viscosity: The viscosity of the polymerizable composition was measured using a B-type viscometer. -Appearance: Color and transparency were visually observed. -Refractive index, Abbe number: 20 using a Pulfrich refractometer
Measured in ° C. Impact resistance: An iron ball of 28.3 g from a height of 127 cm was dropped on the center of a minus lens having a center thickness of 1.5 mm to check for cracks. ：: No crack on lens ×: Crack on lens

Example 1 As a polymerizable compound, 25.0 g of an acrylate compound represented by the following formula (1-1) (formula 11) and resorcin represented by the following formula (2-1) (formula 11) 2.0 g of epoxy acrylate of diglycidyl ether, 1.0 g of tetracyclododecyl acrylate represented by the following formula (3-1) (formula 11), and ethylene glycol dimethacrylate 6 of the following formula (4-1) (formula 11) 2.0 g of 2-hydroxy-2-methyl-1-
720 mg of phenylpropan-1-one (0.2% by weight based on the total weight of the polymerizable compound) was added, mixed well and dissolved. The viscosity of the obtained colorless transparent polymerizable composition was 400 cps. The polymerizable composition was sufficiently defoamed under reduced pressure, filtered through a filter (1 micron diameter), and then poured into a mold composed of a glass mold and a tape. Metal halide lamp (80W
/ Cm) for 60 seconds to carry out polymerization, followed by heat treatment (annealing) at 110 ° C. for 1 hour. Then, it was cooled to room temperature to obtain a minus lens having a diameter of 30 mm and a center thickness of 1.5 mm. The lens was colorless and transparent, the refractive index (ne) was 1.595, and the Abbe number (νe) was 42.4. The glass transition temperature (Tg) according to the TMA method was 119 ° C., and no depression was observed. Also, as a result of the impact resistance test according to the above method,
No cracking of the lens was observed.

[0077]

Embedded image

Examples 2 to 4 In the same manner as in Example 1, the following Table 2 (Table 2)
A lens was prepared by preparing a polymerizable composition having the composition shown in 1). Table 2 shows the results of evaluation of the physical properties of the lens.
The compounds used in Examples 3 and 4 are compounds represented by the following formula (d) and formula (2-2) (Formula 12), respectively.

[0079]

Embedded image

Comparative Example 1 In Example 1, the compound represented by the formula (1-1) was
Instead of using the (meth) acrylate compounds represented by (2-1), (3-1) and the formula (4-1), a known acrylic acid (described in JP-A-4-161410) is used. Except for using 24 g of 2,5-bis (acryloyloxyethylthiomethyl) -1,4-dithiane (hereinafter referred to as DTAET) and 6 g of dimethyloltricyclodecane acrylate (hereinafter referred to as DCPA) which are ester compounds. In the same manner as described in Example 1, a polymerizable composition was prepared to prepare a lens.
Table 2 shows the results of evaluation of the physical properties of the lens.

Comparative Example 2 In Example 1, the compound represented by the formula (1-1) was
Instead of using the (meth) acrylate compounds represented by (2-1), (3-1) and the formula (4-1), a known acrylic acid (described in JP-A-3-217412) is used. 1,4-bis (2-methacryloyloxyethylthio) xylylene (hereinafter referred to as XD
MET) and 2,2-bis (4-methacryloyloxyethoxyphenyl) propane (hereinafter, referred to as MET)
A polymerizable composition was prepared and a lens was prepared in the same manner as in Example 1, except that 6 g of BSAM was used. Table 2 shows the results of evaluation of the physical properties of the lens.

Comparative Example 3 In Example 1, the compound represented by the formula (1-1) was
Instead of using the (meth) acrylic acid ester compounds represented by (2-1), (3-1) and the formula (4-1), a known (meth) acrylate (described in JP-A-63-248814) is used. ) Acrylate compound 1,3-bis [2-methacryloyloxy-3- (2,4,6-tribromophenoxy) propoxy] benzene (hereinafter referred to as BM
18 g of chlorostyrene (hereinafter referred to as CB)
A polymerizable composition was prepared and a lens was prepared in the same manner as in Example 1 except that 12 g of the polymer was used (referred to as ST). Table 2 shows the results of evaluation of the physical properties of the lens.

[0083]

[Table 21]

[0084]

The polymerizable composition of the present invention is characterized in that a (meth) acrylate compound having a specific structure is used in combination as a polymerizable compound, and the polymerizable composition can be polymerized and cured by light, heat, or the like. A composition. Further, the optical component obtained by curing the polymerizable composition of the present invention has excellent optical properties (transparency, high refractive index, high Abbe number), good thermal properties, good mechanical properties, and It can be polymerized and molded and cured in a short time (high productivity), and is useful as various plastic lenses typified by corrective spectacle lenses, optical information recording medium substrates, plastic substrates for liquid crystal cells, optical fiber coating materials, and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) C07C 323/52 C07C 323/52 323/62 323/62 327/28 327/28 C07D 277/12 C07D 277 / 12 277/18 277/18 277/56 277/56 333/40 333/40 339/06 339/06 339/08 339/08 341/00 341/00 (72) Inventor Masatoshi Takagi 580 Nagaura, Sodegaura City, Chiba Prefecture No. 32 Mitsui Chemicals, Inc. (72) Inventor Kenichi Fujii 580-32, Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc. 4C023 HA02 NA00 PA07 4C033 AC10 AC17 AD03 AD17 4H006 AB46 TA04 TB32 TB35 TB36 TB40 TB42 TB61 TB73 TB74 TB76 TB81 TC09 4J100 AL08R AL66P AL66Q AL66R BA02P BA02Q BA02R BA03Q BA05P BA15P BA41P BA51P BA53PBC BC01BC 3P CA04 CA05 DA52 DA62 DA66 FA03 JA33

Claims (6)

[Claims] 1. A polymerizable composition comprising a polymerizable compound and a polymerization initiator as essential components, wherein the polymerizable compound is a sulfur-containing (meth) compound represented by the following formula (1) (formula 1). A polymerizable composition comprising an acrylate compound and a (meth) acrylate compound having at least one hydroxyl group in a molecule. Embedded image (Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a nitro group or a halogen atom, and R ₅ each independently represent a hydrogen atom or an alkyl group; R ₆ each independently represents a substituent containing a sulfur atom, and R ₇ each independently represents a hydrogen atom or a methyl group.) 2. A (meth) acrylate compound having at least one hydroxyl group in a molecule is represented by the following formula (2):
The polymerizable composition according to claim 1, which is a (meth) acrylate compound represented by the following formula (2). Embedded image (In the formula, R ₈ independently represents a hydrogen atom or an alkyl group, and R ₉ each independently represents a hydrogen atom or a methyl group.) 3. The polymerizable compound further comprises at least one (meth) acrylate compound represented by the following formula (3) or (4) (formula 3). Or the polymerizable composition according to 2. Embedded image (In the above formula, R ₁₀ , R ₁₁ and R ₁₂ each independently represent a hydrogen atom or a methyl group, and m represents an integer of 1 to 10.) 4. A cured product obtained by polymerizing the polymerizable composition according to claim 1. 5. An optical component comprising the cured product according to claim 4. 6. The optical component according to claim 5, wherein the optical component is an optical lens.