JP4504669B2 - Polymerizable composition and use thereof - Google Patents

Description

  The present invention relates to a polymerizable composition that gives a transparent resin by radical polymerization by the action of light or the like. Furthermore, it is related with the hardened | cured material obtained by superposing | polymerizing this polymeric composition, and the optical component which consists of this hardened | cured material.

  Inorganic glass is used in a wide range of fields as a transparent optical material because it is excellent in various properties such as excellent transparency and small optical anisotropy. However, there are disadvantages such as being heavy and prone to breakage, and poor productivity when manufacturing optical parts by processing, and the development of transparent organic polymer materials (optical resins) as an alternative to inorganic glass has been developed. It is actively done. In recent years, optical resins have been improved in functionality and quality, and as optical parts obtained by molding such optical resins, for example, eyeglass lenses for correcting vision, plastic lenses for photographing devices such as digital cameras, It is spreading in the fields of LCD projectors and Fresnel lenses for projector TVs.

  One of the most important basic properties as an optical resin is transparency. Examples of optical resins having good transparency to date include polymethyl methacrylate (PMMA), polycarbonate (BPA-PC), polycycloolefin (COP), diethylene glycol bisallyl carbonate polymer (DAC), polythiourethane ( PTU) has been put into practical use.

  Among these optical resins, polymethyl methacrylate (PMMA) has excellent transparency, small optical anisotropy (low birefringence), and good moldability, weather resistance, etc. It is widely used as one of typical optical resins. However, the refractive index (nd) is as low as 1.49 and has a high water absorption rate, and the improvement is continued.

  Similarly, polycarbonate (BPA-PC), which is one of typical optical resins, includes 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A) and a carbonate compound (for example, chloride). Obtained by a polycondensation reaction of carbonyl, diphenyl carbonate, etc.), having excellent properties such as transparency, heat resistance and impact resistance, and a relatively high refractive index (nd = 1.59). It is widely used in optical applications including disk substrates for vision and eyeglass lenses for correcting vision. However, it has disadvantages such as chromatic aberration (refractive index dispersion), birefringence is relatively high, and melt viscosity is high, resulting in slightly inferior moldability, and further improvements in material aspects to improve performance. It has been continued.

  Diethylene glycol diallyl carbonate polymer (DAC) is a thermosetting resin having a crosslinked polymer structure obtained by casting polymerization of monomer diethylene glycol diallyl carbonate by radical reaction, and has good transparency and heat resistance. It has a feature such as low chromatic aberration, and is most frequently used in general-purpose vision correction plastic spectacle lens applications. However, there is a problem that the refractive index is low (nd = 1.50) and the lens becomes thick depending on the power used.

 Polythiourethane (PTU) is a thermosetting resin having a crosslinked polymer structure obtained by cast polymerization by reaction of a diisocyanate compound and a polythiol compound. It is an excellent optical resin having excellent transparency, impact resistance, high refractive index (nd ≧ 1.6), and relatively low chromatic aberration. Currently used most frequently in high-quality vision-correcting plastic eyeglass lenses that have been made thinner and lighter, but only a long time (ten hours to two days) is used for cast thermal polymerization. There is room for improvement due to productivity constraints.

  In order to solve such problems, in order to mold optical components such as plastic glasses for vision correction in a short time, radical polymerizability in the presence of a compound that initiates polymerization by the action of light such as ultraviolet rays. There has been proposed or suggested a method for polymerizing and molding a compound having a desired yield in a short time (Patent Documents 1 to 3, etc.). Furthermore, as a compound having radical polymerizability, for example, by photopolymerization using a (meth) acrylic acid ester compound or a (meth) acrylic acid (thio) ester compound containing a bromine atom or a sulfur atom, A method for producing a cured product or optical component having a refractive index and a high Abbe number is disclosed. (Patent Documents 4 to 5).

  In addition, a reaction in which a thiol group is added to a carbon-carbon unsaturated bond by the action of a compound (hereinafter referred to as a polymerization initiator) that decomposes by light such as ultraviolet rays or heat to generate radical species (so-called ene-thiol reaction). It has been known. Such an ene-thiol reaction between a compound having at least two carbon-carbon unsaturated bond groups (hereinafter referred to as polyene compound) and a compound having at least two thiol groups (hereinafter referred to as polythiol compound). It has been proposed to use a cured product obtained by polymerization and polymerization as an optical component. (Patent Documents 6 to 11)

  However, although these methods enable polymerization in a short time, the obtained polymerized cured product has transparency, optical properties (for example, refractive index, Abbe number, etc.), thermal properties (for example, heat distortion temperature). In view of the balance of various physical properties such as mechanical properties (for example, impact resistance, bending strength, etc.), it is difficult to say that the optical component is sufficiently satisfactory.

As described above, although the conventionally known optical resins have excellent characteristics, the current situation is that they each have drawbacks to be overcome. Under these circumstances, polymerization and molding can be performed in a short time by high-speed molding, and the resulting cured product or optical component is excellent in transparency and optical properties (high refractive index, high Abbe number). In addition, development of optical resins having good thermal characteristics and mechanical characteristics is desired.
JP 63-207632 A JP-A-61-194401 JP 58-105101 A Japanese Patent Laid-Open No. 4-180911 Japanese Patent Laid-Open No. 63-248811 Japanese translation of PCT publication No. 2002-500784 JP-A-11-305001 JP-A-8-259648 JP-A-1-315701 JP 63-234032 A JP 59-87126 A

  The objective of this invention is providing the optical resin which can solve the said problem regarding the optical resin used for an optical component. More specifically, the polymerization time can be greatly shortened compared to conventional thermosetting resins, and various properties such as transparency, optical properties (refractive index, Abbe number), heat resistance, mechanical properties, weather resistance, etc. It is intended to provide a polymerizable composition that gives a cured product having good physical properties, and a cured product and an optical component obtained by polymerizing the polymerizable composition.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies in order to solve the above problems.

That is, the present invention
Polymerization comprising a compound (A) having at least two carbon-carbon unsaturated bonds in the molecule, a compound (B) having at least two thiol groups in the molecule, and a polymerization initiator (C) And an acrylic ester compound represented by the general formula (1) as the compound (A) having at least two carbon-carbon unsaturated bonds in the molecule, wherein at least 2 in the molecule A polymerizable composition comprising at least one thiol compound represented by formula (2) or formula (3) as the compound (B) having at least one thiol group;

(Wherein R1 and R2 each independently represents a hydrogen atom or a methyl group,
R3 and R4 each independently represents an alkyl group, a halogen atom, an aralkyl group or an aryl group, m and n each independently represents an integer of 0 to 4,
X1 and X2 each independently represent an alkylene group which may have a substituent,
p and q each independently represents an integer of 0 to 8,
Y represents a direct bond, a —S— group, a —SO ₂ — group or a group represented by the following formula (a);
R5 and R6 in the formula (a) each independently represent a hydrogen atom, an alkyl group, an aralkyl group or a phenyl group, and R5 and R6 may combine to form a ring)

Furthermore, it is related with the hardened | cured material obtained by superposing | polymerizing the said polymeric composition, and the optical component consisting of this hardened | cured material.

  The polymerizable composition of the present invention can be polymerized and cured in a short time by light such as ultraviolet rays, and has high productivity in a molding process of a product (for example, an optical component) by cast polymerization.

  The cured product and optical component of the present invention are excellent in transparency and optical properties (high refractive index, high Abbe number), and also have thermal properties, mechanical properties, and weather resistance.

  The present invention will be described in detail below.

  The polymerizable composition of the present invention includes a compound (A) having at least two carbon-carbon unsaturated bonds in the molecule, a compound (B) having at least two thiol groups in the molecule, and polymerization initiation. An acrylic ester represented by the general formula (1) as a compound (A), which is a polymerizable composition containing an agent (C) and has at least two carbon-carbon unsaturated bonds in the molecule Polymericity containing a compound and containing at least one thiol compound represented by formula (2) or formula (3) as compound (B) having at least two thiol groups in the molecule It is a composition.

(Wherein R1 and R2 each independently represents a hydrogen atom or a methyl group,
R3 and R4 each independently represents an alkyl group, a halogen atom, an aralkyl group or an aryl group, m and n each independently represents an integer of 0 to 4,
X1 and X2 each independently represent an alkylene group which may have a substituent,
p and q each independently represents an integer of 0 to 8,
Y represents a direct bond, a —S— group, a —SO ₂ — group or a group represented by the following formula (a);
R5 and R6 in the formula (a) each independently represent a hydrogen atom, an alkyl group, an aralkyl group or a phenyl group, and R5 and R6 may combine to form a ring)

  The polymerization initiator (C) in the polymerizable composition of the present invention, which will be described in detail later, is a compound that decomposes by the action of light or heat to generate radical species to initiate a radical polymerization reaction. A radical species generated from such a polymerization initiator is newly selected by extracting a hydrogen atom from a thiol group of a compound (B) (hereinafter referred to as a polythiol compound) having at least two thiol groups in the molecule. The radical species is added and reacted with an unsaturated bond in the compound (A) (hereinafter referred to as a polyene compound) having at least two carbon-carbon unsaturated bonds in the molecule. Such a reaction proceeds in a chain and increases the cross-linked molecular weight, thereby giving a polymerized cured product (hereinafter referred to as polyene-polythiol reaction). Such a polyene-polythiol reaction itself is a known reaction, and a method for obtaining a polymer using such a reaction has been proposed.

  The polymerizable composition of the present invention contains a compound represented by the general formula (1) as a polyene compound of the polymerizable compound, and a thiol compound represented by the formula (2) or the formula (3) as a polythiol compound. It contains at least 1 type of these.

  By combining such specific compounds, it has become possible to realize physical properties that are not present in polymerizable compositions using the conventionally known polyene-polythiol reaction. That is, the photopolymerizability is good and the polymerization time can be greatly shortened, and the resulting cured product can be used as an optical component such as transparency, optical properties (refractive index, Abbe number), heat resistance, mechanical properties, and weather resistance. Various physical properties required for the application can be satisfied.

  In the compound represented by the general formula (1) of the present invention, R1 and R2 each independently represent a hydrogen atom or a methyl group.

  R3 and R4 in the general formula (1) each independently represents an alkyl group, a halogen atom, an aralkyl group or an aryl group.

As R3 and R4,
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, n-amyl group, isoamyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, A chlorine atom, a bromine atom, a benzyl group, a phenylethyl group, a phenyl group, a naphthyl group, etc. are mentioned.

  R3 and R4 are preferably an alkyl group having 1 to 4 carbon atoms, a bromine atom, a benzyl group, or a phenyl group, and more preferably a methyl group or a phenyl group.

  M and n in the general formula (1) each independently represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and still more preferably an integer. 0 or 1 is represented. The integer 0 is particularly preferable as m and n.

  X1 and X2 in the general formula (1) each independently represent an alkylene group which may have a substituent. Although it does not specifically limit as an alkylene group, For example, a methylene group, ethylene group, a propylene group, a trimethylene group etc. are mentioned.

When X1 and X2 are an optionally substituted alkylene group,
Such substituents are not particularly limited, and examples thereof include alkyl groups, aralkyl groups, aryl groups, alkoxy groups, aralkyloxy groups, aryloxy groups, halogen atoms, and hydroxy groups.

Examples of the substituent include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, n-amyl group, isoamyl group, hexyl group, heptyl group, octyl group. Group, nonyl group, decyl group,
Benzyl group, 4-methylbenzyl group, phenylethyl group,
Phenyl group, naphthyl group, methoxy group, ethoxy group, n-propyloxy group, isopropoxy group, butoxy group, benzyloxy group, phenyloxy group,
A chlorine atom, a bromine atom, etc. are mentioned.

  X1 and X2 are preferably an alkylene group having 1 to 3 carbon atoms which may be substituted with a hydroxy group. Examples of the linking group include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a 2-hydroxytrimethylene group.

  X1 and X2 are more preferably an ethylene group, a propylene group, or a 2-hydroxytrimethylene group.

P and q in General formula (1) represent the integer of 0-8 each independently. Considering the desired effect of the present invention, p and q are preferably integers of 0 to 4, more preferably integers of 0 to 3, and still more preferably integers of 0 to 2.
As p and q, the integer 0 or 1 is particularly preferred.

Y in the general formula (1) represents a direct bond, —S— group, —SO ₂ — group or a group represented by the following formula (a).

  The Y group is preferably a —S— group or a group represented by the formula (a).

  R5 and R6 in the above formula (a) each independently represent a hydrogen atom, an alkyl group, an aralkyl group or a phenyl group, or R5 and R6 may be bonded to form a ring.

  Examples of the R5 and R6 groups include hydrogen atom, methyl group, ethyl group, n-propyl group, n-butyl group, isobutyl group, amyl group, hexyl group, octyl group, benzyl group, phenylethyl group, and phenyl group. And so on.

  When R5 and R6 are combined to form a ring, specific examples include a cyclopentane ring, a cyclohexane ring, and a 3,3,5-trimethylcyclohexane ring.

  The R5 and R6 groups are preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a benzyl group, and a phenyl group, or R5 and R6 may form a cyclohexane ring.

More preferably, they are a hydrogen atom, a methyl group, and a phenyl group.
As the R5 and R6 groups, a methyl group is particularly preferred.

  The compound represented by the general formula (1) in the present invention is a known compound, and is typically available as an industrial chemical.

Examples of the compound represented by the general formula (1) according to the present invention include various known compounds,
For example,

[1] Methacrylate;

2,2-bis (4-methacryloyloxyphenyl) propane,
Bis [4- (2-methacryloyloxyethoxy) phenyl] methane,
1,1-bis [4- (2-methacryloyloxyethoxy) phenyl] ethane,
2,2-bis [4- (2-methacryloyloxyethoxy) phenyl] propane,
2,2-bis [4- (2-methacryloyloxyethoxy) phenyl] -5-methylhexane,
1,1-bis [4- (2-methacryloyloxyethoxy) phenyl] cyclohexane,
1,1-bis [4- (2-methacryloyloxyethoxy) phenyl] -1-phenylethane,

4,4 ′-(2-methacryloyloxyethoxy) biphenyl,
Bis [4- (2-methacryloyloxyethoxy) phenyl] sulfide,
Bis [4- (2-methacryloyloxyethoxy) phenyl] sulfone,

Bis [4- (2-methacryloyloxypropyloxy) phenyl] methane,
1,1-bis [4- (2-methacryloyloxypropyloxy) phenyl] ethane,
2,2-bis [4- (2-methacryloyloxypropyloxy) phenyl] propane,
2,2-bis [4- (2-methacryloyloxypropyloxy) phenyl] -5-methylhexane,
1,1-bis [4- (2-methacryloyloxypropyloxy) phenyl] cyclohexane,
1,1-bis [4- (2-methacryloyloxypropyloxy) phenyl] -1-phenylethane,
4,4 ′-(2-methacryloyloxypropyloxy) biphenyl,
Bis [4- (2-methacryloyloxypropyloxy) phenyl] sulfide,
Bis [4- (2-methacryloyloxypropyloxy) phenyl] sulfone,
2,2-bis [4- (3-methacryloyloxy-2-hydroxypropyloxy) phenyl] propane,
Bis [4- (3-methacryloyloxy-2-hydroxypropyloxy) phenyl] sulfone,

[2] acrylate;
2,2-bis (4-acryloyloxyphenyl) propane,

Bis [4- (2-acryloyloxyethoxy) phenyl] methane,
1,1-bis [4- (2-acryloyloxyethoxy) phenyl] ethane,
2,2-bis [4- (2-acryloyloxyethoxy) phenyl] propane,
2,2-bis [4- (2-acryloyloxyethoxy) phenyl] -5-methylhexane,
1,1-bis [4- (2-acryloyloxyethoxy) phenyl] cyclohexane,
1,1-bis [4- (2-acryloyloxyethoxy) phenyl] -1-phenylethane,
4,4 ′-(2-acryloyloxyethoxy) biphenyl,
Bis [4- (2-acryloyloxyethoxy) phenyl] sulfide,
Bis [4- (2-acryloyloxyethoxy) phenyl] sulfone,
Bis [4- (2-acryloyloxypropyloxy) phenyl] methane,
1,1-bis [4- (2-acryloyloxypropyloxy) phenyl] ethane,
2,2-bis [4- (2-acryloyloxypropyloxy) phenyl] propane,
2,2-bis [4- (2-acryloyloxypropyloxy) phenyl] -5-methylhexane,
1,1-bis [4- (2-acryloyloxypropyloxy) phenyl] cyclohexane,
1,1-bis [4- (2-acryloyloxypropyloxy) phenyl] -1-phenylethane,
4,4 ′-(2-acryloyloxypropyloxy) biphenyl,
Bis [4- (2-acryloyloxypropyloxy) phenyl] sulfide,
Bis [4- (2-acryloyloxypropyloxy) phenyl] sulfone,

2,2-bis [4- (3-acryloyloxy-2-hydroxypropyloxy) phenyl] propanebis [4- (3-acryloyloxy-2-hydroxypropyloxy) phenyl] sulfone may be mentioned.

In order to obtain the desired effect of the present invention, as the compound represented by the general formula (1),
Preferably, it is a compound represented by the formula (1-A), and a compound represented by the formula (1-Ai) is more preferable.

(Wherein R1, R2, X1, X2, p and q represent the same as above)

(Wherein R1, R2, p and q are the same as above)

  The thiol compounds represented by the formulas (2) and (3) in the present invention are known compounds, and are suitably produced by, for example, the method described in JP-A-2-270859.

The content of the polyene compound (A) in the total weight of the polymerizable compound contained in the polymerizable composition of the present invention is usually 95 to 5% by weight, preferably 90 to 10% by weight,
More preferably, it is 90-20 weight%, More preferably, it is 90-30 weight%.

  Here, the total weight of the polymerizable compound is the total weight of the polyene compound (A) and the polythiol compound (B) as described above.

  On the other hand, the content of the polythiol compound (B) in the total weight of the polymerizable compound contained in the polymerizable composition of the present invention is usually 5 to 95% by weight, preferably 10 to 90% by weight. Yes, more preferably 10 to 80% by weight, still more preferably 10 to 70% by weight.

  The polymerization initiator (C) used in the polymerizable composition of the present invention is not particularly limited, and is a compound that initiates a radical polymerization reaction by the action of heat (hereinafter referred to as a thermal polymerization initiator), or A compound that initiates a radical polymerization reaction by light (hereinafter referred to as a photopolymerization initiator) can be used.

  In the polymerizable composition of the present invention, it is particularly preferable to use a photopolymerization initiator in order to realize the purpose of performing polymerization in a short time.

  The photopolymerization initiator is not particularly limited as long as the desired effect is not impaired, and various known compounds can be exemplified.

Examples of the compound include benzophenone, 4-methylbenzophenone, 4,4′-dichlorobenzophenone, 2,4,6-trimethylbenzophenone,
o-benzoylbenzoic acid methyl ester, 4-phenylbenzophenone, 4- (4-methylphenylthio) benzophenone, 3,3-dimethyl-4-methoxybenzophenone,
4- (1,3-acryloyl-1,4,7,10,13-pentaoxatridecyl) benzophenone, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone,
4-benzoyl-N, N, N-trimethylbenzenemethananium chloride, 2-hydroxy-3- (4-benzoylphenoxy) -N, N, N-trimethyl-1-propanaminium chloride, 4-benzoyl-N , N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2- Propenyloxy) ethyl] benzenemethananium bromide,
2-isopropylthioxatone, 4-isopropylthioxatone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone 2-hydroxy-3- (3,4-dimethyl-9-oxo-9H-thioxanthone-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride, 2-benzoylmethylene-3-methylnaphtho Carbonyl compounds such as (1,2-d) thiazoline;
Benzyl, 1,7,7-trimethyl-bicyclo [2,2,1] heptane-2,3-dione (common name, camphorquinone), 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1 -Dicarbonyl compounds such as chloroanthraquinone, 2-amylanthraquinone, 9,10-phenanthrenequinone, α-oxophenylacetic acid methyl ester;
Acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- [4- (2-hydroxy Ethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone,
Dimethoxyacetophenone, diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxy-1,2-diphenylethane-1-one, 1,1-dichloroacetophenone, N, N-dimethylaminoacetophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1 Acetophenones such as 1-phenyl, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 3,6-bis (2-methyl-2-morpholinopropanoyl) -9-butylcarbazole Compound;
Benzoin ether compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether;
Allylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,6-dichlorobenzoyl)-(4-n-propylphenyl) phosphine oxide;
4-dimethylaminobenzoic acid methyl ester, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid-n-butoxyethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, benzoic acid-2-dimethylaminoethyl ester, 4,4′-bisdimethylaminobenzophenone (Michler's ketone), 4,4′-bisdiethylaminobenzophenone, 2,5′-bis (4-dimethylaminobenzal) cyclopentanone, 2,5′-bis (4-diethylamino) Benzal) aminocarbonyl compounds such as cyclopentanone;
2,2,2-trichloro-1- (4′-tert-butylphenyl) ethane-1-one, 2,2-dichloro-1- (4-phenoxyphenyl) ethane-1-one, α, α, α -Tribromomethylphenyl sulfone, 2,4,6-tris (trichloromethyl) triazine, 2,4-trichloromethyl-6- (4-methoxyphenyl) triazine, 2,4-trichloromethyl-6- (4-methoxy Styryl) triazine, 2,4-trichloromethyl-6-piperonyl-triazine 2,4-trichloromethyl-6- (3,4-methylenedioxyphenyl) -triazine, 2,4-trichloromethyl-6- ( 4-methoxynaphthyl) triazine, 2,4-trichloromethyl-6- [2-furylethylidene] triazine, 2,4-trichloromethyl-6 [2- (5-methyl-Free-2-yl) ethylidene] halogen compounds such as triazine;
9-phenylacridine, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2-biimidazole, 2,2-azobis (2-aminopropane) dihydrochloride 2,2-azobis [2- (imidazolin-2-yl) propane] dihydrochloride and the like. These may be used alone or in combination of two or more.

  The amount of the photopolymerization initiator used is 0.001 to 10 parts by weight, preferably 0.001 to 5 parts by weight, and more preferably 0.01 to 100 parts by weight of the polymerizable compound. ~ 2 parts by weight.

  Examples of the thermal polymerization initiator include peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, diisopropyl peroxycarbonate, di-2-ethylhexyl peroxycarbonate, tert-butyl peroxypivalate; azobisiso Examples include azo compounds such as butyronitrile. These may be used alone or in combination of two or more.

  The amount of the thermal polymerization initiator used is usually 0.001 to 10 parts by weight, preferably 0.001 to 5 parts by weight, more preferably 0 to 100 parts by weight of the polymerizable compound. 0.01 to 2 parts by weight.

  Furthermore, in the polymerizable composition of the present invention, a photopolymerization initiator and a thermal polymerization initiator as described above may be used in combination.

  As the compound (A) containing at least two carbon-carbon unsaturated bonds in the molecule according to the present invention, the compound represented by the general formula (1) is essential for obtaining the desired effect to the maximum. Needless to say, it is a compound containing at least two carbon-carbon unsaturated bonds in the molecule to the extent that the desired effect is not impaired, and other polymerizability other than the compound of general formula (1). It may contain a compound.

  Examples of such compounds include bifunctional or polyfunctional (meth) acrylates, epoxy (meth) acrylates obtained by allowing (meth) acrylic acid compounds to act on known bifunctional or higher epoxy compounds, and divinylbenzene. Bifunctional or higher radical polymerizable monomers represented by bifunctional or higher vinyl compounds, bifunctional or higher allyl group-containing compounds, etc .; or urethane (meth) acrylates, epoxy (meth) acrylates, polyesters (meta ) Bifunctional or higher radical polymerizable oligomers such as acrylates and polyether (meth) acrylates.

  The content of the polymerizable compound other than the compound of the general formula (1) in the total weight of the polymerizable compound contained in the polymerizable composition of the present invention is not particularly limited. It is 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less, and still more preferably 20% by weight or less.

  The compound (B) containing at least two or more thiol groups in the molecule according to the present invention may contain at least one of the compound represented by the formula (2) or the compound represented by the formula (3). Needless to say, it is indispensable for obtaining the effects of the present invention to the maximum, but is a compound containing at least two or more thiol groups in the molecule to the extent that the desired effects are not impaired. ) Or other polythiol compounds other than the thiol compound of the formula (3) may be contained.

Examples of such compounds include known polythiol compounds.
For example, methanedithiol,
Ethanedithiol,
1,1-propanedithiol,
1,3-propanedithiol,
1,2,3-propanetrithiol,
1,1-cyclohexanedithiol,
1,2-cyclohexanedithiol,
2,2-dimethylpropane-1,3-dithiol,
3,4-dimethoxy-1,2-dithiol,
2-methylcyclohexane-2,3-dithiol,
1,1-bis (mercaptomethyl) cyclohexane,
Thiomalic acid bis (2-mercaptoethyl ester),
2,3-dimercapto-1-propanol (2-mercaptoacetate),
2,3-dimercapto-1-propanol (3-mercaptopropionate),
Diethylene glycol bis (2-mercaptoacetate),
Diethylene glycol bis (3-mercaptopropionate),
1,2-dimercaptopropyl methyl ether,
2,3-dimercaptopropyl methyl ether,
2,2-bis (mercaptomethyl) -1,3-propanedithiol,
Bis (2-mercaptoethyl) ether,
Ethylene glycol bis (2-mercaptoacetate),
Ethylene glycol bis (3-mercaptopropionate),
Trimethylolpropane bis (2-mercaptoacetate),
Trimethylolpropane bis (3-mercaptopropionate),
Pentaerythritol tetrakis (2-mercaptoacetate),
Pentaerythritol tetrakis (3-mercaptopropionate),
Aliphatic polythiol compounds such as tetrakis (mercaptomethyl) methane;

1,2-dimercaptobenzene,
1,3-dimercaptobenzene,
1,4-dimercaptobenzene,
1,2-bis (mercaptomethyl) benzene,
1,3-bis (mercaptomethyl) benzene,
1,4-bis (mercaptomethyl) benzene,
1,2,3-trimercaptobenzene,
1,2,4-trimercaptobenzene,
1,3,5-trimercaptobenzene,
1,2,3-tris (mercaptomethyl) benzene,
1,2,4-tris (mercaptomethyl) benzene,
1,3,5-tris (mercaptomethyl) benzene,
1,2,3-tris (mercaptoethyl) benzene,
1,2,4-tris (mercaptoethyl) benzene,
1,3,5-tris (mercaptoethyl) benzene,
2,5-toluenedithiol,
3,4-toluenedithiol,
1,3-di (p-methoxyphenyl) propane-2,2-dithiol,
1,3-diphenylpropane-2,2-dithiol,
Phenylmethane-1,1-dithiol,
Aromatic polythiol compounds such as 2,4-di (p-mercaptophenyl) pentane;

1,2-bis (mercaptoethylthio) benzene,
1,3-bis (mercaptoethylthio) benzene,
1,4-bis (mercaptoethylthio) benzene,
1,2,3-tris (mercaptomethylthio) benzene,
1,2,4-tris (mercaptomethylthio) benzene,
1,3,5-tris (mercaptomethylthio) benzene,
1,2,3-tris (mercaptoethylthio) benzene,
1,2,4-tris (mercaptoethylthio) benzene,
Aromatic polythiol compounds containing sulfur atoms in addition to mercapto groups such as 1,3,5-tris (mercaptoethylthio) benzene and the like, and aromatic ring nucleus alkylated products thereof;

Bis (mercaptomethyl) sulfide,
Bis (mercaptoethyl) sulfide,
Bis (mercaptopropyl) sulfide,
Bis (2-mercaptoethylthio) methane,
Bis (3-mercaptopropylthio) methane,
1,2-bis (2-mercaptoethylthio) ethane,
1,2-bis (3-mercaptoethylthio) propane,
1,2,3-tris (2-mercaptoethylthio) propane,
1,2,3-tris (3-mercaptopropylthio) propane,

Tetrakis (3-mercaptoethylthiomethyl) methane,
Tetrakis (3-mercaptoethylthiomethyl) methane,
Bis (2,3-dimercaptopropyl) sulfide,
Bis (1,3-dimercaptopropyl) sulfide,

2,5-dimercapto-1,4-dithiane,
2,5-dimercaptomethyl-1,4-dithiane,
2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane,
Bis (mercaptoethyl) disulfide,
Bis (mercaptopropyl) disulfide and the like, and ester compounds of these thioglycolic acid and mercaptopropionic acid;

Hydroxymethyl sulfide bis (2-mercaptoacetate),
Hydroxymethyl sulfide bis (3-mercaptopropionate),
Hydroxyethyl sulfide bis (2-mercaptoacetate),
Hydroxyethyl sulfide bis (3-mercaptopropionate),
Hydroxypropyl sulfide bis (2-mercaptoacetate),
Hydroxypropyl sulfide bis (3-mercaptopropionate),
Hydroxymethyl disulfide bis (2-mercaptoacetate),
Hydroxymethyl disulfide bis (3-mercaptopropionate),
Hydroxymethyl disulfide bis (2-mercaptoacetate),
Hydroxymethyl disulfide bis (3-mercaptopropionate),
Hydroxyethyl disulfide bis (2-mercaptoacetate),
Hydroxyethyl disulfide bis (3-mercaptopropionate),
Hydroxypropyl disulfide bis (2-mercaptoacetate),
Hydroxypropyl disulfide bis (3-mercaptopropionate),
2-mercaptoethyl ether bis (2-mercaptoacetate),
2-mercaptoethyl ether bis (3-mercaptopropionate),
2-mercaptoethyl ether bis (2-mercaptoacetate),
2-mercaptoethyl ether bis (3-mercaptopropionate),
1,4-dithian-2,5-diol bis (2-mercaptoacetate),
1,4-dithian-2,5-diol bis (3-mercaptopropionate),
Thiodiglycolic acid bis (2-mercaptoethyl ester),
Thiodipropionic acid bis (2-mercaptoethyl ester),
4,4-thiodibutyric acid bis (2-mercaptobutyl ester),
Dithiodiglycolic acid bis (2-mercaptoethyl ester),
Dithiodipropionic acid bis (2-mercaptoethyl ester),
4,4-dithiodibutyric acid bis (2-mercaptobutyl ester),
Thiodiglycolic acid bis (2,3-dimercaptopropyl ester),
Thiodipropionic acid bis (2,3-dimercaptopropyl ester),
Dithiodiglycolic acid bis (2,3-dimercaptopropyl ester),
An aliphatic polythiol compound containing a sulfur atom in addition to a mercapto group such as bis (2,3-dimercaptopropyl ester) dithiodipropionate;

Heterocyclic polythiol compounds containing sulfur atoms in addition to mercapto groups such as 3,4-thiophenedithiol and 2,5-dimercapto-1,3,4-thiadiazole;

Glycerin di (mercaptoacetate),
2,4-dimercaptophenol,
3,4-dimercapto-2-propanol,
1,3-dimercapto-2-propanol,
2,3-dimercapto-1-propanol,
1,2-dimercapto-1,3-butanediol,
Pentaerythritol tris (3-mercaptopropionate),
Pentaerythritol bis (3-mercaptopropionate),
Pentaerythritol tris (thioglycolate),

Dipentaerythritol pentakis (3-mercaptopropionate),
Examples include polythiol compounds containing hydroxy groups other than mercapto groups such as hydroxymethyl-tris (mercaptoethylthiomethyl) methane.

  The content of these other polymerizable compounds in the total weight of the polymerizable compounds contained in the polymerizable composition of the present invention is not particularly limited, but is usually 50% by weight or less, preferably 40%. % By weight or less, more preferably 30% by weight or less, and further preferably 20% by weight or less.

  Specifically as a manufacturing method of the polymeric composition of this invention, the compound represented by General formula (1) and the thiol compound represented by Formula (2) or / and Formula (3) are mixed. If desired, the above-mentioned various known polymerizable compounds are used in combination, and the polymerization initiator is further added, and then mixed and dissolved.

  The polymerizable composition of the present invention is used for polymerization and curing by removing insoluble matters, foreign matters, and the like by filtering before polymerization, if necessary, and sufficiently defoaming under reduced pressure.

  When producing the polymerizable composition, an internal mold release agent, a light stabilizer, an ultraviolet absorber, an antioxidant, a color pigment (for example, cyanine green) may be used as long as the effects of the present invention are not impaired. , Cyanine blue, etc.), dyes, flow regulators, inorganic fillers (for example, talc, silica, alumina, barium sulfate, magnesium oxide, etc.) can also be added.

  The cured product of the present invention and the optical component comprising the cured product are obtained by polymerizing and curing the polymerizable composition. As these methods, various conventionally known methods are adopted and preferably carried out. Typically, the polymerizable composition obtained as described above is injected into a mold and started by heat or light. And cast polymerization in which a radical polymerization reaction is performed.

  The mold is composed of, for example, two molds that are mirror-polished through a gasket made of polyethylene, ethylene-vinyl acetate copolymer, polyvinyl chloride, or the like. Examples of the mold include glass and glass, glass and plastic plate, glass and metal plate, and the like. Further, as the gasket, in addition to using the soft thermoplastic resin (polyethylene, ethylene-vinyl acetate copolymer, polyvinyl chloride, etc.), two molds may be fixed with a polyester adhesive tape or the like. Moreover, you may perform well-known processing methods, such as a mold release process, with respect to a casting_mold | template.

  As described above, as the radical polymerization reaction, a method using a polymerization reaction by heat (thermal polymerization), a polymerization reaction by light such as ultraviolet rays or visible light (photopolymerization), a polymerization reaction by active energy rays such as gamma rays, etc., Or the method etc. which combined these plural are illustrated.

  When polymerization is performed by light, after the curing, the cured product obtained by releasing the mold or the optical component made of the cured product may be annealed for the purpose of removing internal stress and distortion.

  Among these methods, thermal polymerization requires several hours to several tens of hours, whereas photopolymerization using ultraviolet rays or the like can be cured in several seconds to several minutes, and the optical component of the present invention is manufactured. This is a preferable method in consideration of productivity.

  When thermal polymerization is performed, the polymerization temperature is affected by polymerization conditions such as the type of polymerization initiator and is not limited, but is usually 25 to 200 ° C, and preferably 50 to 170 ° C.

  As described above, as a method for molding an optical lens, for example, there is a method in which cast polymerization is performed by light or / and heat to obtain a lens (for example, JP-A-60-135901, JP-A-10-101). No. 67736, JP-A-10-130250, etc.).

  That is, the polymerizable composition of the present invention produced by the above-described method is defoamed by an appropriate method, if necessary, and then poured into a mold, and is usually polymerized by light irradiation. Is preferably implemented. In addition, the polymerization by heat is preferably carried out by a method of polymerizing by gradually heating from a low temperature to a high temperature.

  The obtained optical lens may be annealed as necessary after curing. If necessary, surface polishing, antistatic treatment, hard coat treatment, non-reflective coating treatment, dyeing treatment, dyeing treatment, antireflection, high hardness, wear resistance improvement, antifogging or fashionability. Various known physical or chemical treatments such as light treatment (for example, photochromic lens formation treatment) may be performed.

  The polymerizable composition of the present invention takes about several minutes to 1 hour for polymerization and molding by photopolymerization and is compared with existing thermosetting optical resins represented by polydiethylene glycol diallyl carbonate and polythiourethane. Polymerization and molding are possible in a short time, and productivity in these processes is high.

  The cured product and optical component of the present invention are excellent in transparency, have a high refractive index and a high Abbe number, and have good thermal characteristics, mechanical characteristics, and weather resistance.

  Examples of the optical component of the present invention include eyeglass lenses for correcting vision, Fresnel lenses for liquid crystal projectors and projector televisions, various plastic lenses represented by lenticular lenses, contact lenses, and the like, sealing materials for light emitting diodes (LEDs), Optical coatings used for optical waveguides, optical lenses and optical waveguides, antireflection coatings used for optical lenses, etc., transparent coatings or transparency used for liquid crystal display-related materials (substrates, light guide plates, films, sheets, etc.) Examples include substrates.

  In particular, the cured product or optical component of the present invention can be molded in a short time by photopolymerization and has a high refractive index, optical properties (transparency, Abbe number), and thermal properties (heat deformation). Temperature, etc.) and mechanical properties (impact resistance, etc.) are favorable, preferably for eyeglass lenses for correcting vision, plastic lenses such as Fresnel lenses, optical waveguides, optical lenses, optical lenses and optical waveguides Used as an optical adhesive, a light emitting diode (LED) encapsulant, a transparent coating, and the like.

  The polymerizable composition of the present invention is used for applications such as hologram recording and dental materials as a photopolymerizable material providing a high refractive index transparent material in addition to the optical components as described above.

 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

<Preparation of polymerizable composition of the present invention>

  43.40 g (0.096 mol) of the compound represented by the formula (1-1) as the polyene compound and 6.60 g (0.0256 mol) of the compound represented by the formula (2) as the polythiol compound were shielded from light. After weighing each into a glass container, 25 mg of 2-hydroxy-2-methyl-1-phenylpropan-1-one as a photopolymerization initiator (total amount of polymerizable compounds) was obtained from the liquid obtained by mixing. 0.05% by weight with respect to the weight) was added and dissolved by stirring.

  Next, the mixture is sufficiently deaerated at room temperature while stirring slowly under reduced pressure until no foaming is observed, and then filtered under pressure using a filter made of Teflon (registered trademark). 00 g was obtained.

  The photopolymerization initiators used in the above examples were obtained and used as follows.

2-hydroxy-2-methyl-1-phenylpropan-1-one; Darocur-1173 (manufactured by Ciba Specialty Chemicals)

  40.80 g (0.090 mol) of the compound represented by the formula (1-1) as a polyene compound, 9.20 g (0.0250 mol) of the compound represented by the formula (3) as a polythiol compound, The same procedure as described in Example 1 was performed except that 50 mg of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (0.1 wt% based on the total weight of the polymerizable compound) was used as a polymerization initiator. A colorless transparent liquid polymerizable composition was obtained.

◇ Production of cured product by curing of the polymerizable composition of the present invention Physical properties of cured products or optical components (lenses) produced in the following examples were evaluated using the following methods.
・ Appearance: Visually and microscopically confirmed the presence of color, transparency, optical distortion and striae
did.
Refractive index and Abbe number: Measured at 20 ° C. using a Purfrich refractometer.
Specific gravity: Measured using DENSIMETER D-1 (manufactured by Toyo Seiki Seisakusho).
-Heat resistance: Change of TMA curve of cured product by needle penetration method using thermomechanical analysis (TMA method)
The glass transition temperature (Tg) was measured from the coordinate point.

(Production of cured product by photopolymerization of polymerizable composition of the present invention)
The polymerizable composition prepared in Example 1 was poured into a mold prepared using silicon rubber as a spacer between two mirror-finished glass plates. Using a metal halide lamp (120 W / cm), polymerization was performed by irradiating ultraviolet rays from both the upper and lower surfaces of the glass mold for 600 seconds. After completion of the polymerization, the cured product was gradually cooled and released from the mold and taken out. The obtained flat cured product was heat treated (annealed) at 100 ° C. for 1 hour and then observed, and as a result, the cured product was colorless and transparent, and no optical distortion or striae was observed.

The physical properties of the cured product were refractive index (ne) 1.585, Abbe number (νe) 36.0, specific gravity 1.22, and glass transition temperature (Tg) 73.0 ° C.

(Production of cured product by photopolymerization of polymerizable composition of the present invention)
Photopolymerization was carried out in the same manner as in Example 3 except that the polymerizable composition prepared in Example 2 was used to obtain a colorless and transparent flat cured product. When the cured product was observed, it was colorless and transparent, and no optical distortion or striae was observed.

The physical properties of the cured product were refractive index (ne) 1.590, Abbe number (νe) 35.8, and specific gravity 1.22. The heat resistance was good.

(Production of lens)
The polymerizable composition prepared in Example 1 was sufficiently degassed under reduced pressure under light shielding. A mold mold composed of a pair of glass mold and tape was adjusted to a negative lens shape, and the above-described polymerizable composition was injected into this mold mold. The metal halide lamp (120 W / cm) was used to irradiate ultraviolet rays from both the upper and lower surfaces of the mold for 600 seconds, followed by annealing at 80 ° C. for 1 hour. After the heating, it was allowed to cool at room temperature to obtain a minus lens having a diameter of 80 mm and a center thickness of 1.00 mm. The obtained lens was colorless and transparent, and was optically homogeneous without any optical distortion or striae being observed.

  The lens of the present invention had good heat resistance (heating deformation temperature), impact resistance, and weather resistance, and had no practical problems.

  As can be seen from the results of Examples, the polymerizable composition of the present invention can be polymerized and cured in a short time by photopolymerization. The obtained cured product and optical component of the present invention are excellent in transparency and optical properties (high refractive index), and also have thermal properties, mechanical properties, and weather resistance.

  The polymerizable composition of the present invention can be polymerized and cured in a short time by photopolymerization. The obtained cured product and optical component of the present invention are excellent in transparency and optical properties (high refractive index), and also have thermal properties, mechanical properties, and weather resistance. From these features, for example, eyeglass lenses for correcting vision, Fresnel lenses for liquid crystal projectors and projection televisions, lenticular lenses, various plastic lenses such as contact lenses, light emitting diode (LED) sealing materials, optical waveguides, For optical adhesives used for bonding optical lenses and optical waveguides, anti-reflection films used for optical lenses, etc., transparent coatings or transparent substrates used for liquid crystal display related materials (substrates, light guide plates, films, sheets, etc.) used.

Claims (3)

As the polymerizable compound, only the compound (A) having at least two carbon-carbon unsaturated bonds in the molecule and the compound (B) having at least two thiol groups in the molecule are contained, and polymerization starts An acrylic ester represented by the general formula (1) as a compound (A), which is a polymerizable composition containing an agent (C) and has at least two carbon-carbon unsaturated bonds in the molecule Polymericity containing a compound and containing at least one thiol compound represented by formula (2) or formula (3) as compound (B) having at least two thiol groups in the molecule Composition.

(Wherein R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, R ₃ and R ₄ each independently represent an alkyl group, a halogen atom, an aralkyl group or an aryl group, and m and n are each Independently represents an integer of 0 to 4, X ₁ and X ₂ each independently represents an optionally substituted alkylene group, p and q each independently represents an integer of 0 to 8 , Y represents a single bond, —S— group, —SO ₂ — group or a group represented by the following formula (a), and R ₅ and R ₆ in the formula (a) are each independently a hydrogen atom. Represents an alkyl group, an aralkyl group or a phenyl group, and R ₅ and R ₆ may combine to form a ring)

  A cured product obtained by polymerizing the polymerizable composition according to claim 1.   An optical component comprising the cured product according to claim 2.