CN101228202A - Polythiourethane-based polymerizable composition and optical resin obtained from the same - Google Patents
Polythiourethane-based polymerizable composition and optical resin obtained from the same Download PDFInfo
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- CN101228202A CN101228202A CNA2006800264179A CN200680026417A CN101228202A CN 101228202 A CN101228202 A CN 101228202A CN A2006800264179 A CNA2006800264179 A CN A2006800264179A CN 200680026417 A CN200680026417 A CN 200680026417A CN 101228202 A CN101228202 A CN 101228202A
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Abstract
The present invention provides a polymerizable composition for giving a resin which has a high refractive index and low dispersion, and is especially excellent in impact resistance and tintability; and a resin and an optical component each obtained by curing the composition. There used a polymerizable composition comprising (A) a compound represented by Formula (1) and/or by Formula (2), at least one compound as the following component (B), and at least one compound as the following component (C): (B) polythiol compounds optionally having at least one (poly)sulfide bond in a molecule, and (C) compounds represented by Formula (3): HO-[R1-(Y) n ] m -R2-X (3) (in above Formula (3), X is an OH group or a SH group; Y is an oxygen atom or a sulfur atom; R1 and R2 are each independently an optionally substituted methylene group or an optionally substituted alkylene group having carbon atoms of not smaller than 2 and not larger than 4; n is an integer of 0 or 1 when Y is an oxygen atom, or 0 or an integer of not smaller than 1 and not larger than 2 when Y is a sulfur atom; and m is 0 or an integer of not smaller than 1 and not larger than 3, provided that (carbon number of R1+n) m + (carbon number of R2) is 3 or larger).
Description
Technical field
The present invention relates to Polymerizable composition, resin and optics.
Background technology
Plastic lens is compared lightweight and not fragile with inorganic lenses, can dye, and therefore popularizes just apace as optical elements such as eyeglass lens, camera lens in recent years.
Eyeglass lens particularly, consider from its purposes aspect, except that require to have (1) high refractive index, (2) low optical property of disperseing (high Abbe number), also requirement has multiple functions such as excellent processability such as (3) excellent heat resistance, (4) excellent impact resistance, (5) dyeing easily, (6) machining, has developed so far and has used multiple lens resin raw material.
Wherein, as typical example, can enumerate polythiourethane resinoid (patent documentation 1,2).
In addition, in the polythiourethane resinoid, use the polythiourethane resinoid (patent documentation 3) of the isocyanate compound of following formula (1) expression that the plastic lens of high refractive index, low dispersion and thermotolerance, excellent impact resistance can be provided, and be widely used in eyeglass lens.
In addition, nearest eyeglass lens carries out the processing of raising value addeds such as the silicon class is coated with firmly, the coating of mineral-type antireflection usually on the lens of base material.But, knownly carry out above-mentioned coating and handle and cause the shock-resistance of lens impaired.Particularly, in the U.S., standard for the shock-resistance that satisfies FDA (Food and Drug Adminstration) (FDA) regulation, sometimes the polythiourethane resinoid system lens of excellent impact resistance are also implemented the priming paint coating of improvement shock-resistance before being coated with processing firmly, so require the shock-resistance (patent documentation 4) of further improvement base material.
Recently, eyeglass lens also requires fashion, so the increase in demand of dyeing lens.
Usually, there is the relation of compromise selection in the thermotolerance of dyeability and base material, when thermotolerance is too high, and the dyeability variation.In addition, when reducing thermotolerance in order to improve dyeability, the thermotolerance difference between above-mentioned hard coat film, anti reflection coating and the lens substrate produces the crack on filming when causing using.
So, require can be fully practical thermotolerance and the good lens resin of dyeability about 100～110 ℃ of having.
More than be example with the plastic lens, but for the polythiourethane resinoid, require the balance of improvement optical characteristics, dyeability and mechanical strength of resin.
Patent documentation 1: the spy opens flat 2-270859 communique
Patent documentation 2: the spy opens flat 7-252207 communique
Patent documentation 3: the spy opens flat 3-124722 communique
Patent documentation 4: the spy opens flat 9-113852 communique
Summary of the invention
The present invention In view of the foregoing finishes, and provides a kind of shock-resistance to be better than existing resin, has sufficient thermotolerance, the resin that dyeability is modified and the Polymerizable composition that forms this resin.
The inventor etc. further investigate in order to address the above problem, and found that a kind of polythiourethane resinoid, this resin can fully satisfy desired rerum natura, thereby finished the present invention, described polythiourethane resinoid makes following (A), (B) reach (C) to react and obtains
(A) at least a ester ring type isocyanate compound of representing by following formula (1) and/or following formula (2);
(B) can have at least a in the multi-thioalcohol compound of (many) sulfide linkages more than 1 in 1 molecule;
(C) at least a in the diol compound of formula (3) expression or the mercaptoalcohol compound.
That is, the present invention includes following scheme:
[1] a kind of Polymerizable composition, described composition contain (A) by the ester ring type isocyanate compound of following formula (1) and/or following formula (2) expression,
(B) can have in 1 molecule in the multi-thioalcohol compound of (many) sulfide linkages more than 1 at least a,
(C) at least a in the compound of following formula (3) expression,
HO-[R1-(Y)
n]
m-R2-X (3)
(in the above-mentioned formula (3), X represents OH base or SH base.Y represents Sauerstoffatom or sulphur atom, and R1 and R2 are independent separately, and expression can have substituent methylene radical, and maybe can to have substituent carbonatoms be 2～4 alkylidene group.When Y was Sauerstoffatom, n was 0 or 1, and when Y was sulphur atom, n represented 0 or 1～2 integer.M represents 0 or 1～3 integer.Wherein, (carbonatoms of R1+n) * m+ (carbonatoms of R2) is more than 3.)；
[2] as [1] described Polymerizable composition, wherein, described (A) by the multi-thioalcohol compound that can have (many) sulfide linkages more than 1 in the ester ring type isocyanate compound of formula (1) and/or formula (2) expression, described (B) 1 molecule, and the usage ratio of the compound represented of described (C) formula (3) with functional group's molar ratio computing of NCO/ (SH+OH), be 0.5～3.0
If the hydroxyl of the compound of described (C) formula (3) expression and the mole number of thiol group are respectively p, q, when the mole number that can have the thiol group in the multi-thioalcohol compound of (many) sulfide linkages more than 1 in described (B) 1 molecule was r, p/ (p+q+r) was 0.001～0.40;
[3] as [1] described Polymerizable composition, wherein, the multi-thioalcohol compound that can have (many) sulfide linkages more than 1 in described (B) 1 molecule is to be selected from 4-mercapto methyl-1,8-dimercapto-3,6-dithia octane, 1,1,3,3-four (sulfydryl methylthio group) propane, 5,7-dimercapto methyl-1,11-dimercapto-3,6,9-three thia undecanes, 4,7-dimercapto methyl-1,11-dimercapto-3,6,9-three thia undecanes and 4,8-dimercapto methyl-1,11-dimercapto-3,6, one or two above compounds in the 9-three thia undecanes;
[4] as [1] described Polymerizable composition, wherein, in the described formula (3) of expression described (C) composition, m is 0;
[5] as [4] described Polymerizable composition, wherein, described (C) composition is 1, the 4-butyleneglycol;
[6] as [1] described Polymerizable composition, wherein, in the described formula (3) of expression described (C) composition, m is 1～3 integer;
[7] as [6] described Polymerizable composition, wherein, in the described formula (3) of expression described (C) composition, n is 1, and Y is a Sauerstoffatom;
[8] as [7] described Polymerizable composition, wherein, in the described formula (3) of expression described (C) composition, it is 2 or 3 alkylidene group that R1 and R2 represent to have substituent carbonatoms independently of one another;
[9] as [8] described Polymerizable composition, wherein, described (C) composition is triglycol or glycol ether;
[10] as [5] or [9] described Polymerizable composition, wherein, described (A) is the ester ring type isocyanate compound of described formula (1) expression by the ester ring type isocyanate compound of formula (1) and/or formula (2) expression,
The multi-thioalcohol compound that can have (many) sulfide linkages more than 1 in described (B) 1 molecule is to be selected from 4-mercapto methyl-1,8-dimercapto-3,6-dithia octane, 5,7-dimercapto methyl-1,11-dimercapto-3,6,9-three thia undecanes, 4,7-dimercapto methyl-1,11-dimercapto-3,6,9-three thia undecanes and 4,8-dimercapto methyl-1,11-dimercapto-3,6, one or two above compounds in the 9-three thia undecanes;
[11] a kind of preparation method of resin, described preparation method make each described Polymerizable composition polymerization in [1]～[10];
[12] a kind of resin, make following (A), (B) and (C) reaction obtain,
(A) the ester ring type isocyanate compound of representing by following formula (1) and/or following formula (2),
(B) can have at least a in the multi-thioalcohol compound of (many) sulfide linkages more than 1 in 1 molecule,
(C) at least a in the compound of following formula (3) expression;
HO-[R1-(Y)
n]
m-R2-X (3)
(in the above-mentioned formula (3), X represents OH base or SH base.Y represents Sauerstoffatom or sulphur atom, and R1 and R2 are independent separately, and expression can have substituent methylene radical, and maybe can to have substituent carbonatoms be 2～4 alkylidene group.When Y was Sauerstoffatom, n was 0 or 1, and when Y was sulphur atom, n represented 0 or 1～2 integer.M represents 0 or 1～3 integer.Wherein, (carbonatoms of R1+n) * m+ (carbonatoms of R2) is more than 3.)
[13] a kind of optics, described optics contain [12] described resin;
[14] a kind of lens, described lens are made of [13] described optics;
[15] a kind of eyeglass lens, described eyeglass lens is made of [14] described lens;
[16] each described Polymerizable composition is as the application of optics in [1]～[10];
[17] make [1]～[10] in the resin that obtains of each described Polymerizable composition polymerization as the application of optics.
Embodiment
Polymerizable composition of the present invention contains following composition, promptly
(A) by the ester ring type isocyanate compound of following formula (1) and/or following formula (2) expression,
(B) can have in 1 molecule in the multi-thioalcohol compound of (many) sulfide linkages more than 1 at least a, and
(C) at least a in the compound of following formula (3) expression.
HO-[R1-(Y)
n]
m-R2-X (3)
(in the above-mentioned formula (3), X represents OH base or SH base.Y represents Sauerstoffatom or sulphur atom, and R1 and R2 represent to have substituent methylene radical independently of one another maybe can to have substituent carbonatoms be 2～4 alkylidene group.When Y was Sauerstoffatom, n was 0 or 1, and when Y was sulphur atom, n represented 0 or 1～2 integer.M represents 0 or 1～3 integer.Wherein, (carbonatoms of R1+n) * m+ (carbonatoms of R2) is more than 3.)
Need to prove that so-called Polymerizable composition contains (A)～(C) composition, is meant the Polymerizable composition that is combined with (A)～(C) composition.Each material composition can not exclusively consume, and can be that a part of composition is consumed by reaction.
In addition, resin of the present invention makes following (A), (B) reach (C) to react and obtains,
(A) the ester ring type isocyanate compound of representing by following formula (1) and/or following formula (2),
(B) can have at least a in the multi-thioalcohol compound of (many) sulfide linkages more than 1 in 1 molecule,
(C) at least a in the compound of following formula (3) expression.
HO-[R1-(Y)
n]
m-R2-X (3)
(in the above-mentioned formula (3), X represents OH base or SH base.Y represents Sauerstoffatom or sulphur atom, and R1 and R2 are independent separately, and expression can have substituent methylene radical, and maybe can to have substituent carbonatoms be 2～4 alkylidene group.When Y was Sauerstoffatom, n was 0 or 1, and when Y was sulphur atom, n represented 0 or 1～2 integer.M represents 0 or 1～3 integer.Wherein, (carbonatoms of R1+n) * m+ (carbonatoms of R2) is more than 3.)
This resin is owing to containing (A)～(C) composition, so have good dyeability and good shock-resistance.
As resin of the present invention, specifically can enumerate the resin that the Polymerizable composition of polymerization the invention described above obtains.
Below utilize concrete example that each composition is described, but the present invention is not limited to the following compound of enumerating.In addition, in the present invention, each composition can use the compound of enumerating separately, also can be used in combination a plurality of.
(A) ester ring type isocyanic ester by above-mentioned formula (1) and/or above-mentioned formula (2) expression at first, is described.
Ester ring type isocyanate compound as above-mentioned formula (1) expression, for example can enumerate 2, two (isocyanatomethyl)-two ring of 5-[2.2.1] heptane, 2, two (isocyanatomethyl)-two of 6-encircle [2.2.1] heptane, reach 2, two (isocyanatomethyl)-two ring of 5-[2.2.1] heptane and 2, the mixture of two (isocyanatomethyl)-two ring of 6-[2.2.1] heptane etc.
As the ester ring type isocyanate compound of above-mentioned formula (1) expression, more specifically can use 2,5 (6)-two (isocyanatomethyl)-two ring [2.2.1] heptane.Herein, 2,5 (6)-two (isocyanatomethyl)-two ring [2.2.1] heptane comprise 2, two (isocyanatomethyl)-two ring of 5-[2.2.1] heptane and 2, in two (isocyanatomethyl)-two ring of 6-[2.2.1] heptane at least one, particularly, can be in following (i)～(iii) any one.
(i) 2, the Dan Pin of two (isocyanatomethyl)-two ring of 5-[2.2.1] heptane,
(ii) 2, the Dan Pin of two (isocyanatomethyl)-two ring of 6-[2.2.1] heptane,
(iii) 2, two (isocyanatomethyl)-two ring of 5-[2.2.1] heptane and 2, two (isocyanatomethyl)-two of 6-encircle the mixture of [2.2.1] heptane.
In addition, as the ester ring type isocyanate compound of above-mentioned formula (2) expression, for example can enumerate 1, two (isocyanatomethyl) hexanaphthenes, 1 of 4-, two (isocyanatomethyl) hexanaphthenes, 1 of 3-, two (isocyanatomethyl) hexanaphthenes of 2-etc. can use wherein one or two or more kinds.
Need to prove that (A) composition can be any one in the compound of the compound of above-mentioned formula (1) expression and above-mentioned formula (2) expression, also it can be used in combination.
Next, (B) composition is described.
As the multi-thioalcohol compound that can have (many) sulfide linkages more than 1 in (B) 1 molecule, for example can enumerate following compound.
First two mercaptan, 1,1,1-dimercaptopropane, 1,2-dimercaptopropane, 1,3-dimercaptopropane, 2,2-dimercaptopropane, 1,4-succinimide mercaptans, 2,3-succinimide mercaptans, 1,5-pentane disulfide thioalcohol, 1,6-ethanthiol, 1,2,3-trithioglycerin, 1,1-hexamethylene two mercaptan, 1,2-hexamethylene two mercaptan, 2,2-dimethylpropane-1,3-two mercaptan, 3,4-dimethoxy-butane-1,2-two mercaptan, 2-methylcyclohexane-2, fatty group polythiol compounds such as 3-two mercaptan;
4-mercapto methyl-1,8-dimercapto-3,6-dithia octane, 4,8-dimercapto methyl-1,11-dimercapto-3,6,9-three thia undecanes, 5,7-dimercapto methyl-1,11-dimercapto-3,6,9-three thia undecanes, 4,7-dimercapto methyl-1,11-dimercapto-3,6,9-three thia undecanes, four (mercapto methyl) methane, 1,1,3,3-four (sulfydryl methylthio group) propane, 1,1,5,5-four (sulfydryl methylthio group)-3-thia pentane, 1,1,6,6-four (sulfydryl methylthio group)-3,4-dithia hexane, 2, two (mercapto methyl)-1 of 2-, the 3-dimercaptopropane, two (mercapto methyl) thioether, two (mercapto methyl) disulfide, two (mercaptoethyl) thioether, two (mercaptoethyl) disulfide, two (sulfydryl propyl group) thioether, two (sulfydryl propyl group) disulfide, two (sulfydryl methylthio group) methane, three (sulfydryl methylthio group) methane, two (sulfydryl ethylmercapto group) methane, three (sulfydryl ethylmercapto group) methane, two (sulfydryl rosickyite base) methane, 1,2-two (sulfydryl methylthio group) ethane, 1,2-two (sulfydryl ethylmercapto group) ethane, 1,3-two (sulfydryl methylthio group) propane, 1,3-two (sulfydryl ethylmercapto group) propane, 1,3-two (sulfydryl rosickyite base) propane, 1,2,3-three (sulfydryl methylthio group) propane, 1,2,3-three (sulfydryl ethylmercapto group) propane, 1,2,3-three (sulfydryl rosickyite base) propane, four (sulfydryl methylthio group) methane, four (sulfydryl ethylmercapto group methyl) methane, four (sulfydryl rosickyite ylmethyl) methane, 2,5-dimercapto-1, the 4-dithiane, 2,5-dimercapto methyl-1,4-dithiane etc. has the fatty group polythiol compound of (many) sulfide linkages;
Ethylene glycol bisthioglycolate (2-mercaptoacetate), ethylene glycol bisthioglycolate (3-mercaptopropionic acid ester), glycol ether (2-mercaptoacetate), glycol ether (3-mercaptopropionic acid ester), 2,3-dimercapto-1-propyl alcohol (3-mercaptopropionic acid ester), 3-sulfydryl-1,2-propylene glycol two (2-mercaptoacetate), 3-sulfydryl-1,2-propylene glycol two (3-mercaptopropionic acid ester), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionic acid ester), trimethylolethane trimethacrylate (2-mercaptoacetate), trimethylolethane trimethacrylate (3-mercaptopropionic acid ester), tetramethylolmethane four (2-mercaptoacetate), tetramethylolmethane four (3-mercaptopropionic acid ester), glycerine three (2-mercaptoacetate), glycerine three (3-mercaptopropionic acid ester), 1,4-cyclohexanediol two (2-mercaptoacetate), 1,4-cyclohexanediol two (3-mercaptopropionic acid ester), methylol thioether two (2-mercaptoacetate), methylol thioether two (3-mercaptopropionic acid ester), hydroxyethyl thioether (2-mercaptoacetate), hydroxyethyl thioether (3-mercaptopropionic acid ester), methylol disulfide (2-mercaptoacetate), methylol disulfide (3-mercaptopropionic acid ester), Thiovanic acid (2-mercaptoethyl ester), thio-2 acid two (2-mercaptoethyl ester) etc. has the fatty group polythiol compound of ester bond;
1, the 2-thioresorcin, 1, the 3-thioresorcin, 1, the 4-thioresorcin, 1,2-two (mercapto methyl) benzene, 1,4-two (mercapto methyl) benzene, 1,2-two (mercaptoethyl) benzene, 1,4-two (mercaptoethyl) benzene, 1,2,3-tri-thiol benzene, 1,2,4-tri-thiol benzene, 1,3,5-tri-thiol benzene, 1,2,3-three (mercapto methyl) benzene, 1,2,4-three (mercapto methyl) benzene, 1,3,5-three (mercapto methyl) benzene, 1,2,3-three (mercaptoethyl) benzene, 1,3,5-three (mercaptoethyl) benzene, 1,2,4-three (mercaptoethyl) benzene, 2, the 5-toluene-dithiolate, 3, the 4-toluene-dithiolate, 1,4-naphthyl disulfide phenol, 1,5-naphthyl disulfide phenol, 2,6-naphthyl disulfide phenol, 2,7-naphthyl disulfide phenol, 1,2,3,4-four sulfydryl benzene, 1,2,3,5-four sulfydryl benzene, 1,2,4,5-four sulfydryl benzene, 1,2,3,4-four (mercapto methyl) benzene, 1,2,3,5-four (mercapto methyl) benzene, 1,2,4,5-four (mercapto methyl) benzene, 1,2,3,4-four (mercaptoethyl) benzene, 1,2,3,5-four (mercaptoethyl) benzene, 1,2,4,5-four (mercaptoethyl) benzene, 2,2 '-dimercapto biphenyl, 4,4 '-dimercapto biphenyl etc. has the compound of aromatic nucleus.Above-claimed cpd can use one or more.
Wherein, the multi-thioalcohol compound that (B) can have (many) sulfide linkages more than 1 in 1 molecule further preferably contains 4-mercapto methyl-1,8-dimercapto-3,6-dithia octane, 1,1,3,3-four (sulfydryl methylthio group) propane, 5,7-dimercapto methyl-1,11-dimercapto-3,6,9-three thia undecanes, 4,7-dimercapto methyl-1,11-dimercapto-3,6,9-three thia undecanes, and 4,8-dimercapto methyl-1,11-dimercapto-3,6, at least a in the 9-three thia undecanes.
Next (C) composition is described.
In the compound of (C) above-mentioned formula (3) expression, be the compound of SH base as X, can enumerate following compound.
For example, as the compound of m=0, can enumerate 3-mercaprol, 4-Mercaptobutanol etc.
As the compound of m=1 and n=0, can enumerate 5-sulfydryl amylalcohol, 6-sulfydryl hexanol, 7-sulfydryl enanthol, 8-sulfydryl octanol etc.
As the compound of m=1, Y=S and n=1, can enumerate 5-sulfydryl-3-thia amylalcohol etc., but be not limited to the above-mentioned compound of enumerating.
In the compound of (C) above-mentioned formula (3) expression, be the compound of OH base as X, can enumerate following compound.
At first, as the compound of m=0, for example can enumerate following alkanediol.1, ammediol, 1,4-butyleneglycol, 1,3 butylene glycol.
Wherein, preferably use 1, the 4-butyleneglycol.
Be the compound of 1～3 integer as m, for example, can enumerate following compound.
At first, as the compound of m=1 and n=0, can enumerate following compound.
1,5-pentanediol, 1,4-pentanediol, 1,3-pentanediol, 1,6-hexylene glycol, 1,5-hexylene glycol, 1,4-hexylene glycol, 1,3-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol.
As the compound of n=1 and Y=O, be the compound that has ehter bond in the molecular structure, for example, can enumerate following compound.
As the compound of m=1, n=1 and Y=O, can enumerate two alkylene glycolss such as glycol ether, dipropylene glycol.
As the compound of m=2, n=1 and Y=O, can enumerate three alkylene glycol classes such as triglycol, tripropylene glycol.
In the above-mentioned compound of enumerating, because X is the OH base, so X and Y are Sauerstoffatom.In the above-mentioned compound of enumerating, it is 2 or 3 alkylidene group that R1 and R2 represent to have substituent carbonatoms independently of one another.Wherein, preferably use triglycol and glycol ether.
As n=1 or 2 and Y=S, be the compound that has sulfide linkage in the molecular structure, for example, can enumerate following compound.
As the compound of m=1, n=1 and Y=S, can enumerate sulfo-dioxane alcohols such as thiodiethanol, sulfo-two propyl alcohol.
As the compound of m=1, n=2 and Y=S, can enumerate dithio dioxane alcohols such as dithio di-alcohol, dithio dipropyl alcohol.
In the above-mentioned compound of enumerating, it is 2 or 3 alkylidene group that R1 and R2 represent to have substituent carbonatoms independently of one another.
Be the compound of 1～3 integer as m, wherein, preferred m is 1～3 integer, n are 1, Y is Sauerstoffatom compound, is the compound that has ehter bond in the molecular structure.By using the compound of above-claimed cpd as above-mentioned formula (3) expression, heating in the time of can further suppressing mixing element when the preparation resin and violent viscosity rise.Therefore, can improve the preparation stability of resin.
At above-mentioned X is in the compound of OH base, as particularly preferred compound, can enumerate glycol ether, triglycol, 1, the 4-butyleneglycol.
In addition, be not limited to the above-mentioned compound of enumerating, above-claimed cpd can be used alone, can also be two or more kinds in combination respectively.
Herein, (A) by can have in the ester ring type isocyanate compound of above-mentioned formula (1) and/or above-mentioned formula (2) expression, (B) 1 molecule the multi-thioalcohol compound of (many) sulfide linkages more than 1 and (C) usage ratio of the compound represented of above-mentioned formula (3) with functional group's molar ratio computing of NCO/ (SH+OH), usually in 0.5～3.0 scope, preferably in 0.5～1.5 scope, in 0.8～1.2 scope.Can access specific refractory power, shock-resistance, dyeability and thermotolerance equilibrated resin thus.
Need to prove that when the value of NCO/ (SH+OH) was too small, the curing characteristics of Polymerizable composition might deterioration.By making NCO/ (SH+OH) be more than 0.5, be preferably more than 0.8, can further improve the curing characteristics of Polymerizable composition.And then can further improve the mechanical characteristics such as mechanical strength of resin, shock-resistance of resin.
The amount of SH base is many more in the resin, and specific refractory power is big more, so, if the value of NCO/ (SH+OH) is excessive, then might reduce the specific refractory power of resin.Be below 3.0 by making NCO/ (SH+OH), be preferably below 1.5, more preferably below 1.2, the specific refractory power of resin increased.Therefore, for example can further be preferably used as optics.
And, if (C) hydroxyl of the compound of above-mentioned formula (3) expression and the mole number of thiol group are respectively p, q, when the mole number that can have the thiol group in the multi-thioalcohol compound of (many) sulfide linkages more than 1 in above-mentioned (B) 1 molecule is r, p/ (p+q+r) is usually in 0.001～0.40 scope, preferably in 0.03～0.3 5 scope, in 0.05～0.30 scope.Also can obtain specific refractory power, shock-resistance, dyeability and thermotolerance equilibrated resin in such cases thus.
Need to prove that the amount of OH base is many more in the resin, shock-resistance is strong more, so, when the value of p/ (p+q+r) is too small, might reduce the shock-resistance of resin.Be more than 0.001 by making p/ (p+q+r), be preferably more than 0.03, more preferably more than 0.05, can increase the shock-resistance of resin.
On the other hand, if the amount of OH base is basic too much with respect to SH, then might reduce the specific refractory power of resin.Be below 0.40 by making p/ (p+q+r), be preferably below 0.35, more preferably below 0.30, can further suppress the decline of the specific refractory power of resin.
The mol ratio of the functional group by making NCO/ (SH+OH) is in above-mentioned scope, and p/ (p+q+r) can further improve the balance of mechanical characteristics and specific refractory power also in above-mentioned scope.
Particularly, Polymerizable composition of the present invention is following composition, promptly
(A) the ester ring type isocyanate compound by above-mentioned formula (1) and/or above-mentioned formula (2) expression can be the ester ring type isocyanate compound of above-mentioned formula (1) expression,
(B) multi-thioalcohol compound that can have (many) sulfide linkages more than 1 in 1 molecule can be to be selected from 4-mercapto methyl-1,8-dimercapto-3,6-dithia octane, 5,7-dimercapto methyl-1,11-dimercapto-3,6,9-three thia undecanes, 4,7-dimercapto methyl-1,11-dimercapto-3,6,9-three thia undecanes and 4,8-dimercapto methyl-1,11-dimercapto-3,6, more than one compounds in the 9-three thia undecanes.
More specifically, if Polymerizable composition of the present invention uses following combination, the resin that then polymerization said composition obtains not only shock-resistance, dyeability is better, simultaneously, can fully satisfy specific refractory power, Abbe number, stable on heating requirement, described being combined as:
(A) the ester ring type isocyanate compound by above-mentioned formula (1) and/or above-mentioned formula (2) expression is the ester ring type isocyanate compound of above-mentioned formula (1) expression,
(B) multi-thioalcohol compound that can have (many) sulfide linkages more than 1 in 1 molecule is to be selected from 4-mercapto methyl-1,8-dimercapto-3,6-dithia octane, 5,7-dimercapto methyl-1,11-dimercapto-3,6,9-three thia undecanes, 4,7-dimercapto methyl-1,11-dimercapto-3,6,9-three thia undecanes and 4,8-dimercapto methyl-1,11-dimercapto-3,6, more than one compounds in the 9-three thia undecanes
(C) compound of above-mentioned formula (3) expression is glycol ether or triglycol.
In addition,, for example improve thermotolerance etc., in Polymerizable composition of the present invention, can use above-mentioned active dydrogen compounds in addition on a small quantity so that resin is modified as purpose.The active dydrogen compounds of Shi Yonging is that polyvalent alcohol (molecular end has the compound of 2 above hydroxyls), mercaptan or amine compound etc. have the compound bearing active hydrogen with isocyanate reaction herein, for example, can enumerate 2 mercapto ethanol, thioglycerol, glycerine, thiophenol, diphenyl disulfide phenol, ethylene glycol, 1,4-dithio-erythritol, 1,4-dithiothreitol dithio etc.Above-claimed cpd can be used alone, but also also mix together more than 2 kinds.
The following describes the preparation method of resin of the present invention.
The reaction of resin of the present invention above-mentioned by making (A)～(C) composition obtains.Order by merging to composition is not particularly limited, and for example, can enumerate following method:
(i) after making (A) composition in advance and (C) composition reacting, add (B) composition and carry out the polymeric method, reach
(ii) be mixed together (A), (B) and (C) composition, make its polymeric method.In addition, polymerization process for example can adopt the method that is heating and curing.
(C) composition is when all not containing the compound of ehter bond and thioether bond in the molecular structure, preferred aforesaid method (i).Violent heating in the time of can further suppressing mixing element thus and violent viscosity increase.
Resin shock-resistance, the dyeability utilizing aforesaid method (i) or (ii) obtain are good, and fully satisfy specific refractory power, Abbe number, stable on heating requirement.
Resin of the present invention can obtain by the Polymerizable composition of polymerization the invention described above.
More specifically, polythiourethane resinoid of the present invention can contain following (A), (B) and Polymerizable composition (C) by mixing, carries out polymerization and obtains.
(A) the ester ring type isocyanate compound of representing by above-mentioned formula (1) and/or formula (2),
(B) can have at least a in the multi-thioalcohol compound of (many) sulfide linkages more than 1 in 1 molecule,
(C) at least a in the compound of above-mentioned formula (3) expression.
Polymerizable composition of the present invention solidifies through polymerization.Particularly, can be in the presence of catalyzer, the Polymerizable composition of the invention described above that is heating and curing obtains resin.
Polythiourethane resinoid high refractive index, the low dispersion of utilizing preparation method of the present invention to obtain, particularly shock-resistance and dyeability are good, and have sufficient thermotolerance.
In addition, when Polymerizable composition of the present invention being solidified, can add various materials such as chain extension agent, linking agent, photostabilizer, UV light absorber, antioxidant, anti-coloring agent, bluing agent in the same manner with the known method of forming according to purpose by polymerization.Need to prove, have no particular limits, for example can adopt method that is heating and curing etc. for heating means.
In order to be adjusted to desired speed of response, can also suitably add known catalysts.Catalyzer as preferred use, for example, can use amine compound such as tin compounds such as dibutyl tin laurate, dibutyl tin dichloride, dimethyltin chloride, tetramethyl-diacetoxy distannoxane, tetraethyl-diacetoxy distannoxane, tetrapropyl diacetoxy distannoxane or tertiary amine as the polyurethane-reinforcement catalyzer.Above-claimed cpd can use separately, and also two or more kinds may be used.As the addition of catalyzer, preferably in that monomeric gross weight is to use in the scope of 0.001wt%～1wt% with respect to composition.In the time of in this scope, polymerizability is better, considers from the transparency, optics rerum natura, the photostabilization aspect of working life in when blending and gained resin and preferred.
About the catalyzer that uses and the interpolation order of releasing agent, for example, can enumerate following method: the method that in advance it is dissolved in isocyanate compound, multi-thioalcohol compound, diol compound and/or mercaptoalcohol compound; Add it to method in the mixture of isocyanate compound and diol compound and/or mercaptoalcohol, multi-thioalcohol compound etc., but be not limited to the above-mentioned method of enumerating, can be according to operability, security, suitability etc., the time in office adds.As the state that adds, can add with the original state of catalyzer, releasing agent and other additives, also it can be dissolved in a part of employed monomer class, be mixed with mother liquor after, add with the state of mother liquor.
Resin of the present invention obtains by the injection moulding polymerization usually.Particularly, in advance in the monomer that uses various additives such as mixed catalyst, UV light absorber, internal mold release etc. make mixed solution.As required, adopt appropriate means, after this mixed solution is outgased, inject the injection mould that constitutes by 2 glass sheets and band or packing ring and make its polymerization.Viscosity during injection is not particularly limited, but the viscosity of preferred monomers mixed solution is 20mPas～1000mPas.Polymerizing condition during polymerization, because of the difference of the shape of the kind of the monomeric species that uses, catalyzer, its addition, injection mould etc., and very big-difference is arranged, therefore can't limit, but when thermopolymerization, under-20 ℃～200 ℃ temperature, carried out 1～100 hour greatly.
In addition polythiourethane resinoid of the present invention also can contain thiocarbamate S-alkyl ester bond, allophanic acid ester bond, urea key, biuret linkage according to purpose based on amino-formate bond that is formed by isocyanate group and hydroxyl and the thiourethane key that is formed by isocyanate group and thiol group.For example, make amino-formate bond or thiocarbamate S-alkyl ester bond further increase cross-linking density and obtain ideal results usually with the isocyanic ester radical reaction.At this moment, temperature of reaction is increased to more than 100 ℃ at least, and uses isocyanate prepolymer composition in a large number.Perhaps also can and with a part of amine etc., thereby utilize urea key, biuret linkage.When use removing the polyol compound that reacts with isocyanate compound, compound the multi-thioalcohol compound as mentioned above, aspect painted, must pay special attention to.
By the present invention as can be known, make and contain the ester ring type isocyanate compound by the expression of above-mentioned formula (1) and/or above-mentioned formula (2) as (A) of the polyisocyanate compounds that is preferably used as transparent resin material, (B) can have at least a in the multi-thioalcohol compound of (many) sulfide linkages more than 1 in 1 molecule, and (C) the polythiourethane resinoid that obtains of at least a Polymerizable composition polymerization in the compound of above-mentioned formula (3) expression, and resin and existing resin that the reaction of above-mentioned (A)～(C) composition is obtained compare, shock-resistance, dyeability is good, and has and satisfy specific refractory power simultaneously, Abbe number, the performance that thermotolerance requires.
Therefore, polythiourethane resinoid of the present invention for example water white transparency and optics rerum natura is also good, is preferably used as optics or optical element raw materials such as lens, prism, camera lens, optical fiber, information gauging board, spectral filter, photodiode such as eyeglass lens.
Particularly, can access a kind of composition and resin according to the present invention, described composition can obtain comparing with resin with existing lens, and shock-resistance, dyeability are good, and satisfies the lens resin of specific refractory power, Abbe number, stable on heating requirement simultaneously.
According to the present invention, as the optical material in the field of using high-index material etc., can access shock-resistance, transparent cured resin that dyeability is good, particularly can obtain being suitable for lens such as eyeglass lens is the material in the optics field of representative.In addition, polythiourethane lens of the present invention for example have following characteristics, i.e. high refractive index, the low dispersion; Thermotolerance, dyeability are good; And mechanical strength of resin, excellent impact resistance, therefore, preferably as opticses such as eyeglass lens, camera lens.
Polythiourethane lens of the present invention can be provided with coating as required on single face or two sides.As coating, can enumerate primer coating, hard coat, antireflection rete, antifog coating layer, anti-contamination layer, waterproof layer etc.Above-mentioned coating can be distinguished use separately, also can use laminated coating.When the two sides is provided with coating, on the two sides identical coating can be set, also different coatings can be set.Above-mentioned coating can be respectively and in order to protection lens and eyes avoid UV light absorber that uv damage is a purpose, with the protection eyes avoid infrared absorbent that the infrared rays injury is a purpose, with the weathering resistance that improves lens be the photostabilizer of purpose or antioxidant, with the fashion that improves lens be the dyestuff of purpose or pigment and light-sensitive coloring agent or photochromic pigment, anti-live agent, other are used to improve the known additive of lens performance.Can use the various levelling agents that are used to improve coating to the layer that is covered by coating.
Primer coating is the coating that is used to improve the adaptation between hard coat and the lens, can also improve shock-resistance sometimes.Can use the high any raw material of adaptation in the primer coating to the optical lens that obtains, can use usually with polyurethanes resin, redix, polyester resin, trimeric cyanamide resinoid, polyvinylacetal be paint base composition of principal constituent etc.
Hard coat is the coating that is used to give functions such as lens surface scuff resistance, wear resistance, wet fastness, heatproof water-based, thermotolerance, weathering resistance.Hard coat uses hard coating composition usually, said composition contain silicoorganic compound with solidified nature and be selected from the oxide fine particle of element of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In and Ti more than one and/or by in the particulate that the composite oxides of element constitute more than two kinds that is selected from above-mentioned element set more than one.
As required, on above-mentioned hard coat, form anti-reflection layer usually.Anti-reflection layer comprises mineral-type and organic class, during for mineral-type, uses SiO
2, TiO
2Deng inorganic oxide, form by drying processes such as vacuum vapour deposition, sputtering method, ion plating method, Assisted by Ion Beam method, CVD methods.Anti-reflection layer is organic time-like, uses to contain silicoorganic compound and inner composition with silica-based fine particles of cavity, forms by wet type.
As required, can on the antireflection rete, form antifog coating layer, anti-contamination layer, waterproof layer.As the method that forms antifogging coating, anti-contamination layer, waterproof layer, so long as do not have dysgenic method to get final product to anti-reflective function, to its treatment process, handle material etc. and be not particularly limited, can use known antifog cloth treatment method, anti-pollution treatment process, method for waterproofing, and the material known of being coated with.
In order to give the polythiourethane lens fashion that obtains or photosensitivity etc., can use the pigment that the meets the demands back of dyeing to use.Can implement the dyeing of lens by known dyeing process, profit is implemented dyeing in the following method usually.(1) lens being immersed in method in the staining fluid, (2) use the method that the coating agent that contains pigment is coated with or be provided with can painted coating, with method, (3) of this coating dyeing starting monomer is contained can painted material carry out the polymeric method, and (4) heating sublimation pigment make the method etc. of its distillation.
The lens material that method (1) will be finish-machined to the optical surface of regulation is immersed in dissolving or homodisperse and has in the staining fluid of used pigment (dyeing process), and as required, adds thermal lens fixed pigment (dyeing after annealing operation).Be used for the pigment of dyeing process so long as known pigment gets final product, be not particularly limited, use oil-soluble dyes or dispersed dye usually.Be used for the solvent of dyeing process as long as can dissolve or the pigment of homodisperse use, be not particularly limited.In this dyeing process, can add as required be used for making pigment be dispersed in staining fluid tensio-active agent, promote painted carrier.
Method (2) is not that plastic lens material is directly carried out painted method, but is coated with the organic coating fluid that has dispersed or dissolved pigment on plastic lens, by being cured processing, forms the method for the coating that is colored at lens surface; Or after the painted coating of plastic lens surface formation energy, plastic lens is immersed in the staining fluid, carry out painted method by heating.Plastic lens is immersed in the staining fluid, carries out painted method by heating.
Method (3) is to carry out the polymeric method in advance in the starting monomer of plastic lens after the dissolving dye.As long as the pigment that uses can dissolve or be scattered in the starting monomer with the degree of not destroying optical property equably, be not particularly limited.
Method (4) comprises following method:
(1) makes the distillation of solid sublimability pigment, plastic lens is carried out painted method;
(2) make the matrix and the plastic lens that are coated with the solution formation that contains the sublimability pigment opposed, carry out painted method by adding hot basal body and lens with contactless state;
(3) after will being transferred on the plastic lens by the transfer printing layer that pigmented layer that contains the sublimability pigment and bonding coat constitute, carry out painted method by heating, optical lens of the present invention can utilize any one method to dye.The pigment that uses is not particularly limited so long as have the pigment of sublimability and get final product.
Embodiment
Specify the present invention below by embodiment.
Prepare resin in the following embodiments,, carried out following evaluation in order to estimate the suitability of this resin as optics.The performance test of gained resin (specific refractory power, thermotolerance, mechanical strength of resin, dyeability and shock-resistance) is estimated by following test method(s).
Specific refractory power (ne), Abbe number (ve): use general ear Ritchie (Pulfrich) refractometer to measure down at 20 ℃.
Thermotolerance: will adopt TMA penetration degree method (Tg of 10 ℃ of load 50g, pin front end 0.5mm φ, heat-up rates/min) obtain (℃) as thermotolerance.
Mechanical strength of resin: estimate by stretching maximum point stress.Use the system AUTOGRAPH AGS-J of Shimadzu Seisakusho Ltd., the polythiourethane resin treatment is become the dumb bell specimen of thick 3mm, long 85mm, wide 5mm, use this test film, under 20 ℃ of temperature with the draw speed of 1mm/min (being deformed into 0.35%)～5mm/min to the test film applying load, calculate the maximum load (N/mm of this moment
2).
Dyeability: in the 995g pure water, add three pond dyestuff corporate system eyeglass lens dispersed dye " MLP-Blue ", 2.0g " MLP-Yellow ", the 1.5g " MLP-Red " of 1.5g, the preparation dye dispersion liquid as staining agent.After being heated to 90 ℃, the polythiourethane resin sheet that with thickness is 9mm dyes at 90 ℃ of dippings 5 minutes down.Resin sheet after the dyeing is scanned under wavelength 400nm～800nm, and (the system UV-1600 of Shimadzu Seisakusho Ltd.) measures the transmissivity (%T) under the 565nm with the UV spectrometer.Transmissivity be the test film below 40% be zero (well), transmissivity greater than 40% be lower than 60% test film be △ (equal), transmissivity with existing resin be more than 60% test film for * (bad).
Shock-resistance: based on the test method of FDA, make steel ball, obtain 50% and do not destroy weight according to by gently falling on the lens that center thickness is 1.0mm from the height of 127cm to heavy order.50% not destroy weight be that the above test film of 1000g is that not destroy test film that weight is lower than 1000g greater than 300g be that not destroy weight be that the following test film of 300g is * (bad) to △ (with existing equal), 50% to zero (well), 50%.
The proportioning that each is routine etc. is shown in table 1, and evaluation result is shown in table 2.
(embodiment 1)
Under 20 ℃, at 57.38g 2, mixed dissolution 0.10g is as the dibutyltin chloride of curing catalysts in 5 (6)-two (isocyanatomethyl)-two ring [2.2.1] heptane, 0.25g internal mold release (trade(brand)name: ZelecUN), 0.05g UV light absorber (trade(brand)name: BioSorb583), make homogeneous solution.Add 7.52g 1 in this homogeneous solution, the 4-butyleneglycol after stirring 20 minutes under 30 ℃, is cooled to 20 ℃, restir 30 minutes.Then, add 3 5.10g 4-mercapto methyls-1,8-dimercapto-3,6-dithia octane makes its mixed dissolution.
Under 600Pa, make this homogeneous solution deaeration after 1 hour, utilize 1 μ m PTFE filter made device to filter, inject the injection mould that constitutes by glass mold and band.This injection mould is put into baking oven, slowly be warming up to 120 ℃ through 20 hours from 25 ℃ and carry out polymerization.Polymerization is taken out injection mould after finishing from baking oven, the demoulding obtains resin.Further the gained resin was annealed 4 hours down in 120 ℃.
The gained resin is colourless and transparent high good resin, and specific refractory power (ne) is 1.597, and Abbe number (ve) is 41, and thermotolerance is 109 ℃, and the maximum point stress of tension test is 95 (N/mm
2), chromatic UV transmissivity is 37%, it is more than the 1000g that 50% of shock-resistance is not destroyed weight.Evaluation result is shown in table 2.
(embodiment 2)
Under 20 ℃, at 54.22g 2, mixed dissolution 0.10g is as the dibutyltin chloride of curing catalysts, 0.25g internal mold release (trade(brand)name: ZelecUN), 0.05g UV light absorber (trade(brand)name: BioSorb583), make homogeneous solution in 5 (6)-two (isocyanatomethyl)-two ring [2.2.1] heptane.In this homogeneous solution, add the 7.89g triglycol, 30 ℃ stir 20 minutes down after, be cooled to 20 ℃ after restir 30 minutes.Add 37.89g 4-mercapto methyl-1 then, 8-dimercapto-3,6-dithia octane makes its mixed dissolution.
Under 600Pa, make this homogeneous solution deaeration after 1 hour, utilize 1 μ m PTFE filter made device to filter, inject the injection mould that constitutes by glass mold and band.This injection mould is put into baking oven, slowly be warming up to 120 ℃ through 20 hours from 25 ℃ and carry out polymerization.Polymerization is taken out injection mould after finishing from baking oven, the demoulding obtains resin.Further the gained resin was annealed 4 hours down in 120 ℃.
The gained resin is colourless and transparent high good resin, and specific refractory power (ne) is 1.603, Abbe number (ve) is 40, thermotolerance is that 103 ℃, the maximum point stress of tension test are 95 (N/mm
2), chromatic UV transmissivity is 23%, shock-resistance 50% not destroy weight be more than the 1000g.Evaluation result is shown in table 2.
(embodiment 3)
Under 20 ℃, at 54.22g 2, mixed dissolution 0.10g is as the dibutyltin chloride of curing catalysts, 0.25g internal mold release (trade(brand)name: ZelecUN), 0.05g UV light absorber (trade(brand)name: BioSorb583), make homogeneous solution in 5 (6)-two (isocyanatomethyl)-two ring [2.2.1] heptane.In this homogeneous solution, together add 7.89g triglycol, 37.89g 4-mercapto methyl-1,8-dimercapto-3,6-dithia octane through 30 minutes mixed dissolutions, is made homogeneous solution under 20 ℃, in the water-bath.
Under 600Pa, make this homogeneous solution deaeration after 1 hour, utilize 1 μ m PTFE filter made device to filter, inject the injection mould that constitutes by glass mold and band.This injection mould is put into baking oven, slowly be warming up to 120 ℃ through 20 hours from 25 ℃ and carry out polymerization.Polymerization is taken out injection mould after finishing from baking oven, the demoulding obtains resin.Further the gained resin was annealed 4 hours down in 120 ℃.
Confirm that the gained resin is colourless and transparent high good resin, equal with embodiment 2.Evaluation result is shown in table 2.
(embodiment 4)
Under 20 ℃, at 56.63g 2, mixed dissolution 0.10g is as the dibutyltin chloride of curing catalysts, 0.25g internal mold release (trade(brand)name: ZelecUN), 0.05g UV light absorber (trade(brand)name: BioSorb5 83), make homogeneous solution in 5 (6)-two (isocyanatomethyl)-two ring [2.2.1] heptane.In this homogeneous solution, add the 8.74g glycol ether, 30 ℃ stir 20 minutes down after, be cooled to 20 ℃ after restir 30 minutes.Add 34.63g 4-mercapto methyl-1 then, 8-dimercapto-3,6-dithia octane makes its mixed dissolution.
Under 600Pa, make this homogeneous solution deaeration after 1 hour, utilize 1 μ m PTFE filter made device to filter, inject the injection mould that constitutes by glass mold and band.This injection mould is put into baking oven, slowly be warming up to 120 ℃ through 20 hours from 25 ℃ and carry out polymerization.Polymerization is taken out injection mould after finishing from baking oven, the demoulding obtains resin.Further the gained resin was annealed 4 hours down in 120 ℃.
The gained resin is colourless and transparent high good resin, and specific refractory power (ne) is 1.597, Abbe number (ve) is 41, thermotolerance is that 104 ℃, the maximum point stress of tension test are 96 (N/mm
2), chromatic UV transmissivity is 21%, shock-resistance 50% not destroy weight be more than the 1000g.Evaluation result is shown in table 2.
(embodiment 5)
Under 20 ℃, at 56.63g 2, mixed dissolution 0.10g is as the dibutyltin chloride of curing catalysts, 0.25g internal mold release (trade(brand)name: ZelecUN), 0.05g UV light absorber (trade(brand)name: BioSorb583), make homogeneous solution in 5 (6)-two (isocyanatomethyl)-two ring [2.2.1] heptane.In this homogeneous solution, together add 8.74g glycol ether, 34.63g 4-mercapto methyl-1,8-dimercapto-3,6-dithia octane through 30 minutes mixed dissolutions, is made homogeneous solution under 20 ℃, in the water-bath.
Under 600Pa, make this homogeneous solution deaeration after 1 hour, utilize 1 μ m PTFE filter made device to filter, inject the injection mould that constitutes by glass mold and band.This injection mould is put into baking oven, slowly be warming up to 120 ℃ through 20 hours from 25 ℃ and carry out polymerization.Polymerization is taken out injection mould after finishing from baking oven, the demoulding obtains resin.Further the gained resin was annealed 4 hours down in 120 ℃.
Confirm that the gained resin is colourless and transparent high good resin, equal with embodiment 4.Evaluation result is shown in table 2.
(embodiment 6)
Under 20 ℃, at 57.68g 2, mixed dissolution 0.05g is as the dibutyltin chloride of curing catalysts, 0.25g internal mold release (trade(brand)name: ZelecUN), 0.05g UV light absorber (trade(brand)name: BioSorb583), make homogeneous solution in 5 (6)-two (isocyanatomethyl)-two ring [2.2.1] heptane.Add the 4.45g glycol ether in this homogeneous solution, stirring is after 60 minutes down at 20 ℃, and adding 2.60g ethylene glycol stirred 60 minutes down at 20 ℃.Add 34.63g 4-mercapto methyl-1 then, 8-dimercapto-3,6-dithia octane makes its mixed dissolution.
Under 600Pa, make this homogeneous solution deaeration after 1 hour, utilize 1 μ m PTFE filter made device to filter, inject the injection mould that constitutes by glass mold and band.This injection mould is put into baking oven, slowly be warming up to 120 ℃ through 20 hours from 25 ℃ and carry out polymerization.Polymerization is taken out injection mould after finishing from baking oven, the demoulding obtains resin.Further the gained resin was annealed 4 hours down in 120 ℃.
The gained resin is colourless and transparent high good resin, and specific refractory power (ne) is 1.598, Abbe number (ve) is 41, thermotolerance is that 109 ℃, the maximum point stress of tension test are 101 (N/mm
2), chromatic UV transmissivity is 25%, shock-resistance 50% not destroy weight be more than the 1000g.Evaluation result is shown in table 2.
(comparative example 1)
Under 20 ℃, at 45.71g isophorone diisocyanate, 9.14g1, mixed dissolution 0.15g is as the dibutyltin chloride of curing catalysts, 0.20g internal mold release (trade(brand)name: ZelecUN), 0.05g UV light absorber (trade(brand)name: BioSorb583), make homogeneous solution in the hexamethylene-diisocyanate.In this homogeneous solution, add 45.14g 4-mercapto methyl-1,8-dimercapto-3,6-dithia octane makes its mixed dissolution.
Under 600Pa, make this homogeneous solution deaeration after 1 hour, utilize 1 μ m PTFE filter made device to filter, inject the injection mould that constitutes by glass mold and band.This injection mould is put into baking oven, slowly be warming up to 120 ℃ through 20 hours from 25 ℃ and carry out polymerization.Polymerization is taken out injection mould after finishing from baking oven, the demoulding obtains resin.Further the gained resin was annealed 4 hours down in 120 ℃.
The specific refractory power of gained resin (ne) is 1.601, Abbe number (ve) is 39, thermotolerance is that 119 ℃, the maximum point stress of tension test are 83 (N/mm
2), chromatic UV transmissivity is 48%, shock-resistance 50% not destroy weight be 33g.Evaluation result is shown in table 2.
(comparative example 2)
Under 20 ℃, at 50.57g 2, mixed dissolution 0.06g is as the dibutyltin chloride of curing catalysts, 0.12g internal mold release (trade(brand)name: ZelecUN), 0.05g UV light absorber (trade(brand)name: BioSorb583), make homogeneous solution in 5 (6)-two (isocyanatomethyl)-two ring [2.2.1] heptane.In this homogeneous solution, add 23.86g tetramethylolmethane four (3-mercaptopropionic acid esters), 25.57g 4-mercapto methyl-1,8-dimercapto-3,6-dithia octane makes its mixed dissolution.
Under 600Pa, make this homogeneous solution deaeration after 1 hour, utilize 1 μ m PTFE filter made device to filter, inject the injection mould that constitutes by glass mold and band.This injection mould is put into baking oven, slowly be warming up to 120 ℃ through 20 hours from 25 ℃ and carry out polymerization.Polymerization is taken out injection mould after finishing from baking oven, the demoulding obtains resin.Further the gained resin was annealed 4 hours down in 120 ℃.
The specific refractory power of gained resin (ne) is 1.598, Abbe number (ve) is 41, thermotolerance is that 117 ℃, the maximum point stress of tension test are 88 (N/mm
2), chromatic UV transmissivity is 56%, shock-resistance 50% not destroy weight be 542g.Evaluation result is shown in table 2.
(comparative example 3)
Under 20 ℃, at 62.2g 2, mixed dissolution 0.10g is as the dibutyltin chloride of curing catalysts, 0.30g internal mold release (trade(brand)name: ZelecUN), 0.05g UV light absorber (trade(brand)name: BioSorb583), make homogeneous solution in 5 (6)-two (isocyanatomethyl)-two ring [2.2.1] heptane.In this homogeneous solution, add 11.9g 2 mercapto ethanol, 25.9g 4-mercapto methyl-1,8-dimercapto-3,6-dithia octane makes its mixed dissolution.
Under 600Pa, make this homogeneous solution deaeration after 1 hour, utilize 1 μ m PTFE filter made device to filter, inject the injection mould that constitutes by glass mold and band.This injection mould is put into baking oven, slowly be warming up to 120 ℃ through 20 hours from 25 ℃ and carry out polymerization.Polymerization is taken out injection mould after finishing from baking oven, the demoulding obtains resin.Further the gained resin was annealed 4 hours down in 120 ℃.
The gained resin is colourless and transparent high good resin, and specific refractory power (ne) is 1.596, Abbe number (ve) is 41, thermotolerance is that 118 ℃, the maximum point stress of tension test are 88 (N/mm
2), chromatic UV transmissivity is 42%, shock-resistance 50% not destroy weight be 114g.Evaluation result is shown in table 2.
Table 1
| Isocyanate compound | Mercaptan compound | Active dydrogen compounds | H | I％ | ||||
| Kind | Mole | Kind | Mole | Kind | Mole | |||
| Embodiment 1 | (A)-1 | 0.28 | (B)-1 | 0.13 | (C)-1 | 0.083 | 0.98 | 30 |
| Embodiment 2 | (A)-1 | 0.26 | (B)-1 | 0.15 | (C)-2 | 0.053 | 0.93 | 20 |
| Embodiment 3 | (A)-1 | 0.26 | (B)-1 | 0.15 | (C)-2 | 0.053 | 0.93 | 20 |
| Embodiment 4 | (A)-1 | 0.27 | (B)-1 | 0.13 | (C)-3 | 0.082 | 0.98 | 29 |
| Embodiment 5 | (A)-1 | 0.27 | (B)-1 | 0.13 | (C)-3 | 0.082 | 0.98 | 29 |
| Embodiment 6 | (A)-1 | 0.28 | (B)-1 | 0.13 | (C)-3 (F)-1 | 0.042 0.042 | 1.00 | 30 |
| Comparative example 1 | (D)-1 (D)-2 | 0.21 0.054 | (B)-1 | 0.17 | 1.04 | 0 | ||
| Comparative example 2 | (A)-1 | 0.25 | (B)-1 (B)-2 | 0.098 0.049 | 1.02 | 0 | ||
| Comparative example 3 | (A)-1 | 0.30 | (B)-1 (E)-1 | 0.099 0.15 | 1.01 | 0 | ||
Need to prove, in embodiment 1～6 and comparative example 2, as 2,5 (6)-two (isocyanatomethyl)-two ring [2.2.1] heptane, use 2, two (isocyanatomethyl)-two ring of 5-[2.2.1] heptane and 2, the mixture of two (isocyanatomethyl)-two ring of 6-[2.2.1] heptane.
The following content of symbolic representation in the table 1.
(A)-and 1:2,5 (6)-two (isocyanatomethyl)-two ring [2.2.1] heptane
(B)-and 1:4-mercapto methyl-1,8-dimercapto-3,6-dithia octane
(B)-2: tetramethylolmethane four (3-mercaptopropionic acid ester)
(C)-and 1:1, the 4-butyleneglycol
(C)-2: triglycol
(C)-3: glycol ether
(D)-1: isophorone diisocyanate
(D)-and 2:1, hexamethylene-diisocyanate
(E)-the 1:2-mercaptoethanol
(F)-1: ethylene glycol
H: functional group's mol ratio of NCO/ in the usage ratio of isocyanic ester, mercaptan compound and active dydrogen compounds (SH+OH).
I: when the mole number that the mole number of establishing the hydroxyl of compound of (C) formula (3) expression and thiol group is respectively the thiol group of p and q, mercaptan compound was r, the mole number of hydroxyl accounted for the ratio (%) of the total mole number of thiol group and hydroxyl: 100 * p/ (P+q+r)
Table 2
| Specific refractory power (ne) | Abbe number (ve) | Thermotolerance (℃) | Mechanical strength of resin (N/mm 2) | Dyeability (565nm/%T) | Shock-resistance (50% does not destroy weight) | |
| Embodiment 1 | 1.597 | 41 | 109 | 95 | ○ | ○ |
| Embodiment 2 | 1.603 | 40 | 103 | 95 | ○ | ○ |
| Embodiment 3 | 1.603 | 40 | 103 | 95 | ○ | ○ |
| Embodiment 4 | 1.597 | 41 | 104 | 96 | ○ | ○ |
| Embodiment 5 | 1.597 | 41 | 104 | 96 | ○ | ○ |
| Embodiment 6 | 1.598 | 41 | 109 | 101 | ○ | ○ |
| Comparative example 1 | 1.601 | 39 | 119 | 83 | △ | × |
| Comparative example 2 | 1.598 | 41 | 117 | 88 | △ | △ |
| Comparative example 3 | 1.596 | 41 | 118 | 88 | △ | × |
By above result as can be known, compare, the dyeability of the resin of embodiment, excellent impact resistance, and can obtain the balance of thermotolerance, mechanical strength of resin with comparative example.
In addition, according to above embodiment, can obtain a kind of transparent resin, this resin has good optics balances such as high refractive index, high Abbe number, is low-gravity, and has sufficient thermotolerance, mechanical strength of resin, and particularly shock-resistance, dyeability are good.The gained resin is suitable as the optical material in the high refractive index field, is a kind of material that is particularly suitable for the eyeglass lens field.
Claims (17)
1. Polymerizable composition, described Polymerizable composition contains following composition:
(A) the ester ring type isocyanate compound of representing by following formula (1) and/or following formula (2),
(B) can have at least a in the multi-thioalcohol compound of (many) sulfide linkages more than 1 in 1 molecule,
(C) at least a in the compound of following formula (3) expression,
HO-[R1-(Y)
n]
m-R2-X (3)
In the above-mentioned formula (3), X represents OH base or SH base, Y represents Sauerstoffatom or sulphur atom, and R1 and R2 represent to have substituent methylene radical independently of one another maybe can to have substituent carbonatoms be 2～4 alkylidene group, when Y is Sauerstoffatom, n is 0 or 1, when Y was sulphur atom, n represented 0 or 1～2 integer, and m represents 0 or 1～3 integer, wherein, (carbonatoms of R1+n) * m+ (carbonatoms of R2) is more than 3.
2. Polymerizable composition as claimed in claim 1, wherein, described (A) by the multi-thioalcohol compound that can have (many) sulfide linkages more than 1 in the ester ring type isocyanate compound of formula (1) and/or formula (2) expression, described (B) 1 molecule, and the usage ratio of the compound represented of described (C) formula (3) be 0.5～3.0 with functional group's molar ratio computing of NCO/ (SH+OH)
If the hydroxyl of the compound of described (C) formula (3) expression and the mole number of thiol group are respectively p, q, when the mole number that can have the thiol group in the multi-thioalcohol compound of (many) sulfide linkages more than 1 in described (B) 1 molecule was r, p/ (p+q+r) was 0.001～0.40.
3. Polymerizable composition as claimed in claim 1, wherein, the multi-thioalcohol compound that can have (many) sulfide linkages more than 1 in described (B) 1 molecule is to be selected from 4-mercapto methyl-1,8-dimercapto-3,6-dithia octane, 1,1,3,3-four (sulfydryl methylthio group) propane, 5,7-dimercapto methyl-1,11-dimercapto-3,6,9-three thias ten-alkane, 4,7-dimercapto methyl-1,11-dimercapto-3,6,9-three thias ten-alkane, and 4,8-dimercapto methyl-1,11-dimercapto-3,6, in 9-three thias ten-alkane-individual or two above compounds.
4. Polymerizable composition as claimed in claim 1, wherein, in the described formula (3) of expression described (C) composition, m is 0.
5. Polymerizable composition as claimed in claim 4, wherein, described (C) composition is 1, the 4-butyleneglycol.
6. Polymerizable composition as claimed in claim 1, wherein, in the described formula (3) of expression described (C) composition, m is 1～3 integer.
7. Polymerizable composition as claimed in claim 6, wherein, in the described formula (3) of expression described (C) composition, n is 1, Y is a Sauerstoffatom.
8. Polymerizable composition as claimed in claim 7, in the described formula (3) of expression described (C) composition, it is 2 or 3 alkylidene group that R1 and R2 represent to have substituent carbonatoms independently of one another.
9. Polymerizable composition as claimed in claim 8, wherein, described (C) composition is triglycol or glycol ether.
10. as claim 5 or 9 described Polymerizable compositions, wherein, described ester ring type isocyanate compound (A) by formula (1) and/or formula (2) expression is the ester ring type isocyanate compound of described formula (1) expression,
The multi-thioalcohol compound (B) that can have (many) sulfide linkages more than 1 in described 1 molecule is to be selected from 4-mercapto methyl-1,8-dimercapto-3,6-dithia octane, 5,7-dimercapto methyl-1,11-dimercapto-3,6,9-three thias ten-alkane, 4,7-dimercapto methyl-1,11-dimercapto-3,6,9-three thias, ten-alkane and 4,8-dimercapto methyl-1,11-dimercapto-3,6, one or two above compounds in the 9-three thia undecanes.
11. the preparation method of a resin, this preparation method make each described Polymerizable composition polymerization in the claim 1～10.
12. a resin makes following (A), (B) and (C) reaction and obtaining,
(A) the ester ring type isocyanate compound of representing by following formula (1) and/or following formula (2),
(B) can have at least a in the multi-thioalcohol compound of (many) sulfide linkages more than 1 in 1 molecule,
(C) at least a in the compound of following formula (3) expression,
HO-[R1-(Y)
n]
m-R2-X (3)
In the above-mentioned formula (3), X represents OH base or SH base, Y represents Sauerstoffatom or sulphur atom, and R1 and R2 represent to have substituent methylene radical independently of one another maybe can to have substituent carbonatoms be 2～4 alkylidene group, when Y is Sauerstoffatom, n is 0 or 1, when Y was sulphur atom, n represented 0 or 1～2 integer, and m represents 0 or 1～3 integer, wherein, (carbonatoms of R1+n) * m+ (carbonatoms of R2) is more than 3.
13. an optics, described optics contain the described resin of claim 12.
14. lens, described lens are made of the described optics of claim 13.
15. an eyeglass lens, described eyeglass lens is made of the described lens of claim 14.
16. each described Polymerizable composition is as the application of optics in the claim 1～10.
17. make the application of each described Polymerizable composition polymerization obtains in the claim 1～10 resin as optics.
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| JP2005339720 | 2005-11-25 | ||
| PCT/JP2006/315485 WO2007020817A1 (en) | 2005-08-18 | 2006-08-04 | Polythiourethane-based polymerizable composition and optical resin obtained from the same |
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| CN106232660A (en) * | 2014-05-02 | 2016-12-14 | 三井化学株式会社 | Polymerizable composition for optical material and optical material therefrom and manufacture method thereof |
| CN108892763A (en) * | 2018-05-28 | 2018-11-27 | 岭南师范学院 | A kind of polyurethane binary mercaptan prepolymer, photosensitive resin composition and its preparation method and application |
| CN112521573A (en) * | 2020-11-25 | 2021-03-19 | 山东益丰生化环保股份有限公司 | Modified polythiol and metal anticorrosion UV (ultraviolet) coating using same |
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| CN107721892B (en) * | 2017-10-31 | 2020-10-23 | 淮阴师范学院 | Thio-polythiol, preparation method and application in transparent polyurethane material |
| CN109294208A (en) * | 2018-09-30 | 2019-02-01 | 上海康耐特光学有限公司 | Photochromic urethane composition and its preparation method and application, the color-changing lens comprising it |
| EP3919967A4 (en) | 2020-01-27 | 2022-12-21 | Mitsui Chemicals, Inc. | Polymerizable composition for optical material, polymerizable prepolymer composition for optical material, cured product, and method for producing optical material |
| EP4332140A3 (en) | 2020-01-27 | 2024-04-10 | Mitsui Chemicals, Inc. | Polymerizable composition for optical material, polymerizable prepolymer composition for optical material, cured product, and method of producing optical material |
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| US5087758A (en) * | 1988-12-22 | 1992-02-11 | Mitsui Toatsu Chemicals, Inc. | Mercapto compound, a high refractive index resin and lens and a process for preparing them |
| AU637662B2 (en) * | 1989-12-28 | 1993-06-03 | Hoya Corporation | Polythiol compound, and optical material and product produced therefrom |
| US5679756A (en) * | 1995-12-22 | 1997-10-21 | Optima Inc. | Optical thermoplastic thiourethane-urethane copolymers |
| KR100769373B1 (en) * | 2004-03-12 | 2007-10-22 | 미쓰이 가가쿠 가부시키가이샤 | Polyurethanes polymerizable composition and method for producing optical resin of the same |
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| CN106232660A (en) * | 2014-05-02 | 2016-12-14 | 三井化学株式会社 | Polymerizable composition for optical material and optical material therefrom and manufacture method thereof |
| US10196501B2 (en) | 2014-05-02 | 2019-02-05 | Mitsui Chemicals, Inc. | Polymerizable composition for optical material, optical material produced from same, and process for producing same |
| CN106232660B (en) * | 2014-05-02 | 2020-03-20 | 三井化学株式会社 | Polymerizable composition for optical material, optical material obtained therefrom, and method for producing same |
| CN108892763A (en) * | 2018-05-28 | 2018-11-27 | 岭南师范学院 | A kind of polyurethane binary mercaptan prepolymer, photosensitive resin composition and its preparation method and application |
| CN112521573A (en) * | 2020-11-25 | 2021-03-19 | 山东益丰生化环保股份有限公司 | Modified polythiol and metal anticorrosion UV (ultraviolet) coating using same |
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