CN100497425C - Transparent molded article - Google Patents
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- CN100497425C CN100497425C CNB2004800160664A CN200480016066A CN100497425C CN 100497425 C CN100497425 C CN 100497425C CN B2004800160664 A CNB2004800160664 A CN B2004800160664A CN 200480016066 A CN200480016066 A CN 200480016066A CN 100497425 C CN100497425 C CN 100497425C
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Abstract
A transparent molded article comprised of polythiourethane obtained by polymerizing monomer components comprising the following component (A) and component (B1). A transparent molded article obtained by polymerizing monomer components comprising the following component (A), component (B1), component (B2) and component (C). Component (A): one or more polythiol compound denoted by general formula (I) (In general formula (I), m is 1, 2, 3, 4, 5 or 6.) Component (B1): one or more polyisocyanate compound denoted by general formula (II) (In general formula (II), n 1 , n 2 and n 3 are each independently 3, 4, 5, 6, 7 or 8.) Component (B2): one or more aliphatic diisocyanate compound having an intramolecular cyclic structure Component (C): aliphatic diol compound
Description
Technical field
The present invention relates to high refractive index, low dispersive, the transparency is excellent, and shock-resistance, the molding that is applicable to optical applications that weathering resistance is also excellent.In more detail, the present invention relates to high refractive index, high Abbe (Abbe) number, optical characteristics excellence, and the transparent molded article of shock-resistance excellence, be applicable to based on glasses with the transparent molded article of various lens, prism, optical fiber, recording medium usefulness substrate, optical filtering etc.
Background technology
With the glassy phase ratio, plastics in light weight is not easy to break, and dyeing easily, and therefore, it is used in the optical applications such as various lens in recent years.As the material of optics, use poly-diethylene glycol bis-allyl carbonate (CR-39) and polymethylmethacrylate (PMMA) usually with plastics.Yet the specific refractory power of these plastic materials all is below 1.5, therefore, for example is being used for the situation of lens material, and the number of degrees are high more, and lens are thick more, and this will damage the superiority of so-called lightweight plastics, considers it also is not preferred from the viewpoint of taste.In addition, particularly in concavees lens, the thickness of rims of the lens thickens, and therefore form dielectric grid and colo(u)r bias are not preferred easily.
Therefore, in order to access the feature of the little plastics of proportion, make the wall thickness attenuation of lens, the plastic material that refractive index is high is developed.As such material, can enumerate the polythiourethane that obtains by tetramethylolmethane four (mercaptopropionic acid ester) and diisocyanate cpd, by 4-mercapto methyl-1,8-dimercapto-3, the polythiourethane that 6-dithio octane and diisocyanate cpd obtain etc. (with reference to the spy open clear 63-No. 46213 communiques (below, be referred to as " document 1 ") and the spy open flat 2-No. 270859 communiques (below, be referred to as " document 2 ")).
Yet, document 1 and 2 described polythiourethane specific refractory power height, but have problems at aspects such as weathering resistance, thermotolerances.
By comparison, the inventor's etc. group addresses these problems a little to have carried out meticulous research, found that by 2,5-dimercapto methyl-1, the polythiourethane that 4-dithiane and its oligopolymer and polymeric polyisocyanate reaction obtain, its specific refractory power is improved certainly, therefore weathering resistance, the thermotolerance as problem be greatly improved (with reference to the spy open flat 3-No. 236386 communiques (below, be referred to as " document 3 ") and the spy open flat 11-No. 202101 communiques (below, be referred to as " document 4 ")).Document 3 is compared with 2 described polythiourethanes with document 1 with 4 described polythiourethanes, have excellent in impact resistance, but in practicality, also have bigger problem, in recent years, in the optical material based on glasses lens, expectation has the more material of high-impact.
Summary of the invention
It is big that first purpose of the present invention provides a kind of shock strength, and the transparency is excellent, and the specific refractory power height, is suitable for the molding of optical applications.
Second purpose of the present invention provide have with present optical materials such as lens in the identical or above specific refractory power and the transparency of molding used, and have than the molding that uses in the present optical materials such as the lens transparent molded article that is suitable for optical applications of high impact more.
The inventor etc. have carried out meticulous research for realizing above-mentioned first purpose, found that, the transparent molded article that the polythiourethane that obtains by polythiol that is had ad hoc structure by polymerization and the polyisocyanate compounds with ad hoc structure constitutes can achieve the above object, thereby finishes the present invention.
That is, be used to realize that the scheme of the present invention's first purpose is as described below.
(1) a kind of transparent molded article, it is made of the polythiourethane that the monomer component that contains following compositions (A) and composition (B1) by polymerization obtains:
Composition (A): the poly-thiol compound more than a kind or 2 kinds (in the general formula (I), m is 1,2,3,4,5 or 6) of general formula (I) expression,
Composition (B1): a kind or 2 kinds or above polyisocyanate compounds of general formula (II) expression.
(in the general formula (II), n
1, n
2, n
3Be 3,4,5,6,7 or 8 independently of one another)
(2) as (1) described transparent molded article, wherein, above-mentioned monomer component also contains following compositions (B2).
Composition (B2): the aliphatic diisocyanate compound more than a kind or 2 kinds that has ring texture in the molecule
(3) transparent molded article described in (2), wherein, in above-mentioned polymerization, the total amount of the NCO base that has with respect to composition (B1) and composition (B2), the shared ratio of NCO base in the composition (B1) is more than the 25mol%.
(4) as each described transparent molded article in (1)～(3), wherein, the m in the general formula (I) of composition (A) is l or 2.
(5) as each described transparent molded article in (1)～(4), wherein, n in the general formula (II) of composition (B1)
1, n
2, n
3Be 4,5 or 6 independently of one another.
(6) as each described transparent molded article in (1)～(5), wherein, in above-mentioned polymerization, with respect to the contained thiol group of composition (A), the mol ratio of the isocyanate group that composition (B1) and composition (B2) are contained is 1.00～1.15.
(7) as each described transparent molded article in (1)～(6), wherein transparent molded article is lens.
(8) as (7) described molding, lens are glasses lens.
The inventor etc. have carried out meticulous research for realizing above-mentioned second purpose, found that, the transparent molded article that the polythiourethane that polythiol, aliphatic diol compound by being had ad hoc structure by polymerization and the polyisocyanate compounds with ad hoc structure obtain obtains can be realized above-mentioned purpose, thereby finishes the present invention.
That is, be used to realize that the scheme of the present invention's second purpose is as described below.
(9) a kind of transparent molded article, it obtains by the monomer component that polymerization contains following compositions (A), composition (B1), composition (B2) and composition (C):
Composition (A): the poly-thiol compound more than a kind or 2 kinds of general formula (I) expression (general formula (I) is planted, and m is 1,2,3,4,5 or 6)
General expression (I)
Composition (B1): the polyisocyanate compounds more than a kind or 2 kinds of general formula (II) expression.
(in the general formula (II), n
1, n
2, n
3Be 3,4,5,6,7 or 8 independently of one another)
Composition (B2): the aliphatic diisocyanate compound more than a kind or 2 kinds that has ring texture in the molecule
Composition (C): aliphatic diol compound
(10) as (9) described transparent molded article, wherein, with respect to the total mass of composition in the above-mentioned monomer component (A) and composition (C), the mass ratio of composition (C) is 3～60%.
(11) as (9) or (10) described transparent molded article, wherein, in above-mentioned polymerization, the total amount of the NCO base that contains with respect to composition (B1) and composition (B2), the shared ratio of composition (B1) is 10～80mol%.
(12) as each described transparent molded article in (9)～(11), wherein, the m in the general formula (I) of composition (A) is 1 or 2.
(13) as each described transparent molded article in (9)～(12), wherein, mentioned component (C) has 300～2000 number-average molecular weight.
(14) as (13) described transparent molded article, wherein, mentioned component (C) has 600～1500 number-average molecular weight.
(15) as each described transparent molded article in (9)～(14), wherein, the aliphatic diol compound of mentioned component (C) is the polyethers diol compound.
(16) as (15) described transparent molded article, wherein, above-mentioned polyethers diol compound is a polypropylene glycol.
(17) as each described transparent molded article in (9)～(16), wherein, the n in the general formula (II) of mentioned component (B1)
1, n
2, n
3Be 4,5 or 6 independently of one another.
(18) as each described transparent molded article in (9)～(17), wherein, in above-mentioned polymerization, with respect to the total amount of hydroxyl contained in contained sulfydryl of composition (A) and the composition (C), the mol ratio of the isocyanate group that composition (B1) and composition (B2) are contained is 1.00～1.15.
(19) as each described transparent molded article in (9)～(18), wherein, transparent molded article is lens.
(20) as (19) described molding, wherein, lens are glasses lens.
The best mode that is used to carry out an invention
Below, the present invention will be described in more detail.
The transparent molded article of the present invention's first mode (below, be referred to as " transparent molded article 1 ") is made of the polythiourethane that the monomer component that contains composition (A) and composition (B1) by polymerization obtains.
The transparent molded article of the present invention's second mode (below, be referred to as " transparent molded article 2 ") obtains by the monomer component that polymerization contains composition (A) and composition (B1), composition (B2) and composition (C).
In addition, in the present invention,, include in " transparent molded article " so long as in use, have the molding of the transparency that does not have defective as optical material.As the expression index of transparency, can use corresponding index respectively according to the optical material of use transparent molded article of the present invention, for example light penetration, turbidity value, visual etc.
Below, only " transparent molded article " is called " molding ".
Embodiment
[first mode]
Transparent molded article 1 of the present invention is made of the polythiourethane that the monomer component that contains composition (A) and composition (B1) by polymerization obtains.
Mentioned component (A) is that general formula (I) is (in the formula, m formula 1,2,3,4,5 or 6) (1 of expression, 4-dithiane ring is the poly-thiophene hydride compounds of main framing, by containing this main framing, not only do not sacrifice weathering resistance, in the molding that obtains by polymerization, can also pay high refractive index and high Abbe number simultaneously.In above-mentioned general formula (I), if m be 6 or below, the viscosity of composition (A) can be not too high, when can keeping good operability, because high with the intermiscibility of other composition, therefore can improve the optical transparence of the molding that obtains by polymerization yet.From obtaining the viewpoint that has high refractive index and high Abbe number and have the good optical transparency, in general formula (I), m is preferably 1 or 2.In addition, composition (A) can formula m be the simplification compound of arbitrary integer between 1～6, also can be the different mixture more than 2 kinds of m value.
It is synthetic that mentioned component (A) for example can be opened the known method described in flat 3-No. 236386 communiques and flat 10-No. 120676 communiques of Te Kai by the spy.
On the other hand, mentioned component (B1) is general formula (II) expression (n
1, n
2, n
3Be 3,4,5,6,7 or 8 independently of one another) to have in the chlorinated isocyanurates ring by carbon number be the polyisocyanate compounds that 3～8 alkylidene group combines the isocyanic ester structure.By with a kind of as raw material of this compound, transparent molded article 1 of the present invention has obtained suitable crosslinking structure, pay higher measure equilibrated thermotolerance and shock-resistance in, solvent resistance is also excellent.
In above-mentioned general formula (II), if n
1, n
2, n
3Any be 2 or below, obtained having the molding of high heat resistance, but the shock-resistance of the molding that obtains reduces, on the other hand, if n
1, n
2, n
3Any be more than 9, obtained having the molding of high-impact, but the thermotolerance of the molding that obtains reduces.Therefore, if n
1, n
2, n
3Be 3～8, the thermotolerance of the molding that obtains and the balance of shock-resistance are good, composition (B1) is good with the intermiscibility of other material composition, can obtain the molding of optical transparence excellence, consider it is preferred from this viewpoint, from thermotolerance and shock-resistance, and the viewpoint of optical transparence is considered n
1, n
2, n
3Be preferably 4,5 or 6.
Mentioned component (B1) can be synthetic by known method, can also obtain as commercially available product.For example, as the concrete example of composition (B1), can enumerate three (6-hexyl isocyanate base) chlorinated isocyanurates and three (4-butyl isocyanate base) chlorinated isocyanurates.These materials can be synthetic by known method, in addition, for three (6-hexyl isocyanate base) chlorinated isocyanurates, contains it and can buy with the trade(brand)name of コ ロ ネ-ト from Japanese polyurethane industrial for the material of principal constituent.
The monomer component that contains mentioned component (A) and composition (B1) can also contain composition (B2).Composition (B2) is the aliphatic diisocyanate compound more than a kind or 2 kinds that has ring texture in the molecule.Wherein, so-called " the aliphatic diisocyanate compound that has ring texture in the molecule " is meant the aliphatic diisocyanate compound that has ring texture on main chain or side chain.Above-mentioned ring texture can be alicyclic ring, aromatic nucleus or heterocyclic any one.Wherein, so-called " alicyclic ring " is meant that carbon number is the cyclic hydrocarbon group that does not demonstrate aromatic series that constitutes more than 3, as dithiane, a part of methylene radical that constitutes ring is by the ring of replacements such as sulphur atom, and two such rings of norbornylene are also included within wherein.In addition, so-called " aromatic nucleus " is meant the cyclic hydrocarbon group that demonstrates aromatic series, and condensed rings such as naphthalene nucleus are also included within wherein.In addition, so-called " heterocycle " is meant in the ring that ring is made of heteroatomss such as carbon atom and oxygen and sulphur, demonstrates the ring of aromatic series.In addition, directly the compound in conjunction with isocyanate group is commonly called aromatic isocyanate compound in above-mentioned " aromatic nucleus " and " heterocycle " such ring that demonstrates aromatic series, in the present invention as having the aliphatic diisocyanate compound of ring texture in the molecule of composition (B2) and not meeting.Therefore, in the present invention in the aliphatic diisocyanate compound with ring texture of Shi Yonging, so-called ring texture is the aliphatic diisocyanate compound of " aromatic nucleus " or " heterocycle ", is meant that isocyanate group is an alkylidene group bonded compound more than 1 by carbon number.In addition, substituting groups such as the alicyclic ring of enumerating as above-mentioned ring texture, aromatic nucleus, heterocycle debond alkyl.
The aliphatic diisocyanate compound that has ring texture in the molecule is from the xanthochromia of the molding that prevents to obtain, and keep the viewpoint of sufficient elasticity and hardness to set out, has diisocyanate cpd as the alicyclic ring of ring texture (below, be referred to as " ester ring type diisocyanate cpd ") in the preferred molecule.Compare with the ester ring type vulcabond, use has the molding that the isocyanic ester of aromatic nucleus obtains and is easy to generate xanthochromia, and the molding that the isocyanic ester that uses the aliphatics chain obtains feels like jelly, its shape-holding property has the tendency of reduction, therefore, in the present invention, as composition (B2), preferred ester ring type vulcabond.
As the ester ring type diisocyanate cpd, for example, can enumerate 4,4 '-methylene-bis (cyclohexyl isocyanate), isophorone diisocyanate, 1,2-two (isocyanatomethyl) hexanaphthenes, 1,3-two (isocyanatomethyl) hexanaphthenes, 1,4-two (isocyanatomethyl) hexanaphthenes, 1,2-vulcabond hexanaphthene, 1,3-vulcabond hexanaphthene, 1,4-vulcabond hexanaphthene, 2,5-two (isocyanatomethyl)-1,4-dithiane, 2,3-two (isocyanatomethyl)-1,4-dithiane, 2,6-two (isocyanatomethyl)-1,4-dithiane, 2,4-two (isocyanatomethyl)-1,3-dithiane, 2,5-two (isocyanatomethyl)-1,3-dithiane, 4,6-two (isocyanatomethyl)-1,3-dithiane, 4,5-two (isocyanatomethyl)-1,3-dithiane, 2,5-vulcabond-1,4-dithiane, 2,3-vulcabond-1,4-dithiane, 2,6-vulcabond-1,4-dithiane, 2,4-vulcabond-1,3-dithiane, 2,5-vulcabond-1,3-dithiane, 4,6-vulcabond-1,3-dithiane, 4,5-vulcabond-1,3-dithiane, 4,5-two (isocyanatomethyl)-1,3-thiacyclopentanes, 4,5 vulcabond-1,3-thiacyclopentane, 2,2-two (isocyanatomethyl)-1,3-dithiane etc.
In addition, as having the aliphatic diisocyanate compound of aromatic nucleus in the molecule as ring texture, for example, can enumerate an eylylene diisocyanate, adjacent eylylene diisocyanate, to eylylene diisocyanate, a tetramethyl-eylylene diisocyanate etc.
As having the aliphatic diisocyanate compound of heterocycle in the molecule, for example, can enumerate 2,5-two (isocyanatomethyl)-thiophene, 3,4-two (isocyanatomethyl)-thiophene etc. as ring texture.
In addition, composition (B2) is from the viewpoint of photostabilization and weathering resistance, preferably be selected from 4,4 '-methylene-bis (cyclohexyl isocyanate), isophorone diisocyanate, 1,3-two (isocyanatomethyl) hexanaphthenes and 2, in 5-two (isocyanatomethyl)-1,4-dithiane at least a kind.
In the polymerization of transparent molded article 1 of the present invention, the total amount of the NCO base that has with respect to composition (B1) and composition (B2), the shared ratio of NCO base in the composition (B1) is preferably more than the 25mol%.If this ratio is more than the 25mol%, in polymerization, can obtain sufficient degree of crosslinking in the reality, can obtain having the molding of high heat resistance, mechanical characteristics.From viewpoints such as thermotolerance, mechanical characteristicies, the total amount of the NCO base that has with respect to composition (B1) and composition (B2), the shared ratio of the NCO base in the composition (B1) is more preferably more than the 35mol%.
For obtaining transparent molded article 1, when polymerization contains the monomer component of composition (A) and composition (B1), with respect to the contained thiol group of composition (A), the mol ratio of the isocyanic ester that composition (B1) is contained is 1.00～1.15, from the viewpoint of the molding that obtains having abundant toughness (intensity), it is preferred.In addition, when polymerization contains the monomer component of composition (A), composition (B1) and composition (B2), with respect to the contained thiol group of composition (A), the mol ratio of the isocyanic ester that composition (B1) and composition (B2) are contained is 1.00～1.15, from the viewpoint of the molding that obtains having abundant toughness (intensity), it is preferred.In in office-kind of situation, above-mentioned mol ratio all more preferably 1.02～1.12.
At the monomer component that contains composition (A) and composition (B1) by polymerization, thereby obtain in the situation of transparent molded article 1 of the present invention, for example, can use the method that comprises the steps, in mentioned component (A) and composition (B1) injection molding mould, heating composition (A) and composition (B1) carry out polymerization then, thereby obtain molding.In addition, at the monomer component that contains composition (A), composition (B1) and composition (B2) by polymerization, thereby obtain in the situation of transparent molded article 1 of the present invention, for example, can use the method that comprises the steps, in mentioned component (A), composition (B1) and composition (B2) injection molding mould, then heated polymerizable composition (A) and composition (B1) and composition (B2) thus obtain molding.Heating temperature wherein is generally-20～160 ℃.Heating temperature is not certain in polymerization, and interim variation also can be arranged.In addition, cannot treat different things as the same according to conditions such as Heating temperatures heat-up time, is generally about 0.5～120 hour.In addition, in the polymerization of composition (A) and composition (B1) and composition (B2), can use the polymerizing catalyst that is used to improve polymerizability, specifically, can use based on the organometallic compound of organotin and tertiary amine etc.The usage quantity of catalyzer can be 0.001～1mol% for example with respect to isocyanate group.
In addition, in transparent molded article 1 of the present invention, except that mentioned component (A), composition (B1) and composition (B2), can also be according to expectation, be not useful on the UV light absorber of improving extinction characteristic, pigment, pigment etc., be used to improve the antioxidant of weathering resistance and anti-coloring agent etc., be used to improve various additives such as the softening agent of shaping processability and releasing agent transparent molded article being had suitably contain under the degree that hinders.These compositions can mix in each composition before polymerization, also can mix when polymerization, flood in the molding that can also obtain after polymerization.
In transparent molded article 1 of the present invention, can apply be used for further improving the sclerosis coating of scuff resistance after the forming process handle and be used to reduce reflectivity prevent surface treatment such as reflection coating processing.
Transparent molded article 1 of the present invention for example can be the recording medium substrate that uses in lens such as glasses lens and optical lens, prism, optical fiber, CD and disk etc., can also be optical materials such as filter.Preferred transparent molded article of the present invention 1 can be lens, especially preferably can be eyeglass lens.
[second mode]
Transparent molded article 2 of the present invention obtains by the monomer component that polymerization contains composition (A), composition (B1), composition (B2) and composition (C).
Composition (A) is that general formula (I) is (in the formula, m formula 1,2,3,4,5 or 6) (1 of expression, 4 one dithiane rings are the poly-thiophene hydride compounds of main framing, by containing this main framing, not only do not sacrifice weathering resistance, in the molding that obtains by polymerization, can also pay high refractive index and high Abbe number simultaneously.
Composition (B1) is general formula (II) expression (n
1, n
2, n
3Be 3,4,5,6,7 or 8 independently of one another) to have in the chlorinated isocyanurates ring by carbon number be the polyisocyanate compounds that 3～8 alkylidene group combines the isocyanic ester structure.By with a kind of as raw material of this compound, transparent molded article 1 of the present invention has obtained suitable crosslinking structure, pay higher measure equilibrated thermotolerance and shock-resistance in, solvent resistance is also excellent.
Composition (B2) is the aliphatic diisocyanate compound more than a kind or 2 kinds that has ring texture in the molecule.By in monomer component, containing such composition (B2), can obtain the more excellent molding of thermotolerance.
The detailed description of composition (A), composition (B1), composition (B2) is as described in the explanation in previous first mode.
Next, composition (C) is described.
Composition (C) is the aliphatic diol compound.In the present invention, by contain the aliphatic diol compound in monomer component, in the molding that obtains, not only weathering resistance and photostabilization do not reduce, and can also pay toughness.Therefore, in the present invention, can obtain transparent molded article 2 based on the mechanical characteristics excellence of shock strength.
In order further to improve these mechanical characteristicies, the aliphatic diol compound of composition (C) preferably has 300～2000 number-average molecular weight.If the number-average molecular weight of above-mentioned glycol is more than 300, in the molding that obtains, can pay toughness effectively, if be below 200, keep the hardness of the molding that obtains easily, keep shape.The number-average molecular weight of above-mentioned diol compound more preferably 600～1500.
As such diol compound, for example can enumerate with polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycols etc. are main polyethers diol compound, with the polyester glycol that generates by ethylene glycol and hexanodioic acid, polyester glycol by propylene glycol and hexanodioic acid generation, polyester glycol by glycol ether and hexanodioic acid generation, by 1, the polyester glycol that 4-butyleneglycol and hexanodioic acid generate, polyester glycol by neopentyl glycol and hexanodioic acid generation, by 1, the polyester glycol that 6-hexylene glycol and hexanodioic acid generate, by 1, the polyester glycol that 10-decanediol and hexanodioic acid generate, by 1, the polyester glycol that 4-butyleneglycol and pentanedioic acid generate, by 1, the polyester glycol that 4-butyleneglycol and sebacic acid generate, polycaprolactone glycol by ethylene glycol and ε-caprolactone generation, polycaprolactone glycol by propylene glycol and ε-caprolactone generation, polycaprolactone glycol by glycol ether and ε-caprolactone generation, by 1, the polycaprolactone glycol that 4-butyleneglycol and ε-caprolactone generates, polycaprolactone glycol by neopentyl glycol and ε-caprolactone generation, by 1, the polycaprolactone glycol that 6-hexylene glycol and ε-caprolactone generates, the polycaprolactone glycol that is generated by 1,10-decanediol and ε-caprolactone etc. is main polyester diol compound, based on polycarbonate-based diol compound of polycarbonate diol etc. etc.In addition because in same molecular weight, the low then operability excellence of viscosity, therefore above-mentioned aliphatic diol compound optimization polycarbonate class diol compound, in addition, from the viewpoint of the intermiscibility of other composition, preferred polypropylene glycol.Such aliphatic diol compound can be synthetic by known method, in addition, also can be used as commercially available product and obtain.
In the polymerization of transparent molded article 2 of the present invention, with respect to the total mass of composition (A) and composition (C), the mass ratio of composition (C) is preferably 3～60%.If this ratio is more than 3%, can pay the molding toughness that obtains effectively, in addition,, pay sufficient thermotolerance of the molding that obtains and high specific refractory power easily if be below 60%.From viewpoints such as the mechanical characteristics of the molding that obtains, thermotolerance, optical characteristics, above-mentioned mass ratio more preferably 8～40%.
In second mode of the present invention, in the polymerization of above-mentioned monomer component, the total amount of the NCO base that has with respect to composition (B1) and composition (B2), the shared ratio of NCO base in the composition (B1) is preferably 10～80mol%.If aforementioned proportion is more than the 10mol%, in polymerization, can obtain practical sufficient degree of crosslinking, the molding that can obtain having high heat resistance and mechanical characteristics.On the other hand, if aforementioned proportion is below the 80mol%, composition (B1) and composition (B2), the intermiscibility height of composition (A) and composition (C) can obtain having the practical molding of the transparency fully of going up.From viewpoints such as such thermotolerance, mechanical characteristics, the transparencys, in the polymerization of monomer component, the total amount of the NCO base that has with respect to composition (B1) and composition (B2), the shared ratio of the NCO base in the composition (B1) is 15～65mol% more preferably.
In second mode of the present invention, in the polymerization of above-mentioned monomer component, the total amount of the hydroxyl contained with respect to the contained thiol group of composition (A) and composition (C), the mol ratio of the isocyanic ester that composition (B1) and composition (B2) are contained is 1.00～1.15, from the viewpoint of the molding that obtains having abundant toughness (intensity), it is preferred.Above-mentioned mol ratio more preferably 1.02～1.12.
At the monomer component that contains composition (A), composition (B1), composition (B2) and composition (C) by polymerization, thereby obtain in the situation of transparent molded article 2 of the present invention, for example, can use the method that comprises the steps, in mentioned component (A), composition (B1), composition (B2) and composition (C) injection molding mould, heating composition (A), composition (B1), composition (B2) and composition (C) carry out polymerization then, thereby obtain molding.Wherein, the mixture that injects in shaping dies can mix composition (A), composition (B1), composition (B2) and composition (C) separately, perhaps also can be in advance with composition (C) and composition (B1) and composition (B2) for example under 0～80 ℃, in 5 minutes～50 hours, use as required based on polyurethane reaction catalyzer such as the organometallic compound of organo-tin compound and tertiary amines and react, after generating urethane bonds, add composition (A) and form mixture.In addition, can also in advance composition (C) and composition (B1) for example with under the above-mentioned same condition reacted, after generating urethane bonds, to form mixture as composition (B2) and composition (A), and also can in advance composition (C) and composition (B2) for example with under the above-mentioned same condition reacted, after generating urethane bonds, will form mixture as composition (B1) and composition (A).
Heating temperature during the polymerization said mixture is-20～160 ℃ in either event.Heating temperature is not certain in polymerization, and interim variation also can be arranged.In addition, cannot treat different things as the same according to conditions such as Heating temperatures heat-up time, is generally about 0.5～120 hour.In addition, when the polymerization said mixture, in either event, all can use the polymerizing catalyst that is used to improve polymerizability, specifically, can use based on the organometallic compound of organotin and tertiary amine etc.The usage quantity of catalyzer can be 0.001～1mol% for example with respect to isocyanate group.
In addition, in transparent molded article 2 of the present invention, except that mentioned component (A), composition (B1), composition (B2) and composition (C), can also be according to expectation, be not useful on the UV light absorber of improving extinction characteristic, pigment, pigment etc., be used to improve the antioxidant of weathering resistance and anti-coloring agent etc., be used to improve various additives such as the softening agent of shaping processability and releasing agent transparent molded article being had suitably contain under the degree that hinders.These compositions can mix in each composition before polymerization, also can mix when polymerization, flood in the molding that can also obtain after polymerization.
In transparent molded article 2 of the present invention, can apply be used for further improving the sclerosis coating of scuff resistance after the forming process handle and be used to reduce reflectivity prevent surface treatment such as reflection coating processing.
Transparent molded article 2 of the present invention for example can be the recording medium substrate that uses in lens such as glasses lens and optical lens, prism, optical fiber, CD and disk etc., can also be optical materials such as filter.Preferred transparent molded article of the present invention 2 can be lens, especially preferably can be eyeglass lens.
Embodiment
Below, the present invention will be described in more detail by embodiment, however the present invention is not subjected to the qualification of these embodiment.
According to method shown below the rerum natura of the optical material that obtains is estimated.
(1) specific refractory power (nD) and Abbe number (γ D)
Use ア go society to produce Abbe refractomecer, under 20 ℃, measure.
(2) painted
The lens that visual observation obtains will not have painted material to be designated as A, and slightly the material of painted (yellow) is designated as B, and obvious painted material is designated as C.
(3) transparency
The lens that obtain are placed the dark place, under luminescent lamp, carry out visual observation, will not have inner material fuzzy and that opaque material is separated out to be designated as A.On the other hand, the material of observing faint fuzzy grade is designated as B, the material that fuzzy degree is serious and can obviously observe the material that opaque material separates out and be designated as C.B, C are not suitable for use in lens respectively.
(4) optical strain
The lens that obtain by schlieren method (schlieren method) visual observation.To not have the strained material to be designated as A, and will only have faint strained material to be designated as B in the edge section, will all produce strained and be designated as C.
(5) shock-resistance
By the lens that obtain, prepare wide 5mm, the mensuration sheet of dark 5mm, high 16mm, use Japan smart mechanism work グ イ Application ス Star De テ ス that produces-, under 20 ℃, carry out rupture test.By the result who obtains, calculate the energy that destruction needs, with the index of this value as shock-resistance.Energy value is big more, means that shock-resistance is strong more.
[first mode]
(embodiment 1)
Evenly stir 0.29mol2,5-two (mercapto methyl)-1,4-dithiane (in table 1, being expressed as DMMD), 0.08mol three (6-hexyl isocyanate base) chlorinated isocyanurates (in table 1, being expressed as CX), 0.18mol1,3-two (isocyanatomethyl) hexanaphthenes (in table 1, being expressed as HXDI) and 2.9 * 10
-4The mixture of mol dibutyltin dilaurate (in table 1, being expressed as DBTDL), inject the forming lens glass mold, heated 10 hours down, heated 5 hours down at 60 ℃ afterwards at 50 ℃, heat down at 120 ℃ again and carried out polymerization in 3 hours, thereby obtain plastic lens.Each rerum natura of the plastic lens that obtains is shown in the table 1.Found out that by table 1 index of refraction in lens of embodiment 1 (nD) is 1.61, and is higher, Abbe number is 40, and is also higher, do not have paintedly, and the transparency is also excellent, does not have optical strain.In addition, the energy of rupture value also is shown as 120 (kgcm/cm
2), the shock-resistance height.
(embodiment 2～6)
Except that using the monomer composition shown in the table 1, carry out operation similarly to Example 1, obtain plastic lens.Each rerum natura of these plastic lenss is shown in the table 1.Found out that by table 1 index of refraction in lens of embodiment 2～6 (nD) is 1.60～1.64, and is higher, Abbe number is 39～41, and is also higher, do not have paintedly, and the transparency is also excellent, does not have optical strain.In addition, the energy of rupture value also is shown as 90～120kgcm/cm
2, the shock-resistance height.
(comparative example 1)
Evenly stir 0.20mol4-mercapto methyl-1,8-dimercapto-3,6-two thiophene octanes (in table 1, being expressed as MMMO), 0.30mol norbornylene vulcabond (in table 1, being expressed as NDI) and 3.0 * 10
-4The mixture of mol dibutyltin dilaurate (in table 1, being expressed as DBTDL), inject the forming lens glass mold, heated 10 hours down, heated 5 hours down at 60 ℃ afterwards at 50 ℃, heat down at 120 ℃ again and carried out polymerization in 3 hours, thereby obtain plastic lens.Each rerum natura of the plastic lens that obtains is shown in the table 1.Found out that by table 1 index of refraction in lens of comparative example 1 (nD) is 1.60, and is higher, Abbe number is 41, and is also higher, do not have paintedly, and the transparency is also excellent, does not have optical strain.In addition, the energy of rupture value also is shown as 35kgcm/cm
2, shock-resistance is low.
(comparative example 2～3)
Except that using the monomer composition shown in the table 1, carry out the operation same with comparative example 1, obtain plastic lens.Each rerum natura of these plastic lenss is shown in the table 1.Found out that by table 1 index of refraction in lens of comparative example 2 (nD) is 1.62, and is higher, do not have paintedly that the transparency is also excellent, does not also observe optical strain, Abbe number is 38, and some is low a little.In addition, in the evaluation of shock-resistance, shock-resistance is lower, and the energy of rupture value can't be calculated.In addition, the index of refraction in lens of comparative example 1 (nD) is 1.64, and is higher, and Abbe number is 40, and is also higher, do not have paintedly, and the transparency is also excellent, does not have optical strain.In addition, the energy of rupture value also is shown as 45 (kgcm/cm
2), shock-resistance is low.
Represent that with ellipsis the compound title is as described below in the table 1
DMMD:2,5-two (mercapto methyl)-1,4-dithiane
MMDDi:2, the disulphide dipolymer of 5-two (mercapto methyl)-1,4-dithiane
CX: three (6-hexyl isocyanate base) chlorinated isocyanurates
CY: three (4-hexyl isocyanate base) chlorinated isocyanurates
HXDI:1,3-two (isocyanatomethyl) hexanaphthenes
BIMD:2,5-two (isocyanatomethyl)-1,4-dithiane
DBTDL: di-n-butyl tin dilaurate, DBTDC: di-n-butyl tin dichloride
MMMO:4-mercapto methyl-1,8-dimercapto-3,6-two thiophene octanes
NDI: norbornylene vulcabond, LTI: Lysine triisocyanate
[second mode]
(embodiment 7)
With the 0.04mol number-average molecular weight is 1000 polypropylene glycol (composition C: be expressed as P1000 in table 2), 0.11mol three (6-hexyl isocyanate base) chlorinated isocyanurates (composition (B1): be expressed as CX in table 2), 0.65mol1,3-two (isocyanatomethyl) hexanaphthenes (composition (B2): be expressed as HXDI in table 2) and 0.4 * 10
-4The mixture of mol dibutyltin dilaurate (being expressed as DBTDL in table 1) reacted 40 ℃ of even down stirrings in 2 hours simultaneously.Then, add 0.75mol2,5-two (mercapto methyl)-1,4-dithiane (composition (A): in table 2, be expressed as DMMD) and 7.5 * 10
-4MolDBTDL evenly after the stirring, injects the forming lens glass mold, and heating is 10 hours under 50 ℃, heats 5 hours down at 60 ℃ afterwards, heats down at 120 ℃ and carries out polymerization in 3 hours, thereby obtain plastic lens.Each rerum natura of the plastic lens that obtains is shown in the table 2.Found out that by table 2 index of refraction in lens of embodiment 7 (nD) is 1.61, and is higher, Abbe number is 41, and is also higher, do not have paintedly, and the transparency is also excellent, does not have optical strain.In addition, the energy of rupture value also is shown as 155kgcm/cm
2, the shock-resistance height.
(embodiment 8～12)
Except that using the monomer composition shown in the table 2, carry out operation similarly to Example 7, obtain plastic lens.Each rerum natura of these plastic lenss is shown in the table 2.Found out that by table 2 index of refraction in lens of embodiment 8～12 (nD) is 1.60～1.64, and is higher, Abbe number is 39～42, and is also higher, do not have paintedly, and the transparency is also excellent, does not have optical strain.In addition, the energy of rupture value also is shown as 135～160kgcm/cm
2, the shock-resistance height.
(embodiment 13)
Uniform mixing 0.60mol2,5-two (isocyanatomethyl)-1,4-dithiane (composition (A): be expressed as DMMD in table 2), 0.02mol number-average molecular weight are 700 polypropylene glycol (composition C: be expressed as P700 in table 2), 0.18mol three (6-hexyl isocyanate base) chlorinated isocyanurates (composition (B1): be expressed as CX in table 2), 0.38mol1,3-two (isocyanatomethyl) hexanaphthenes (composition (B2): be expressed as HXDI in table 2) and 6.2 * 10
-4The mixture of mol dibutyltin dilaurate (in table 1, being expressed as DBTDL), inject the forming lens glass mold, heated 10 hours down, heated 5 hours down at 60 ℃ afterwards at 50 ℃, heat down at 120 ℃ again and carried out polymerization in 3 hours, thereby obtain plastic lens.Each rerum natura of the plastic lens that obtains is shown in the table 2.Found out that by table 2 index of refraction in lens of embodiment 7 (nD) is 1.60, and is higher, Abbe number is 40, and is also higher, do not have paintedly, and the transparency is also excellent, does not have optical strain.In addition, the energy of rupture value also is shown as 131kgcm/cm
2, the shock-resistance height.
Result by embodiment 7～13 obviously finds out, according to the present invention, can obtain specific refractory power and be 1.60 or more than, Abbe number is more than 39, it is excellent to have the transparency, does not also have these excellent specific properties of optical strain, shows to remove 130kgcm/cm
2More than, the lens that shock-resistance is also excellent.
(comparative example 4)
With 0.20mol 4-mercapto methyl-1,8-dimercapto-3,6-two thiophene octanes (in table 2, being expressed as MMMO), 0.30mol norbornylene vulcabond (in table 2, being expressed as NDI) and 3.0 * 10
-4The mixture of mol dibutyltin dilaurate (in table 2, being expressed as DBTDL), inject the forming lens glass mold, heated 10 hours down, heated 5 hours down at 60 ℃ afterwards at 50 ℃, heat down at 120 ℃ again and carried out polymerization in 3 hours, thereby obtain plastic lens.Each rerum natura of the plastic lens that obtains is shown in the table 2.Found out that by table 2 index of refraction in lens of comparative example 4 (nD) is 1.60, and is higher, Abbe number is 41, and is also higher, do not have paintedly, and the transparency is also excellent, does not have optical strain.In addition, the energy of rupture value also is shown as 35kgcm/cm
2, shock-resistance is low.
(comparative example 5 and 6, reference example 1)
Except that using the monomer composition shown in the table 2, carry out the operation same with comparative example 4, obtain plastic lens.Each rerum natura of these plastic lenss and embodiment 7～13, each rerum natura of the lens of comparative example 4 is together shown in the table 2.The plastic lens of comparative example 5 is that the monomer component that is used to make transparent molded article 2 of the present invention is removed the lens that composition (C) and composition (B1) post polymerization obtain.Found out that by table 2 index of refraction in lens of comparative example 5 (nD) is 1.62, and is higher, do not have paintedly that the transparency is also excellent, does not also observe optical strain, Abbe number is 38, and some is low a little.In addition, in the evaluation of shock-resistance, shock-resistance is lower, and the energy of rupture value can't be calculated.
The plastic lens of comparative example 6 is found out by table 2, and its specific refractory power (nD) is 1.63, and is higher, and Abbe number is 41, and is also higher, does not have paintedly, and the transparency is also excellent, does not have optical strain.In addition, the energy of rupture value also is shown as 45kgcm/cm
2, shock-resistance is low.
The plastic lens of reference example 1 is that the monomer component that is used to make transparent molded article 2 of the present invention is removed the lens that composition (C) post polymerization obtains.Found out that by table 2 index of refraction in lens of reference example 1 (nD) is 1.61, and is higher, Abbe number is 41, and is also higher, do not have paintedly, and the transparency is also excellent, does not have optical strain.In addition, the energy of rupture value also is shown as 120kgcm/cm
2, than the lens shock-resistance height of the comparative example 5 that does not contain composition (B1), but poorer than the transparent molded article of the present invention 2 that contains composition (C).
Table 2
| Embodiment | Composition A (mol) | Composition B1 (mol) | Composition B2 (mol) | Composition C (mol) | Catalyzer (mol) | Relatively and the total amount of composition (A) and composition (B), the ratio (weight %) of composition (C) |
| 7 | DMMD(0.75) | GX(0.11) | HXDI(0.65) | P1000(0.04) | DBTDL (7.9×10 -4) | 20.0 |
| 8 | DMMD(0.62) | GX(0.18) | BIMD(0.43) | P1000(0.06) | DBTDL (6.8×10 -4) | 31.3 |
| 9 | DMMD(0.36) | GY(0.06) | BIMD(0.38) | P1000(0.08) | DMTDG (4.4×10 -4) | 51.2 |
| 10 | DMMD(0.56) MMDDi(0.08) | GX(0.24) | BIMD(0.36) | P700(0.05) | DMTDG (6.9×10 -4) | 18.7 |
| 11 | DMMD(0.42) | GX(0.06) | HXDI(0.36) | P1200(0.02) | DMTDG (4.4×10 -4) | 21.2 |
| 12 | DMMD(0.44) | GX(0.06) | BIMD(0.44) | PBG(0.06) | DMTDG (5.0×10 -4) | 39.1 |
| 13 | DMMD(0.60) | GX(0.18) | HXDI(0.38) | P700(0.02) | DBTDG (6.2×10 -4) | 9.9 |
| Comparative example | Composition A (mol) | Composition B1 (mol) | Composition B2 (mol) | Composition C (mol) | Catalyzer (mol) | Relatively and the total amount of composition (A) and composition (B), the ratio (weight %) of composition (C) |
| 4 | MMMO(020) | - | NDI(0.30) | - | DBTDL (3.0×10 -4) | - |
| 5 | DMMD(0.29) | - | HXDI(0.30) | - | DBTDL (2.9×10 -4) | 0.0 |
| 6 | DMMD(0.29) | LTI(008) | HXDI(0.18) | - | DBTDL (2.9×10 -4) | - |
| Reference example | Composition A (mol) | Composition B1 (mol) | Composition B2 (mol) | Composition B (mol) | Catalyzer (mol) | Relatively and the total amount of composition (A) and composition (B), the ratio (weight %) of composition (C) |
| 1 | DMMD(0.29) | GX(0.08) | HXDI(0.18) | - | DBTDL (2.9×10 -4) | 0.0 |
Table 2 is continuous
| Embodiment | nD/vD | Painted | The transparency | Optical strain | Shock-resistance (energy of rupture value) |
| 7 | 1.61/41 | A | A | A | 155kg·cm/cm 2 |
| 8 | 1.62/40 | A | A | A | 145kg·cm/cm 2 |
| 9 | 1.60/42 | A | A | A | 140kg·cm/cm 2 |
| 10 | 1.64/41 | A | A | A | 2 135kg·cm/cm 2 |
| 11 | 1.61/40 | A | A | A | 160kg·cm/cm 2 |
| 12 | 1.62/39 | A | A | A | 142kg·cm/cm 2 |
| 13 | 1.60/40 | A | A | A | 131kg·cm/cm 2 |
| Comparative example | nD/vD | Outward appearance | The transparency | Optical strain | Shock-resistance (energy of rupture value) |
| 4 | 1.60/41 | A | A | A | 35kg·cm/cm 2 |
| 5 | 1.62/38 | A | A | A | A little less than can't estimating |
| 6 | 1.63/40 | A | A | A | 45kg·cm/cm 2 |
| Reference example | nD/vD | Outward appearance | The transparency | Optical strain | Shock-resistance (energy of rupture value) |
| 1 | 1.61/40 | A | A | A | 120kg·cm/cm 2 |
In addition, the compound title represented of the ellipsis in the table 2 is as described below.
DMMD:2,5-two (mercapto methyl)-1,4-dithiane, MMDDi:2,5-two (mercapto methyl)-1, the disulphide dipolymer of 4-dithiane, P1000: number-average molecular weight is 1000 polypropylene glycol, P700: number-average molecular weight is 700 polypropylene glycol, PBG: by number-average molecular weight be 1000 1, the polyester glycol that 4-butyleneglycol and pentanedioic acid generate, CX: three (6-hexyl isocyanate base) chlorinated isocyanurates, CY: three (4-hexyl isocyanate base) chlorinated isocyanurates, HXDI:1,3-two (isocyanatomethyl) hexanaphthenes, BIMD:2,5-two (isocyanatomethyl)-1,4-dithiane, DBTDL: di-n-butyl tin dilaurate, DBTDC: di-n-butyl tin dichloride, MMO:4-mercapto methyl-1,8-dimercapto-3,6-two thiophene octanes, PETMP: tetramethylolmethane four (3-mercaptopropionic acid ester), NDI: norbornylene vulcabond, LTI: Lysine triisocyanate
Utilize possibility on the industry
Transparent molded article 1 of the present invention has refractive index, Abbe number, against weather, solvent resistance, transparency excellence, does not find the features such as optical strain, particularly has the feature of resistance to impact excellence. Therefore, transparent molded article 1 of the present invention goes for take eyeglass, camera lens as main optical lens etc.
According to the second mode of the present invention, can provide to have refractive index and the transparency identical or above with the formed body that is used at present the optical material such as lens, and have the transparent molded article that is applicable to optical applications of the impact strength higher than the formed body that is used at present the optical material such as lens. In addition, transparent molded article 2 of the present invention has the Abbe number height, and against weather, solvent resistance are also excellent, does not find the advantageous feature of optical strain. Transparent molded article 2 of the present invention goes for take eyeglass, camera lens as main various lens, prism, optical fiber, recording medium substrate, in the filter etc.
Claims (7)
1, a kind of transparent molded article, it is made of the polythiourethane that the monomer component that contains following compositions (A) and composition (B1) by polymerization obtains,
Composition (A): the poly-thiol compound more than a kind or 2 kinds of general formula (I) expression, in the general formula (1), m is 1,2,3,4,5 or 6
General formula (I)
Composition (B1): the polyisocyanate compounds more than a kind or 2 kinds of general formula (II) expression, in the general formula (II), n
1, n
2, n
3Be 3,4,5,6,7 or 8 independently of one another
General formula (II).
2, transparent molded article according to claim 1, wherein, the m in the general formula (I) of composition (A) is 1 or 2.
3, transparent molded article according to claim 1 and 2, wherein, n in the general formula (II) of composition (B1)
1, n
2, n
3Be 4,5 or 6 independently of one another.
4, transparent molded article according to claim 1 and 2, wherein, transparent molded article is lens.
5, transparent molded article according to claim 3, wherein, transparent molded article is lens.
6, transparent molded article according to claim 4, wherein, lens are glasses lens.
7, transparent molded article according to claim 5, wherein, lens are glasses lens.
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|---|---|---|---|
| JP2003163144 | 2003-06-09 | ||
| JP163144/2003 | 2003-06-09 | ||
| JP279777/2003 | 2003-07-25 |
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