KR100859759B1 - Polythiourethane - Google Patents

Abstract

The polythiourethane of the present invention comprises at least one polythiocarbonate polythiol [preferably-(CO-SRS)-structure (where R represents a divalent hydrocarbon group) and a number average molecular weight of 200 to 2500. Having a high refractive index, low dispersibility, plastic lenses, prisms, optical fibers, information It is useful for recording substrates, coloring filters, infrared absorption filters, and the like.

Description

Polythiourethane {POLYTHIOURETHANE}

The present invention relates to polythiourethanes useful as optical plastic materials. More specifically, the present invention relates to a polythiourethane comprising a polythiocarbonate polythiol as a polythiol component. The polythiourethane of the present invention has excellent optical properties such as high refractive index and low dispersion, and is useful as a raw material for plastic lenses, prisms, optical fibers, information recording substrates, color filters, infrared absorption filters, and the like.

 In general, plastic materials are light, rich in toughness, and easy to dye. Therefore, plastic materials have recently been used for various optical applications such as lenses. However, when the plastic material is used for a spectacle lens or the like, when the refractive index is low, it is accompanied by an increase in the desired number of refractions, and the thickness of the lens corresponding thereto is significantly increased, so that the mass is also large. There is a problem that it becomes difficult to utilize the characteristics of the plastic material. In addition, since plastic materials generally have a lower Abbe number as the refractive index is higher, and chromatic aberration tends to be large, a problem arises in that the color appears on the subject by the large chromatic aberration. For these reasons, the development of high refractive index and high Abbe's number of materials for optical plastic materials is required.

As such an optical plastic material, JP-A 4-58489 (Patent Document 1) discloses a polythiourethane obtained by reacting polythiol and polyisocyanate, and JP-A-5-148340 ( In patent document 2), using the thing with high content of a sulfur atom as a polythiol component of a polythiourethane is disclosed. In addition, Japanese Unexamined Patent Application Publication No. 2001-11182 (Patent Document 3) discloses a polythiourethane obtained by ring-opening polymerization of a cyclic thiocarbamate compound. Since the polythiourethane of the said prior art generally has a high refractive index of 1.6 or more, and has a high Abbe number of about 30, it is increasingly used for thin lightweight eyeglass lenses.

However, polythiourethane has a problem that cannot be ignored in view of the fact that the higher the refractive index is, the lower the strength (dynamic performance) against loads such as tension, bending and impact. For example, spectacle lenses require high refractive index and high Abbe number as described above for optical performance, and excellent tensile properties and high elasticity (high elongation, high shape recoverability) are required for mechanical performance. There has been a demand for the development of plastic materials.

On the other hand, a thiocarbonate-based plastic material is proposed as a high refractive index and high Abbe's optical plastic material. For example, Japanese Patent Laid-Open No. 6-116337 (Patent Document 4) discloses a polymer of a thiocarbonate compound having a vinylphenyl group at its terminal and a polythiol compound, and Japanese Patent Laid-Open No. 11-228697 The publication (patent document 5) discloses the thiocarbonate type | system | group sulfur containing polymer obtained by ring-opening-polymerizing a cyclic thiocarbonate compound. However, the former does not exceed the refractive index of the polythiourethane so that the manufacturing method itself of the raw material thiocarbonate is complicated, and the refractive index of the polymer obtained is slightly over 1.6, and the latter is the specific of the sulfur-containing polymer obtained. Since the physical properties are not clear and the raw material is limited to a specific cyclic compound (that is, a specific cyclic compound having a small number of carbon atoms), there is a problem that the kind of the sulfur-containing polymer obtained is limited.

 In addition, JP-A-11-292969 (Patent Document 6) discloses a thiocarbonate polymer obtained by reacting carbon disulfide with an epoxide compound (propylene oxide, etc.) and ring-opening-polymerizing the resulting heterocyclic compound, A thiocarbonate polymer obtained by ring-opening polymerization of a heterocyclic compound obtained by reacting a carbonate ester with a compound having a hydroxyl group and a thiol group in a molecule, and a thiocarbon obtained by reacting the heterocyclic compound with a polyactive hydrogen compound. Nate polymers and the like are disclosed as thiocarbonate-based plastic materials having high refractive index and excellent mechanical strength. However, since these polymers all use a heterocyclic compound as a raw material, there is a problem in that the kind of raw material is limited, and therefore, there is a limitation in the kind of the obtained polymer. In addition, in patent document 6, manufacture example and product physical property are specifically disclosed only the ring-opened polymer of the first heterocyclic compound, and the physical property of another polymer is not clear.

Furthermore, POLYMER, 35, 7, 1564 (1994) (Non Patent Literature 1) and POLYMER COMMUNICATIONS, 1990, 31, 431 (Non Patent Literature 2), polythiocarbonates obtained by reacting phosgene with alkanedithiol have a high refractive index. It is disclosed as a plastic material having a. However, this polythiocarbonate is produced using a highly toxic phosgene as a raw material, and also has a high molecular weight and a chlorine atom at the terminal. It was not suitable for the raw material to be obtained.

 <Patent Document 1>

Japanese Patent Publication No. Hei 4-58489

<Patent Document 2>

Japanese Patent Laid-Open No. 5-148340

<Patent Document 3>

Japanese Patent Publication No. 2001-11182

<Patent Document 4>

Japanese Patent Laid-Open No. 6-116337

<Patent Document 5>

Japanese Patent Laid-Open No. 11-228697

<Patent Document 6>

Japanese Patent Laid-Open No. 11-292969

<Non Patent Literature 1>

POLYMER, 35, 7, 1564 (1994)

<Non Patent Literature 2>

POLYMER COMMUNICATIONS, 1990, 31, 431

The object of the present invention is to provide excellent tensile properties and high elasticity (high elongation, high shape recovery), in addition to the performance of optical plastic materials that can be used for spectacle lenses and the like, in particular, excellent optical performance (high refractive index, high Abbe's number). It is to provide a polythiourethane having excellent mechanical performance. Moreover, the polythiocarbonate polythiol used as a raw material for manufacture of the polythiourethane of this invention is also a novel compound.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors transesterified this carbonate compound and a polythiol compound by using diaryl carbonate as a carbonate compound, for example, and the said polythiol By finding that the polythiocarbonate polythiol corresponding to a compound can be obtained easily, and using this polythiocarbonate polythiol, the polythiourethane which has desired performance can be obtained, and this invention is found. Came to complete.

The polythiourethane of the present invention is produced by the reaction of a polythiol component comprising at least one polythiocarbonate polythiol and a polyisocyanate component comprising at least one selected from polyisocyanates and polyisothiocyanates. It is.

In the polythiourethane of the present invention, it is preferable that the polythiocarbonate polythiol for the polythiol component contains a repeating unit represented by the following general formula (I) and has a number average molecular weight of 200 to 2500:

In the above formula, R represents a divalent hydrocarbon group, provided that the hydrocarbon group R may have one or more substituents not involved in the reaction with the polyisocyanate component, and in the carbon chain of the hydrocarbon group, It may contain one or more selected from hetero atoms and -OCO- groups.

In the polythiourethane of the present invention, it is preferable that the polythiol component includes two or more polythiocarbonate polythiols having a repeating unit represented by the formula (I) and having a number average molecular weight of 200 to 2500. .

In the polythiourethane of the present invention, the terminal aryloxy group content of the polythiocarbonate polythiol is preferably 0 to 5 mol% based on the total terminal groups.

It is preferable that the polythiourethane of the present invention has a repeating unit represented by the following general formula (II):

In the above formula, R is the same as above, Y represents a divalent hydrocarbon group, provided that the divalent hydrocarbon group Y may have one or more substituents not involved in the reaction with the polythiol component, and One or more hetero atoms may be contained in the carbon chain of the said hydrocarbon group, X represents an oxygen atom or a sulfur atom, and n represents an integer of 1 or more.

In the polythiourethane of the present invention, the polythiocarbonate polythiol is preferably liquid at room temperature.

In the polythiourethane of the present invention, the color of the polythiocarbonate polythiol measured according to JIS K 1557 is APHA No. It is preferable that it is 60 or less.

In the polythiourethane of the present invention, the molar amount of the thioether structure produced by the deCOS reaction of the thiocarbonate structure portion in the polythiocarbonate polythiol is an unreacted thiocarbonate structure. And 3% or less of the total molar amount of the thioether structure generated above.

In the polythiourethane of the present invention, the polythiocarbonate polythiol is a polythiol compound having a diphenyl carbonate and a divalent hydrocarbon group containing 4 to 14 carbon atoms. Preferred are those prepared by transesterification in the presence.

In the polythiourethane of the present invention, the transesterification catalyst preferably contains a basic compound.

According to the present invention, in addition to excellent optical performance (high refractive index, high Abbe's number), it has excellent mechanical properties such as excellent tensile properties and high elasticity (high elongation, high shape recovery), and is useful as an optical plastic material. Thiourethane can be provided. For example, the polythiourethane of the present invention is useful for optical materials such as thin high strength plastic lenses, prisms, optical fibers, information recording substrates, color filters, infrared absorption filters, and the like. Moreover, since the polythiourethane of the present invention not only has excellent optical performance but also excellent mechanical performance, it can contribute to the high strength of various optical materials.

Moreover, the polythiocarbonate polythiol used in the present invention is a novel compound, and the polythiourethane of the present invention obtained by using this has a high level of performance which was not obtained in the prior art in terms of optical performance and mechanical performance. To have.

The polythiourethane of the present invention is obtained by reacting a polythiol component containing at least one polythiocarbonate polythiol with a polyisocyanate component containing polyisocyanate and / or polyisothiocyanate. Moreover, it is preferable that the polythiocarbonate polythiol contained in the said polythiol component is obtained by transesterifying a carbonate compound and a polythiol compound.

 The carbonate compound used as a raw material for producing polythiocarbonate polythiol is dialkyl such as dimethyl carbonate, diethyl carbonate, di-n-butyl carbonate and diisobutyl carbonate. Carbonates; Diaryl carbonates such as diphenyl carbonate; Alkylene carbonates such as ethylene carbonate and propylene carbonate; And alkylaryl carbonates such as methylphenyl carbonate and the like. In these carbonate compounds, it is preferable to use diaryl carbonate, and it is more preferable to use diphenyl carbonate especially.

 The polythiol compound used as a raw material for producing polythiocarbonate polythiol includes a polythiol compound corresponding to a polyol compound used in the production of known polycarbonate polyols and the like. Specifically, the compound in which the terminal group of the polyvalent (divalent or more) hydrocarbon group is comprised by the mercapto group is mentioned. The hydrocarbon group is an aliphatic (including alicyclic) hydrocarbon group (preferably having 2 to 14 carbon atoms), aromatic (may contain an aliphatic hydrocarbon substituent or an aliphatic hydrocarbon structure) hydrocarbon group (preferably a carbon atom) The number: 6-14) may be sufficient, and the said polyhydric hydrocarbon group may have a substituent (alkyl group, nitro group, etc.) which is not involved in the production | generation reaction of the said polythiocarbonate polythiol, and the said The carbon main chain of the polyvalent hydrocarbon group may contain at least one hetero atom (such as an oxygen atom, a sulfur atom or a nitrogen atom) and at least one selected from the group -OCO-. When the said polyvalent hydrocarbon group is a bivalent hydrocarbon group, the R group in the said Formula (I) and (II) is corresponded to this bivalent hydrocarbon group.

The polythiol compound including an aliphatic hydrocarbon group as the hydrocarbon group is, for example, 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6 -Hexanedithiol, 1,7-heptaneddithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol, 1,12-dodecanedithiol, 2,2-dimethyl Alkanedithiols such as -1,3-propanedithiol, 3-methyl-1,5-pentanedithiol and 2-methyl-1,8-octanedithiol; Cycloalkanedithiols such as 1,4-cyclohexanedithiol and 1,4-bis (mercaptomethyl) cyclohexane; Alkanedithiols containing hetero atoms such as 2-mercaptoethyl ether, 2-mercaptoethyl sulfide, 2-mercaptoethyl disulfide, and 2,2 '-(ethylenedithio) diethan thiol; Cycloalkanedithiols containing hetero atoms such as 2,5-bis (mercaptomethyl) -1,4-dioxane and 2,5-bis (mercaptomethyl) -1,4-dithiane; Alkantrithiols such as 1,1,1-tris (mercaptomethyl) ethane and 2-ethyl-2-mercaptomethyl-1,3-propanedithiol; Alcantetrathiols such as tetrakis (mercaptomethyl) methane, 3,3'-thiobis (propane-1,2-dithiol) and 2,2'-thiobis (propane-1,3-dithiol) ; And alcantetrakis (mercaptoalkylate) such as pentaerythritol tetrakis (mercaptopropionate) and pentaerythritol tetrakis (mercaptoacetate).

 In addition, as the polyvalent hydrocarbon group, the polythiol compound containing an aromatic hydrocarbon group is, for example, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 1,2-bis (mer) Arendidithiols (aromatic dithiols) such as captomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) benzene, and toluene-3,4-dithiol; and 1 And an arentityol (aromatic trithiol) such as 3,5-benzenetritriol and 1,3,5-tris (mercaptomethyl) benzene.

The polythiol component for producing polythiocarbonate polythiol may consist of a single kind of polythiol compound, or may be a combination of plural (two or more kinds) polythiol compounds. In the latter case, when the polyvalent hydrocarbon group in the polythiol compound is a divalent hydrocarbon group, the polythiocarbonate polythiol obtained has a plurality of types (2 or more types) of repeating units represented by the formula (I) (copolymerization). Water) and using a combination of the following polythiol compounds, it is possible to obtain a polythiocarbonate polythiol which is liquid at room temperature (10 to 40 ° C) with a low melting point and a crystallization temperature. For example, the following combinations are mentioned in the said polythiol compound. Such liquid polythiocarbonate polythiol is capable of pouring polymerization at room temperature, which is very useful for practical reasons.

(1) a combination of two aliphatic straight chain dithiol compounds having different chain lengths of carbon chains, such as a combination of 1,5-pentanedithiol and 1,6-hexanedithiol and a mercaptoalkylsulfide (eg, 2- Mercaptoethyl sulfide and the like) and 1,6-hexanedithiol, etc.

(2) combinations of aliphatic linear dithiols and aliphatic branched polythiols, such as combinations of 1,6-hexanedithiol and 3-methyl-1,5-pentanedithiol, and the like,

(3) a combination of an aliphatic linear dithiol or aliphatic branched polythiol compound and an alkanedithiol having an aliphatic hydrocarbon ring, such as a combination of 1,6-hexanedithiol, 1,4-bis (mercaptomethyl), cyclohexane, and the like. ,

(4) a combination of an aliphatic linear dithiol or aliphatic branched polythiol compound with an alkanedithiol having a hetero atom and an aliphatic hydrocarbon ring, such as 1,6-hexanedithiol and 2,5-bis (mercaptomethyl) -1, Combinations of 4-dithiane and the like.

In the production of the polythiocarbonate polythiol, an alcohol (particularly an aryl alcohol) in which a carbonate compound (especially a diaryl carbonate) and a polythiol compound are by-produced in the presence of a transesterification catalyst It is preferable to make it by transesterification, taking out) continuously out of the system. At this time, the polythiol compound is preferably 0.8 to 3.0 times molar, more preferably, to the carbonate compound so that all or almost all of the ends of the molecular chain of the polythiocarbonate polythiol obtained are constituted by mercapto groups. Is preferably used in an amount of 0.85 to 2.5 times mole, more preferably 0.9 to 2.5 times mole. Moreover, it is preferable that the usage-amount of a transesterification catalyst is 1-5000 ppm on a molar basis with respect to a polythiol compound, More preferably, it is 10-1000 ppm.

In the transesterification reaction, it is preferable to use diphenyl carbonate as the diaryl carbonate, and in that case, it is preferable to use a polythiol compound having a divalent hydrocarbon group as the polyvalent hydrocarbon group R, Moreover, it is preferable that carbon number of the said bivalent hydrocarbon group R is 4-14. At this time, it is preferable that it is 1.05-3.0 times mole with respect to diphenyl carbonate, and, as for the usage-amount of the polythiol compound which has a bivalent hydrocarbon group R containing 4-14 carbon atoms, it is more preferable that it is 1.1-2.5 times mole. . By doing in this way, a coloring degree is low (that is, APHA No. becomes like this. Preferably it is 60 or less, More preferably, it is 40 or less, More preferably, it is 20 or less), and also all or almost all the terminal of a polythiol compound molecular chain is carried out. Is a mercapto group (i.e., the content ratio of the aryloxy group (especially phenoxy group) forming the terminal group) is preferably 0 to 5%, more preferably 0 to 2%, even more preferably 0 1%) polythiocarbonate polythiol can be obtained easily. Thus, by controlling the content rate of the aryloxy group in an end group to near zero, the polythiourethane which is excellent in optical performance and also excellent in mechanical performance can be obtained. In addition, APHA No. shows the color of the polythiocarbonate polythiol at the time of heat-melting, and the content rate of the aryloxy group of this compound is measured on a molar basis (it is the same below).

The conditions (temperature, pressure, time) of the transesterification reaction are not particularly limited as long as the target product can be produced, but the carbonate compound and the polythiol compound can be produced in the presence of a transesterification catalyst to efficiently produce the target product. It is preferable to provide to a multistage reaction, for example, it reacts for about 1 to 24 hours at the temperature of 110-200 degreeC under normal pressure or reduced pressure, and about 110-240 degreeC (especially 140-240 degreeC) under reduced pressure It is preferable to further react for about 0.1 to 20 hours so that the final pressure may be 2.7 kPa (20 mmHg) or less while gradually increasing the degree of vacuum at the temperature. In the case of using a plurality of polythiol compounds, for example, x species, the carbonate component and the polythiol compound of y (<x) species are subjected to transesterification under the same conditions as described above. Nate polythiol may be produced and the desired polythiocarbonate may be prepared by reacting the polythiol compound of the remaining (xy) species. At this time, when the carbonate compound is diphenyl carbonate, first, transesterification of the diphenyl carbonate and the polythiol compound having a hydrocarbon group R containing 4 to 14 carbon atoms is carried out. The desired compound may be prepared by reacting the resulting polythiocarbonate polythiol with a polythiol compound having a hydrocarbon group R containing 2 to 4 carbon atoms. On the other hand, in order to take out by-product alcohol, it is preferable to provide a distillation apparatus in a reactor, and you may make it react, flowing inert gas (nitrogen, helium, argon, etc.) in a reactor.

The transesterification catalyst is not particularly limited as long as it is a catalytic compound effective for the transesterification reaction. Examples of the catalyst compound include basic compounds such as potassium carbonate, sodium alkoxide (such as sodium methoxide and sodium ethoxide), and quaternary ammonium salts (tetraalkylammonium hydroxides such as tetrabutylammonium hydroxide), 4 Titanium compounds such as titanium chloride and tetraalkoxytitanium (such as tetra-n-butoxytitanium, tetraisopropoxytitanium, etc.), metal tin, tin hydroxide, tin chloride, dibutyl tin dilaurate, dibutyl tin oxide and butyl It can select from tin compounds, such as tin tris (2-ethylhexanoate).

In the said transesterification catalyst, basic compounds, such as potassium carbonate, sodium alkoxide (for example, sodium methoxide, sodium ethoxide, etc.), and a quaternary ammonium salt (for example, tetraalkylammonium hydroxide, such as tetrabutylammonium hydroxide) And tetraalkoxy titanium (eg, tetra-n-butoxytitanium, tetraisopropoxytitanium, etc.) are preferably used. Among these, the basic compound has a high reaction rate, and has a low coloration with an APHA No. of 60 or less of the resulting compound obtained, and further, by de-COS reaction of the thiocarbonate structure (-CO-S-) moiety. The high-quality polythiocarbon of which the content rate of the thioether structure (-RSR-) produced | generated is 3% or less of the total molar amount of an unreacted thiocarbonate structure and the said thioether structure on a molar basis (similarly below). It is particularly preferable because it makes it possible to impart a nate polythiol. In the basic compound, the quaternary ammonium salt (particularly tetraalkylammonium hydroxide such as tetrabutylammonium hydroxide) has an APHA No. of 60 or less, the content ratio of the thioether structure is 1% or less, and It is more preferable because it makes it possible to obtain a polythiocarbonate polythiol containing no metal component. By controlling the content ratio of the thioether structure as low as possible, it becomes possible to maintain the optical and mechanical performance of the polythiourethane obtained at a high level.

As the polythiocarbonate polythiol used in the present invention, the number average molecular weight (M _n) is preferably selected from of 200-2500, the more preferred number average molecular weight of about 400-2000. When this molecular weight is out of the range of 200-2500, the polythiourethane obtained from this polythiocarbonate polythiol is unsatisfactory in the mechanical performance. That is, when the number average molecular weight of the polythiocarbonate polythiol is lower than 200, the elongation at break of the polythiourethane obtained becomes insufficient, and when it is higher than 2500, the shape recoverability of the obtained polythiourethane becomes low. For this reason, each usage-amount of a carbonate compound and a polythiol compound is adjusted suitably so that a desired molecular weight may be obtained. When the number average molecular weight calculated from the mercapto group of the reaction product is outside the range of 200 to 2500, that is, when the molecular weight is less than 200, it is preferable to further advance the transesterification reaction while distilling the polythiol compound further under reduced pressure. It is preferable to adjust the molecular weight to a desired value by adding a polythiol compound and further transesterifying when the molecular weight exceeds 2500. By doing in this way, the molecular weight of the target polythiocarbonate polythiol can be adjusted. In Formula II, n represents an integer of 1 or more indicating the degree of polymerization of the polythiocarbonate polythiol compound and is related to its molecular weight.

It is preferable to deactivate the transesterification catalyst which remain | survives in polythiocarbonate polythiol, if necessary after making molecular weight adjustment as mentioned above. When tetraalkoxy titanium is used, inactivation of a transesterification catalyst can be performed by the well-known method of adding a phosphorus compound (for example, phosphoric acid, butyl phosphate, dibutyl phosphate, etc.), and using a basic compound as a catalyst. In this case, it can be carried out by adding an equimolar amount of an inorganic or organic acid (such as sulfuric acid, paratoluenesulfonic acid, and the like) under heating at 40 to 150 ° C. On the other hand, when an insoluble salt precipitates by this acid addition, it is preferable to remove this by water washing.

 On the other hand, the coloring degree (APHA No.) of polythiocarbonate polythiol can be made lower by washing with water. For example, when tetraalkylammonium hydroxide is used as a catalyst, the APHA No. of the polythiocarbonate polythiol obtained is already 60 or less, but this is 40 or less, more preferably 20 or less (preferably by water washing). 10 or less). Moreover, also when a titanium compound is used as a catalyst, although APHA No. of the obtained polythiocarbonate polythiol normally exceeds 100, this can be reduced by the said water washing in the same way as mentioned above. In addition, water washing can be performed by melt | dissolving a polythiocarbonate polythiol in good solvents, such as methylene chloride, adding an appropriate amount of water to this, and mixing or stirring it uniformly. This operation may be performed as many times as necessary. In addition, even if any of the said basic compound for catalysts and a titanium compound is used, the amount of residual catalyst in a polythiocarbonate polythiol is 10 ppm or less (preferably 2 ppm or less) by weight with water washing | cleaning by water washing. Can be reduced. By controlling the amount of residual catalyst low, the optical and mechanical performance of the polythiourethane obtained can be improved.

As described above, the desired polythiocarbonate polythiol can be easily produced by transesterifying the carbonate compound and the polythiol compound in the presence of a transesterification catalyst. In such a polythiocarbonate polythiol, in particular, when the polythiol compound is a compound in which a mercapto group is bonded to both terminals of a divalent hydrocarbon group (i.e., a dithiol compound), one of the compounds represented by the above formula (I), or It has 2 or more types of repeating units, The number average molecular weight becomes like this. Preferably it is 200-2500, More preferably, it is 400-2000. In addition, the polythiocarbonate polythiol used in the present invention has a low degree of coloring (APHA No. is preferably 60 or less, more preferably 40 or less, and even more preferably 20 or less), and further, the molecular terminal. It is preferable that all or almost all of the mercapto group occupies (the content ratio of the aryloxy group present at the terminal of the molecule is 0 to 5% of the total molar amount of the terminal group, more preferably 0 to 2%, particularly More preferably 0 to 1%). Moreover, the polythiocarbonate polythiol used in the present invention has a low ratio of the thioether structure produced by the de-COS reaction in the thiocarbonate structure portion (the molar basis and the remaining thiocarbonate structure and It is preferable that it is 3% or less of the total amount of the said thioether structure), It is preferable that it is 10 ppm or less, and it is more preferable that it is 2 ppm or less.

The polythiourethane of the present invention reacts a polythiol component including at least one of the polythiocarbonate polythiols with a polyisocyanate component including at least one selected from polyisocyanates and polyisothiocyanates. (I.e., by polythiourethane reaction of polythiocarbonate polythiol). Under the present circumstances, a polyisocyanate component may consist of a single compound, or may consist of a mixture of 2 or more types of compounds.

As polyisocyanate for polyisocyanate component, the polyisocyanate used in manufacture of polyurethane can be used, Specifically, the compound which the isocyanate group couple | bonded with the free terminal of the polyvalent (divalent or more) hydrocarbon group is contained. The polyhydric hydrocarbon group is an aliphatic hydrocarbon group (preferably containing 2 to 14 carbon atoms, alicyclic hydrocarbon group), aromatic hydrocarbon group (preferably having 6 to 14 carbon atoms, aliphatic hydrocarbon substituent or aliphatic hydrocarbon structure) May be included), and may have one or more substituents (for example, an alkyl group, a nitro group, etc.) that do not participate in the reaction with the polythiol component. It may contain a hetero atom (oxygen atom, sulfur atom, nitrogen atom, etc.). When the hydrocarbon group is a divalent hydrocarbon group, "Y" in the formula (II) corresponds to the divalent hydrocarbon group derived from the polyisocyanate component.

As the polyisothiocyanate for the polyisothiocyanate component, a polyisothiocyanate compound corresponding to the polyisocyanate compound can be used.

Polyisocyanate compounds include various polyisocyanates of aliphatic or aromatic. Examples of the aliphatic polyisocyanates include 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, Alkanes polyisocyanates such as 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 1,9-nonamethylene diisocyanate and 1,10-decamethylene diisocyanate; Cycloalkane polyisocyanates such as 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, hydrogenated xylylene diisocyanate, and 1,3,5-tris (isocyanomethyl) cyclohexane ; 2,2'-diethyl ether diisocyanate, 2,2'-diethyl sulfide diisocyanate, hexamethylene diisocyanate-bilet body, 2-isocyanoethylthio-1,3-isocyanopropane, 1 , 1-bis (isocyanomethylthio) -4-isocyanobutane, 3,3-bis (isocyanoethylthio) -1-isocyanobutane and 2,3-bis (isocyanoethylthio Alkanesocyanates containing hetero atoms such as) -1-isocyanomethylthiopropane; Isophorone diisocyanate, 1,4-dithiane-2,5-diisocyanate, 2,3-bis (isocyanomethyl) -1,4-dithiane, 2,5-bis (isocyanomethyl)- 1,4-dithiane, 2,5-bis (isocyanoethyl) -1,4-dithiane, cyclopentane-1,3-disulfide-4,5-diisocyanate, 4,5-bis (iso Cyanomethyl) cyclopentane-1,3-disulfide, 2-methyl-4,5-bis (isocyanomethyl) cyclopentane-1,3-disulfide, 2,2-bis (isocyanopropyl) Cyclopentane-1,3-disulfide, tetrahydrothiophene-2,5-diisocyanate, 2,5-bis (isocyanomethyl) tetrahydrothiophene and 3,4-bis (isocyanomethyl) tetra Cycloalkanes polyisocyanates which have hetero atoms, such as hydrothiophene, etc. can be used.

Moreover, as aromatic polyisocyanate, p-phenylene diisocyanate, 4,4'- diphenyl diisocyanate, 1, 5- naphthalene diisocyanate, tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), 4, 4'-diphenylmethane diisocyanate (MDI), 3,3'-methyleneditolylene-4,4'- diisocyanate, tolylene diisocyanate trimethylolpropane adduct, 4,4'- diphenyl ether diisocyanate, tetra Chlorophenylene diisocyanate, 3,3'-dichloro-4,4'-diphenylmethane diisocyanate, triphenylmethanetriisocyanate, 1,3,5-tris (isocyanomethyl) benzene and triisocyanatephenylthiophosphate Can be mentioned.

The polyisothiocyanate compound used for this invention contains the polyisothiocyanate compound corresponding to each of the said polyisocyanate compounds.

In the production of the polythiourethane of the present invention, one or more chain extenders may be used as the hard segment in the polythiourethanation reaction. As such a chain extender, what is normally used in manufacture of a polyurethane can be used. As such a compound for chain extenders, a low molecular compound having two or more hydrogen atoms reacting with an isocyanate group and / or isothiocyanate group, for example, a polyol compound, a polythiol compound, a polyamine compound, or the like can be used.

The polyol compound used as the chain extender is, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1, 6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, neopentylglycol, 3-methyl-1,5-pentanediol, 3 , 3-dimethylolheptane, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-bis (hydroxyethyl) cyclohexane, 2-hydroxyethyl ether, 2-hydroxyethylsul Feed, 2,5-bis (hydroxymethyl) -1,4-dioxane, 2,5-bis (hydroxymethyl) -1,4-dithiane, trimethylolethane, trimethylolpropane and pentaerythritol Aliphatic polyols; And catechol, resorcinol, hydroquinone, 1,3,5-benzenetriol, 1,2-bis (hydroxymethyl) benzene, 1,3-bis (hydroxymethyl) benzene, 1,4-bis ( Aromatic polyols such as hydroxymethyl) benzene and 1,3,5-tris (hydroxymethyl) benzene.

 The polythiol compound used as the chain extender is, for example, 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentane Dithiol, 1,6-hexanedithiol, 1,7-heptanedthiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol, 1,12-dodecanedithiol , 2,2-dimethyl-1,3-propanedithiol, 3-methyl-1,5-pentanedithiol, 2-methyl-1,8-octanedithiol, 1,4-cyclohexanedithiol, 1, 4-bis (mercaptomethyl) cyclohexane, 2-mercaptoethyl ether, 2-mercaptoethyl sulfide, 2-mercaptoethyl disulfide, 2,5-bis (mercaptomethyl) -1,4-di Oxane, 2,5-bis (mercaptomethyl) -1,4-dithiane, 1,1,1-tris (mercaptomethyl) ethane, 2-ethyl-2-mercaptomethyl-1,3-propanedithi Ol, tetrakis (mercaptomethyl) methane, 3,3'-thiobis (propane-1,2-dithiol), 2,2'-thiobis (propane-1,3-dithiol), pentaerythritol tetra Kiss (mercaptopropionate) and pentaerythritol tetrakis (mercap Acetate), aliphatic thiols and the like; And 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 1,3,5-benzenetrithiol, 1,2-bis (mercaptomethyl) benzene, 1,3 Aromatic polythiols such as bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene and toluene-3,4-dithiol Include.

The polyamine compound used as the chain extender is, for example, an aliphatic poly such as ethylenediamine, 1,2-propylenediamine, 1,6-hexamethylenediamine, isophoronediamine, bis (4-aminocyclohexyl) methane and piperazine. Aromatic polyamines, such as amines and meta (and para) xylylenediamine, are included.

Moreover, as a compound for chain extenders other than the above-mentioned, For example, aliphatic and aromatic amino alcohols, such as 2-ethanolamine, N-methyl diethanolamine, and N-phenyldipropanolamine; Hydroxyalkyl sulfamides such as hydroxyethyl sulfamide and hydroxyethylaminoethyl sulfamide; Mercapto alcohols such as 2-mercaptoethanol, 1,2-dihydroxy-3-mercaptopropane, 2,3-dimercapto-1-propanol, and 4-mercaptophenol; Aminothiols such as aminoethylmercaptan, 2-aminothiophenol, 3-aminothiophenol and 4-aminothiophenol, urea, water and the like can also be used.

In the polythiourethanation reaction, one or more polycarbonate polyols made of a polyol compound and a carbonate compound may be used instead of a part of the polythiol component (50 wt% or less). Such a polycarbonate polyol has one or more repeating units in which the sulfur atom is substituted with an oxygen atom in the formula (I), and has two or more hydroxyl groups at the terminal of the molecule.

As a polyol compound used as a raw material of the polycarbonate polyol, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, neopentylglycol, 3-methyl-1,5-pentanediol , 3,3-dimethylolheptane, 1,4-cyclo hexanediol, 1,4-cyclohexanedimethanol, 1,4-bis (hydroxyethyl) cyclohexane, 2-hydroxyethyl ether, 2-hydroxy Methylsulfide, 2,5-bis (hydroxymethyl) -1,4-dioxane, 2,5-bis (hydroxymethyl) -1,4-dithiane, trimethylolethane, trimethylolpropane and pentaerythritol Aliphatic polyols such as catechol, resorcinol, hydroquinone, 1,3,5-benzenetriol, 1,2-bis (hydroxymethyl) benzene, 1,3-bis (hydroxymethyl) benzene, Rooms such as 1,4-bis (hydroxymethyl) benzene and 1,3,5-tris (hydroxymethyl) benzene Aromatic polyols can be used.

The polythiourethanation reaction may be performed under a solvent-free, or may be performed in presence of a solvent inactive with respect to an isocyanate group and / or isothiocyanate group. In the case of reaction under a solvent, a polyisocyanate component consisting of a polyisocyanate compound and / or a polyisothiocyanate compound is mixed with the polythiol component, a chain extender is further mixed as necessary, and the entire amount is reacted in one step. Alternatively, or after the polythiol component and the polyisocyanate component are reacted to prepare a prepolymer containing an isocyanate group and / or isothiocyanate group, a chain extender is mixed and reacted thereto, or A part of the polyisocyanate component is mixed with the polythiol component, and if necessary, a chain extender is further mixed and reacted to prepare a prepolymer having a mercapto group, and then the remaining polyisocyanate component is mixed and reacted, The polythiourethanation reaction may be completed. In the case of reaction under a solvent, it is preferable that reaction temperature is 60-150 degreeC. On the other hand, when using a multistage reaction via a prepolymer, first, a low molecular weight prepolymer can be obtained, and this can be heated to appropriately increase its molecular weight.

In the case of a reaction in the presence of a solvent, after dissolving the polythiol component in a solvent (mixing a chain extender as necessary), the polyisocyanate component may be mixed therewith and the whole amount may be reacted at once, or the poly The thiol component may be dissolved in a solvent, the polyisocyanate component may be mixed and reacted to prepare a prepolymer having an isocyanate group and / or isothiocyanate group, and then a chain extender may be mixed and reacted thereto. After dissolving the polythiol component in a solvent (mixing a chain extender as necessary), a part of the polyisocyanate component is mixed and reacted thereto to prepare a prepolymer having a mercapto group, and the remaining poly Polythiourethane-ized reaction can be performed by mixing and reacting an isocyanate component. In the presence of a solvent, the reaction temperature is preferably 20 to 100 ° C. In addition, as a solvent, it is preferable to use 1 or more types, such as methyl ethyl ketone, ethyl acetate, toluene, dioxane, dimethylformamide, dimethylacetamide, and dimethyl sulfoxide.

In the polythiourethane-ized reaction, it is preferable that the ratio of the usage-amount of a polythiol component and a chain extender exists in the range of 0-10 mol with respect to 1 mol of former electrons. The usage-amount of these components is suitably set according to the desired physical property of the target polythiourethane. The polyisocyanate component composed of a polyisocyanate compound and / or a polyisothiocyanate compound is such that the total amount of the isocyanate group and the isothiocyanate group is almost equal to the total amount of the active hydrogen of the polythiol component and the chain extender. It is preferable to use. More specifically, the equivalent ratio of the total amount of active hydrogens contained in the polythiol component and the chain extender to the total amount of the isocyanate group and the isothiocyanate group is preferably 1: 0.8 to 1: 1.2, more preferably. Preferably, the amount of polyisocyanate component added is controlled to be 1: 0.95 to 1: 1.05. In addition, in a polythiourethanation reaction, you may use the catalyst of the amine type or tin system used by normal polyurethane reaction in order to promote reaction.

The polythiourethane of the present invention thus obtained may have a molecular terminal formed of a mercapto group or an isocyanate group and / or an isothiocyanate group, and may also be a terminal group of a chain extender (mercapto group, hydroxyl group, amino group). Or the like).

Moreover, the polythiourethane of this invention is a compound (polythiol, polyamine, etc.) which has 2 or more hydrogen atoms reacting with an isocyanate group and / or isothiocyanate group, or a molecule | numerator, such as a mercapto group, a hydroxyl group, an amino group, etc. By further reacting with a compound having two or more functional groups and / or substituents (carboxyl groups, halo groups, etc.) reacting with the end groups, it can be made high molecular weight or meshed. Moreover, in the polythiourethane of the present invention, various additives such as polyether, polythioether, polyester, polythioester, polyamide, polymethacrylate, polyolefin and poly 1 or more types, such as carbonate, may be added and mixed.

<Example>

The invention is further illustrated by the following examples. On the other hand, the physical properties of polythiocarbonate polythiol and polythiourethane were measured by the following method.

[Physical Properties of Polythiocarbonate Polythiol]

(1) Mercaptogium (SH value; mgKOH / g): The sample is placed in a 100 ml sample bottle and weighed (mass is accurately read to four decimal places in grams), and acetic anhydride-tetrahydrofuran is added to the sample. The sample was added by adding 5 ml of solution (containing 4 g of acetic anhydride in 100 ml of solution) and 10 ml of 4-dimethylaminopyridine-tetrahydrofuran solution (containing 1 g of 4-dimethylaminopyridine in 100 ml of solution). After completely dissolved, the sample solution was left to stand at room temperature for 1 hour, 1 ml of ultrapure water was added to this sample solution, and the mixed solution was left to stand at room temperature for 30 minutes with occasional stirring. SH was used for the measurement and this mixed solution was titrated with 0.25 M potassium hydroxide-ethanol solution (indicator: phenolphthalein). The SH value was calculated by the following formula:

SH is (mgK0H / g) = 14.025 × (B-A) × f / S

[Wherein S is the sampling amount (g), A is the amount of 0.25 M potassium hydroxide-ethanol solution in the titration of the sample (ml), B is the amount of 0.25 M potassium hydroxide-ethanol solution in the blank test ( ml), f represents the factor of the 0.25 M potassium hydroxide-ethanol solution]

(2) Number average molecular weight (Mn): From said SH value, it calculated by the following formula.

M _n = 112200 / SH

(3) Acid value (mgKOH / g): The sample was dissolved in 200 ml of a toluene-ethanol solution (equivalent mixed solution), and this solution was used for measurement of acid value, and titrated using 0.1 M potassium hydroxide-ethanol solution ( Indicator: phenolphthalein). The acid value was calculated by the following formula:

Acid value (mgKOH / g) = 5.61 (C-D) f '/ S'

[Wherein S 'is the sampling amount (g), C is the amount of 0.1 M potassium hydroxide-ethanol solution in the titration of the sample (ml), and D is the amount of 0.1 M potassium hydroxide-ethanol solution in the blank test (ml), f 'represents the factor of 0.1 M potassium hydroxide-ethanol solution]

(4) Melting | fusing point (degreeC) and crystallization temperature (degreeC): Temperature rising rate in the temperature range of -100-100 degreeC in nitrogen gas atmosphere using a differential scanning calorimeter (The Shimadzu Seisakusho make; DSC-50). : 10 degrees C / min and temperature-fall rate: It measured on the conditions of 10 degrees C / min.

(5) Viscosity (mPasec): It measured at 100 degreeC using the E-type rotational viscometer (The Brookfield make; programmable digital viscometer DV-II +).

(6) Color (APHA No): Measured according to JIS-K1557. The test sample was melted and placed in an internal diameter of 23 mm and a volume of about 100 ml of nasal canal, which was then treated with APHA standard solution No. 10 to No. The color of the sample was compared with 500 and the color of the sample was represented by APHA standard solution No. having the color closest to it.

It calculated for ¹ mole of the content of the terminal aryloxy group of the integral value from, the entire terminal groups of the H-NMR: (7) the terminal aryloxy (content ratio (mol%) of -OAr- group.

(8) Content ratio (%) of thioether (-RSR-) structure produced by a de-COS reaction: From the integral of ¹ H-NMR, the unreacted thiocarbonate structure and the de-COS reaction produced | generated. The sum total content (mol) of a thioether structure was calculated | required, and the content rate of the said thioether structure with respect to this total amount was calculated | required.

(9) Residual catalyst amount (ppm): From the disclosed polythiocarbonate polythiol, a 30% chloroform solution is prepared, and tetrabutylammonium hydroxide in the solution is extracted using the same capacity of water, It was used for high performance liquid chromatography, and the residual amount (mass ppm) of the catalyst was measured.

[Material of Polythiourethane]

(1) Tensile characteristics: In accordance with JIS-K7311, a specimen was prepared, and it was made to write to a tensile force tester (Orientech; Tensilon UCT-5T), and the initial elastic modulus and tension | strength in 23 degreeC and 50% RH. Stress (stress at 100%, 200%, 300%), tensile strength, and elongation at break were measured.

(2) Permanent elongation: A specimen was prepared in accordance with JIS-K7312, and marked with a mark of interval length L _{0 on} it, which was then used in a tensile force tester (Orientech; Tensilon UCT-5T), 23 ° C. At 50% RH, the specimens were stretched to 100% elongation and held for 10 minutes. Subsequently, after the contraction of the elongated specimen is rapidly contracted (return rate 500 mm / min), the specimen is removed from the chuck, left at room temperature for 24 hours in the air, and the length L (the elongation between the marks). The previous length measured L ₀ ), and the permanent elongation of the specimen was calculated from the following equation. In this measurement, L ₀ was 40 mm.

Permanent Elongation (%) = [(LL ₀ ) / L ₀ ] × 100

(3) Refractive index: The e-ray ((lambda = 546 nm) was irradiated to the sample using the refractive index meter (Avego refractometer; MR-04), and the refractive index was measured.

(4) Abbe number (ν _e ): The e-line (λ = 546 nm), the F 'line (λ = 480 nm), and the C' line (λ = 644 nm) were irradiated to the sample using the refractive index meter. Refractive index (n _e , n _{F '} , n _C' ) at each time was measured, and Abbe's number (ν _e ) was calculated by the following equation:

υ _e = (n _e -1) / (n _{F '} -n _C' )

<Example 1>

[Production of Polythiocarbonate Polythiol (A)]

166 g (1.10 moles) of 1,6-hexanedithiol in a 500 ml glass reactor equipped with a stirrer, thermometer, and distillation column (equipped with a sorting tube, reflux head and condenser at the top of the tower) 156 g (0.728 mol) of carbonate and 0.860 g (0.331 mmol) of 10 mass% tetrabutylammonium hydroxide-methanol solution (catalyst) were added thereto, and the mixture was refluxed under conditions of 27 kPa (200 mmHg) and 160 ° C. I kept it for 2 hours. Subsequently, while phenol was distilled off, the pressure was gradually reduced to 6.7 kPa (50 mmHg) over 8 hours, and then the pressure was gradually increased over 4.0 hours from 4.0 kPa (30 mmHg) to 2.0 kPa (151 mmHg) where phenol did not spill. Under reduced pressure, the mixture of 1,6-hexanedithiol and phenol was further reacted while flowing out to obtain the target polythiocarbonate polythiol compound.

The measurement result of <^1> H-NMR (it is the same in heavy chloroform below) of the obtained polythiocarbonate polythiol is shown next.

¹ H-NMR: 1.33 ppm (t, J = 7.3 Hz, SH), 1.39 ppm (m, CH ₂ ), 1.62 ppm (m, CH ₂ ), 2.52 ppm (q, J = 7.3 Hz, CH ₂ SH) , 2.53 ppm (q, J = 7.3 Hz, CH ₂ SH), 2.97 ppm (t, J = 7.3 Hz, CH ₂ SCO), 2.98 ppm (t, J = 7.3 Hz, CH ₂ SCO)

To this polythiocarbonate polythiol, equimolar p-toluenesulfonic acid-hydrate was added to the catalyst and stirred at 13 kPa (100 mmHg) at 130 ° C for 2 hours to deactivate the catalyst. Subsequently, 430 g of methylene chloride are added, the polythiocarbonate polythiol compound is dissolved therein, and the obtained solution is washed three times with the same amount of water, dried over anhydrous magnesium sulfate, and the solid contained therein is filtered. Methylene chloride was distilled away. The physical properties of the finally obtained polythiocarbonate polythiol (A) are shown in Table 2. On the other hand, the SH value (200.3 mgKOH / g) was consistent with the measurement result by ¹ H-NMR.

[Production of Polythiourethane]

A stirrer, a thermometer, and a cooling tube were mounted, and 39.70 g (70.88 mmol) of the polythiocarbonate polythiol (A) in 70 ml of dimethylacetamide was used in a 300 ml glass reactor. The solution was completely dissolved in the solution, and 12.38 g (71.08 mmol) of 2,4-tolylene diisocyanate was added to the solution at the above temperature and reacted for 3 hours. 0.390 g (2.24 mmol) of 2, 4- tolylene diisocyanate was further added to the obtained reaction solution, and it was made to react at 80 degreeC, and reaction was stopped at the time point (after 4 hours) when viscosity rise was hardly seen in a reaction solution. . The final viscosity of the solution was 20.7 Pa · sec at 50 ° C.

After heating the obtained solution (polythiourethane solution) to 60 degreeC, it cast on the glass plate with mold release property, and heat-processes at 60 degreeC for 2 hours, and then 110 degreeC for 3 hours, and the film of about 200 micrometers in thickness ( I) The physical properties of this film (I) are shown in Table 4.

Comparative Example 1

[Production of Polythiourethane]

In the same reactor as in Example 1, 20.42 g (l 35.9 mmol) of 1,6-hexanedithiol were completely dissolved in 180 g of dimethylacetamide at 35 ° C. and 2,4- at this temperature in this solution. 23.66 g (135.9 mmol) of tolylene diisocyanate was added, and the obtained reaction liquid was made to react for 3 hours, keeping temperature at 70 degreeC. Subsequently, 0.690 g (3.96 mmol) of 2,4-tolylene diisocyanate was further added to this solution, and it reacted at 80 degreeC. The reaction was stopped at the time point (after 8 hours) when the viscosity was almost not seen in the reaction liquid. The final viscosity of the solution was 20.3 Pa · sec at 50 ° C.

The obtained solution (polythiourethane solution) was processed in the same manner as in Example 1 to produce a film (II) having a thickness of about 200 μm. The physical properties of this film are shown in Table 4.

Comparative Example 2

[Production of Polyurethane]

In the same reactor as in Example 1, 39.90 g (79.98 mmol) of polycarbonatediol (UH-CARB50; manufactured by Ubego Usan, 224.9 mgKOH / g) was completely dissolved in 162 g of dimethylacetamide at 70 ° C. In this solution, 13.93 g (79.98 mmol) of 2,4-tolylene diisocyanate was added at this temperature to react for 5 hours. 0.400 g (2.30 mmol) of 2, 4- tolylene diisocyanate were further added to the obtained solution, and it was made to react at 80 degreeC. The reaction was stopped at the time point (after 10 hours) when the viscosity was almost not seen in the reaction liquid. The final viscosity of the solution was 9.8 Pa · sec at 50 ° C.

The obtained solution (polyurethane solution) was processed similarly to Example 1, and film (III) about 200 micrometers in thickness was produced. The physical properties of this film are shown in Table 4.

<Example 2>

[Production of Polythiocarbonate Polythiol (B)]

In the same reactor as in Example 1, 163 g (1.05 mol) of 2-mercaptoethyl sulfide, 156 g (0.726 mol) of diphenylcarbonate and 10% tetrabutylammonium hydroxide-methanol solution (catalyst) 0.856 g (0.330 mmol) was added thereto and the mixed reaction solution was kept for 1 hour while refluxing under 27 kPa (200 mmHg) and 160 ° C. While distilling phenol from the obtained reaction liquid, the pressure was gradually reduced to 4.0 kPa (30 mmHg) over 4 hours, after which the phenol did not flow out, and then the pressure was reduced from 2.7 kPa (20 mmHg) to 0.93 kPa (7 mmHg). The mixture was gradually decompressed over 1.5 hours, and further maintained at a pressure of 0.93 kPa (7 mmHg) for 3 hours, whereupon the reaction was carried out while distilling 2-mercaptoethyl sulfide and phenol to obtain the desired polythiocarbonate poly. Thiols were prepared.

The measurement result of <^1> H-NMR (in heavy chloroform) of the obtained polythiocarbonate polythiol is shown below.

¹ H-NMR: 1.73 ppm (t, J = 7.9 Hz, SH), 1.75 ppm (t, J = 7.9 Hz, SH), 2.78 ppm (m, CH ₂ SCH ₂ CH ₂ SH) 3.19 ppm (t, J = 7.9 Hz, CH ₂ SCO), 3.20 ppm (t, J = 7.9 Hz, CH ₂ SCO)

The catalyst in the polythiocarbonate polythiol was inactivated in the same manner as in Example 1. The physical properties of the finally obtained polythiocarbonate polythiol (B) are shown in Table 2.

[Production of Polythiourethane]

In the same reactor as in Example 1, 39.83 g (63.74 mmol) of the polythiocarbonate polythiol (B) was completely dissolved in 153 g of dimethylacetamide at 70 ° C to obtain the solution at the above temperature. 11.08 g (63.62 mmol) of 2, 4- tolylene diisocyanate were added, and it was made to react for 3 hours. 0.330 g (1.89 mmol) of 2, 4- tolylene diisocyanate was further added to the obtained reaction solution, and it reacted at 80 degreeC. The reaction was stopped at the time point (after 3 hours) when the viscosity increase was hardly seen in the obtained reaction solution. The final viscosity of the solution was 13.3 Pa · sec at 50 ° C.

The obtained solution (polythiourethane solution) was processed similarly to Example 1, and the film (IV) of about 200 micrometers in thickness was produced. The physical properties of this film are shown in Table 4.

Comparative Example 3

[Production of Polythiourethane]

In the same reactor as in Example 1, 19.22 g (124.5 mmol) of 2-mercaptoethyl sulfide were completely dissolved in 162 g of dimethylacetamide at 35 ° C., and this solution was subjected to 2,4 at the above temperature. 21.69 g (124.5 mmol) of tolylene diisocyanate were added and reacted for 3 hours, keeping the temperature of the obtained reaction liquid at 70 degreeC. 0.650 g (3.73 mmol) of 2,4-tolylene diisocyanate was further added to the obtained reaction solution, and the mixture was reacted at 80 ° C. The reaction was stopped when the viscosity increase of the obtained reaction solution was hardly seen (after 12 hours). The final viscosity of the solution was 50.1 Pa · sec at 50 ° C.

The obtained solution (polythiourethane solution) was processed similarly to Example 1, and the film V of about 200 micrometers in thickness was produced. The physical properties of this film are shown in Table 4.

<Example 3>

[Production of Polythiocarbonate Polythiol (C)]

In the same reactor as in Example 1, 90.1 g (0.599 mol) of 1,6-hexanedithiol, 77.2 g (0.500 mol) of 2-mercaptoethyl sulfide, 155 g (0.725 mol) of diphenylcarbonate and 10% 0.861 g (0.332 mmol) of tetrabutylammonium hydroxide-methanol solution was added, and the obtained liquid mixture was hold | maintained for 1 hour, refluxing under conditions of 27 kPa (200 mmHg) and 160 degreeC. While distilling phenol from the obtained reaction liquid, the pressure was gradually reduced to 4.0 kPa (30 mmHg) over 4 hours, after which the phenol did not flow out, and then the pressure was adjusted from 2.7 kPa (20 mmHg) to 0.93 kPa (7 mmHg). ) And slowly reduced the pressure to 1.5 hours, and maintained at a pressure of 0.93 kPa (7 mmHg) for 3 hours while reacting while distilling the mixture of phenol, 1,6-hexanedithiol, and 2-mercaptoethylsulfide, Desired polythiocarbonate polythiols were prepared.

The measurement result of <^1> H-NMR of the obtained polythiocarbonate polythiol is shown below.

¹ H-NMR: 1.33 ppm (t, J = 7.3 Hz, SH), 1.39 ppm (m, CH ₂ ), 1.62 ppm (m, CH ₂ ), 1.74 ppm (m, SH), 2.52 ppm (m, CH ₂ SH), 2.78 ppm (m, CH ₂ SCH ₂ and CH ₂ SH), 2.97 ppm (m, CH ₂ SCO), 3.19 ppm (m, CH ₂ SCO)

In the same manner as in Example 1, the polythiocarbonate polythiol was subjected to deactivation of the catalyst, methylene chloride addition, washing with water, drying, filtration, and methylene chloride distillation. The physical properties of the finally obtained polythiocarbonate polythiol (C) are shown in Table 2.

[Production (1) of polythiourethane]

In the same reactor as in Example 1, 40.21 g (76.74 mmol) of the polythiocarbonate polythiol (C) was completely dissolved in 161 g of dimethylacetamide at 70 ° C, and the solution obtained was at the above temperature. 13.40 g (76.94 mmol) of 2,4-tolylene diisocyanate were added and reacted for 3 hours. 0.370 g (2.12 mmol) of 2, 4- tolylene diisocyanate was further added to the obtained reaction solution, and it was made to react at 80 degreeC. The reaction was stopped at the time point (after 3 hours) when the viscosity was almost not seen in the reaction liquid. The final viscosity of the solution was 10.3 Pa · sec at 50 ° C.

The obtained solution (polythiourethane solution) was treated in the same manner as in Example 1 to prepare a film (VI) having a thickness of about 200 μm. The physical properties of this film are shown in Table 4.

[Production (2) of polythiourethane]

In the same reactor as in Example 1, 33.61 g (64.14 mmol) of the polythiocarbonate polythiol (C) and 3.280 g (21.25 mmol) of 2-mercaptoethyl sulfide were added to 161 g of dimethylacetamide at 70 ° C. It was dissolved completely and 18.98 g (85.39 mmol) of isophorone diisocyanate were added at this temperature and reacted for 1 hour. Subsequently, 0.153 g (0.242 mmol) of dibutyl tin dilaurate was injected into the reaction solution and reacted at the same temperature for 3 hours, followed by addition of 0.570 g (2.56 mmol) of isophorone diisocyanate and reacted at 80 ° C. The reaction was stopped at the time when the rise was almost invisible (after 4 hours). The final viscosity of the solution was 18.9 Pa · sec at 50 ° C.

 The obtained solution (polythiourethane solution) was processed in the same manner as in Example 1 to obtain a film (VII) having a thickness of about 200 μm. The physical properties of this film are shown in Table 4.

<Comparative Example 4>

[Production of Polythiocarbonate Polythiol (D)]

In the same reactor as in Example 1, 105 g (0.700 mol) of 1,6-hexanedithiol, 61.7 g (0.400 mol) of 2-mercaptoethyl sulfide, 155 g (0.725 mol) of diphenylcarbonate and 10 weight 0.861 g (0.332 mmol) of a% tetrabutylammonium hydroxide-methanol solution was added thereto, and the mixed solution was kept at reflux under a condition of 27 kPa (200 mmHg) and 160 ° C for 1 hour. The pressure was gradually reduced to 4.0 kPa (30 mmHg) over 4 hours while the phenol was distilled from the obtained reaction solution, and then the pressure was reduced from 2.7 kPa (20 mmHg) to 0.93 kPa (7 mmHg) after the phenol did not flow out. The mixture was slowly decompressed over 1.5 hours and further maintained at 0.93 kPa (7 mmHg) for 3 hours to distill a mixture of phenol, 1,6-hexanedithiol and 2-mercaptoethylsulfide. Subsequently, the reaction was carried out at 0.93 to 0.67 kPa (7 to 5 mmHg) for 5 hours while allowing a mixture of 1,6-hexanedithiol and 2-mercaptoethyl sulfide to flow out to prepare a polythiocarbonate polythiol. .

The measurement result of <^1> H-NMR of the obtained polythiocarbonate polythiol is shown below.

¹ H-NMR: 1.33 ppm (t, J = 7.3 Hz, SH), 1.39 ppm (m, CH ₂ ), 1.62 ppm (m, CH ₂ ), 1.74 ppm (m, SH), 2.52 ppm (m, CH ₂ SH), 2.78 ppm (m, CH ₂ SCH ₂ and CH ₂ SH), 2.97 ppm (m, CH ₂ SCO), 3.19 ppm (m, CH ₂ SCO)

In the same manner as in Example 1, the polycarbonate polyol was subjected to deactivation of the catalyst, methylene chloride addition, water washing, drying, filtration, and methylene chloride distillation. The physical properties of the finally obtained polythiocarbonate polythiol (D) are shown in Table 2. On the other hand, the SH value (40.88 mgKOH / g) was consistent with the measurement result of ¹ H-NMR.

[Production of Polythiourethane]

In the same reactor as in Example 1, 30.69 g (11.18 mmol) of the polythiocarbonate polythiol (D) was completely dissolved in 101 g of dimethylacetamide at 70 ° C, and the solution obtained was at the above temperature. 1.95 g (11.2 mmol) of 2,4-tolylene diisocyanate were added and reacted for 3 hours. To the obtained reaction solution, 0.060 g (0.34 mmol) of 2,4-tolylene diisocyanate was further added and reacted at 80 ° C. The reaction was stopped at the point in time when the viscosity increase was hardly seen in the obtained reaction solution (after 4 hours). The final viscosity of the solution was 9.8 Pa · sec at 50 ° C.

The obtained solution (polythiourethane solution) was treated in the same manner as in Example 1 to prepare a film having a thickness of about 200 μm. However, when peeling the formed film from a glass plate, the film extended | stretched and it did not return to original (that is, tensile strength was low and shape recovery was low). In addition, since this film had a haze, the optical substance could not be measured.

On the other hand, melting | fusing point (40.8 degreeC) was recognized and this polythiourethane was crystalline. The measuring method was the same as that of the said method.

<Example 4>

[Production of Polythiocarbonate Polythiol (E)]

In the same reactor as in Example 1, 114 g (0.761 mol) of 1,6-hexacidithiol, 76.7 g (0.435 mol) of 1,4-bis (mercaptomethyl) cyclohexane, 160 g (0.747) of diphenylcarbonate Mole) and 0.908 g (0.350 mmol) of 10 wt% tetrabutylammonium hydroxide-methanol solution were added, and the resultant mixed solution was kept at reflux at 27 kPa (200 mmHg) at 160 ° C for 1 hour. The pressure was gradually reduced to 4.0 kPa (30 mmHg) over 4 hours, distilling phenol out of the obtained reaction liquid. After the phenol did not flow out of the reaction solution, the pressure was gradually decompressed over 1.5 hours from 2.7 kPa (20 mmHg) to 0.93 kPa (71 mmHg) and further maintained at 0.93 kPa (7 mmHg) for 3 hours. The mixture of, 6-hexanedithiol and 1,4-bis (mercaptomethyl) cyclohexane was reacted while flowing out to prepare a polythiocarbonate polythiol of interest.

The measurement result of <^1> H-NMR of the obtained polythiocarbonate polythiol is shown below.

^{1 H-NMR: 0.98ppm (m} , CH 2), 1.26-1.50ppm (m, SH and _{CH 2), 1.62ppm (m,} CH 2), 1.70ppm (m, CH 2), 1.87ppm (m, CH and CH ₂ ), 2.41 ppm (t, J = 7.3 Hz, CH ₂ SH), 2.42 ppm (t, J = 7.3 Hz, CH ₂ SH), 2.52 ppm (m, CH ₂ SH), 2.89 ppm (m , CH ₂ SCO), 2.98 ppm (m, CH ₂ SCO)

The polythiocarbonate polythiol was subjected to deactivation of the catalyst, methylene chloride addition, washing with water, drying, filtration and methylene chloride distillation in the same manner as in Example 1. The physical properties of the finally obtained polythiocarbonate polythiol (E) are shown in Table 2. On the other hand, the SH value (208.4 mgKOH / g) was consistent with the measurement result of ¹ H-NMR.

<Example 5>

[Production of Polythiocarbonate Polythiol (F)]

In the same reactor as in Example 1, 49.8 g (0.331 mol) of 1,6-hexanedithiol, 40.2 g (0.189 mol) of 2,5-bis (mercaptomethyl) -1,4-dithiane, diphenylcarbo 67.5 g (0.315 mol) of Nate and 0.423 g (0.163 mmol) of 10% by weight tetrabutylammonium hydroxide-methanol solution were added, and the mixture was kept at reflux at 27 kPa (200 mmHg) and 160 ° C for 1 hour. The pressure was gradually reduced to 4.0 kPa (30 mmHg) over 4 hours, distilling phenol out of the obtained reaction liquid. After the phenol did not flow out of the reaction solution, the pressure was gradually reduced from 2.7 kPa (20 mmHg) to 0.93 kPa (7 mmHg) for 1.5 hours and further maintained at 0.93 kPa (7 mmHg) for 3 hours. The mixture of 1,6-hexanedithiol and 2,5-bis (mercaptomethyl) -1,4-dithiane was reacted with the outflow, and the target polythiocarbonate polythiol was produced.

The measurement result of <^1> H-NMR of the obtained polythiocarbonate polythiol is shown below.

¹ H-NMR: 1.33 ppm (t, J = 7.3 Hz, SH), 1.39 ppm (m, CH ₂ ), 1.62 ppm (m, CH ₂ and SH), 2.52 ppm (q, J = 7.3 Hz, CH ₂ SH), 2.53 ppm (q, J = 7.3 Hz, CH ₂ SH), 3.00 ppm (m, CH ₂ SCH, CH, CH ₂ SH and CH ₂ SCO), 3.36 ppm (m, CH ₂ SCO)

The polythiocarbonate polythiol was subjected to deactivation of the catalyst, methylene chloride addition, washing with water, drying, filtration and methylene chloride distillation in the same manner as in Example 1. The physical properties of the finally obtained polythiocarbonate polythiol (F) are shown in Table 2. On the other hand, the SH value (194.9 mgKOH / g) was consistent with the measurement result of ¹ H-NMR.

<Example 6>

[Production of Polythiocarbonate Polythiol (G)]

In the same reactor as in Example 1, 135 g (0.900 mol) of 1,6-hexanedithiol, 116 g (0.753 mol) of 2-mercaptoethylsulfide, 233 g (1.09 mol) of diphenylcarbonate and 10 weight 1.29 g (0.498 mmol) of% tetrabutylammonium hydroxide-methanol solution was added to the obtained mixture, and a mixture of phenol, 1,6-hexanedithiol, and 2-mercaptoethylsulphide was prepared in the same manner as in Example 2. Was spilled. Subsequently, the mixture was reacted while flowing a mixture of 1,6-hexanedithiol and 2-mercaptoethyl sulfide over 0.27 kPa (2 mmHg) for 1 hour to obtain a polythiocarbonate polythiol of interest.

The measurement result of <^1> H-NMR of the obtained polythiocarbonate polythiol is shown below.

¹ H-NMR: 1.33 ppm (t, J = 7.3 Hz, SH), 1.39 ppm (m, CH ₂ ), 1.62 ppm (m, CH ₂ ), 1.74 ppm (m, SH), 2.52 ppm (m, CH ₂ SH), 2.78 ppm (m, CH ₂ SCH ₂ and CH ₂ SH), 2.97 ppm (m, CH ₂ SCO), 3.19 ppm (m, CH ₂ SCO)

The polythiocarbonate polythiol was subjected to deactivation of the catalyst, methylene chloride addition, washing with water, drying, filtration and methylene chloride distillation in the same manner as in Example 1. The physical properties of the finally obtained polythiocarbonate polythiol (G) are shown in Table 2. On the other hand, the SH value (96.74 mgKOH / g) was consistent with the measurement result of ¹ H-NMR.

[Production of Polythiourethane (I)]

In the same reactor as in Example 1, 30.17 g (26.01 mmol) of the polythiocarbonate polythiol (G) and 3.230 g (20.93 mmol) of 2-mercaptoethyl sulfide were added to 124 g of dimethylacetamide at 70 ° C. The solution was completely dissolved and reacted for 3 hours by adding 8.180 g (46.97 mmol) of 2,4-tolylene diisocyanate at this temperature. Subsequently, 0.240 g (1.38 mmol) of 2,4-tolylene diisocyanate was further added to this reaction solution, and it was made to react at 80 degreeC, and reaction was stopped at the time point (after 4 hours) when a viscosity rise was hardly seen. The final viscosity of the solution was 21.2 Pa · sec at 50 ° C.

The obtained solution (polythiourethane solution) was processed in the same manner as in Example 1 to obtain a film (VIII) having a thickness of about 200 μm. The physical properties of this film are shown in Table 4.

[Production (2) of polythiourethane]

In the same reactor as in Example 1, 21.08 g (18.17 mmol) of the polythiocarbonate polythiol (G) and 24.94 g (46.32 mmol) of the polythiocarbonate polythiol (E) were added to 172 g of dimethylacetamide. The solution was completely dissolved at 70 ° C, and reacted for 3 hours by adding 11.20 g (64.31 mmol) of 2,4-tolylene diisocyanate at this temperature. Subsequently, 0.330 g (1.89 mmol) of 2,4-tolylene diisocyanate was further added to this reaction solution, and it was made to react at 80 degreeC, and reaction was stopped at the time point (after 4 hours) when a viscosity rise was hardly seen. The final viscosity of the solution was 20.5 Pa · sec at 50 ° C.

The obtained solution (polythiourethane solution) was processed in the same manner as in Example 1 to obtain a film (IX) having a thickness of about 200 μm. The physical properties of this film are shown in Table 4.

<Example 7>

[Production of Polythiocarbonate Polythiol (H)]

In the same reactor as in Example 1, 105 g (0.700 mol) of 1,6-hexanedithiol, 61.7 g (0.400 mol) of 2-mercaptoethyl sulfide, 155 g (0.725 mol) of diphenylcarbonate and 10 weight A mixture of phenol, 1,6-hexanedithiol, and 2-mercaptoethylsulphide was added to 0.861 g (0.332 mmol) of a% tetrabutylammonium hydroxide-methanol solution and subjected to the same operation as in Example 2. Was spilled. Subsequently, the mixture was reacted with 0.93 to 0.67 kPa (7 to 5 mmHg) over 3 hours while flowing a mixture of 1,6-hexanedithiol and 2-mercaptoethylsulfide to obtain the desired polythiocarbonate polythiol. .

The measurement result of <^1> H-NMR of the obtained polythiocarbonate polythiol is shown below.

¹ H-NMR: 1.33 ppm (t, J = 7.3 Hz, SH), 1.39 ppm (m, CH ₂ ), 1.62 ppm (m, CH ₂ ), 1.74 ppm (m, SH), 2.52 ppm (m, CH ₂ SH), 2.78 ppm (m, CH ₂ SCH ₂ and CH ₂ SH), 2.97 ppm (m, CH ₂ SCO), 3.19 ppm (m, CH ₂ SCO)

The polythiocarbonate polythiol was subjected to deactivation of the catalyst, methylene chloride addition, washing with water, drying, filtration, and methylene chloride distillation in the same manner as in Example 1. The physical properties of the finally obtained polythiomocarbonate polythiol (H) are shown in Table 2. On the other hand, the SH value (59.29 mgKOH / g) was consistent with the measurement result of ¹ H-NMR.

[Production (1) of polythiourethane]

In the same reactor as in Example 1, 21.20 g (11.21 mmol) of the polythiocarbonate polythiol (H) and 9.870 g (63.95 mmol) of 2-mercaptoethyl sulfide were added to 133 g of dimethylacetamide at 70 ° C. The solution was completely dissolved and reacted for 3 hours by adding 13.09 g (75.16 mmol) of 2,4-tolylene diisocyanate at this temperature. Subsequently, 0.390 g (2.24 mmol) of 2,4-tolylene diisocyanate was further added to this reaction solution, and it was made to react at 80 degreeC, and reaction was stopped at the time point (after 4 hours) when a viscosity rise was hardly seen. The final viscosity of the solution was 17.8 Pa · sec at 50 ° C.

The obtained solution (polythiourethane solution) was processed in the same manner as in Example 1 to obtain a film (X) having a thickness of about 200 μm. The physical properties of this film are shown in Table 4.

[Production (2) of polythiourethane]

In the same reactor as in Example 1, 23.50 g (40.82 mmol) of the polythiocarbonate polythiol (F), 20.76 g (10.97 mmol) of the polythiocarbonate polythiol (H) and 2-mercaptoethylsulfonate 1.440 g (9.330 mmol) of the feed was completely dissolved in 170 g of dimethylacetamide at 70 ° C, and 10.64 g (61.09 mmol) of 2,4-tolylene diisocyanate was added thereto and reacted for 3 hours. Subsequently, 0.320 g (1.84 mmol) of 2,4-tolylene diisocyanate was further added to the reaction solution to react at 80 ° C, and the reaction was stopped when the viscosity increase was hardly seen (after 4 hours). The final viscosity of the solution was 19.1 Pa · sec at 50 ° C.

The obtained solution (polythiourethane solution) was processed in the same manner as in Example 1 to obtain a film (XI) having a thickness of about 200 μm. The physical properties of this film are shown in Table 4.

<Example 8>

[Production of Polythiocarbonate Polythiol (I)]

In the same reactor as in Example 1, 167 g (0.949 mol) of 1,4-bis (mercaptomethyl) cyclohexane, 131 g (0.616 mol) of diphenylcarbonate and 10% by weight tetrabutylammonium hydroxide-methanol 0.870 g (0.335 mmol) of the solution was added thereto, and the resultant mixture was subjected to the same operation as in Example 2 to react while distilling out a mixture of phenol and 1,4-bis (mercaptomethyl) cyclohexane to give a desired polythiocarbo. Nate polythiol was obtained.

The measurement result of <^1> H-NMR of the obtained polythiocarbonate polythiol is shown below.

¹ H-NMR: 0.96 ppm (m, CH 2), 1.29 ppm (t, J = 8.0 Hz, SH), 1.30 ppm (t, J = 8.0 Hz, SH), 1.32-1.50 ppm (m, CH ₂ ), 1.57 ppm (m, CH ₂ ), 1.70 ppm (m, CH ₂ ), 1.86 ppm (m, CH and CH ₂ ), 2.41 ppm (t, J = 8.0 Hz, CH ₂ SH), 2.42 ppm (t, J = 8.0 Hz, CH ₂ SH), 2.49 ppm (t, J = 8.0 Hz, CH ₂ SH), 2.50 ppm (t, J = 8.0 Hz, CH ₂ SH), 2.89 ppm (m, CH ₂ SCO), 2.97 ppm (m, CH ₂ SCO)

The polythiocarbonate polythiol was subjected to deactivation of the catalyst, methylene chloride addition, water washing, drying, filtration, and methylene chloride distillation as in Example 1. The physical properties of the finally obtained polythiocarbonate polythiol (I) are shown in Table 2. On the other hand, the SH value (209.9 mgKOH / g) was consistent with the measurement result of ¹ H-NMR.

[Production of Polythiourethane]

In the same reactor as in Example 1, 16.48 g (30.83 mmol) of the polythiocarbonate polythiol (I) and 28.80 g (24.83 mmol) of the polythiocarbonate polythiol (G) were added to 167 g of dimethylacetamide. It dissolved completely at 90 degreeC, and it was made to react for 3 hours by adding 9.700 g (55.70 mmol) of 2, 4- tolylene diisocyanate at this temperature. Subsequently, 0.290 g (1.67 mmol) of 2,4-tolylene diisocyanate was further added to the reaction solution to react at 90 ° C, and the reaction was stopped when the viscosity increase was hardly seen (after 3 hours). The final viscosity of the solution was 25.6 Pa · sec at 50 ° C.

The obtained solution (polythiourethane solution) was processed in the same manner as in Example 1 to obtain a film (XII) having a thickness of about 200 μm. The physical properties of this film are shown in Table 4.

Example 9

[Production of Polythiocarbonate Polythiol (J)]

In the same reactor as in Example 1, 212 g (1.41 mol) of 1,6-hexanedithiol, 201 g (0.936 mol) of diphenylcarbonate and 1.15 g (0.444) of 10 wt% tetrabutylammonium hydroxide-methanol solution Mmol), and the mixture of phenol and 1,6-hexanedithiol was distilled out by performing the operation similar to Example 2 to the obtained liquid mixture. Subsequently, the reaction was carried out at 0.27 kPa (2 mmHg) for 5 hours while distilling 1,6-hexanedithiol, and then 37.0 g (0.342 mol) of 1,3-propanedithiol was added and reacted for 6 hours under normal pressure. The desired polythiocarbonate polythiol was obtained.

The measurement result of <^1> H-NMR of the obtained polythiocarbonate polythiol is shown below.

^{1 H-NMR: 1.31ppm (t} , J = 7.3Hz, SH), 1.39ppm (m, CH 2), 1.61ppm (m, CH 2), 1.92ppm (quin, J = 7.3Hz, CH 2.) , 1.94 ppm (quin., J = 7.3 Hz, CH ₂ ) 2.52 ppm (q, J = 7.3 Hz, CH ₂ SH), 2.53 ppm (q, J = 7.3 Hz, CH ₂ SH), 2.60 ppm (q, J = 7.3 Hz, CH ₂ SH), 2.66 ppm (q, J = 7.3 Hz, CH ₂ SH), 2.97 ppm (t, J = 7.3 Hz, CH ₂ SCO), 2.98 ppm (t, J = 7.3 Hz, CH ₂ SCO), 3.04 ppm (t, J = 7.3 Hz, CH ₂ SCO), 3.11 ppm (t, J = 7.3 Hz, CH ₂ SCO)

The polythiocarbonate polythiol was subjected to deactivation of the catalyst, methylene chloride addition, washing with water, drying, filtration, and methylene chloride distillation in the same manner as in Example 1. The physical properties of the finally obtained polythiocarbonate polythiol (J) are shown in Table 2. On the other hand, the SH value (215.2 mgKOH / g) was consistent with the measurement result of ¹ H-NMR.

[Production of Polythiourethane]

In the same reactor as in Example 1, 30.73 g (58.94 mmol) of the polythiocarbonate polythiol (J) and 3.610 g (23.39 mmol) of 2-mercaptoethyl sulfide were added to 147 g of dimethylacetamide at 70 ° C. It was dissolved completely and 14.34 g (82.34 mmol) of 2,4-tolylene diisocyanate was added at this temperature and reacted for 3 hours. Subsequently, 0.430 g (2.47 mmol) of 2,4-tolylene diisocyanate was further added to the reaction solution to react at 80 ° C, and the reaction was stopped at the point in time when the viscosity increase was hardly seen (after 4 hours). The final viscosity of the solution was 11.2 Pa · sec at 50 ° C.

The obtained solution (polythiourethane solution) was processed in the same manner as in Example 1 to obtain a film (XIII) having a thickness of about 200 μm. The physical properties of this film are shown in Table 4.

<Example 10>

[Production of Polythiocarbonate Polythiol (K)]

In the same reactor as in Example 1, 93.4 g (0.622 mol) of 1,6-hexanedithiol, 93.4 g (0.622 mol) of 3-methyl-1,5-pentanedithiol, 182 g (0.850 mol) of diphenylcarbonate ) And 3.07 g (1.18 mmol) of 10 wt% tetrabutylammonium hydroxide-methanol solution, and the obtained mixture was subjected to the same operation as in Example 2 to obtain phenol, 1,6-hexanedithiol and 3-methyl-1 The mixture of, 5-pentanedithiol was allowed to react while flowing out to obtain the desired polythiocarbonate polythiol.

The measurement result of <^1> H-NMR of the obtained polythiocarbonate polythiol is shown below.

¹ H-NMR: 0.92 ppm (d, J = 7.5 Hz, CH ₃ ), 0.95 ppm (d, J = 5 Hz, CH ₃ ), 1.33 ppm (t, J = 7.5 Hz, SH), 1.39 ppm (m, CH ₂ ), 1.49 ppm (m, CH), 1.62 ppm (m, CH ₂ ), 2.52 ppm (t, J = 5 Hz, CH ₂ SH), 2.53 ppm (t, J = 7.5 Hz, CH ₂ SH), 2.97 ppm (m, CH ₂ SCO)

The polythiocarbonate polythiol was subjected to inactivation of the catalyst, methylene chloride addition, water washing, drying, filtration, and methylene chloride distillation in the same manner as in Example 1. The physical properties of the finally obtained polythiocarbonate polythiol (K) are shown in Table 2. On the other hand, the SH value (173.4 mgKOH / g) was consistent with the measurement result of ¹ H-NMR.

[Production of Polythiourethane]

In the same reactor as in Example 1, 30.00 g (46.36 mmol) of the polythiocarbonate polythiol (K) and 2.390 g (15.49 mmol) of 2-mercaptoethyl sulfide were added to 129 g of dimethylacetamide at 70 ° C. It was dissolved completely and 10.76 g (61.78 mmol) of 2,4-tolylene diisocyanate was added at this temperature and reacted for 3 hours. Subsequently, 0.320 g (1.84 mmol) of 2, 4- tolylene diisocyanate was further added to this reaction solution, and it reacted at 80 degreeC, and reaction was stopped at the time point (after 4 hours) when a viscosity rise was hardly seen. The final viscosity of the solution was 10.1 Pa · sec at 50 ° C.

The obtained solution (polythiourethane solution) was processed in the same manner as in Example 1 to obtain a film (XIV) having a thickness of about 200 μm. The physical properties of this film are shown in Table 4.

In addition, Table 1 shows the polythiol compound used as a raw material of polythiocarbonate polythiol, and Table 3 shows the polythiol component and chain extender which comprise polythiourethane, respectively. In Table 3, an isocyanate component is isophorone diisocyanate only in the case of film number (VII), and another is 2, 4- tolylene diisocyanate.

sign Polythiol compounds Example 1 A 1,6-hexanedithiol Example 2 B 2-mercaptoethyl sulfide Example 3 C 1,6-hexanedithiol + 2-mercaptoethyl sulfide Comparative Example 4 D 1,6-hexanedithiol + 2-mercaptoethyl sulfide Example 4 E 1,6-hexanedithiol + 1,4-bis (mercaptomethyl) cyclohexane Example 5 F 1,6-hexanedithiol + 2,5-bis (mercaptomethyl) cyclohexane-1,4-dithiane Example 6 G 1,6-hexanedithiol + 2-mercaptoethyl sulfide Example 7 H 1,6-hexanedithiol + 2-mercaptoethyl sulfide Example 8 I 1,4-bis (mercaptomethyl) cyclohexane Example 9 J 1,6-hexanedithiol + 1,3-propanedithiol Example 10 K 1,6-hexanedithiol + 3-methyl-1,5-pentanedithiol

Poly (thio) urethane Film number Polythiocarbonate polythiols and polycarbonate polyols Chain extender Example 1 I A - Comparative Example 1 II - 1,6-hexanedithiol Comparative Example 2 III Polycarbonate diols - Example 2 IV B - Comparative Example 3 V - 2-mercaptoethyl sulfide Example 3 VI C - VII C 2-mercaptoethyl sulfide Comparative Example 4 - D - Example 4 - E - Example 5 - F - Example 6 VIII G 2-mercaptoethyl sulfide IX G + E - Example 7 X H 2-mercaptoethyl sulfide XI H + F 2-mercaptoethyl sulfide Example 8 XII I + G - Example 9 XIII J 2-mercaptoethyl sulfide Example 10 XIV K 2-mercaptoethyl sulfide

The polythiourethane of the present invention has excellent optical properties and excellent tensile properties such as high refractive index and low dispersibility, and also has excellent mechanical performance of showing high elasticity, plastic lenses, prisms, optical fibers, substrates for information recording, It is useful for optical materials, such as a coloring filter and an infrared absorption filter.

Claims (11)

Polythiourethane produced by the reaction of a polythiol component comprising at least one polythiocarbonate polythiol and a polyisocyanate component comprising at least one selected from polyisocyanate and polyisothiocyanate, The polythiourethane polythiol for the polythiol component is a polythiourethane comprising a repeating unit represented by the following general formula (I) and having a number average molecular weight of 200 to 2500: Formula I

In the above formula, R represents a divalent hydrocarbon group, provided that the hydrocarbon group R has or does not have an alkyl group, a nitro group, or an alkyl group and a nitro group, and in the carbon chain of the hydrocarbon group, a hetero atom and a -OCO- It contains or does not contain one or more selected from groups. delete The polythio according to claim 1, wherein the polythiol component includes two or more polythiocarbonate polythiols having a repeating unit represented by the above formula (I) and having a number average molecular weight of 200 to 2500. urethane. The polythiourethane of Claim 1 whose terminal aryloxy group content rate of the said polythiocarbonate polythiol is 0-5 mol% with respect to all terminal groups. The polythiourethane of claim 1 having a repeating unit represented by the following formula (II): Formula II

In the above formula, R represents a divalent hydrocarbon group, provided that the hydrocarbon group R has or does not have an alkyl group, a nitro group, or an alkyl group and a nitro group, and in the carbon chain of the hydrocarbon group, a hetero atom and a -OCO- Containing or not containing at least one selected from the group, Y represents a divalent hydrocarbon group, provided that the divalent hydrocarbon group Y has or does not have an alkyl group, a nitro group, or an alkyl group and a nitro group, and also In the carbon chain, one or more hetero atoms are included or not included, X represents an oxygen atom or a sulfur atom, and n represents an integer of 1 or more. The polythiourethane of claim 1, wherein the polythiocarbonate polythiol is liquid at room temperature. The color of the polythiocarbonate polythiol measured according to JIS K 1557 is APHA No. Polythiourethane which is 60 or less. The molar amount of the thioether structure produced by the de-COS reaction of the thiocarbonate structure moiety in the polythiocarbonate polythiol is unreacted thiocarbonate structure and the resulting moiety. The polythiourethane which is 3% or less of the total molar amount of a thioether structure. The polythiol compound according to claim 1, wherein the polythiocarbonate polythiol is a polythiol compound having a diphenylcarbonate and a divalent hydrocarbon group containing 4 to 14 carbon atoms in the presence of a transesterification catalyst, Polythiourethane prepared by transesterification. The polythiourethane of Claim 9 in which the said transesterification catalyst contains a basic compound. 2. The poly according to claim 1, wherein the polythiol component comprises at least two repeating units represented by the formula (I) and further comprises a polythiocarbonate polythiol having a number average molecular weight of 200 to 2,500. 3. Thiourethane.