JP3048573B2 - UV absorbing polymer and weatherable resin composition using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a UV-absorbing polymer and a resin composition exhibiting excellent weather resistance over a long period of time.

[0002]

2. Description of the Related Art Benzotriazole compounds such as 2-hydroxyphenylbenzotriazole are known as so-called ultraviolet absorbers useful for protecting plastics from ultraviolet rays. However, most of the benzotriazole compounds are low molecular weight compounds, and therefore have many problems. For example, since it is a low molecular weight compound, it has a high vapor pressure and evaporates when it is blended with a resin and molded. Thus, there is a problem that the working environment is deteriorated and a mold is contaminated.

Further, since the above compound is a so-called additive type ultraviolet absorber which is simply used by being mixed with a base resin, there is a problem that the compound bleeds over time from the surface of a molded article or a coating film. In particular, when used outdoors, there is a problem that the ultraviolet absorber flows out due to rain or water containing detergent. Therefore, the conventional benzotriazole compound cannot exhibit the ultraviolet absorbing ability for a long period of time.

[0004]

In order to solve the above problems, a method for polymerizing a benzotriazole compound has been proposed. JP-B-38-25036, JP-A-60-51181 and JP-A-61-1
Japanese Patent Publication No. 112062 discloses a polymerizable benzotriazole compound. However, the compounds disclosed in these publications can only be used for the polymerization reaction with an addition polymerizable monomer, and cannot be applied to polymers obtained by a polycondensation reaction such as polyester and polycarbonate.

JP-A-2-188581 and JP-A-3-200788 disclose polycondensable benzotriazole compounds having two or more carboxyl groups in the molecule. The compounds disclosed in these publications are:
It can be applied to polycondensation with diols and the like, and can produce polyesters and the like. However, the above compounds cannot be applied to the production of polycarbonate, which is remarkably deteriorated by ultraviolet rays and is strongly required to have improved weather resistance, or the production of polyurethane by polyaddition with diisocyanate.

On the other hand, it has been proposed to dimerize a benzotriazole compound in order to further enhance the ultraviolet absorbing ability. Japanese Patent Application Laid-Open No. 3-39326 discloses that a dimerized benzotriazole compound is used as a diol component. The polycarbonate copolymer used is disclosed.
However, when using the dimerization compound disclosed in the above publication,
A phenolic hydroxyl group, which is a functional group indispensable for exhibiting ultraviolet absorbing ability, is lost by participating in the polymerization reaction. Therefore, even if a polycarbonate copolymer is produced using such a dimerized compound, or a polyester copolymer, a polyurethane copolymer or the like is produced, a copolymer having excellent ultraviolet absorbing ability cannot be obtained. .

Accordingly, an object of the present invention is to prevent the ultraviolet ray absorbing ability from being impaired by the polymerization reaction, evaporate or bleed out the ultraviolet ray absorbing component, and to exhibit excellent ultraviolet ray absorbing ability for a long period of time. To provide a UV-absorbing polymer that can. Another object of the present invention is to provide a weatherable resin composition capable of exhibiting excellent ultraviolet absorbing ability over a long period of time.

[0008]

Means for Solving the Problems The present inventor has made intensive studies to solve the above-mentioned problems, and as a result, general formula (7):

[0009]

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Wherein A is a direct bond or has 1 to 1 carbon atoms.
6 linear or branched alkylene group, group: —O
—, Group: —NH—, group: —S—, group: —SO—, or group: —SO ₂ —. R ¹ and R ² are the same or different and each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom. R ³ and R ⁶ are the same or different and are directly bonded to each other or represent a linear or branched alkylene group having 1 to 12 carbon atoms. R ⁴ , R ⁵ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. m and p are the same or different,
Indicates an integer of 20. n and q are the same or different and are 1
And an integer of 10 to 10. ), A bisbenzotriazole-based compound having excellent ultraviolet absorbing ability is used as a diol component, and (i) the bisbenzotriazole-based compound
When (7) is reacted with phosgene or a previously prepared diphenyl carbonate, dicarboxylic acid or dicarboxylic acid ester, or diisocyanate or biscarbamic acid ester together with another predetermined diol component, (ii) the bisbenzotriazole-based compound
(7) is melted together with a polycarbonate resin produced in advance, when transesterification is performed, or (iii) the bisbenzotriazole-based compound (7)
Is reacted with a diamine after being converted to a bischloroformate, without impairing the ultraviolet absorbing ability peculiar to the bisbenzotriazole-based compound represented by the general formula (7) by a polymerization reaction, excellent ultraviolet absorption. The present inventors have found a new fact that an ultraviolet-absorbing polymer capable of exhibiting a function can be obtained, and have completed the ultraviolet-absorbing polymer of the present invention.

That is, the first ultraviolet absorbing polymer of the present invention has the general formula (1):

[0012]

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(Wherein A, R ¹ , R ² , R ³ ,
R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , m, n, p and q are the same as described above. a represents an integer of 1 or more. ) And the general formula (2):

[0014]

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(In the formula (2), B is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, a group: —O
-, Group: -CO-, group: -NH-, group: -S-, group:-
SO-, or a group: -SO ₂ - shows a. R ⁹ , R ¹⁰ , R
¹¹ and R ¹² are the same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom. b represents an integer of 1 or more. ), Wherein the content of the repeating unit represented by the formula (1) is 0.01 to 70% by weight and the viscosity average molecular weight is 5,000 to 100,000. Features.

The second ultraviolet absorbing polymer of the present invention comprises:
General formula (3):

[0017]

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(In the formula (3), A, R ¹ , R ² , R ³ ,
R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , m, n, p and q are the same as described above. Y represents phenylene, naphthalene, or a linear or branched alkylene group having 2 to 9 carbon atoms. c represents an integer of 1 or more. ) And the general formula (4):

[0019]

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(In the formula (4), X is a straight-chain having 2 to 9 carbon atoms;
It represents a branched or cyclic alkylene group. Y is the same as above. d shows an integer of 1 or more. ), Wherein the content of the repeating unit represented by the formula (3) is 0.01 to 70% by weight and the viscosity average molecular weight is 5,000 to 100,000. Features.

The third ultraviolet absorbing polymer of the present invention has a general formula (5):

[0022]

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(In the formula (5), A, R ¹ , R ² , R ³ ,
R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , m, n, p and q are the same as described above. Z represents phenylene, naphthalene, or a linear or branched alkylene group having 2 to 9 carbon atoms. e represents an integer of 1 or more. ) And the general formula (6):

[0024]

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(In the formula (6), X and Z are the same as above, and f represents an integer of 1 or more.) The repeating unit represented by the formula (5) The unit content is 0.01 to 70% by weight of the whole, and the viscosity average molecular weight is 5000 to 100,000. The bisbenzotriazole-based compound represented by the general formula (7) has a group having a very high reactivity, a polycondensation reactivity or a polyaddition reactivity, so that a polycondensation monomer and a polyaddition monomer are used. Polymerizes easily. Therefore, by performing any one of the above-mentioned (i) to (iii), the bisbenzotriazole-based compound (7) is used as an ultraviolet absorbing unit to form a chemical in the main chain or side chain of polycarbonate, polyester or polyurethane. By bonding, it can be introduced at a ratio capable of exhibiting a sufficient ultraviolet absorbing ability.

The first to third UV-absorbing polymers according to the present invention are difficult to evaporate due to the large molecular weight of the UV-absorbing unit derived from the bisbenzotriazole-based compound (7). (7) Since the phenolic hydroxyl group in the polymer does not take part in the polymerization reaction, the UV absorbing unit loses its UV absorption performance due to heating during high-temperature reaction or molding, and the UV absorbing unit evaporates or bleeds out. There is no. Therefore, according to the ultraviolet absorbing polymer of the present invention, excellent ultraviolet absorbing ability can be exhibited for a long period of time.

Further, the present inventors have found that when a predetermined amount of the above-mentioned first to third UV-absorbing polymers according to the present invention is blended in a base resin having excellent compatibility with the polymer, a long period of time can be obtained. The present inventors have found a new fact that a resin composition capable of exhibiting excellent ultraviolet absorbing ability can be obtained, and have completed the weather-resistant resin composition according to the present invention. That is, in the first weatherable resin composition of the present invention, the first UV-absorbing polymer is added to the polycarbonate-based resin in an amount of 0.1%.
It is characterized by containing from 0.5 to 50% by weight.

The second weatherable resin composition of the present invention is characterized in that the second ultraviolet-absorbing polymer is contained in the polyester resin in an amount of 0.05 to 50% by weight. Further, the third weatherable resin composition of the present invention is characterized in that the third UV-absorbing polymer is added to the polyurethane-based resin in an amount of 0.05%.
-50% by weight. The UV-absorbing polymer according to the present invention is blended, according to the weather-resistant resin composition of the present invention, while maintaining the excellent UV-absorbing ability of the UV-absorbing polymer itself, the UV-absorbing polymer and Due to the good compatibility with the base resin constituting the resin composition, excellent ultraviolet absorbing ability can be exhibited for a long period of time.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION The bisbenzotriazole-based compound represented by the general formula (7) has a plurality of highly reactive hydroxy groups in a molecule, and thus is a monomer capable of polycondensation or polyaddition with the compound. Does not lose the phenolic hydroxyl group. Further, the bisbenzotriazole-based compound (7) is a compound of the general formula (1)
The ultraviolet absorbing unit represented by (3) or (5) is formed, and this ultraviolet absorbing unit can be introduced into the main chain or side chain of the polymer with an arbitrary composition.

Therefore, the polymer obtained by the above-mentioned polycondensation or polyaddition reaction can maintain 100% of the ultraviolet absorbing ability of the bisbenzotriazole compound (7), and expresses such ultraviolet absorbing ability at an arbitrary intensity. Can be done. The bisbenzotriazole-based compound
Since (7) has an extremely low vapor pressure and a remarkably high decomposition temperature of 350 ° C. or more, even when it is subjected to a polycondensation reaction or a polyaddition reaction at a high temperature, it does not cause evaporation or decomposition during the reaction. Therefore, an ultraviolet-absorbing polymer can be produced with an extremely high yield and an arbitrary molecular weight.

The bisbenzotriazole compound (7)
In one molecule, one benzotriazolylphenol becomes a bulky substituent for the phenolic hydroxyl group of the other benzotriazolylphenol, and thus protects the phenolic hydroxyl group. As a result, there is no problem such as discoloration due to contact with metal ions, and excellent metal ion resistance is exhibited.

Further, since the bisbenzotriazole-based compound (7) has a plurality of long-chain polyester groups in the molecule, it is not only easily soluble in an organic solvent and other monomers during polymerization, but also other Extremely high compatibility with general-purpose resins. Therefore, it is easy to carry out the polycondensation reaction or the polyaddition reaction, and the polymer obtained as a result of the reaction shows extremely good compatibility with other polycondensation or polyaddition polymers.

In the bisbenzotriazole compound represented by the general formula (7) and the repeating unit represented by the general formulas (1), (3) and (5), the compound having 1 to 1 carbon atoms represented by A Examples of 6 linear or branched alkylene groups include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, ethylidene, propylene, propylidene, isopropylidene,
Ethyl ethylene, 1,1-butanediyl, 2,2-butanediyl, 3,3-pentanediyl, 3,3-hexanediyl, 1-methyltrimethylene, 2-methyltrimethylene, 2,2-dimethyltrimethylene and the like. Can be

The group A represents the above-mentioned alkylene group, and in addition to the oxy group (-O-), amino group (-NH-), thio group (-S-), sulfinyl group (-SO-) or sulfonyl group (—SO ₂ —) or a single bond. When A represents a single bond, benzotriazolylphenol on both sides of A is directly bonded as shown in the following general formula (77).

The bisbenzotriazole compound (7)
In the repeating unit represented by the general formulas (1), (3) and (5), the alkyl group having 1 to 4 carbon atoms represented by R ¹ and R ² includes, for example, methyl, ethyl, propyl, Isopropyl, butyl, isobutyl, s
ec-butyl, tert-butyl and the like. Examples of the aryl group include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group and a naphthyl group which may have a halogen atom or the like on a phenyl ring. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The bisbenzotriazole compound (7)
And in the repeating unit represented by the general formulas (1), (3) and (5), a linear or branched alkylene group having 1 to 12 carbon atoms represented by R ³ and R ⁶ includes: In addition to the aforementioned alkylene groups having 1 to 6 carbon atoms, for example, heptamethylene, octamethylene, nonamethylene,
Examples thereof include a linear or branched alkylene group having 7 to 12 carbon atoms, such as decamethylene, undecamethylene, and dodecamethylene. In the present invention, among the above alkylene groups, those having 2 to 4 carbon atoms are particularly preferred.

The bisbenzotriazole compound (7)
And in the repeating unit represented by the general formulas (1), (3) and (5), the alkyl group having 1 to 10 carbon atoms represented by R ⁴ , R ⁵ , R ⁷ and R ⁸ is as defined above. In addition to alkyl groups having 1 to 4 carbon atoms, pentyl, hexyl,
Examples include heptyl, octyl, nonyl, decyl and the like.

By changing the number m, n, p and q of the repeating units of the chain polyester arbitrarily, the properties of the compound can be adjusted to a crystal, wax or oil. The bisbenzotriazole-based compound represented by the general formula (7), which forms the repeating unit represented by the general formula (1), (3) or (5), is specifically a compound represented by the general formula (71): It is represented by (77).

[0039]

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[0040]

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(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ , R ⁷ , R ⁸ , m, n, p and q are the same as described above. C represents a linear or branched alkylene group having 1 to 6 carbon atoms. The bisbenzotriazole compound used in the present invention
Specific compound names of (7) are shown below. .2,2′-methylenebis [6- (2H-1,2,3-
Benzotriazol-2-yl) -4- (glycoloyloxyethyl) phenol], 2,2'-methylenebis [6- (2H-1,2,3-
Benzotriazol-2-yl) -4- (3-hydroxypropanoyloxyethyl) phenol], 2,2′-methylenebis [6- (2H-1,2,3-
Benzotriazol-2-yl) -4- (4-hydroxybutanoyloxyethyl) phenol], 2,2′-methylenebis [6- (2H-1,2,3-
Benzotriazol-2-yl) -4- (5-hydroxyheptanoyloxyethyl) phenol], 2,2′-methylenebis [6- (2H-1,2,3-
Benzotriazol-2-yl) -4- (6-hydroxyhexanoyloxyethyl) phenol], 2,2′-methylenebis [6- (2H-1,2,3-
Benzotriazol-2-yl) -4- (16-hydroxy-4,11-dioxo-3,10-dioxahexadecyl) phenol], 2,2′-methylenebis [6- (2H-1,2,2 3-
Benzotriazol-2-yl) -4- (23-hydroxy-4,11,18-trioxo-3,10,17-
Trioxatricosyl) phenol], 2,2'-methylenebis [6- (2H-1,2,3-
Benzotriazol-2-yl) -4- (30-hydroxy-4,11,18,25-tetraoxo-3,1
0,17,24-tetraoxatriacontyl) phenol], 2,2'-methylenebis [6- (2H-1,2,3-
Benzotriazol-2-yl) -4- (37-hydroxy-4,11,18,25,32-pentaoxo-
3,10,17,24,31-pentaoxaheptatriacontyl) phenol] In the repeating unit represented by the general formula (2), a linear or branched C 1-10 carbon atom represented by B Alternatively, as the cyclic alkylene group, for example, the above-mentioned exemplified carbon number 1 to 1
6, alkylene group, 4,4-heptanediyl,
4,4-octanediyl, 5,5-nonanediyl, 5,
5-decanediyl, 1,4-cyclohexanediyl, cyclohexylidene and the like.

The above-mentioned group B represents the above-mentioned alkylene group, oxy group (-O-), keto group (-CO-), amino group (-NH-), thio group (-S-), sulfinyl group. (—SO—) or a sulfonyl group (—SO ₂ —). In the repeating unit represented by the general formula (2), R
^9, R ^10, an alkyl group having 1 to 4 carbon atoms represented by R ¹¹ and R ^12, the alkoxy groups and halogen atoms of 1 to 4 carbon atoms, may be the same as those exemplified above.

In the repeating unit represented by the general formula (3), A, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷
And the substituents represented by R ⁸ are the same as those exemplified above. In the repeating unit represented by the general formula (3), as the linear or branched alkylene group having 2 to 9 carbon atoms represented by Y, the linear or branched alkylene group having 1 to 10 carbon atoms described above is used. Among the chain-like alkylene groups, those having a carbon number other than 1 and 10 are exemplified.

In the repeating unit represented by the general formula (4), the linear, branched or cyclic alkylene group having 2 to 9 carbon atoms represented by X includes the above-mentioned 1 to 1 carbon atoms.
Among the 0 linear, branched or cyclic alkylene groups, those having a carbon number other than 1 and 10 are exemplified. Examples of the linear or branched alkylene group having 2 to 9 carbon atoms represented by Y include the same as those described above.

In the repeating unit represented by the general formula (5), A, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷
And the substituents represented by R ⁸ are the same as those exemplified above. In the repeating unit represented by the general formula (5), examples of the linear or branched alkylene group having 2 to 9 carbon atoms represented by Z include the same as those exemplified above.

In the repeating unit represented by the general formula (6), the linear, branched or cyclic alkylene groups having 2 to 9 carbon atoms represented by X and Z are the same as those exemplified above. Is mentioned. The ultraviolet absorbing polymer according to the present invention comprises a first ultraviolet absorbing polymer which is a polycarbonate copolymer, a second ultraviolet absorbing polymer which is a polyester copolymer, and a third ultraviolet absorbing polymer which is a polyurethane copolymer. It is classified into three types of polymers.

Hereinafter, the first to third ultraviolet absorbing polymers according to the present invention and the weather resistant resin composition using the ultraviolet absorbing polymer of the present invention will be described in detail. [Polycarbonate copolymer and resin composition using the same] (Polycarbonate copolymer) The first ultraviolet absorbing polymer according to the present invention uses the bisbenzotriazole-based compound (7) as a diol component, a) This bisbenzotriazole-based compound (7) is represented by the following general formula (8):

[0048]

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Wherein B, R ⁹ , R ¹⁰ , R ¹¹ and R ¹²
Is the same as above. Phosgene is reacted with the diol component represented by () (interfacial polymerization method, pyridine method)
Alternatively, the bisbenzotriazole-based compound (7) is directly reacted with a previously produced diphenyl carbonate (melt kneading method), or (b) the bisbenzotriazole-based compound (7) is melted together with a previously produced polycarbonate-based resin and subjected to transesterification (re-mixing). Active processing method), which contains the repeating unit represented by the formula (1) in a proportion of 0.01 to 70% by weight of the whole.
It is a polycarbonate copolymer having a viscosity average molecular weight of 5,000 to 100,000.

When the content of the repeating unit represented by the above formula (1) is less than 0.01% by weight, the ultraviolet absorbing ability of the obtained polymer decreases. Conversely, when the content of the repeating unit represented by the above formula (1) exceeds 70% by weight, the physical properties of the polymer deteriorate. The content ratio of the repeating unit represented by the formula (1) is particularly preferably 0.05 to 50% by weight, more preferably 0.1 to 30% by weight in the above range.

The molecular weight of the first ultraviolet absorbing polymer (polycarbonate copolymer) is determined by the viscosity average molecular weight Mv.
5,000 to 100,000. Viscosity average molecular weight Mv
Is less than 5,000, the component derived from the bisbenzotriazole-based compound represented by the general formula (7) easily oozes out of the ultraviolet-absorbing polymer, or the ultraviolet-absorbing polymer is contained in the polycarbonate-based resin. When a weather-resistant resin composition is used, the UV-absorbing polymer itself easily oozes out. Conversely, when the viscosity average molecular weight Mv is 1000
If it exceeds 00, the compatibility will be reduced when the UV-absorbing polymer is contained in the polycarbonate-based resin to form a weather-resistant resin composition, so that a sufficient amount cannot be contained.

The viscosity-average molecular weight Mv of the first UV-absorbing polymer is preferably in the range of 10,000 to 800.
It is preferably 00, more preferably 20,000 to 50,000. (Synthesis Method of Polycarbonate Copolymer) In the case of synthesizing the first UV-absorbing polymer (polycarbonate copolymer), as described in (a) above, the interface is a general polycarbonate synthesis method. The reaction may be performed based on a polymerization method or a pyridine method, or may be performed based on a melt-kneading method.

In the interfacial polymerization method, in a two-phase system of an organic solvent inert to the reaction and an aqueous alkali solution, a molecular weight regulator and a terminal terminator are appropriately blended, and a bisbenzo compound represented by the general formula (7) is added. The triazole compound may be reacted with phosgene together with the diol component represented by the general formula (8). In this method, a bisbenzotriazole-based compound (7) is reacted with phosgene to form a dichloroformate, and then another diol component is added to carry out a copolymerization reaction. A method of preparing a dichloroformate of another diol component and then adding a bisbenzotriazole-based compound (7) to carry out a copolymerization reaction can also be suitably used.

In the above interfacial polymerization method, the reaction temperature is set at 0
The reaction may be performed at a temperature of from about 50 ° C., preferably from 10 to 30 ° C., for about 1 to 10 hours, preferably about 2 to 5 hours. In the pyridine method, the bisbenzotriazole compound (7)
And a diol component represented by the general formula (8) and a molecular weight regulator or a terminal terminator are dissolved in pyridine (or a mixed solvent of pyridine and an organic solvent inert to the reaction),
Then, phosgene may be blown into the reaction.

In the above pyridine method, the reaction temperature is set at 0
The reaction may be performed at a temperature of from about 50 ° C., preferably from 10 to 30 ° C., for about 1 to 10 hours, preferably about 2 to 5 hours. In the melt-kneading method, the bisbenzotriazole-based compound represented by the general formula (7), together with the diol component represented by the general formula (8), a diphenyl carbonate previously produced, an alkali metal salt, and a transition metal The reaction may be performed by melt-kneading under reduced pressure in the presence of a polymerization catalyst such as a metal halide, a tertiary amine or a quaternary amine.

In the melt-kneading method, the reaction temperature is set at 1
00 to 350 ° C., preferably 200 to 300 ° C.
The reaction may be performed under a reduced pressure of 0 mmHg or less for 0.5 to 10 hours, preferably 1 to 5 hours. The interfacial polymerization method,
In the pyridine method and the melt-kneading method, the amount of the bisbenzotriazole-based compound (7) used is appropriately determined so as to set the content of the repeating unit represented by the formula (1) in the ultraviolet absorbing polymer within a predetermined range. Is set. For example, the use ratio of the bisbenzotriazole compound (7) to the total amount of the bisbenzotriazole compound (7) and the diol component represented by the general formula (8) is approximately 0.01 to 70.
%, Preferably 0.05 to 50% by weight, more preferably 0.1 to 30% by weight.

Specific examples of the diol component represented by the general formula (8) include conventionally known diol components used for producing polycarbonate. For example, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide,
Bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4
-Hydroxyphenyl) propane, 2,2-bis (4-
Hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-
(Hydroxy-3,5-dibromophenyl) propane,
2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-
Bromophenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) And dihydric phenol compounds such as 1-phenylethane. These may be used alone or in combination of two or more.

As the polymerization catalyst, conventionally known polymerization catalysts can be used widely, for example, sodium hydroxide, potassium hydroxide,
Alkali metals such as lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, sodium methoxide, sodium ethoxide, lithium methoxide, lithium ethoxide, potassium t-butoxide, and fatty acid salts of sodium Salts; alkaline earth metal salts such as calcium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate; transition metal halides such as tin chloride, zinc chloride, ferric chloride, lead chloride; trimethylamine, triethylamine, tributylamine Tertiary amines such as trimethylamine, tripropylamine, trihexylamine, tridecylamine, N, N-dimethylcyclohexylamine, pyridine, quinoline, and dimethylaniline; Ammonium chloride, quaternary ammonium salts such as triethylbenzylammonium chloride and the like.

The reaction solvent is preferably inert to the reaction, for example, dichloromethane, chloroform,
Halogenated hydrocarbons such as 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, carbon tetrachloride, monochlorobenzene, dichlorobenzene, benzene, toluene, xylene, ethylbenzene, etc. Aromatic hydrocarbons, diethyl ether,
Examples thereof include ethers such as dibutyl ether, and these organic solvents can be used alone or as a mixture of two or more. If desired, a solvent having an affinity for water such as ketones, esters or nitriles other than those described above may be mixed with another solvent, and the mixed solvent may be used within a limit that is not completely compatible with water. Good.

Examples of the molecular weight modifier or terminal terminator include:
Usually, compounds having a monovalent phenolic hydroxyl group, for example, phenol, p- (t-butyl) phenol, tribromophenol, long-chain alkylphenol, and the like are used, and the amount of use thereof is all polycondensation monomers (bisbenzotriazole compounds). (1) 0.5 to the total amount of other diol components such as dihydric phenol compounds and phosgene).
５０50 mol%, preferably 1-30 mol%. In addition, the above-exemplified molecular weight regulators or terminal stoppers may be used alone or in combination of two or more.

When the first ultraviolet absorbing polymer (polycarbonate copolymer) is synthesized by the reactive processing method (b), the viscosity average molecular weight is 50.
The transesterification reaction may be performed using a general-purpose polycarbonate resin having a molecular weight of 100 to 100,000. In the reactive processing method, the bisbenzotriazole-based compound represented by the general formula (7) may be blended and kneaded together with the transesterification catalyst at a temperature at which the general-purpose polycarbonate melts.

As the transesterification catalyst used in the reactive processing method, specifically, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate , Sodium methoxide, sodium ethoxide, lithium methoxide, lithium ethoxide, potassium t-butoxide, alkali metal salts such as sodium fatty acid salts; alkaline earths such as calcium hydroxide, magnesium hydroxide, calcium carbonate and magnesium carbonate Metal salts; tin chloride, zinc chloride, ferric chloride,
Halides of transition metals such as lead chloride; triethylamine, trimethylamine, diethylamine, dimethylamine, pyridine, trimethylamine, diethylamine, dimethylamine, pyridine, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1 , 4-diazabicyclo [2.2.2] octane (DABCO) and the like, and these can be used alone or in combination of two or more.

The amount of the transesterification catalyst to be used is suitably set in the range of 0.0005 to 5 parts by weight per 100 parts by weight of the polycarbonate resin. The general-purpose polycarbonate resin used in the reactive processing method is not particularly limited except that the viscosity average molecular weight is in the above-mentioned range, but 2,2-bis (hydroxyphenyl) propane known as bisphenol A, and phosgene It is preferred to use the reaction product of

The method of the transesterification reaction is not particularly limited. For example, after dry-blending the polycarbonate resin, the transesterification catalyst and the bisbenzotriazole compound represented by the general formula (7), the mixture is charged into a molding machine. After heating and melting at a temperature of about 230-330 ° C,
By aging for about 1 to 15 minutes, a transesterification reaction of the polycarbonate resin can be performed.

In the above reactive processing method, the amount of the bisbenzotriazole compound (7) used is
The content of the repeating unit represented by the formula (1) in the ultraviolet absorbing polymer is appropriately set so as to be within a predetermined range. For example, the use ratio of the bisbenzotriazole-based compound (7) to the total amount of the general-purpose polycarbonate-based resin and the bisbenzotriazole-based compound (7) that performs a transesterification reaction on the resin is approximately 0.01 to 70% by weight. Preferably, it is set in the range of 0.05 to 50% by weight, more preferably 0.1 to 30% by weight.

The first UV-absorbing polymer (polycarbonate copolymer) according to the present invention is produced by essentially including each of the above-mentioned components. ~ 3 mol%, preferably 0.1
A branched polycarbonate copolymer may be used in combination within the range of from 1.0 to 1.0 mol%. As a branching agent,
Phloroglysin, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -3-heptene, 1,3
5-tri (2-hydroxyphenyl) pentane, 2,6
Polyhydroxy such as -bis (2-hydroxyphenyl) benzotriazole, 1,1,1-tri (4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol Examples include compounds.

(Weather-Resistant Resin Composition Using Polycarbonate Copolymer) The first UV-absorbing polymer (polycarbonate copolymer) according to the present invention may be used alone, but it may be a general-purpose polycarbonate resin. Resin as a base resin, blending the above UV-absorbing polymer with this,
It can also be used as a weather resistant resin composition.

The content ratio of the ultraviolet absorbing polymer in the weather resistant resin composition is set to 0.05 to 50% by weight based on the polycarbonate resin. If the content of the ultraviolet absorbing polymer is less than 0.05% by weight, the weather resistant resin composition cannot exhibit a sufficient ultraviolet absorbing ability. Conversely, if it exceeds 50% by weight, physical properties such as mechanical strength and hardness of the molded article of the weather-resistant resin composition and moldability of the resin composition will be reduced.

The content of the ultraviolet absorbing polymer is preferably 1 to 30% by weight in the above range.
More preferably, it is 5 to 20% by weight. The first UV-absorbing polymer according to the present invention may be a weather-resistant resin composition based on a synthetic resin other than the polycarbonate resin. Such a synthetic resin is not particularly limited, and various conventionally known resins can be used. However, it is preferable to use a thermoplastic resin in consideration of the easiness of adding an ultraviolet absorbing polymer. As the thermoplastic resin, for example, polyvinyl chloride,
Polyvinylidene chloride, polyolefin, polystyrene,
Acrylic resin, methacrylic resin, polyamide, polyester, acrylonitrile-butadiene-styrene (AB
S) Resin, thermoplastic polyurethane resin, polyurethane urea resin, vinyl chloride-vinylidene chloride-acrylonitrile copolymer, acrylonitrile-styrene (AS) resin, vinyl acetate resin, polyphenylene ether, polysulfone, polyether sulfone, polyether ether ketone, And liquid crystal plastics. Among them, for example, polyester, thermoplastic polyurethane resin and the like can be preferably used.

(Other Additives) In addition to the above-mentioned components, the first ultraviolet absorbing polymer (polycarbonate copolymer) and the resin composition using the same according to the present invention include:
Further, other additives can be blended as required. Examples of such other additives include various conventionally known additives such as a light stabilizer, an antioxidant, a flame retardant, an antistatic agent, a plasticizer, a filler, a pigment, and a colorant.

(Use of Polycarbonate Copolymer and Resin Composition Using the Same) The first ultraviolet absorbing polymer (polycarbonate copolymer) according to the present invention and the resin composition using the same were all excellent. Due to its ability to absorb ultraviolet light, it is particularly effective in applications where high weather resistance is required. It can be molded in the same manner as a normal polycarbonate resin, and can be molded by a known molding method, for example, injection molding, extrusion molding, blow molding, biaxial centrifugal blow molding, press molding, melt spinning, etc. It can be used as a coating by dissolving or dispersing in a suitable solvent or aqueous solvent.

The molded article obtained from the first UV-absorbing polymer (polycarbonate copolymer) and the resin composition using the same according to the present invention is not particularly limited. It can be used particularly suitably for applications that may be exposed. Specific examples thereof include window glass substitutes for homes, facilities, transportation equipment and the like, and coating materials therefor; architectural and civil engineering materials such as daylighting plates, carports, rain gutters, and gratings; fluorescent lamps, mercury lamps, halogen lamps, and the like. Light source member that emits ultraviolet light; headlamp lens,
Automotive parts such as consoles, cluster panels, and outer panel parts; precision mechanical parts such as camera and VTR mechanical parts and exterior parts; electric / electronic / OA equipment parts such as housings for personal computers and printers; CRT displays , Liquid crystal display, filter material for various displays such as plasma display; CD, MD,
Optical discs such as DVDs; security equipment such as helmets and dust-proof glasses; daily miscellaneous goods such as microwave oven containers, baby tableware and lightweight cups; medical equipment such as artificial dialysis machines and blood filters; Surface coating agents for vessels and the like. In addition, the first ultraviolet absorbing polymer (polycarbonate copolymer) according to the present invention and a molded product such as a glass substitute or a food packaging material obtained from the resin composition using the same are in a state where the contents are visible. For protecting the contents by blocking ultraviolet rays.

[Polyester Copolymer and Resin Composition Using the Same] (Polyester Copolymer) The second ultraviolet absorbing polymer according to the present invention is the bisbenzotriazole-based compound
(7) is used as a diol component, and (c) the bisbenzotriazole-based compound (7) is represented by the following general formula (9):

[0074]

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(Wherein X is as defined above), together with a diol component represented by the following general formula (10):

[0076]

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[0077] The (wherein, Y is the same as defined above, and.) In is lower alkyl esters and transesterification of dicarboxylic acid represented make further polycondensation by, or; (d) bis benzotriazole compounds (7) It is obtained by polycondensation with a diol component represented by the general formula (9) and a dicarboxylic acid represented by the general formula (10) by dehydration condensation, and represented by the formula (3). It is a polyester copolymer having a viscosity-average molecular weight of 5,000 to 100,000 and containing the repeating unit in an amount of 0.01 to 70% by weight of the whole.

When the content of the repeating unit represented by the formula (3) is less than 0.01% by weight, the ultraviolet absorbing ability of the obtained polymer decreases. Conversely, when the content of the repeating unit represented by the above formula (3) exceeds 70% by weight, the physical properties of the polymer deteriorate. The content ratio of the repeating unit represented by the formula (3) is particularly preferably from 0.05 to 50% by weight, more preferably from 0.1 to 30% by weight in the above range.

The molecular weight of the second ultraviolet absorbing polymer (polyester copolymer) is 5 in terms of viscosity average molecular weight Mv.
000 to 100,000. Viscosity average molecular weight Mv of 5
If it is less than 000, the component derived from the bisbenzotriazole-based compound represented by the general formula (7) easily oozes out of the UV-absorbing polymer, or the UV-absorbing polymer is contained in the polyester-based resin to provide weather resistance. When the resin composition is used, the UV-absorbing polymer itself easily oozes out. Conversely, when the annual average molecular weight Mv exceeds 100,000, when the UV-absorbing polymer is contained in the polyester-based resin to form a weatherable resin composition, the compatibility may be reduced and a sufficient amount may be contained. become unable.

The viscosity-average molecular weight Mv of the second UV-absorbing polymer is preferably in the range of 10,000 to 8
0000, preferably 20,000 to 50,000
Is more preferable. (Synthesis Method of Polyester Copolymer) When the second UV-absorbing polymer (polyester copolymer) is synthesized by the method (c), first, the bisbenzotriazole-based compound (7) and the general A diol component represented by the formula (9) is added in excess to the lower alkyl ester of the dicarboxylic acid represented by the general formula (10),
Heating is performed at 350 ° C., preferably 150 to 300 ° C., for about 0.5 to 5 hours, preferably about 1 to 3 hours, while distilling off the generated alcohol. Then, under reduced pressure, preferably under high vacuum, for about 1 to 20 hours, preferably 5 to 1 hour.
The reaction may be performed for about 5 hours.

On the other hand, when synthesizing by the method (d), the temperature is 100 to 350 ° C., preferably 200 to 300 ° C.
The reaction may be performed at a temperature of about 1 to 20 hours, preferably about 5 to 15 hours. Specific examples of the diol component represented by the general formula (9) include conventionally known diol components used in the production of polyester. For example, ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, nonamethylene glycol, cyclohexanedimethanol, diethylene glycol and the like can be mentioned. These may be used alone or in a mixture of two or more. Furthermore, trifunctional or higher polyfunctional compounds, such as glycerin, trimethylolpropane, pentaerythritol, trimellitic acid,
Trimesic acid, pyromellitic acid and the like may be used in a range where melt molding is possible.

Specific examples of the dicarboxylic acid represented by the general formula (10) include conventionally known dicarboxylic acids used in the production of polyester. For example, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid; aliphatic dicarboxylic acids such as adipic acid, azelaic acid and sebacic acid; and esters thereof. These may be used alone or in a mixture of two or more.

The lower alkyl in the lower alkyl ester of dicarboxylic acid is, for example, methyl,
Ethyl, n-propyl, i-propyl, n-butyl, t
And C1-C4 alkyl groups, such as -butyl. In the above synthesis methods (c) and (d), the amount of the bisbenzotriazole compound (7) used is such that the content of the repeating unit represented by the formula (3) in the ultraviolet absorbing polymer falls within a predetermined range. It is set as appropriate to set. For example, bisbenzotriazole compound (7), a diol component represented by the general formula (9), and a dicarboxylic acid (or a lower alkyl ester thereof) represented by the general formula (10), and The use ratio of the triazole compound (7) is about 0.01 to 70% by weight, preferably 0.1 to 70% by weight.
05 to 50% by weight, more preferably 0.1 to 30% by weight
May be set in the range.

(Weather-Resistant Resin Composition Using Polyester Copolymer) The second UV-absorbing polymer (polyester copolymer) according to the present invention may be used alone, but may be a general-purpose polyester resin. A resin may be used as a base resin, and the ultraviolet absorbing polymer may be blended with the resin to use as a weather resistant resin composition.

The content ratio of the ultraviolet absorbing polymer in the weather resistant resin composition is set to 0.05 to 50% by weight based on the polyester resin. If the content of the ultraviolet absorbing polymer is less than 0.05% by weight, the weather resistant resin composition cannot exhibit a sufficient ultraviolet absorbing ability.
Conversely, if it exceeds 50% by weight, physical properties such as mechanical strength and hardness of the molded article of the weather-resistant resin composition and moldability of the resin composition will be reduced.

The content of the ultraviolet absorbing polymer is preferably 1 to 30% by weight in the above range.
More preferably, it is 5 to 20% by weight. The second ultraviolet absorbing polymer according to the present invention may be a weather resistant resin composition based on a synthetic resin other than the polyester resin. Such a synthetic resin is not particularly limited, and various conventionally known resins can be used. However, it is preferable to use a thermoplastic resin in consideration of the easiness of adding an ultraviolet absorbing polymer. Examples of the thermoplastic resin include polyvinyl chloride, polyvinylidene chloride, polyolefin, polycarbonate, polystyrene, acrylic resin, methacrylic resin, polyamide, acrylonitrile-butadiene-styrene (ABS) resin, thermoplastic polyurethane resin, polyurethane urea resin, and vinyl chloride. -Vinylidene chloride-acrylonitrile copolymer, acrylonitrile-styrene (A
S) resin, vinyl acetate resin, polyphenylene ether,
Examples thereof include polysulfone, polyether sulfone, polyether ether ketone, and liquid crystal plastic. Among them, for example, polycarbonate, thermoplastic polyurethane resin and the like can be preferably used.

(Other Additives) In addition to the above-mentioned components, the second ultraviolet absorbing polymer (polyester copolymer) and the resin composition using the same according to the present invention may further contain, if necessary, Other additives can be included. Examples of such other additives include various conventionally known additives such as a light stabilizer, an antioxidant, a flame retardant, an antistatic agent, a plasticizer, a filler, a pigment, and a colorant.

(Use of Polyester Copolymer and Resin Composition Using It) The second ultraviolet absorbing polymer (polyester copolymer) according to the present invention and the resin composition using the same were all excellent. Due to its ability to absorb ultraviolet light, it is particularly effective in applications where high weather resistance is required. It can be molded in the same manner as a normal polyester resin, and can be molded by a known molding method, for example, injection molding, extrusion molding, blow molding, biaxial centrifugal blow molding, press molding, melt spinning, etc. It can be used as a coating by dissolving or dispersing in a suitable solvent or aqueous solvent.

The molded product obtained from the second ultraviolet-absorbing polymer (polyester copolymer) and the resin composition using the same according to the present invention is not particularly limited, but is directly exposed to ultraviolet light or sunlight. It can be used particularly suitably for applications that may be exposed. Specific examples thereof include a member for a light source that emits ultraviolet light such as a fluorescent lamp, a mercury lamp, and a halogen lamp; a member for precision machinery such as a clock and a camera; various connectors;
Materials for electronic and electrical equipment such as plugs and key tops of personal computers; Materials for shielding electromagnetic waves generated from various displays such as CRT displays, liquid crystal displays, and plasma displays; Containers or packaging materials for foods, cosmetics, chemicals, drugs, etc. Agricultural or industrial sheets or films; printed materials, dyed goods, anti-fading agents such as dyes and pigments; sportswear, medical textile products such as hats, textiles, curtains,
Household interior goods such as carpets; surface coating materials for sign boards, sign devices and the like. In addition, the molded products such as agricultural and industrial films, fibers, and packaging materials obtained from the second ultraviolet absorbing polymer (polyester copolymer) and the resin composition using the same according to the present invention make the contents visible. It can be suitably used for applications where it is required to protect the contents by blocking ultraviolet rays in a proper state.

[Polyurethane Copolymer and Resin Composition Using the Same] (Polyurethane Copolymer) The third UV-absorbing polymer according to the present invention is the bisbenzotriazole compound
(7) is used as a diol component, and (e) this bisbenzotriazole-based compound (7) is used together with a diol component represented by the aforementioned general formula (9) together with a general formula (11):

[0091]

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(F) wherein the bisbenzotriazole compound (7) is polyadded to a diisocyanate represented by the formula (9), wherein Z is the same as defined above. Along with the diol component, general formula (12):

[0093]

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(Wherein Z is the same as described above.) Transesterification with biscarbamic acid ester, or
(g) The bisbenzotriazole-based compound (7) is converted into a bischloroformate, and the diol component represented by the general formula (9) is used together with the diol component represented by the general formula (9):

[0095]

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(Wherein Z is the same as defined above), which is obtained by reacting with a diamine represented by the above formula (5),
1 to 70% by weight, having a viscosity average molecular weight of 5
000 to 100,000 polyurethane copolymer.

When the content of the repeating unit represented by the above formula (5) is less than 0.01% by weight, the resulting polymer has a low ultraviolet absorbing ability. Conversely, when the content of the repeating unit represented by the above formula (5) exceeds 70% by weight, the physical properties of the polymer deteriorate. The content ratio of the repeating unit represented by the above formula (5) is particularly preferably from 0.05 to 50% by weight, more preferably from 0.1 to 30% by weight in the above range.

The molecular weight of the third ultraviolet absorbing polymer (polyurethane copolymer) is 5 in terms of viscosity average molecular weight Mv.
000 to 100,000. Viscosity average molecular weight Mv of 5
If it is less than 000, the component derived from the bisbenzotriazole-based compound represented by the general formula (7) easily oozes out of the UV-absorbing polymer, or the UV-absorbing polymer is contained in the polyester-based resin to provide weather resistance When the resin composition is used, the UV-absorbing polymer itself easily oozes out. Conversely, when the annual average molecular weight Mv exceeds 100,000, when the UV-absorbing polymer is contained in the polyester-based resin to form a weatherable resin composition, the compatibility may be reduced and a sufficient amount may be contained. become unable.

The viscosity average molecular weight Mv of the third ultraviolet absorbing polymer is preferably 10,000 to 8
0000, preferably 20,000 to 50,000
Is more preferable. (Synthesis Method of Polyurethane Copolymer) When the third UV-absorbing polymer (polyurethane copolymer) is synthesized by the method (e), the bisbenzotriazole-based compound (7) and the general formula (7) 9) and a diisocyanate represented by the general formula (11) at 50 to 200 ° C, preferably 1 to 80 to 120 ° C.
The reaction may be carried out for about 20 hours, preferably for about 2 to 10 hours.

When the third UV-absorbing polymer (polyurethane copolymer) is synthesized by the method (f), it is represented by the bisbenzotriazole compound (7) and the general formula (9). With a diol component, the general formula (12)
Is added in excess to the biscarbamic acid ester represented by the formula, and the formed alcohol is distilled off at 80 to 200 ° C, preferably 100 to 150 ° C, for about 0.5 to 5 hours, preferably about 1 to 3 hours. While heating. Next, the reaction may be performed under reduced pressure, preferably under high vacuum, for about 5 to 50 hours, preferably for about 10 to 30 hours.

On the other hand, when the third ultraviolet absorbing polymer (polyurethane copolymer) is synthesized by the method (g), the bisbenzotriazole compound (7)
A bischloroformate of the diol component represented by the general formula (9) in the presence of a dehydrochlorinating agent at 30 to 150 ° C., preferably 50 to 150 ° C.
-100 ° C for about 0.5-20 hours, preferably 1-1
The reaction may be carried out with the diamine for about 0 hours.

Specific examples of the diisocyanate represented by the general formula (11) include conventionally known diisocyanates used in the production of polyurethane. For example, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, nanomethylene diisocyanate, aliphatic diisocyanate such as cyclohexane diisocyanate, 1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate,
And aromatic diisocyanates such as 2,6-tolylene diisocyanate and 2,4-tolylene diisocyanate. These may be used alone or in a mixture of two or more.

Specific examples of the diol component represented by the general formula (9) include conventionally known diol components used in the production of polyurethane. For example, ethylene glycol, propylene glycol, tetramethylene glycol, heptamethylene glycol, hexamethylene glycol, octamethylene diol, nonamethylene glycol, cyclohexane dimethanol, diethylene glycol and the like can be used, and these can be used alone or in a mixture of two or more. May be.

Examples of the biscarbamic acid ester used in the transesterification reaction include ethyl propylene biscarbamate, ethyl tetramethylenebiscarbamate, ethyl hexamethylenebiscarbamate, ethyl nanomethylenedibiscarbamate, and ethyl cyclohexanedibiscarbamate. N-propyl propylene biscarbamate, n-propyl tetramethylenebiscarbamate, n-propyl hexamethylenebiscarbamate, n-butyl propylenebiscarbamate, n-butyl tetramethylenebiscarbamate, n-hexamethylenebiscarbamate Aliphatic biscarbamic acid esters such as -butyl,
Ethyl 1,4-phenylenebiscarbamate, 1,3-
Ethyl phenylenebiscarbamate, ethyl 2,6-tolylenebiscarbamate, ethyl 2,4-tolylenebiscarbamate, 1,4-phenylenebiscarbamate n
-Propyl, 1,3-phenylenebiscarbamic acid n-
Propyl, n-propyl 2,6-tolylenebiscarbamate, n-propyl 2,4-tolylenebiscarbamate, n-butyl 1,4-phenylenebiscarbamate,
N-butyl 1,3-phenylenebiscarbamate, 2,
Aromatic biscarbamic acid esters such as n-butyl 6-tolylenebiscarbamate and n-butyl 2,4-tolylenebiscarbamate are exemplified. These may be used alone or in a mixture of two or more.

In the above synthesis methods (e) to (f), the amount of the bisbenzotriazole compound (7) used is determined based on the content of the repeating unit represented by the formula (5) in the ultraviolet absorbing polymer. Is appropriately set in order to set the range. For example, a bisbenzotriazole compound (7) and a compound of the general formula
A diol component represented by (9), a diisocyanate represented by the general formula (11), a biscarbamic acid ester represented by the general formula (12) or a general formula (13) The use ratio of the bisbenzotriazole compound (7) to the total amount with the diamine is in the range of about 0.01 to 70% by weight, preferably 0.05 to 50% by weight, more preferably 0.1 to 30% by weight. Just set it.

(Weather-Resistant Resin Composition Using Polyurethane Copolymer) The third UV-absorbing polymer (polyurethane copolymer) according to the present invention may be used alone, but may be a general-purpose polyurethane resin. A resin may be used as a base resin, and the ultraviolet absorbing polymer may be blended with the resin to use as a weather resistant resin composition.

The content ratio of the ultraviolet absorbing polymer in the weather resistant resin composition is set to 0.05 to 50% by weight based on the polyurethane resin. If the content of the ultraviolet absorbing polymer is less than 0.05% by weight, the weather resistant resin composition cannot exhibit a sufficient ultraviolet absorbing ability.
Conversely, if it exceeds 50% by weight, physical properties such as mechanical strength and hardness of the molded article of the weather-resistant resin composition and moldability of the resin composition will be reduced.

The content ratio of the ultraviolet absorbing polymer is preferably 1 to 30% by weight in the above range.
More preferably, it is 5 to 20% by weight. The third UV-absorbing polymer according to the present invention may be a weather-resistant resin composition based on a synthetic resin other than the polyurethane resin. Such a synthetic resin is not particularly limited, and various conventionally known resins can be used. However, it is preferable to use a thermoplastic resin in consideration of the easiness of adding an ultraviolet absorbing polymer. Examples of the thermoplastic resin include polyvinyl chloride, polyvinylidene chloride, polyolefin, polycarbonate, polystyrene, acrylic resin, methacrylic resin, polyamide, polyester, acrylonitrile-butadiene-styrene (ABS) resin, polyurethane urea resin, and vinyl chloride-vinylidene chloride. Acrylonitrile copolymer, acrylonitrile-styrene (AS) resin, vinyl acetate resin, polyphenylene ether, polysulfone, polyethersulfone, polyetheretherketone, liquid crystal plastic, and the like. Among them, for example, polycarbonate, thermoplastic polyurethane resin and the like can be preferably used.

(Other Additives) In addition to the above-mentioned components, the third ultraviolet absorbing polymer (polyurethane copolymer) and the resin composition using the same according to the present invention may further comprise Other additives can be included. Examples of such other additives include various conventionally known additives such as a light stabilizer, an antioxidant, a flame retardant, an antistatic agent, a plasticizer, a filler, a pigment, and a colorant.

(Use of Polyurethane Copolymer and Resin Composition Using the Same) The third ultraviolet absorbing polymer (polyurethane copolymer) according to the present invention and the resin composition using the same were all excellent. Due to its ability to absorb ultraviolet light, it is particularly effective in applications where high weather resistance is required. It can be molded in the same manner as ordinary thermoplastic polyurethane resins, and can be molded by known molding methods, for example, injection molding, extrusion molding, blow molding, biaxial centrifugal blow molding, press molding, melt spinning, and the like. It can also be used as a coating by dissolving or dispersing in a suitable solvent or aqueous solvent.

The molded product obtained from the third ultraviolet absorbing polymer (polyurethane copolymer) and the resin composition using the same according to the present invention is not particularly limited, but is directly exposed to ultraviolet light or sunlight. It can be used particularly suitably for applications that may be exposed. Specific examples include interior / exterior materials and interior / exterior paints for houses, facilities, transportation equipment, and the like;
Automotive components such as handles and bumpers; roofing waterproofing, sealing and other construction and civil engineering materials; adhesives for food packaging; hoses and tubes such as spiral tubes and high-pressure hoses; precision machinery parts such as watches; Electricity such as copy machine
Materials for electronic and OA equipment; Containers or packaging materials for foods, chemicals, drugs, etc .; Sheets or films for agriculture and industry; Discoloration inhibitors such as printed matter, dyed matter, dyes and pigments; Surface of paper for inkjet printing etc. Processing materials; textiles and textiles for clothing such as sportswear, stockings, swimwear, hats, etc .;
Synthetic leather for bags, shoes, clothing, etc .; sporting goods such as ski boots, grips for golf clubs, soles for sports shoes; home interior goods such as curtains, carpets, wallpapers, etc .; And the like. Further, the molded article such as the fiber obtained from the third ultraviolet absorbing polymer (polyurethane copolymer) and the resin composition using the same according to the present invention can protect the contents by blocking ultraviolet rays. It can be suitably used for required applications.

[0112]

(Production of bisbenzotriazole-based compound)

Synthesis Example 1 In a four-necked flask equipped with a cooling tube, a nitrogen introducing tube, a thermometer, and a stirrer, 2,2′-methylenebis [6- (2H-
1,2,3-benzotriazol-2-yl) -4-
(2-hydroxyethyl) phenol] (trade name "RU
VA-100 "(manufactured by Otsuka Chemical Co., Ltd.) 129.3 g and ε-caprolactone (manufactured by Daicel Chemical Industries, Ltd.) 1
70.3 g, and further added a mono-n-butyltin fatty acid salt (trade name "SCAT-24", Sankyoki Gosei Co., Ltd.
Was added at a rate of 50 ppm.

Then, the reaction was carried out for 6 hours while maintaining the reaction temperature at 150 ° C. to obtain 2,2′-methylenebis [6- (2H-1,2,3-benzotriazole-
2-yl) -4- (23-hydroxy-4,11,18
-Trioxo-3,10,17-trioxatricosyl) phenol] (yield 98%). The target compound (bisbenzotriazole compound) is a viscous oil having an acid value (mgKOH / g) of 1.8 and a viscosity of 2
645 cP (60 ° C.), number average molecular weight (Mn) 139
1. Weight average molecular weight (Mw) 1688 and Mw / Mn
= 1.213.

Synthesis Example 2 The amount of “RUVA-100” was 93.7 g, and ε-
Except that the amount of caprolactone was 206.3 g,
The reaction was carried out in the same manner as in Synthesis Example 1, and the target compound, 2,2′-methylenebis [6- (2H-1,2,3-benzotriazol-2-yl) -4- (37-hydroxy-4, 11,18,25,32-pentaoxo-3,
10,17,24,31-pentaoxaheptatriacontyl) phenol] (yield 98%).

The target compound (bisbenzotriazole compound) is a wax-like solid and has an acid value (mg KOH
/ G) 2.5, viscosity 987 cP (60 ° C.), Mn = 20
17, Mw = 2465 and Mw / Mn = 1.222. [Production of Ultraviolet Absorbing Polymer] Example 1 (Production of Polycarbonate Copolymer) 0.356 g of the bisbenzotriazole-based compound obtained in Synthesis Example 1 (0.
295 mmol) and bisphenol-A 1.72
g (7.16 mmol) was dissolved in 60 ml of pyridine. This was stirred under a nitrogen stream while triphosgene [(CCl ₃ O) ₂ CO] 2.08 g (6.87 mmol)
l) was added slowly. After further stirring at room temperature for 1 hour, 250 ml of methanol was added to precipitate a polymer.

Next, the obtained polymer was separated by filtration and dried under reduced pressure to obtain 3.55 g of a white ultraviolet absorbing polymer (polycarbonate copolymer). The content of the ultraviolet absorbing unit in this ultraviolet absorbing polymer was 4.8% by weight. The ultraviolet absorbing unit indicates the content ratio of the bisbenzotriazole component in the polycarbonate copolymer, and measures the UV spectrum of the bisbenzotriazole-based compound and the ultraviolet absorbing polymer. It is calculated by the ratio.

The viscosity average molecular weight Mv of the ultraviolet absorbing polymer was 25,100. The viscosity average molecular weight Mv is calculated from the intrinsic viscosity measured using dichloromethane as a solvent. Example 2 (Production of polycarbonate copolymer) As a bisbenzotriazole-based compound, 0.491 g (0.295 mmol) of the bisbenzotriazole-based compound obtained in Synthesis Example 2 was used.
2. In the same manner as in Example 1 except that l) was used, a white ultraviolet absorbing polymer (polycarbonate copolymer)
79 g were obtained.

The content of the ultraviolet absorbing unit in this ultraviolet absorbing polymer was 5.18% by weight. The UV-absorbing polymer has a viscosity average molecular weight Mv of 29.
600. Example 3 (Production of polycarbonate copolymer) Polycarbonate pellet [trade name "E-200" manufactured by Mitsubishi Gas Chemical Company, Ltd.
0 ", viscosity average molecular weight Mv = 27000], 100 parts by weight of the bisbenzotriazole compound obtained in Synthesis Example 1 and 0.001 part by weight of triethylamine as a transesterification catalyst were dried. The blend was put into an extruder, heated at 270 ° C., and transesterified by melt-kneading for about 3 minutes. Next, this was extruded to obtain a pellet-shaped ultraviolet absorbing polymer (polycarbonate copolymer).

The conversion was measured by gel permeation chromatography (GPC) to be about 83%. The content of the ultraviolet absorbing unit was measured in the same manner as in Example 1, and it was 5.0% by weight. The viscosity average molecular weight Mv of the ultraviolet absorbing polymer was 12,700.

Example 4 (Production of polyester copolymer) 100 g (0.52 mol) of dimethyl terephthalate, ethylene glycol 7
2 g (1.16 mol) and 30 mg of manganese acetate tetrahydrate were mixed, heated to 140 ° C., and further heated to 240 ° C. for about 3 hours while stirring, and about 15 g of methanol was distilled off. Next, 10 mg of phosphorous acid, 50 mg of germanium dioxide, and 8.53 g (1.93 mmol) of the bisbenzotriazole-based compound obtained in Synthesis Example 1
1) was added and polycondensed at 280 ° C. and 0.5 mmHg for about 2 hours to obtain 148.3 g of a light brown solid ultraviolet absorbing polymer (polyester copolymer).

The UV-absorbing polymer had a viscosity average molecular weight Mv of 31,500, and the content of the UV-absorbing unit was 5.02% by weight. The viscosity average molecular weight Mv
Was calculated from the intrinsic viscosity measured using a phenol / 1,1,2,2-tetrachloroethane mixed solution (weight ratio 1: 1). Example 5 (Production of polyurethane copolymer) 4-methylpentane-
25.02 g (0.1 mol) of diphenylmethane-4,4'-diisocyanate was added to 40 ml of 2-one,
Under vigorous stirring under a nitrogen atmosphere, a suspension was obtained. Then
To this suspension was previously added ethylene glycol 6.02.
g (97 mmol) and 3.5 g (2.9 mmol) of the bisbenzotriazole-based compound obtained in Synthesis Example 1 were dissolved in 40 ml of dimethyl sulfoxide. The reaction mixture is stirred for 115
C., and the reaction was carried out for about 2 hours. After completion of the reaction, the reaction mixture was poured into 200 ml of deionized water to precipitate a reaction product (polyurethane copolymer). The precipitate was dispersed in water, washed three times, and then dried under vacuum to obtain a substantially quantitative product. Then, a white ultraviolet absorbing polymer (polyurethane copolymer) was obtained.

The viscosity average molecular weight Mv of this ultraviolet absorbing polymer was 28,700, and the content of the ultraviolet absorbing unit was 4.87% by weight. The viscosity average molecular weight Mv
Was calculated from the intrinsic viscosity measured using phenol as a solvent. Test Examples 1 to 3 The polycarbonate copolymer obtained in Example 1 (Test Example 1), the polycarbonate copolymer obtained in Example 2 (Test Example 2), and the polycarbonate copolymer obtained in Example 3 (Test Example 3) 105 parts by weight of 1, 2, 2,
This was dissolved in 630 parts by weight of 2-tetrachloroethane, and this solution was coated on a circular quartz plate having a diameter of 300 mm using a spinner.

After the obtained coating film was air-dried for 1 hour,
And dried under reduced pressure for 12 hours.
Was formed. Then, this was added to a Dew Cycle Sunshine Weather Meter (“WEL-SUN-DC” manufactured by Suga Test Instruments Co., Ltd.) for 1 cycle every 120 minutes.
8 hours rainfall) and 1200 hours weather resistance test
The degree of yellowing (ΔYI) of the coating film was measured.

If the yellowing degree (ΔYI) after 1200 hours has passed, it can be said that the weather resistance is sufficient. on the other hand,
Commercially available polycarbonate resin containing no ultraviolet absorbent such as bisbenzotriazole-based compound (the trade name "E
-2000 ") in 100 parts by weight of 630 parts by weight of 1,1,2,2-tetrachloroethane.
5 parts by weight of the ultraviolet absorbent A represented by the following formula (Comparative Example 1) or 5 parts by weight of the ultraviolet absorbent B represented by the following formula (B) (Comparative Example 2).

[0125]

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Using the composition solution thus obtained, a film formation and an acceleration test were performed in the same manner as in Test Example 1, and the yellowing degree (ΔYI) of the resin film was measured. Test Examples 1-3 and Comparative Example 1,
Table 1 shows the formulation (parts by weight) and the measurement results of the yellowing degree (ΔYI) in Table 2.

[0127]

[Table 1]

As is clear from Table 1, the ultraviolet absorbent A
Or, while the resin films containing B (Comparative Examples 1 and 2) clearly turned yellow, the case where the polycarbonate copolymer obtained in Examples 1 to 3 was used (Test Examples 1 to 3) was practically used. It was found that it did not yellow and had extremely high weather resistance. Test Examples 4 and 5 105 parts by weight of each of the polycarbonate copolymer synthesized in Example 1 (Test Example 4) and the polycarbonate copolymer synthesized in Example 2 (Test Example 5) were 1,1,2,2-tetrafluoroethylene. The solution was dissolved in 630 parts by weight of chloroethane, and this solution was coated on a 300 mm-diameter circular quartz plate using a spinner.

The resulting coating film was air-dried for 1 hour and then dried at 60 ° C. for 12 hours.
After drying under reduced pressure for a time, a uniform thin film having a thickness of about 1 μm was prepared on a circular quartz plate. Then, this after a circular quartz plate was left for 40 hours in deionized water at 70 ° C., the absorbance was measured U _A of the film after the water resistance test by UV spectrum (wavelength 345 nm), the absorbance of the water resistance test prior to film U _B (wavelength 345n
m) (Test Example 2). Then, the absorbance retention (%) was determined according to the following equation.

Absorbance retention (%) = U _A / U _B × 100 The higher the absorbance retention (%), the better. Particularly, it is required to be 90% or more in order to have excellent weather resistance. On the other hand, 100 parts by weight of a commercially available polycarbonate resin containing no ultraviolet absorbent such as a bisbenzotriazole-based compound (the above- mentioned trade name "E-2000") was added to 1,1,2,2.
-Dissolved in 630 parts by weight of tetrachloroethane and 5 parts by weight of ultraviolet absorber A (Comparative Example 3) or ultraviolet absorber B
Was blended in an amount of 5 parts by weight (Comparative Example 4). The composition solution thus obtained was formed into a film in the same manner as in Test Example 3, and subjected to a water resistance test to measure the absorbance retention.

Table 2 shows the results together with the formulation.

[0132]

[Table 2]

As is clear from Table 2, the ultraviolet absorbent elutes out of the resin film (comparative examples 3 and 4) containing the commercially available ultraviolet absorbent A or B in warm water with time, and after 40 hours, Has almost lost the ability to absorb ultraviolet light.
On the other hand, when the polycarbonate copolymers obtained in Examples 1 and 2 were used (Test Examples 4 and 5), the absorbance was hardly changed, the water resistance was good, and extremely high weather resistance was exhibited. understood.

Test Example 6 The polyester copolymer synthesized in Example 4 was melted to form a film having a thickness of about 100 μm. On the other hand, a commercially available polyethylene terephthalate (PET) resin containing no ultraviolet absorbent such as a bisbenzotriazole-based compound [trade name “MA-2103”,
Unitika Ltd.] 95 parts by weight, formula (C) or (D):

[0135]

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5 parts by weight of each of the ultraviolet absorbents C and D represented by the following formulas were dry-blended and melted to obtain films having a thickness of about 100 μm in the same manner as above (Comparative Example 5).
And 6). In Comparative Example 5, the ultraviolet absorbent C was scattered as a yellow-white sublimate during melt molding. Next, these were transferred to the Dew Cycle Sunshine Weather Meter WEL-SU.
After being subjected to a weathering acceleration test for 1200 hours by N-DC (manufactured by Suga Test Instruments Co., Ltd., rainfall for 18 minutes every 120 minutes),
The degree of yellowing (ΔYI) of each polyester resin was measured.

Table 3 shows the charge and blending of the film preparation and the yellowing degree after the weathering acceleration test.

[0138]

[Table 3]

As is apparent from Table 3, it was found that the polyester copolymer obtained in Example 4 had extremely excellent weather resistance. Test Example 7 100 parts by weight of the polyurethane copolymer synthesized in Example 5 was dissolved in 630 parts by weight of dimethylformamide, and this solution was coated on a 300 mm-diameter circular quartz plate using a spinner. The resulting coating film was air-dried for 1 hour and at 60 ° C.
And dried under reduced pressure for 12 hours.
Was prepared. Next, after this circular quartz plate was left in deionized water at 70 ° C. for 40 hours, Test Examples 3 and 4 were performed.
Absorbance retention after water resistance test (wavelength 34
5 nm). (Test Example 7) On the other hand, 95 parts by weight of a commercially available polyurethane resin containing no ultraviolet absorbent such as a bisbenzotriazole-based compound (trade name: Elastolane C90A50, manufactured by Takeda Birdish Urethane Industry Co., Ltd.) was added in an amount of 95 parts by weight to 630 parts by weight of dimethylformamide. And 5 parts by weight of the ultraviolet absorber A (Comparative Example 7) or 5 parts by weight of the ultraviolet absorber B (Comparative Example 8) were blended with Test Examples 3 and 4. Similarly, the film was subjected to film formation and a water resistance test, and the change with time in the absorbance (wavelength: 345 nm) of the resin film was measured.

The formulation and results are shown in Table 4.

[0141]

[Table 4]

As is clear from Table 4, the ultraviolet absorbent A
Alternatively, the ultraviolet absorbent eluted from the resin film containing B (Comparative Examples 7 and 8) with time in warm water, and the ultraviolet absorbing ability was reduced by half after 40 hours. On the other hand, when the polyurethane copolymer synthesized in Example 5 was used (Test Example 7)
It was found that there was almost no change in the absorbance of the sample, and that the sample exhibited extremely high water resistance.

Test Example 8 Using the polycarbonate copolymer synthesized in Example 1, a thin film having a thickness of about 1 μm was prepared on a circular quartz plate having a diameter of 300 mm in the same manner as in Test Example 1. Next, after leaving this in warm methanol at 60 ° C. for 5 hours, the absorbance of the film was measured, and the residual ratio of the ultraviolet absorbing component (polycarbonate copolymer) in the film was calculated. Test Example 8 On the other hand, 100 parts by weight of a commercially available polycarbonate resin (trade name “E-2000”) containing no ultraviolet absorber such as a bisbenzotriazole-based compound was added to 1,1,2,2-
It was dissolved in 630 parts by weight of tetrachloroethane, and 5 parts by weight of the bisbenzotriazole-based compound obtained in Synthesis Example 1 was further added. The composition solution thus obtained was formed into a film in the same manner as in Test Example 8 described above, left in warm methanol at 60 ° C. for 5 hours, and then measured for the absorbance of the film. The residual ratio of the benzotriazole compound was calculated (Comparative Example 9).

The formulation and results are shown in Table 5.

[0145]

[Table 5]

As is clear from Table 5, in Comparative Example 9 in which the bisbenzotriazole-based compound of Synthesis Example 1 was simply added without being copolymerized with the base resin, Comparative Example 9 used an organic solvent such as alcohol or oil. In a contact use environment, the bisbenzotriazole-based compound elutes, and as a result, sufficient weather resistance cannot be imparted to the base resin for a long period of time.

Comparative Example 10 Polycarbonate pellets (trade name "E-200"
0 ") per 100 parts by weight of formula (E):

[0148]

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An ultraviolet absorbent represented by the formula [RUV
A-100 ", manufactured by Otsuka Chemical Co., Ltd.] 6.0 parts by weight and 0.001 part by weight of triethylamine as a transesterification catalyst were dry-blended and charged into an extruder to obtain 270 parts.
C. and transesterified by melt-kneading for about 3 minutes. Next, this was extruded to obtain a pellet-shaped ultraviolet absorbing polymer (polycarbonate copolymer).

The conversion was measured by gel permeation chromatography (GPC) and found to be about 58%. The content of the ultraviolet absorbing unit was measured in the same manner as in Example 1, and it was 5.0% by weight. The viscosity average molecular weight Mv of the ultraviolet absorbing polymer was 7,600. Using the polycarbonate copolymer thus obtained, a film having a thickness of about 1 μm was formed on a quartz plate in the same manner as in Test Example 3.
m was prepared, and a 1200-hour weather resistance test was performed in the same manner as in Test Example 3 to measure the degree of yellowing (ΔYI) of the coating film.

Table 6 shows the results of the measurement of the degree of yellowing and the formulation, together with the results of Test Example 3.

[0152]

[Table 6]

As is clear from Table 6, polycarbonates obtained by using the above ultraviolet absorbent (E), which does not have a long-chain polyester group in the bisbenzotriazole compound represented by the formula (7), are used. Polymer (Comparative Example 10)
In the above, although the weather resistance is improved as compared with the case of using the conventional addition type ultraviolet absorbers A, B, C and D, the yellowing degree after a 1200-hour weather resistance test is 0.7, It was found that the effect of preventing yellowing was lower than that of the ultraviolet absorbing polymer of the present invention.

[0154]

As described above in detail, according to the ultraviolet absorbing polymer and the weather resistant resin composition of the present invention, excellent ultraviolet absorbing ability can be exhibited for a long period of time.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C08L 75/04 C08L 75/04 // C07D 249/20 502 C07D 249/20 502 (56) References JP-A-9-316060 ( JP, A) JP-A-10-265557 (JP, A) JP-A-8-120065 (JP, A) JP-A-3-39326 (JP, A) JP-A-50-161538 (JP, A) (58) ) Field surveyed (Int.Cl. ⁷ , DB name) C08G 18/00-18/87 C08G 63/00-63/91 C08G 64/00-64/42 C08G 85/00 C08L 1/00-101/14 REGISTRY (STN) CA (STN)

Claims (6)

(57) [Claims] [Claim 1] General formula (1): (In the formula (1), A is a direct bond or a linear or branched alkylene group having 1 to 6 carbon atoms, a group: —O—, a group:
-NH-, group: -S-, group: -SO-, or group: -S
O ₂ -is shown. R ¹ and R ² are the same or different,
A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, an alkoxy group having 1 to 4 carbon atoms or a halogen atom.
R ³ and R ⁶ are the same or different and are directly bonded to each other or represent a linear or branched alkylene group having 1 to 12 carbon atoms. R ⁴ , R ⁵ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. m and p are the same or different and each represents an integer of 1 to 20. n and q are the same or different and 1-10
Indicates an integer. a represents an integer of 1 or more. ) And the general formula (2): (In the formula (2), B is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, a group: —O—, a group: —CO
—, Group: —NH—, group: —S—, group: —SO—, or group: —SO ₂ —. R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are the same or different and each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom. b represents an integer of 1 or more. ) Wherein the content of the repeating unit represented by the formula (1) is 0.01 to 70% by weight and the viscosity average molecular weight is 5,000 to 100,000. Polymer. 2. A weather-resistant resin composition containing the ultraviolet-absorbing polymer according to claim 1 in an amount of 0.05 to 50% by weight in a polycarbonate resin. (3) The general formula (3): (In the formula (3), A is a direct bond or a linear or branched alkylene group having 1 to 6 carbon atoms, a group: —O—, a group:
-NH-, group: -S-, group: -SO-, or group: -S
O ₂ -is shown. R ¹ and R ² are the same or different,
A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, an alkoxy group having 1 to 4 carbon atoms or a halogen atom.
R ³ and R ⁶ are the same or different and are directly bonded to each other or represent a linear or branched alkylene group having 1 to 12 carbon atoms. R ⁴ , R ⁵ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. m and p are the same or different and each represents an integer of 1 to 20. n and q are the same or different and 1-10
Indicates an integer. Y represents phenylene, naphthalene, or a linear or branched alkylene group having 2 to 9 carbon atoms. c represents an integer of 1 or more. ) And a general formula (4): (In the formula (4), X represents a linear, branched or cyclic alkylene group having 2 to 9 carbon atoms. Y is the same as described above.)
d shows an integer of 1 or more. ) Wherein the content of the repeating unit represented by the formula (3) is 0.01 to 70% by weight and the viscosity average molecular weight is 5,000 to 100,000. Polymer. 4. A weatherable resin composition comprising the polyester resin containing the ultraviolet absorbing polymer according to claim 3 in an amount of 0.05 to 50% by weight. 5. A compound of the general formula (5): (In the formula (5), A is a direct bond or a linear or branched alkylene group having 1 to 6 carbon atoms, a group: —O—, a group:
-NH-, group: -S-, group: -SO-, or group: -S
O ₂ -is shown. R ¹ and R ² are the same or different,
A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, an alkoxy group having 1 to 4 carbon atoms or a halogen atom.
R ³ and R ⁶ are the same or different and are directly bonded to each other or represent a linear or branched alkylene group having 1 to 12 carbon atoms. R ⁴ , R ⁵ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. m and p are the same or different and each represents an integer of 1 to 20. n and q are the same or different and 1-10
Indicates an integer. Z represents phenylene, naphthalene, or a linear or branched alkylene group having 2 to 9 carbon atoms. e represents an integer of 1 or more. ) And a repeating unit represented by the general formula (6): (In the formula (6), X represents a linear, branched or cyclic alkylene group having 2 to 9 carbon atoms. Z is the same as described above.)
f represents an integer of 1 or more. ) Wherein the content of the repeating unit represented by the formula (5) is 0.01 to 70% by weight and the viscosity average molecular weight is 5,000 to 100,000. Polymer. 6. A weatherable resin composition comprising the ultraviolet absorbent polymer according to claim 5 in a polyurethane resin in an amount of 0.05 to 50% by weight.