JPS625944B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to protection from ultraviolet light using novel ultraviolet absorbers. More specifically, a photostabilized polymer composition comprising a cyclic iminoester as a novel ultraviolet absorber, and a method for protecting objects that are undesirably affected by ultraviolet rays by using the cyclic iminoester as an ultraviolet absorber. Regarding how to. Organic materials such as synthetic resins, natural resins, rubber, oil paints, inks, dyes, etc. are generally sensitive to ultraviolet light, and many of them deteriorate and decompose due to the action of ultraviolet light, resulting in color change and mechanical strength loss. It may cause changes, etc., and cannot withstand long-term use. In addition, recently, certain plant pathogenic bacteria, such as rice blast fungus and sesame leaf blight fungus that cause rice to wither; sclerotia fungus that occurs on various vegetables such as fruit vegetables, leafy vegetables, and root vegetables;
There is a close relationship between the growth of molds such as potlyteis, carbonaceous fungi, vine blight fungi, black mold fungi, and spot fungi, and ultraviolet rays, and these molds do not grow under conditions of complete shielding of ultraviolet rays of certain wavelengths. has been revealed. Therefore, it is common practice to disperse and contain ultraviolet absorbers in organic materials used outdoors, such as resin molded products, or transparent organic or inorganic materials used in fields that require ultraviolet shielding. As such ultraviolet absorbers, for example, benzophenone-based, benzotriazole-based, salicylic acid-based, or hydroquinone-based compounds are known and often used. However, many of these UV absorbers do not necessarily have sufficient safety against heat or oxidation, and some have the disadvantage of subliming at high temperatures, for example, over 200°C, or bleeding out onto the material surface during use. many. Therefore, an object of the present invention is to provide a novel ultraviolet absorber having a structure completely different from that of conventionally known ultraviolet absorbers. Another object of the present invention is to provide a novel ultraviolet absorber with excellent stability against heat and oxidation. Still another object of the present invention is to provide a novel ultraviolet absorber that has sufficiently low sublimation even at high temperatures, such as 200° C. or higher, and has excellent compatibility with various polymers. Yet another object of the present invention is to be able to reliably melt-mix various polymers with high melting temperatures at the high temperatures at which they are molten, and thus to ensure that the polymers with high melting temperatures can be mixed in a predetermined amount. It is an object of the present invention to provide a novel ultraviolet absorber that can be uniformly dispersed and contained in the ultraviolet absorbent, has excellent heat resistance and compatibility, and has low sublimation property. Still another object of the present invention is to provide a novel ultraviolet absorber that has excellent compatibility with polymers and does not substantially cause problems with bleeding out from polymers containing it during use. . Still another object of the present invention is to provide a specific cyclic iminoester compound as the novel ultraviolet absorber. Still another object of the present invention is to provide a photostabilized polymer composition containing a specific cyclic iminoester as an ultraviolet absorber. Still another object of the present invention is to provide a method of applying a specific cyclic iminoester to a polymer molded article to protect the polymer from deterioration due to ultraviolet light. Still another object of the present invention is to provide a method for isolating an object that needs to be protected from ultraviolet rays by using a polymer molded article to which a specific cyclic iminoester is applied. Further objects and advantages of the invention will become apparent from the description below. According to the present invention, the objects and advantages of the present invention are, firstly, that the following formula () Here, X ¹ is 2, where the two bonds from X ¹ expressed in the above formula are in the positional relationship of the 1st and 2nd positions.
n is a valent aromatic residue; n is 1, 2 or 3; R ¹ is an n-valent hydrocarbon residue which may further contain a heteroatom, or R ¹ is n=
It can be a direct bond when 2, and the following formula () Here, A is the following formula ()-a or the following formula ()-b R ² and R ³ are the same or different monovalent hydrocarbon residues; X ² is a tetravalent aromatic residue, which may further contain a heteroatom This is achieved by a photostabilizing composition containing at least one compound selected from cyclic iminoesters represented by the following in an unreacted form and as an ultraviolet absorber. Numerous compounds included in the cyclic imino esters represented by the above formulas () and () are:
Known as a molecular chain binding agent for aromatic polyesters having a hydroxyl group at the end (U.S. Patent No.
4291152 specification). Furthermore, among the cyclic iminoesters represented by the above formula (), some compounds in which R ¹ is phenyl or substituted phenyl, X ¹ is orthophenylene, and n = 1 and their synthesis methods are known. (For example, Chemical Abstracts vol.65, 1966
year, 15371d). Therefore, these prior arts are cited herein as references with respect to the compounds of the above formulas () and () used in the present invention and their synthesis methods. In the above general formula (), X ¹ is a divalent aromatic residue in which the two bonds from X ¹ represented by the formula () are in the 1st and 2nd positions; n is 1,
2 or 3; R ¹ is an n-valent hydrocarbon residue,
It may further contain heteroatoms or R ¹ may be a direct bond when n=2. X ¹ is preferably, for example, 1,2-phenylene, 1,2-naphthylene, 2,3-naphthylene, the following formula Here, R is -O-, -CO-, -S-, -
Examples include groups represented by SO ₂ , --CH ₂ --, (-CH ₂ --) or --C(CH ₃ ) ₂ --. Among these, 1,2-phenylene is particularly preferred. The above-mentioned aromatic residues exemplified for X ¹ include, for example, alkyl having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, hexyl, decyl, etc.;
Arul of 12, such as phenyl, naphthyl, etc.; cycloalkyl, having 5 to 12 carbon atoms, such as cyclopentyl, cyclohexyl, etc.; aralkyl, having 8 to 20 carbon atoms, such as phenylethyl; alkoxy, having 1 to 10 carbon atoms, such as methoxy, ethoxy, decyloxy, etc.; nitro; Halogens such as chlorine, bromine, etc.; Acyls having 2 to 10 carbon atoms such as acetyl, proponyl,
It may be substituted with substituents such as benzoyl, decanoyl, etc. R ¹ is n-valent (however, n is 1, 2 or 3)
can be a direct bond only when n is a hydrocarbon residue or n is 2. Monovalent hydrocarbon residues (when n = 1) include, for example, unsubstituted aliphatic groups having 1 to 10 carbon atoms, unsubstituted aromatic groups having 6 to 12 carbon atoms, and 5 to 12 carbon atoms.
Twelve unsubstituted alicyclic groups are mentioned. Examples of unsubstituted aliphatic groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, decyl, etc.; examples of unsubstituted aromatic groups having 6 to 12 carbon atoms include phenyl, naphthyl, biphenyl, etc.; Examples of the 5-12 unsubstituted alicyclic group include cyclopentyl and cyclohexyl. Second, as the above-mentioned monovalent hydrocarbon residue, for example, the following formula (c) Here, R ⁴ is alkylene, phenylene or naphthylene having 2 to 10 carbon atoms, a group represented by the following formula (d) Here, R ⁵ is an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a naphthyl group, a group represented by the following formula (e) Here, the definitions of R ⁴ and R ⁵ are the same as above, and R ⁶ is either a hydrogen atom or a group defined for R ⁵ , or a group represented by the following formula (f) Here, the definitions of R ⁴ and R ⁶ are the same as above, and R ⁷ is either a hydrogen atom or a group defined for R ⁵ , a substituted aliphatic residue or an aromatic residue represented by The following groups can be mentioned. In addition, as the monovalent hydrocarbon residue, tertiary
For example, the unsubstituted aromatic residue may be substituted with the same substituent as exemplified as the substituent for the aromatic residue representing X ¹ above. Therefore, examples of substitution with such substituents include tolyl, methylnaphthyl, nitrophenyl, nitronaphthyl, chlorophenyl,
Examples include benzoylphenyl, acetylphenyl, acetylnaphthyl, and the like. As monovalent hydrocarbon residues, the above formulas (c), (d),
Groups represented by (e) or (f), ie substituted aliphatic or aromatic residues, especially substituted aromatic residues thereof, are preferred. As the divalent hydrocarbon residue (in the case of n=2), firstly, for example, an unsubstituted aliphatic residue having 2 to 10 carbon atoms, an unsubstituted aromatic residue having 6 to 12 carbon atoms, Examples include unsubstituted alicyclic residues having 5 to 12 carbon atoms. As unsubstituted aliphatic residues having 2 to 10 carbon atoms,
For example, ethylene, trimethylene, tetramethylene, decamethylene, etc. are used as unsubstituted aromatic residues having 6 to 12 carbon atoms. Examples of alicyclic residues include cyclopentylene and cyclohexylene. In addition, as the above-mentioned divalent hydrocarbon residue, the second
For example, the following formula (g) Here, R ⁸ is any of the groups defined for R ⁴ , or a group represented by the following formula (h) Here, the definition of R ⁸ is the same as above and R ⁹ is
R ⁴ is any of the groups defined, and R ¹⁰
is any of the groups defined for R ⁶ , and can include a substituted aliphatic residue or an aromatic residue represented by the following. In addition, as the above-mentioned divalent hydrocarbon residue, tertiary
Examples include those in which the unsubstituted divalent aromatic residue is substituted with the same substituent as exemplified as the substituent for the aromatic group representing X ¹ above. When n is 2, R ¹ is preferably a direct bond or an unsubstituted or substituted divalent aromatic hydrocarbon residue of the first to third groups above, particularly two Preferred are unsubstituted or substituted aromatic hydrocarbon residues of the first or third group in which the bond emanates from the most distant position, especially p-phenylene, p, p'-biphenylene or 2 , 6-naphthylene is preferred. Examples of the trivalent hydrocarbon residue (when n=3) include aromatic residues having 6 to 12 carbon atoms. Such aromatic residues include, for example,

【formula】

【formula】

【formula】

[Formula] etc. can be mentioned. Such an aromatic residue may be substituted with the same substituent as exemplified as the substituent for the above-mentioned monovalent aromatic residue. In the above general formula (), R ² and R ³ are the same or different monovalent hydrocarbon residues, and X ² is 4
aromatic hydrocarbon residue. Examples of R ² and R ³ include the same groups as exemplified for R ¹ in the case of n=1 in the explanation of the above formula (). Examples of tetravalent aromatic hydrocarbon residues include:

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] or

Examples include a group represented by the following formula (wherein the definition of R is the same as in formula (a)). The above-mentioned tetravalent aromatic residue may be substituted with the same substituent as exemplified as the substituent for the monovalent aromatic residue representing R ¹ in the explanation of the above formula (). Specific examples of the cyclic iminoesters represented by the above formulas () and () used in the present invention include the following compounds. Compound 2-methyl-3,1-benzoxazine-4- when compound n=1 of the above formula ()
on, 2-butyl-3,1-benzoxazine-4-
on, 2-phenyl-3,1-benzoxazine-4
-one, 2-(1- or 2-naphthyl)-3,1-benzoxazin-4-one, 2-(4-biphenyl)-3,1-benzoxazin-4-one, 2-p-nitrophenyl- 3,1-benzoxazin-4-one, 2-m-nitrophenyl-3,1-benzoxazin-4-one, 2-p-benzoylphenyl-3,1-benzoxazin-4-one, 2-p -methoxyphenyl-3,1-benzoxazin-4-one, 2-o-methoxyphenyl-3,1-benzoxazin-4-one, 2-cyclohexyl-3,1-benzoxazin-4-one, 2-p-(or m-)phthalimidophenyl-
3,1-benzoxazin-4-one, N-phenyl-4-(3,1-benzoxazine-4
-on-2-yl)phthalimide, N-benzoyl-4-(3,1-benzoxazine-4-
on-2-yl)aniline, N-benzoyl-
N-methyl-4-(3,1-benzoxazin-4-one-2-yl)aniline, 2-[p-(N-phenyl, N-methylcarbonyl)phenyl]-3,1-benzoxazine-4 -on Compound 2,2'-bis(3,1-benzoxazine-4 when n=2
-one), 2,2'-ethylenebis(3,1-benzoxazin-4-one), 2,2'-tetramethylenebis(3,1-benzoxazin-4-one), 2,2'- Decamethylenebis(3,1-benzoxazin-4-one), 2,2'-p-phenylenebis(3,1-benzoxazin-4-one), 2,2'-m-phenylenebis(3,1- benzoxazin-4-one), 2,2'-(4,4'-diphenylene)bis(3,
1-benzoxazin-4-one), 2,2'-(2,6 or 1,5-naphthalene)bis(3,1-benzoxazin-4-one), 2,2'-(2-methyl- p-phenylene)bis(3,1-benzoxazin-4-one), 2,2'-(2-nitro-p-phenylene)bis(3,1-benzoxazin-4-one), 2,2' -(2-chloro-p-phenylene)bis(3,1-benzoxazin-4-one), 2,2'-(1,4-cyclohexylene)bis(3,1-benzoxazin-4-one) , N-p-(3,1-benzoxazin-4-one-2-yl)phenyl, 4-(3,1-benzoxazin-4-one-2-yl)phthalimide, N-p-(3, Compound 1,3,5-tri(3) when n=3 , 1-benzoxazin-4-one-2-yl)benzene, 1,3,5-tri(3,1-benzoxazin-4-one-2-yl)naphthalene, 2,4,6-tri(3) ,1-benzoxazin-4-one-2-yl)naphthalene Compound of the above formula (2,8-dimethyl-4H,6H-benzo[1,2
-d;5,4-d']bis-[1,3]-oxazine-4,6-dione, 2,7-dimethyl-4H,9H-benzo[1,2
-d;4,5-d']bis[1,3]-oxazine-4,9-dione, 2,8-diphenyl-4H,8H-benzo[1,
2-d;5,4-d']bis[1,3]-oxazine-4,6-dione, 2,7-diphenyl-4H,9H-benzo[1,
2-d;4,5-d']bis[1,3]-oxazine-4,6-dione, 6,6'-bis(2-methyl-4H,3,1-benzoxazin-4-one) , 6,6'-bis(2-ethyl-4H,3,1-benzoxazin-4-one), 6,6'-bis(2-phenyl-4H,3,1-
benzoxazin-4-one), 6,6′-methylenebis(2-methyl-4H,
3,1-benzoxazin-4-one), 6,6'-methylenebis(2-phenyl-4H,
3,1-benzoxazin-4-one), 6,6'-ethylenebis(2-methyl-4H,
3,1-benzoxazin-4-one), 6,6'-ethylenebis(2-phenyl-4H,
3,1-benzoxazin-4-one), 6,6'-butylenebis(2-methyl-4H,
3,1-benzoxazin-4-one), 6,6'-butylenebis(2-phenyl-4H,
3,1-benzoxazin-4-one), 6,6'-oxybis(2-methyl-4H,3,
1-benzoxazin-4-one), 6,6′-oxybis(2-phenyl-4H,
3,1-benzoxazin-4-one), 6,6'-sulfonylbis(2-methyl-4H,
3,1-benzoxazin-4-one), 6,6'-sulfonylbis(2-phenyl-
4H,3,1-benzoxazin-4-one), 6,6'-carbonylbis(2-methyl-4H,
3,1-benzoxazin-4-one), 6,6'-carbonylbis(2-phenyl-
4H,3,1-benzoxazin-4-one), 7,7'-methylenebis(2-methyl-4H,
3,1-benzoxazin-4-one), 7,7'-methylenebis(2-phenyl-4H,
3,1-benzoxazin-4-one), 7,7'-bis(2-methyl-4H,3,1-benzoxazin-4-one), 7,7'-ethylenebis(2-methyl-4H ，
3,1-benzoxazin-4-one), 7,7'-oxybis(2-methyl-4H,3,
1-benzoxazin-4-one), 7,7′-sulfonylbis(2-methyl-4H,
3,1-benzoxazin-4-one), 7,7'-carbonylbis(2-methyl-4H,
3,1-benzoxazin-4-one), 6,7'-bis(2-methyl-4H, 3,1-benzoxazin-4-one), 6,7'-bis(2-phenyl-4H, 3,1-
benzoxazin-4-one), 6,7′-methylenebis(2-methyl-4H,
3,1-benzoxazin-4-one), 6,7′-methylenebis(2-phenyl-4H,
3,1-benzoxazin-4-one), among the above exemplary compounds, the compound of the above formula (), more preferably the above formula () when n=2
A compound of the following formula ()-1 is particularly preferable: Here, R ¹¹ is a divalent aromatic hydrocarbon residue, and a compound represented by the following is advantageously used. Among the compounds of formula ()-1, 2,2′-
p-p-phenylenebis(3,1-benzoxazin-4-one), 2,2'-(4,4'-diphenylene)bis(3,1-benzoxazin-4-one) and 2,2'- (2,6-naphthalene)bis(3,1-benzoxazin-4-one) is preferred. The above formulas () and () used in the present invention
It was not previously known that the cyclic imino ester represented by the following formula could be used as an ultraviolet absorbent, particularly as an ultraviolet absorbent having excellent heat resistance and oxidation resistance. According to the present invention, the cyclic iminoester has excellent compatibility with various polymers and is mixed with the polymers to provide a light-stabilized polymer composition. Such polymers can therefore be thermoplastic resins, thermosetting resins or even uncured elastomers (rubber compounds). The thermoplastic resin can be, for example, a polyester, polyamide, polycarbonate, polyolefin, polyether or polysulfone. Examples of thermosetting resins include phenol formaldehyde resin, melamine resin, polyurethane resin,
It can be a urea resin, an epoxy resin or an unsaturated polyester resin. Further, the uncured elastic material can be, for example, natural rubber or synthetic rubber. Polymers such as those mentioned above are known per se and are well known to those skilled in the art. Examples of polyester include terephthalic acid,
Examples include aromatic polyesters containing isophthalic acid, naphthalene dicarboxylic acid, etc. as the main acid component and ethylene glycol, tetramethylene glycol, etc. as the main glycol component, such as polyethylene terephthalate, polytetramethylene terephthalate, polyethylene 2,6-naphthalate, and the like. In addition, for example, the same dicarboxylic acid as above is used as the main acid component, and hydroquinone, resorcinol, 2,
A wholly aromatic polyester comprising 2-p-hydroxyphenylpropane as the main glycol component and optionally p-benzoic acid as a third component, such as isophthalic acid/hydroquinone/2,2-p
-Hydroxyphenylpropane copolymer, terephthalic acid/isophthalic acid/2,2-p-hydroxyphenylpropane copolymer, isophthalic acid/
A copolymer of hydroquinone/p-benzoic acid, or, for example, terephthalic acid as the main acid component, ethylene glycol, tetramethylene glycol, etc. as the low molecular weight glycol component, and poly(oxytetramethylene) glycol (preferably an average molecular weight of 500 to 5000) , more preferably from 600 to 4000) as a high molecular weight glycol component. Such polyester is substantially linear and
Within the range that has film or fiber forming ability (usually approximately
A trifunctional or higher functional compound may be copolymerized at a ratio of 0.5 mol% or less). As the polycarbonate, 2,2-bis(4-hydroxyphenyl)propane, 1,1-
Aromatic polycarbonates produced by the reaction of aromatic dihydroxy compounds typified by bisphenols such as bis(4-hydroxyphenyl)cyclohexane and carbonate precursors (e.g. phosgene, diphenyl carbonate, etc.) are preferred. . Examples of the polyamide include homopolyamides derived from aminocarboxylic acids or corresponding lactams, such as nylon-6, nylon-7, and nylon-12; homopolyamides derived from aliphatic dicarboxylic acids and aliphatic diamines, such as nylon-6,
6, nylon-6,12, etc.; polyamide derived from aromatic dicarboxylic acid (e.g. terephthalic acid, isophthalic acid, etc.) and aliphatic diamine or aromatic diamine; derived from alicyclic amine such as bis-p-aminocyclohexylmethane. Examples include alicyclic polyamides and the like. Polyolefins include, for example, polymers whose main constituents are ethylene, propylene, vinyl chloride, styrene, methyl methacrylate, etc., homopolymers such as polyethylene, polypropylene, polyvinyl chloride, polystyrene, polymethyl methacrylate, etc., or acrylonitrile/butadiene. Examples include copolymers such as /styrene copolymer (ABS resin), methyl methacrylate/butadiene/styrene copolymer (MBS resin), and acrylonitrile/styrene copolymer (AS resin). Polyethers generally include those of the following formula, such as condensates of orthocresol, 2,4-dimethylphenol, etc. Here, Z ¹ , Z ² and Z ³ are the same or different and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a methyl group. However, either Z ² or Z ³
One is an alkyl group having 1 to 4 carbon atoms. A polymer having a repeating unit represented by the following is preferably used. In addition, examples of polysulfone include aromatic polysulfone, such as Here, Z ⁴ is hydrogen, halogen, alkyl having 1 to 4 carbon atoms, or alkoxy having 1 to 4 carbon atoms,
R ²¹ is alkylene having 8 or less carbon atoms. A polymer having a repeating unit represented by the following is preferably used. As the phenol-formaldehyde resin, those generally known as novolac resins, which are composed of phenol as the main aromatic hydroxy compound component and formaldehyde as the main aldehyde component, are preferably used. As the melamine resin or urea resin, those obtained by heating and reacting melamine or urea with formaldehyde under neutral or slightly alkaline conditions are preferably used. As polyurethane resins, butanediol,
A glycol component selected from low-molecular aliphatic glycols such as diethylene glycol, polyether polyols such as polyoxyethylene glycol, polyoxytetramethylene glycol, and high-molecular glycols such as aliphatic polyester glycol, and tetramethylene diisocyanate, hexamethylene diisocyanate. A so-called prepolymer obtained by reacting a diisocyanate component selected from aliphatic diisocyanates such as soanate, aromatic diisocyanates such as tolylene diisocyanate and naphthalene diisocyanate, and alicyclic isocyanates such as isophorone diisocyanate is preferably used. . As the epoxy resin, a condensate of polyhydric phenols such as 2,2-bis(p-hydroxyphenyl)propane and epochlorohydrin is preferably used. As unsaturated polyester resin, maleic acid,
So-called prepolymers obtained by condensing unsaturated dicarboxylic acids such as fumaric acid, maleic anhydride, and itaconic acid with polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin are preferably used. These prepolymers are usually used in combination with vinyl monomers such as styrene, methyl methacrylate, and diallyl phthalate. As the uncured elastic material, for example, natural rubber or an unvulcanized synthetic rubber such as polybutadiene, polyisoprene, styrene-butadiene copolymer, polychloroprene, etc. is preferably used. The photostabilized polymer composition of the present invention comprises at least one cyclic iminoester of the above formula () or () dispersed in an unreacted form in the above polymer matrix. The light-stabilized polymer composition of the present invention preferably contains a cyclic iminoester of the above formula () or () in an amount of 0.05 to 5 parts by weight, particularly 0.1 to 3 parts by weight, per 100 parts by weight of the polymer. can. The composition of the present invention is generally prepared by mixing a predetermined amount of the cyclic iminoester and a polymer at a temperature equal to or higher than the melting temperature of the polymer, for example, in a melt extrusion mixer when the polymer is a thermoplastic resin. Melt mix or
Or, if the polymer is a thermoset, it can be prepared by mechanical mixing at ambient temperature. The composition of the present invention produced by mixing can be obtained, for example, as an amorphous mixture, as small granules (chips), or as a molded article as it is through molding means. The composition of the invention obtained as an amorphous mixture or chip can be converted into a molded article according to a melt molding method or a molding method using a mold. In order to produce a molded article from the composition of the present invention, any known molding method such as extrusion molding, injection molding, compression molding, vacuum pressure molding, etc. can be used, taking into account the thermal properties of the polymer used. can be used as appropriate. The cyclic iminoester used in the present invention has the ability to react with the terminal hydroxyl group of polyester, as described in the specification of US Pat. No. 4,291,152. The cyclic imino ester not only has the ability to react with aliphatic hydroxyl groups as described above, but also has the ability to react with amino groups. Therefore, when the composition of the present invention is produced using a polymer having an aliphatic hydroxyl group or an amino group, such as a polyester having a terminal hydroxyl group, a polyamide having a terminal amino group, etc., the cyclic iminoester is substantially Careful mixing of the polymer and cyclic iminoester is required so that the polymer is contained in unreacted form. According to the research of the present inventor, in a polymer in which a substantially constant amount of the cyclic imino ester used has been reacted, the polymer of the present invention containing the same cyclic imino ester in a substantially unreacted form is It was revealed for the first time that the wavelength range of ultraviolet rays that it absorbs generally tends to be shifted to the lower wavelength side than the composition, and therefore, it has a tendency to transmit ultraviolet rays at higher wavelengths. The reason why the reacted cyclic imino ester exhibits ultraviolet absorption characteristics different from that of the unreacted cyclic imino ester is thought to be due to the ring opening caused by the reaction. Even when producing the composition of the present invention using polyester or polyamide, polyester or polyamide whose terminal groups are mainly carboxyl groups, or end-capping groups whose terminal hydroxyl groups or amino groups are not reactive with the cyclic imino ester. It will be appreciated that when using a polyester or polyamide capped with , no special precautions need to be taken to prepare a composition containing the cyclic iminoester in an unreacted state. A method for producing the composition of the present invention using a polyester having a terminal hydroxyl group or a polyamide having a terminal amino group includes a method of dry mixing granular or powdery particles of these polymers with a fine powder of a cyclic iminoester. This is one recommended method. In addition, when manufacturing by melt mixing, it is desirable to complete the mixing in as short a time as possible and cool quickly. For example, when using a polyester having a reactive terminal hydroxyl group, melt mixing is performed using the following formula: logt≦−0.008T+4.8 and Tm<T<320, where t is the melt mixing time (seconds), and T is the melt mixing temperature ( ℃) and Tm is the melting temperature of polyester (℃). It is desirable to complete the process in a short time so as to satisfy the following. When the composition of the present invention does not use a polymer having a reactive end as described above, as described above,
They can be easily prepared by simply melt-mixing the polymer and cyclic iminoester without special precautions, or by mechanically mixing at ambient temperature. Since the water contained in the polymer can react with the cyclic imino ester during mixing, it is desirable to use the polymer in a state where the water content is as low as possible. Molded articles manufactured from the composition of the present invention include, for example, fibers, films, sheets, plates, pipes,
Includes tubes, various containers, and various other molded products. Among these resin molded products, transparent or translucent, especially transparent molded products made of amorphous resin, or thin transparent or translucent, especially transparent molded products made of crystalline resin, such as polycarbonate films and sheets. , plate, tube or pipe;
Sheets or films made of polyethylene terephthalate or wholly aromatic polyester; sheets or films made of polyvinyl chloride; films made of polypropylene; sheets or films made of polyethylene; plates made of methacrylic resin, etc. are used for various purposes as described below. It will be done. According to the present invention, at least one compound selected from the above formula () or a cyclic iminoester represented by the above formula () is added to a polymer molded article that needs to delay or prevent deterioration due to ultraviolet rays. or on the surface thereof, in unreacted form,
A method of protecting said polymeric articles from ultraviolet radiation is provided, characterized in that said polymer articles are applied in an amount effective to retard or prevent said deterioration. When applying a cyclic imino ester to a polymer molded article, as in the above molded article obtained from the composition of the present invention, the cyclic imino ester is previously blended into the polymer of the polymer molded article in an unreacted form. This can be done by keeping the polymer molded product free of cyclic imino esters,
This can also be carried out by forming a film containing the cyclic imino ester on the surface of the molded article, or by later impregnating the molded article with the cyclic imino ester. Some of the previously known polymers, such as those already mentioned above, have a considerable resistance to ultraviolet radiation by themselves. However, it is no exaggeration to say that there are almost no materials that do not show deterioration even after being exposed to ultraviolet light for a long time. There are varying degrees of resistance to ultraviolet rays, and it can be said that there are no materials that do not deteriorate due to ultraviolet rays. The method of the invention therefore includes all hitherto known polymeric moldings as mentioned above for protection against UV degradation. In the method of the present invention, the cyclic iminoester acts effectively to delay or prevent the deterioration. The amount can be varied depending on the purpose of use, usage environment, etc., in other words, the amount of ultraviolet rays irradiated, but usually per 100 parts by weight of the polymer in the molded product.
It can be 0.05 to 5 parts by weight. When forming a film containing a cyclic imino ester on the surface of a polymer molded article, a solution containing the cyclic imino ester and a suitable polymer is usually prepared, and this solution is applied or cast onto the surface of the polymer molded article. It is preferable to do so. As the polymer used in preparing the solution, methacrylic acid ester polymers are preferably used. Examples of methacrylic acid ester polymers include esters of methacrylic acid and aliphatic alcohols having 1 to 8 carbon atoms, such as homopolymers of methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate; or these methacrylic acids. Copolymers of esters and copolymerizable vinyl monomers other than methacrylic esters, such as acrylic acid, esters of acrylic acid and aliphatic alcohols having 1 to 8 carbon atoms, methacrylic acid, vinyl chloride, acrylonitrile, are preferred. used. Solvents used when preparing solutions include:
An organic solvent that can dissolve the cyclic imino ester and methacrylic acid ester polymer is preferably used. Examples of such solvents include ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; chlorinated hydrocarbons such as tetrachloroethane and dichlorobenzene; and amides such as dimethylformamide and dimethylacetamide. The solution can also be prepared by separately preparing a solution of the cyclic imino ester and a solution of the methacrylic acid polymer using the same or different organic solvents, and then mixing the two. The solution contains approximately 10% of the methacrylic acid ester polymer.
The cyclic imino ester can be contained in an amount of about 1 to 10% by weight based on the methacrylic acid ester polymer. When coating or casting such a solution to form a film containing a cyclic imino ester on the surface of a polymer molded article, the amount of the cyclic imino ester is 0.05 to 1 part by weight per 100 parts by weight of the polymer in the molded article. is preferable. Application of the solution can be carried out according to known methods such as grapier coating, reverse coating or spray coating. Films produced by solution casting are laminated to polymer moldings. When a cyclic imino ester is later impregnated into a polymer molded article, a solution of the cyclic imino ester in an organic solvent as described above is prepared, and into the solution, if necessary, with appropriate heating, Dipping the polymer molded article is carried out. In this case, the solution contains about cyclic imino ester.
It can be contained in an amount of 0.1 to 5% by weight. When this impregnation method is used, the amount of cyclic iminoester is preferably 0.05 to 1 part by weight per 100 parts by weight of the polymer of the molded article. A polymer molded article to which a cyclic iminoester is applied in an unreacted form has the effect of blocking ultraviolet rays. According to the present invention, the present invention further provides a polymer molded article to which at least one compound selected from the above formula () or the cyclic imino ester represented by the above formula () is applied in an unreacted form, A method of protecting an object from ultraviolet radiation is provided, the object being undesirably affected by ultraviolet radiation, characterized in that the object is substantially shielded from ultraviolet radiation. The polymer molded article should have a form suitable for protecting the object to be protected from ultraviolet rays, such as a planar body such as a film,
sheets, plates or hollow bodies such as tubes,
Pipes, containers, etc. Further, it is preferable that the polymer molded article is substantially transparent or semitransparent to visible light. A substance that transmits approximately 75% or more of the amount of incident light is considered to be substantially transparent to visible light;
A material transmitting 40% or more but less than about 75% is considered to be substantially translucent to visible light. For example, transparent or translucent, preferably transparent films or sheets, such as films or sheets of polyester, polyvinyl chloride, etc., are suitably used for greenhouses or pipe houses, and protect vegetables, garden plants, etc. from ultraviolet rays.
In addition, it is suitably used as an outdoor spreading material for fish farming houses, pool houses, sunshades, beach umbrella cloth, cloth substitutes, etc. According to the method of the present invention, for example, plants such as tomatoes, cucumbers, watermelons, and melons can be protected from ultraviolet rays, and effects such as hastening ripening and promoting growth can be obtained. Hereinafter, the present invention will be explained in further detail with reference to Examples.
"Parts" in the examples mean "parts by weight" unless otherwise specified. In addition, the ultraviolet absorption ability of the compound was measured using tetrachloroethane as a solvent at a concentration of 5 × 10 ^-4 g/
The test was carried out using a Hitachi 330 self-spectrophotometer with a volume of 100 ml and an optical path length of 1 cm. Furthermore, a sunshine weather meter deterioration test of the resin molded product was conducted as follows. Sunshine Weather Meter (Standard Sunshine Weather Meter manufactured by Suga Test Instruments)
WE-Sun-DC type), place the sample around the light source (Mazda Sunshine Carbon) for 1 minute.
The sample was irradiated with light while rotating. Samples were taken out at predetermined intervals, and their elongation at break and film haze were measured. The elongation at break deterioration life is 0% at elongation at break (absolute value).
I extrapolated the time to Here, film haze is measured using JIS-K6714.
It was determined using an integrating sphere BTR meter according to . Examples 1 to 17 Put 16.3 g of isatoic anhydride and 150 ml of pyridine into a 300 ml flask equipped with a reflux condenser and a stirring device.
Dissolve isatoic anhydride in pyridine by heating and stirring to approximately 50°C, then add 18.6 g of p-nitrobenzoyl chloride.
was added dropwise over about 10 minutes, and after the addition was completed, the mixture was heated under reflux for 3 hours. The reaction mixture was cooled to 0°C, the precipitated crystals were separated, and the crystals were thoroughly washed with water and then dried at 120°C for 4 hours using a hot air dryer. The obtained crystals were recrystallized from toluene to give 2-
21 g of p-nitrophenyl-3,1-benzoxazin-4-one was obtained. 2-methyl-3,1-benzoxazin-4-one, 2-phenyl-3,1-
Benzoxazin-4-one, 2-m-nitrophenyl-3,1-benzoxazin-4-one,
2-o-methoxyphenyl-3,1-benzoxazin-4-one, 2-p-methoxyphenyl-
3,1-benzoxazin-4-one,2-p-
Benzoylphenyl-3,1-benzoxazin-4-one, 2-α-naphthyl-3,1-benzoxazin-4-one, 2-β-naphthyl-3,
1-Benzoxazin-4-one, 2-p-phthalimidophenyl-3,1-benzoxazine-
4-on,

[Formula] was obtained. The properties of these compounds as ultraviolet absorbers are summarized in Table 1.

【table】

【table】

【table】

[Table] In Table 1, s represents the wavelength at which absorption begins. As shown in Table 1, the ultraviolet absorber of the present invention starts absorbing from the near ultraviolet region and enters the 300 to 400 nm region.
has max. Examples 19-21 The same compounds as the compound of Example 13, the compound of Example 15, and the compound of Example 16 were each subjected to DTA-TG thermal analysis in a nitrogen stream at a heating rate of 8°C/mm. , the thermal loss onset temperature and melting point were determined. The measurement results are shown in Table 2.

【table】

[Table] The above results show that the cyclic iminoester used in the present invention has a high melting point and is stable without causing weight loss up to the vicinity of the melting point. The compound of Example 19 above was produced as follows. 14.0 parts of anthranilic acid and sodium carbonate
11.7 parts were dissolved in 250 parts of water, and a solution of 10.1 parts of terephthalic acid dichloride dissolved in 60 parts of acetone was added dropwise to the aqueous solution with stirring at 20 to 30°C. After the dropwise addition, the mixture was reacted at room temperature for 2 hours and then for 1 hour under refluxing acetone. Then, the reaction system was made acidic by adding concentrated hydrochloric acid, filtered, and dried to obtain 19.1 parts of terephthaloyl bisanthranilic acid. Next, 100 parts of acetic anhydride was added to the total amount of the compound, and the mixture was reacted for 2 hours under reflux of acetic anhydride. After cooling the reaction mixture, it was filtered and dried to give 2,2'-p-phenylenebis(3,1-benzoxazin-4-one)15.5
I got the department. In addition, in the above reaction, 4,4'-diphenyldicarboxylic acid dichloride and naphthalene-2,6-dicarboxylic acid dichloride were used in place of terephthalic acid dichloride, and the other operations were performed in the same manner as above. '-p,p'-diphenylenebis(3,1-benzoxazin-4-one) (Example
20 compounds),2,2'-(2,6-naphthylene)
Bis(3,1-benzoxazin-4-one)
(Compound of Example 21) were obtained, respectively. Examples 22 to 26 A mixture of 2,5-diaminoterephthalic acid and 4,6-diaminoisophthalic acid (J.Polym.Sci.60
87 g (manufactured according to ISSUE 169.60 (1962)) and 1.5 g of acetic anhydride were added, and the mixture was heated under reflux for 1 hour with stirring. Next, the precipitated crystals were separated by ice cooling and recrystallized from o-dichlorobenzene to give 2-8-dimethyl-4H,6H-benzo[1,
2-d: 5,4-d′]bis-[1,3]-oxazine-4,6-dione and 2,7-dimethyl-
58 g of a mixture with 4H,9H-benzo[1,2-d:4,5-d']bis-[1,3]-oxazine-4,9-dione was obtained. 6,6′-bis(2-methyl-4H,
3,1-benzoxazin-4-one), 6,
6′-methylenebis(2-methyl-4H,3,1-
Benzoxazin-4-one)carbonylbis(2-methyl-4H,3,1-benzoxazine-
4-on) was obtained. In addition, 6,6'-methylenebis(2-phenyl-4H,3,1-benzoxazin-4-one) is 3,3'-dicarboxy-4,
4'-Diaminophenylmethane was synthesized by reaction with benzoyl chloride in pyridine. Table 3 shows the ultraviolet absorption properties of these compounds as ultraviolet absorbers.

【table】

[Table] Example 27 100 parts of polyethylene terephthalate chips with an intrinsic viscosity ([η]) of 0.64 (measured in o-chlorophenol at 35°C) and 2,2'-p-phenylene bis(3,1-benzo oxazine-4-one)
Dry blend 1.0 part and use a twin-screw extruder at a temperature of 280℃ and an average retention time of about 5 minutes.
It was melt-extruded through a T-die and rapidly cooled in a cooling drum at about 10°C to obtain an amorphous film with a thickness of about 800μ.
At this time, no smoke was generated due to sublimation.
The obtained film was simultaneously biaxially stretched at a temperature of 80° C. at a stretching ratio of 3.5×3.5 times, and then heat-treated at 180° C. for 2 minutes using a hot air dryer to obtain a stretched film. The resulting film completely absorbed ultraviolet light below 385 nm. Examples 28 to 36 and Comparative Examples 1 and 2 100 parts of polyethylene terephthalate chips with an intrinsic viscosity of 0.65 and 1.0 part of each of the compounds shown in Table 4 were dry blended, dried, and heated to a temperature of 270 using a twin-screw extruder. The film was melt-extruded through a T-die at a temperature of about 1 minute on average residence time and rapidly cooled in a cooling drum at about 10°C to obtain an unstretched film. then
After stretching 3.5 times in the uniaxial direction at 90°C, stretching 3.5 times in the direction perpendicular to the uniaxial direction at 100°C, and further heat treating at 200°C for 30 seconds, a biaxially stretched film of 125μ was obtained. For comparison, a polyethylene terephthalate film mixed with 1.0 part of 2,4-dihydroxybenzophenone (Comparative Example 1) and a polyethylene terephthalate film containing no ultraviolet absorber (Comparative Example 2) were used. All of these films were produced under the same conditions as above. The conditions during film extrusion, the intrinsic viscosity and light resistance of the obtained film were evaluated, and the results were evaluated in the fourth section.
They are summarized in the table.

【table】

[Table] From the results in Table 4, it is clear that the film containing the cyclic iminoester of the present invention is easier to extrude than the film of Comparative Example 1 containing a normal ultraviolet absorber (the volatility of the additive is is small), and
It can be seen that it exhibits excellent weather resistance in terms of both mechanical properties (elongation at break) and light transmittance (haze). Examples 37 to 39 and Comparative Example 3 0.5 part of the compound shown in Table 5 below was added to 100 parts of polycarbonate (number average molecular weight about 25,000) derived from 2,2-bis(4-hydroxyphenyl)propane. were dry blended and melt extruded through a T-die to obtain a film with a thickness of approximately 400μ. At this time, no smoke was emitted during film formation. The physical properties of the obtained film and the physical properties of the film after 500 hours of light irradiation were measured using a sunshine weather meter, and the results are summarized in Table 5. For comparison, the same test as above was conducted on a film to which no ultraviolet absorber was added, and the results are also listed in Table 5.

【table】

[Table] From the results in Table 5, it can be seen that the film containing the cyclic iminoester of the present invention has excellent weather resistance. Examples 40 to 42 and Comparative Example 4 100 parts of nylon-6 chips having an intrinsic viscosity of 1.12 were each dry-blended with predetermined amounts of the cyclic imino esters shown in Table 6. From each of these blends, use an extruder to a temperature of approx.
A sheet with a thickness of approximately 500μ was created by melt extrusion at 260°C. No smoke was observed during this molding. Table 6 shows the presence or absence of yellowing after this sheet was subjected to a light resistance test for 150 hours in a weather meter. For comparison, a film to which no cyclic iminoester was added was used.

【table】

[Table] Examples 43 to 45 and Comparative Example 5 100 parts of polyvinyl chloride, dioctyl phthalate
50 parts of stearic acid, 0.4 parts of stearic acid, 1 part of Mark AC143 (Ba--Zn stabilizer manufactured by Adeka Argus), and the predetermined amount of the cyclic imino ester shown in Table 7 were kneaded on a roll. Each composition obtained has a thickness of about 1
It was formed into a sheet of mm. Table 7 shows the light resistance test results of the sheet in a weather meter.

[Table] The embrittlement time was determined by the time required for the elongation to decrease to 10% of the initial value. Example 46 and Comparative Example 6 78 parts of maleic anhydride, 178 parts of phthalic anhydride, and 167 parts of propylene glycol were mixed in a nitrogen stream at 150 to 100 parts.
Gradually heat to 160°C, hold at this temperature for 1 hour, and then gradually increase the reaction temperature to 160°C over a further 1 hour.
The temperature was raised to 210℃. Thereafter, the mixture was cooled to 140°C and 0.06 part of hydroquinone was added. This has a styrene content.
Styrene was added to give a concentration of 37 wt% and mixed well to obtain 550 parts of an immiscible polyester resin. Add benzoyl peroxide to 20 parts of this unsaturated polyester resin.
0.4 part, dimethylaniline 0.1 part, and 2,2'-p
-Phenylenebis(3,1-benzoxazine-)
4-one) was added and mixed well at ambient temperature, and the resin liquid was applied to both sides of a glass fiber cloth to obtain a prepreg. Next, three sheets of this prepreg were stacked and pressed together, and cured at 70°C to obtain an FRP board. The obtained FRP board was placed in a weather meter.
When subjected to a 300 hour light resistance test, no yellowing was observed at all. For comparison, an FRP board was prepared in exactly the same manner as above except that 2,2'-p-phenylenebis(3,1-benzoxazin-4-one) was not added. This material turned yellow in the same 300 hrs light resistance test as above. Examples 47, 48 and Comparative Example 7 175 parts of dimethyl terephthalate, 62 parts of ethylene glycol, 104 parts of neopentylene glycol,
0.18 parts of calcium acetate and 0.09 parts of antimony trioxide were gradually heated to 230°C under normal pressure to undergo transesterification reaction, and then trimethyl phosphate was added to the mixture.
Add 0.18 parts and 14.6 parts of adipic acid and bring the temperature to 275
℃ and 30 minutes under normal pressure in a nitrogen stream, approximately 50mmHg.
The polycondensation reaction was carried out under a weak vacuum of 1 mmHg for 15 minutes and then under a high vacuum of 1 mmHg or less for about 80 minutes. Next, the reaction system was returned to normal pressure with a nitrogen stream and trimellitic anhydride was removed.
14.4 parts were added and reacted at the same temperature (275°C) for about 20 minutes. After cooling, the polymer is crushed and terminated.
A COOH polyester resin was obtained. Next, 42.8 parts of titanium oxide, 8.5 parts of triglycidyl isocyanurate, and 0.6 parts of the cyclic imino ester powder shown in Table 8 were thoroughly dry-blended with 100 parts of the above-mentioned pulverized polyester resin, and this was further pulverized to form a powder. Created paint. The powder coating was applied onto a stainless steel plate and heated to 160°C.
Baked for 2 minutes. A light resistance test was conducted on the resulting coating film in a weather meter, and changes in surface gloss were measured. The results are shown in Table 8.

[Table] Measured.
Example 49 The polyester films prepared in Example 28 and Comparative Example 2 were placed in a pipe house (width 3.5 m, depth 12
m, height 2.2 m) used as a covering film,
Two ridges with a ridge spacing of 50cm (height 30cm,
Then, 50 tomato seedlings (variety Wakashio) were planted in the ridge with a spacing of 50 cm (February 25th). The temperature inside this pipe house was controlled by communicating with the outside air through a ventilation fan. The growth status of tomatoes as an average of 50 plants until late May and the yield of tomatoes by weight per plant are shown in Tables 9 and 10, respectively. It can be seen that the growth of tomatoes is promoted by the ultraviolet shielding effect of the ultraviolet absorber of the present invention.

【table】

[Table] Hereinafter, embodiments of the present invention will be described. 1 The following formula () Here, X ¹ has two bonds from X ¹ expressed in the above formula in the positional relationship of 1st and 2nd positions,
is a divalent aromatic residue; n is 1, 2 or 3; R ¹ is an n-valent hydrocarbon residue which may further contain a heteroatom; or R ¹
can be a direct bond when n=2 and the following formula () Here, A is the following formula ()-a Is a group represented by or the following formula ()-b R ² and R ³ are the same or different monovalent hydrocarbon residues; X ² is a tetravalent aromatic residue, which may further contain a heteroatom A photostabilized polymer composition comprising at least one compound selected from cyclic iminoesters represented by the following in an unreacted form and as an ultraviolet absorber. 2 In the above formula () representing a cyclic imino ester, R ¹ is an n-valent aromatic hydrocarbon residue, and n is 1, 2 or 3,
composition of the term. 3. The composition according to item 1 above, wherein in the above formula () representing a cyclic iminoester, R ¹ is a divalent aromatic hydrocarbon residue. 4. The composition according to item 1 above, wherein in the above formula () representing a cyclic iminoester, R ¹ is a divalent aromatic hydrocarbon residue from which the two bonding hands are most distant from each other. 5. The composition according to item 1 above, containing 0.05 to 5 parts by weight of the cyclic iminoester based on 100 parts by weight of the polymer. 6. The composition according to item 1 above, containing 0.1 to 3 parts by weight of the cyclic iminoester based on 100 parts by weight of the polymer. 7 The polymer of the above polymer composition is a thermoplastic resin,
The composition according to item 1 above, which is an (un)cured product of a thermosetting resin or an elastic body. 8 Thermoplastic resin is polyester, polyamide,
The composition of item 7 above, which is a polycarbonate, polyolefin, polyether or polysulfone. 9 The thermosetting resin is phenol formaldehyde resin, melamine resin, polyurethane resin,
The composition of item 7 above, which is a urea resin, an epoxy resin or an unsaturated polyester resin. 10. The composition according to item 7 above, wherein the (un)cured elastomer is natural rubber or synthetic rubber. 11 At least one selected from the above formula () or a cyclic imino ester represented by the above formula ()
A polymer molding characterized in that the seed compound is applied in unreacted form to a polymer molding in which it is necessary to retard or prevent deterioration due to ultraviolet radiation in an amount effective to retard or prevent said deterioration. How to protect items from UV rays. 12. The method of paragraph 11, wherein the polymer molded article comprises a substantially linear polymer or a crosslinked polymer. 13. The method of paragraph 12, wherein said substantially linear polymer is thermoplastic. 14 The above substantially linear polymer is polyester,
The method according to item 12 or 13 above, wherein the material is polyamide, polycarbonate, polyolefin, polyether or polysulfone. 15. The method according to item 12, wherein the crosslinked polymer is a cured thermosetting resin or a cured elastic body. 16 The above thermosetting resin may be phenol formaldehyde resin, melamine resin, polyurethane resin,
The method of item 15 above, wherein the resin is a urea resin, an epoxy resin, or an unsaturated polyester resin. 17. The method of item 15 above, wherein the cured elastic body is a cured body of natural rubber or synthetic rubber. 18 The application of the cyclic iminoester to the polymer molded article is carried out by incorporating the cyclic imino ester in an unreacted form into the polymer of the polymer molded article in advance, Method. 19. The method according to item 11, wherein the cyclic iminoester is applied to the polymer molded article by forming a film containing the cyclic imino ester on the surface of the polymer molded article. 20. The method of item 11 above, wherein the cyclic iminoester is applied in an amount of 0.05 to 5 parts by weight per 100 parts by weight of the polymer of the polymer molded article. 21 At least one selected from the above formula () or a cyclic imino ester represented by the above formula ()
A method for protecting an object from ultraviolet radiation, characterized in that the object is substantially shielded from ultraviolet radiation by a polymeric article to which a seed compound has been applied in unreacted form. . 22. The method of item 21 above, wherein the polymer molded article is substantially transparent or translucent to visible light. 23. The method according to item 22 above, wherein the polymer molded article is a planar body or a hollow body. 24 The above polymer molded product is based on 100 parts by weight of the polymer.
22. The method of item 21 above, wherein the cyclic iminoester is applied in an amount of 0.05 to 5 parts by weight. 25 Use of a cyclic iminoester represented by the above formula () or the above formula () as an ultraviolet absorber. 26 The above cyclic imino ester has the following formula ()-1 The use according to item 25 above, wherein R ¹¹ is a divalent aromatic hydrocarbon residue. 27 Use of the above item 26, wherein in the above formula ()-1, R ¹¹ is a divalent aromatic hydrocarbon residue from which the two bonds are the most distant from each other. 28 The use of the above item 26 or 27, wherein in the above formula ()-1, R ¹¹ is p-phenylene, p,p'-biphenylene or 2,6-naphthylene.

Claims (1)

[Claims] 1. The following formula () Here, X ¹ is 2, where the two bonds from X ¹ expressed in the above formula are in the positional relationship of the 1st and 2nd positions.
n is a valent aromatic residue; n is 1, 2 or 3; R ¹ is an n-valent hydrocarbon residue which may further contain heteroatoms, or R ¹ is n=
2 can be a direct bond and the following formula () Here, A is the following formula ()-a or the following formula ()-b R ² and R ³ are the same or different monovalent hydrocarbon residues; X ² is a tetravalent aromatic residue, which may further contain a heteroatom A photostabilized polymer composition comprising at least one compound selected from cyclic iminoesters represented by the following in an unreacted form and as an ultraviolet absorber. 2. The composition according to claim 1, wherein in the above formula () representing a cyclic iminoester, R ¹ is an n-valent aromatic hydrocarbon residue, and n is 1, 2 or 3. 3. The composition according to claim 1, wherein in the above formula () representing a cyclic iminoester, R ¹ is a divalent aromatic hydrocarbon residue. 4. The composition according to claim 1, wherein in the above formula () representing a cyclic imino ester, R ¹ is a divalent aromatic hydrocarbon residue with two bonding hands coming out from the most distant position. thing. 5 Cyclic imino ester has the following formula ()-1 Here, R ¹¹ is a divalent aromatic hydrocarbon residue, and is a compound represented by Claim 1
composition of the term. 6. The composition according to claim 5, wherein in the above formula ()-1, R ¹¹ is a divalent aromatic hydrocarbon residue with two bonding hands coming out from the farthest position. 7. The composition according to claim 5 or 6, wherein in the above formula ()-1, R ¹¹ is p-phenylene, p,p'-biphenylene or 2,6-naphthylene. 8. The composition according to claim 1, which contains 0.05 to 5 parts by weight of the cyclic iminoester based on 100 parts by weight of the polymer. 9. The composition according to claim 1, which contains 0.1 to 3 parts by weight of the cyclic iminoester based on 100 parts by weight of the polymer. 10. The composition according to claim 1, wherein the polymer of the polymer composition is an (un)cured product of a thermoplastic resin, a thermosetting resin, or an elastomer. 11. The composition of claim 10, wherein the thermoplastic resin is polyester, polyamide, polycarbonate, polyolefin, polyether or polysulfone. 12 The thermosetting resin is phenol formaldehyde resin, melamine resin, polyurethane resin,
11. The composition of claim 10, which is a urea resin, an epoxy resin or an unsaturated polyester resin. 13. The composition according to claim 10, wherein the (un)cured elastomer is natural rubber or synthetic rubber.