JPH0816188B2 - Thermoplastic polyester resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermoplastic polyester resin composition. More specifically, the present invention relates to a polyester resin composition having an excellent UV blocking property.

[Prior Art] Polyester represented by polyethylene terephthalate has been widely used for fibers, films and the like because of its excellent mechanical properties and chemical properties. In recent years, its excellent transparency, gas barrier property, and safety. Due to hygiene and the like, its suitability as a container for carbonated drinks, fruit juice drinks, liquid seasonings, edible oils, liquor and wine has been drawing attention. In addition, as a new application of polyester film, from the viewpoint of energy saving and earthquake countermeasures, window pasting film for the purpose of blocking heat rays and preventing glass from scattering has been rapidly expanding in recent years. There is a strong demand for a transparent film that selectively blocks ultraviolet rays in a specific wavelength range for the purpose of promoting growth and increasing yield (see JP-A-53-98242).

However, although these polyester containers and films are extremely excellent in blocking ultraviolet rays on the short wavelength side up to about 320 nm, they almost pass ultraviolet rays on the longer wavelength side and visible rays. Such polyester containers are filled with liquid seasonings such as edible oil, mirin, and dressing, and after a storage period of several months, there are peculiarities depending on each filled food and storage conditions. Often, the contents are gradually deteriorated, for example, subtle changes in color, taste, and scent occur. Deterioration of the contents occurs due to external factors such as oxygen, heat, light, especially ultraviolet rays, and microorganisms. In the case of a polyester container, the oxygen barrier property is relatively excellent. Therefore, if the ultraviolet barrier property can be further improved, long-term storage is possible. Even under, it is possible to prevent deterioration of the contents to a large extent.

In addition, in window pasting films, for example, if ultraviolet rays from the sun's rays are transmitted, it will cause discoloration of furniture, books, furniture and other indoor installation equipment, so that transmission can be stopped to a minimum or completely blocked. In agricultural and horticultural mulching cultivation, by mulching with a transparent coating material that substantially blocks UV transmission of at least 370 nm or less, it promotes the growth of many useful plants and enables high-quality crops to be produced at an early stage. It is known that a large amount can be harvested (for example, JP-A-53-124556).

At present, an ultraviolet absorber or the like is generally added and used for that purpose in the industry. However, these ultraviolet absorbers are generally expensive, and the applying step is complicated, and since these compounds generally have a large sublimation property and many have poor thermal stability, the applying step is difficult. It is not always preferable because it often causes troubles during molding and processing, and when it is used for food containers and packaging, it may be transferred to the contents.

[Problems to be Solved by the Invention] In view of such circumstances, the present invention is excellent in ultraviolet ray blocking property, good in thermal stability, dispersion stability, and the like, and troubles such as deposits on a molded product during molding. It is an object of the present invention to provide a polyester resin composition that does not generate

[Means for Solving the Problems] The inventors of the present invention have conducted diligent studies on a polyester resin composition that meets such an object, and as a result, by including a specific diimide compound in the polyester resin, not only on the short wavelength side but also on the long wavelength side, The present invention has been accomplished by finding a polyester resin composition capable of sufficiently blocking ultraviolet rays on the wavelength side.

That is, the gist of the first invention of the present invention is a thermoplastic polyester resin composition obtained by adding at least one diimide compound represented by the general formula (1) to a thermoplastic polyester resin in an amount effective for blocking ultraviolet rays, The gist of the second invention of the present invention is a thermoplastic polyester resin composition obtained by adding at least one or more of naphthalenedicarboxylic acid compounds represented by the following general formula (II) or (III) to the above composition. Yes, The gist of the third invention of the present invention is to add at least one diimide compound represented by the general formula (I) to the material before the start of the polycondensation reaction of the thermoplastic polyester resin-forming substance or during the polycondensation reaction. A thermoplastic polyester resin composition obtained by completing the polycondensation reaction by adding an amount effective for blocking ultraviolet rays, and the gist of a fourth invention of the present invention is that the composition has the general formula (II) or The thermoplastic polyester resin composition according to claim 3, wherein at least one kind of the naphthalenedicarboxylic acid compound represented by (III) is further added to complete the polycondensation reaction.

 Hereinafter, the present invention will be described in detail.

In the present invention, an imide compound represented by the general formula (I) is used as a compound added to the thermoplastic polyester resin.

This imide compound can be prepared by a known method (for example, Bull.soc.chi.
m.France, 727-732) and can be synthesized as follows. That is, in an aprotic polar solvent such as dimethylacetamide, 2 mol of the diamino compound represented by the general formula (IV) and the tetracarboxylic acid represented by the general formula (V) or a monoanhydride or a dianhydride thereof are used. It can be produced by reacting the reaction product with 2 mol of trimellitic acid.

H ₂ N-X-NH ₂ (IV) Specific examples of the diamino compound corresponding to the general formula (IV) include 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl and diamino. Diphenylethane 9,9-bis (aminophenyl) anthracene 2,2-bis (aminonophenoxyphenyl) propane 9,10-bis (aminophenyl) anthracene Bis (aminophenyl) 3,4-diphenylthiophene Bis (aminophenyl) benzobisthiazole Diaminobenzobisthiazole Diamino compounds containing various nuclear substitution isomers such as The aromatic nucleus (phenyl nucleus or anthracene nucleus) of these diamino compounds may have a substituent represented by A or A'in the general formula (I).

Among these diamino compounds, in order to realize the effect of the present invention, 3,3′-dimethyl-4,4′-diaminobiphenyl, 9,10-bis (4-aminophenyl) anthracene,
Bis (3-aminophenyl) benzobisthiazole, bis (4-aminophenyl) benzobisthiazole and bis (4-aminophenyl) 3,4-diphenylthiophene are particularly preferably used.

Examples of the tetracarboxylic acid corresponding to the general formula (V) or its monoanhydride or dianhydride include pyromellitic acid, biphenyltetracarboxylic acid, diphenylsulfonetetracarboxylic acid, diphenylsulfidtetracarboxylic acid, diphenylethertetracarboxylic acid. Acid, diphenyl ketone tetracarboxylic acid, diphenyl tetracarboxylic acid, various tetracarboxylic acids such as diphenylethane tetracarboxylic acid or its monoanhydrides or dianhydrides and structural isomers thereof, carboxy group is 2, Those at adjacent positions of the same phenyl nucleus are preferred, such as 3,2 ', 3'- and 3,4,3', 4'-. The phenyl nucleus of these tetracarboxylic acids has the general formula (I)
It may be substituted with a group represented by A or A ′.

Of these tetracarboxylic acids, pyromellitic acid, 3,4,3 ', 4'-biphenyltetracarboxylic acid and their mono- or dianhydrides are particularly preferably used for the purpose of embodying the effects of the present invention. .

A in formula (I), A 'are the same or different halogen, -OH, -O-C (= O) CH 3, -COOH or an ester _{thereof, -NH 2, -CN, -NO 2} , -SO 3 H or a metal salt thereof, an optionally substituted alkoxy group, shows a substituent selected from an aliphatic group or an aromatic group, among these-
COOH or its ester-forming derivative is particularly preferably used.

 Further, m and m'are integers of 0 to 4, preferably 1 to 4.

The amount of the imide compound added is 0.001 part by weight or more per 100 parts by weight of the thermoplastic polyester resin. If the amount is less than 0.001 part by weight, effective UV blocking effect cannot be obtained. A particularly preferred amount of addition is 0.01 to 10 parts by weight.

In the present invention, a naphthalenedicarboxylic acid derivative represented by the following general formula (II) or (III) is used in combination in order to more effectively exhibit the ultraviolet shielding effect as shown in the second and fourth inventions. Is preferred.

In formulas (II) and (III), R ¹ and R ² may be the same or different and are hydrogen, an optionally substituted alkyl group, an aryl group, B: O or N—R ³ where R ³ is hydrogen, optionally substituted aliphatic group or aromatic group, D, E: may be the same or different, halogen, -COOH
Or an ester thereof, -OH, -O-C (= O) CH 3, -N
_{H 2, -CN, -NO 2,} -SO 3 H or a metal salt thereof, an optionally substituted alkoxy group, an aliphatic group or a substituent selected from an aromatic group,, 1, n: each 0-4 Indicates an integer.

The acid anhydride group or imide group of -C (= O) -B-(= O)-forms a ring at any of the 1,2-position, 1,8-position or 2,3-position of the naphthalene ring. To do.

These compounds include 2,6-, 2,7-, 1,8-, 1,5
- or 2,3-naphthalene dicarboxylic acid structural isomers such as dicarboxylic acids, their esters or their acid anhydrides and their halogen, -OH, -O-C (= O) CH 3, -N
O _2, -NH _2, -CN, and -SO ₃ H and their metal salts or -COOH or nuclear substituents and these naphthalenedicarboxylic acid by an ester, ammonia, amines, amino acids, with amino alcohols Examples thereof include imides produced by the reaction.

Specifically, when the 2,3-substituted product is described as a typical example, naphthalene-2,3-dicarboxylic acid and its ester forming products such as dimethyl, diethyl, dipropyl, dibutyl and diphenyl, naphthalene-2,3-dicarboxylic acid. Acid anhydride, naphthalene-2,3-dicarboximide, naphthalene-2,3-dicarboxy (α-carboxymethyl) imide, similar (β-carboxyethyl) imide, [0-
(M- or p-) carboxyphenyl] imide, (α-
Naphthalene-2,3-dicarboxylic acids such as bromomethyl) imide and (α-hydroxymethyl) imide and their derivatives and their 1,4-, 1,5-, 1,8-, 2,6-, 2,7- Structural isomers, as well as their hydroxyls, -O-C (= O)
CH ₃ , chloro, bromo, methoxy, ethoxy, cyano,
Examples thereof include amino-, nitro-, sulfonyl- or metal salts thereof, and 1- to 6-nuclear substitution products with carboxyl or its ester group. It is important to have a naphthalenedicarboxylic acid skeleton in order to exert the combined effect.

Particularly preferred naphthalenedicarboxylic acid compounds are naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid or esters of these dicarboxylic acids. , Especially lower alkyl esters.

When such naphthalenedicarboxylic acid or its derivative is used in combination with the above-mentioned tetracarboxylic acid or its derivative, the addition amount thereof is 0.001 part by weight or more per 100 parts by weight of the thermoplastic polyester resin. If the amount is less than 0.001 part by weight, effective UV blocking effect cannot be obtained. A particularly preferred amount of addition is 0.01 to 10 parts by weight.

The imide compound represented by the general formula (I) and the general formula (I
The naphthalene dicarboxylic acid compounds represented by I) and (III) can be added as they are or in advance in the form of oligomers in the form of oligomers by reacting with, for example, glycols. Further, these compounds may be added at any stage of polyester production, and those added at any stage before molding can similarly exhibit the ultraviolet shielding effect.

That is, it may be added at an arbitrary stage until the molding of the polyester is completed, for example, before the polycondensation reaction is started, during the polycondensation reaction, after the polycondensation reaction is completed, in a powder state, a molding stage, and the like.

Examples of the thermoplastic polyester in the present invention include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, diphenyl ether dicarboxylic acid and diphenyl sulfone dicarboxylic acid, and ester formation products thereof, and the above aromatics such as hexahydroterephthalic acid. Alicyclic dicarboxylic acids which are nuclear hydrogenated compounds of aromatic dicarboxylic acids and ester-formers thereof, succinic acid, adipic acid,
One or more dicarboxylic acid components represented by aliphatic dicarboxylic acids such as sebacic acid and azelaic acid and their ester-forming products, unsaturated dicarboxylic acids such as fumaric acid and 4-carboxycinnamic acid and their ester-forming products, and ethylene glycol Is a polyester obtained from a glycol component mainly composed of, especially polyethylene terephthalate, and these polyesters may contain 20 mol% or less of the above-mentioned dicarboxylic acids other than terephthalic acid as a third component. .

In addition, this polyester, as a glycol component,
Other than ethylene glycol, diethylene glycol, trimethylene glycol, tetramethylene glycol, aliphatic glycol such as neopentyl glycol, alicyclic glycol such as cyclohexanedimethanol, 2,2
-Bis (4'-β-hydroxyethoxyphenyl) propane, bisphenol derivatives such as bis- (4'-β-hydroxyethoxyphenyl) sulfone, and
Polyethylene glycol, polytetramethylene glycol, etc. represented by the general formula HOCH _{2 n} O _m H (wherein n is an integer of 1 ≦ n ≦ 6 and m is an integer of m ≧ 4) is used as a total glycol component of 20 It may be copolymerized in an amount of not more than mol%, or may be a polyester obtained by copolymerizing an oxy acid component such as glycolic acid or hydroxybenzoic acid. As long as the polyester remains substantially linear,
A trifunctional or higher functional compound such as pentaerythritol, trimethylolpropane, trimellitic acid, trimesic acid, and pyromellitic acid, or a monofunctional compound such as o-benzoylbenzoic acid may be copolymerized. In addition to the above polyester, polybutylene terephthalate, polyethylene naphthalate, polyester elastomer,
It may be a blend of another thermoplastic resin such as polycarbonate.

The polyester used in the present invention has an intrinsic viscosity of 0.5 to
It is preferably 2.5, more preferably 0.6 to 1.2. The viscosity of polyester is important particularly in connection with the molding method, for example, when producing a hollow molded body. Particularly in order to obtain a substantially non-oriented hollow molded product by extrusion blow molding, in order to prevent drawdown, it depends on the capacity of the blow molded product, but it is necessary to maintain the fluidity of the molten polyester at a certain level or more, Generally 0.7 or more, preferably
A polyester having an intrinsic viscosity of 0.8 or higher is used. In addition, stretch blow molding, after extrusion into a sheet, an extrusion molding method for obtaining a film by uniaxially or biaxially stretching or an injection molding method for obtaining molded products of various forms, a polymer having a relatively low viscosity as compared with the case of extrusion blow molding. Can also be used, and generally has an intrinsic viscosity
A polyester having a viscosity of 0.5 or more, preferably 0.6 or more is used, but a polyester having a higher viscosity may be used depending on the required physical properties of the molded product.

Further, in the present invention, additives conventionally known as a polyester composition, for example, a stabilizer, a release agent, an antistatic agent, a colorant such as a dispersant and a face wash are added at any stage during polyester production. It can be made, before molding,
It may be added in a so-called masterbatch formulation.

Preferred dyes and pigments in the present invention include titanium oxide, carbon black, phthalocyanine blue, phthalocyanine green, ultramarine blue, cobalt blue, titanium yellow, red iron oxide, baked amber, yellow oxide, etc. An oil-soluble dye, specifically, an oil-soluble dye having a skeleton such as a perinone-based, quinophthalone-based, anthrapyridone-based, or anthraquinone-based skeleton is mentioned, but one having a structure in which a polyester chain is bonded by reacting with a polyester functional group. Is particularly preferable, and also has good compatibility with polyester, shows sufficient heat resistance stability and color stability even at the production and processing temperatures of polyester, and when used as a packaging container for foods, etc., in terms of safety and hygiene, Select and add dyes and pigments that have no problems.

The polyester resin composition of the present invention may be used as it is as a molded article, and if necessary, further under high vacuum or under an inert gas flow, solid phase polymerization is performed to increase the degree of polymerization,
It may be used after being formed into a low aldehyde or low oligomer and then subjected to a post-treatment such as solvent extraction with xylene or chloroform.

Also, it is a so-called masterbatch which is colored with a desired color with a high concentration of several times to 100 times the predetermined concentration, and practically up to about 50 times, and it is diluted with a polyester which is uncolored or colored in another color tone. It is also possible to develop another new color tone and finally use it as a desired color tone.

The polyester resin composition having an excellent UV blocking property obtained in the present invention is melt-molded to obtain a molded product. In that case, all the melt-molding methods generally used in polyester can be applied. Specifically, the usual extrusion blow method,
Excellent in UV blocking property, gas blocking property, toughness, chemical resistance and high-quality glass-like transparency by blow molding such as injection blowing method, cold parison method in which the preform is reheated and then biaxially stretched. It is possible to obtain a hollow molded article having the above, and it is particularly suitable as a seasoning for soy sauce, sauce, mirin, dressing, etc., edible oil, carbonated beverage, fruit juice beverage, liquor, wine and other containers for cosmetics and pharmaceuticals. Also, after being formed into a sheet by extrusion molding, it is used as a uniaxially or biaxially stretched film or as a laminated film with other resins for packaging of general foods, chemicals, cosmetics, etc., and also for mulching coatings used for window pasting and agriculture and horticulture. Also, it is particularly preferably used as a molded article having various shapes by injection molding.

[Examples] Hereinafter, the present invention will be described in detail with reference to Examples. In the examples, "part" means "part by weight".

 Various measuring methods used in this example are shown below.

○ Intrinsic viscosity phenol-tetrachloroethane (50/50 weight ratio)
It was measured at 30 ° C. and a concentration of 1.0 g / dl.

-Ultraviolet transmittance It was measured by a conventional method using Hitachi Spectrum Photometer Model 340.

○ The amount of acetaldehyde was extracted with water at 160 ° C for 2 hours and then quantified with a high-sensitivity gas chromatograph.

○ Inert gas flow rate The inert gas flow rate is indicated by the volume amount () obtained by converting the amount of gas flowing per unit time (hr) and per unit resin amount (kg) into 1 atm and 25 ° C.

Synthesis Example 9,10-Bis (4-aminophenyl) anthracene, synthesis of imide compound represented by general formula (I) consisting of pyromellitic anhydride and trimellitic acid Stirrer, 300 ml four-neck with nitrogen gas inlet tube 9,10-bis (4-aminophenyl) anthracene 1 in a flask
2.98 g and 50 ml of dimethylacetamide were added, and the mixture was sufficiently stirred to form a slurry-like mixed liquid. Next, add 3.93 g of pyromellitic dianhydride and 40 ml of dimethylacetamide, stir at 30 ° C for 3 hours while flowing nitrogen gas, and then at 80 ° C.
At room temperature for 5 hours to obtain a green slurry liquid.

Then, 6.99 g of trimellitic anhydride and 69 ml of dimethylacetamide were added to adjust the concentration of the reaction solution to 15 wt / Vol%, the mixture was stirred at 30 ° C for 3 hours while flowing nitrogen gas, and reacted at 80 ° C for 5 hours.

To the thus obtained green amic acid slurry liquid, 0.06 mol of dimethylaminopyridine and 3 mol of acetic anhydride were added to 1 mol of trimellitic acid, and the temperature was raised to 80 ° C. with stirring,
Hold for 3 hours.

The reaction mixture was poured into a large amount of methanol, filtered and dried to obtain a brownish brown powdery imide compound represented by the formula (VI).

Example 1 To 4,000 parts of bis (β-hydroxyethyl) terephthalate, 0.4 part of germanium dioxide, 0.4 part of orthophosphoric acid and 15 parts of the imide compound represented by the formula (VI) synthesized in Synthesis Example were added, and the temperature was gradually raised from 260 ° C. While heating, the pressure inside the polymerization tank is gradually reduced from atmospheric pressure, and the total polymerization time is 280 ° C under a vacuum of 1 torr.
A polyester having an intrinsic viscosity of 0.70 was obtained in 3.0 hours.

After the polyester was dried under normal vacuum, a sheet having a wall thickness of 350 μ was formed using a 30 mmφ extruder in which each part of the cylinder and the nozzle was 275 ° C., the screw rotation speed was 40 rpm, and the extrusion rate was 80 g / min.

The light transmittances of the sheet at 370, 380 and 400 nm were 0.5%, 0% and 0%, respectively. The light transmittance chart is shown in FIG.

Furthermore, this dry resin is used for each cylinder and nozzle.
250 ° C, screw rotation speed 100 rpm, injection time 10 seconds, mold cooling water temperature set to 10 ° C Toshiba Machine Co., Ltd. injection molding machine IS
-60B continuously ejected a 2m / m thick plate with a size of 100m / m x 100m / m, but no deposits such as white powder were found on the plate even after 500 sheets were injected.

Example 2 The same operation as in Example 1 was repeated except that the amount of the imide compound represented by the formula (VI) synthesized in Synthesis Example was changed to 6 parts.
A polyester having an intrinsic viscosity of 0.70 was obtained.

330, 37 of 345μ thick sheet obtained in the same manner as in Example 1
Light transmittance at 0, 380 and 400 nm is 12.6%,
It showed 2.7%, 0.6% and 0.2%. The light transmittance chart is shown in FIG.

Example 3 A polyester having an intrinsic viscosity of 0.71 was obtained in the same manner as in Example 2 except that 12 parts of 2.6-naphthalenedicarboxylic acid was added. The light transmittance of 350μ thick sheet at 330, 370, 380 and 400nm is 0%, 2.2%, 0.5% and 0.2, respectively.
%showed that.

Example 4 A polyester having an intrinsic viscosity of 0.70 was obtained in the same manner as in Example 2 except that 12 parts of N-carboxymethyl-4-chloro-1,8-naphthalenedicarboxylic acid imide was added. Thickness
The light transmittances of the 355μ sheet at 330, 370, 380 and 400 nm were 0%, 0.9%, 0.2% and 0.2%, respectively.

Examples 5-8 Various imide compounds represented by the general formula (I) in place of the imide compound of the formula (VI) consisting of 9,10-bis (4-aminophenyl) anthracene, pyromellitic dianhydride and trimellitic acid 15 Parts and operating as in Example 1,
Various polyesters were obtained. The light transmittance is summarized in Table 1.

Example 9 The procedure of Example 1 was repeated except that 0.005 part of copper phthalocyanine was added, to obtain a light green transparent polyester having an intrinsic viscosity of 0.60.

 The surface of the polyester chip is solid air (USA
Crystallization at a resin temperature of 165 ° C in a Bepex type stirred crystallizer
After that, transfer to a stationary solid-state polymerization tower and remove 30 / kg ・ hr of nitrogen.
Resin gas temperature after drying at 120-160 ℃ for 3 hours under flowing natural gas.
Solid-state polymerization was carried out at 207 ° C for 10 hours.

The intrinsic viscosity of the solid-state polymerized product is 0.74, which is 3.
It contained 3 ppm of acetaldehyde. A preform was molded from this polyester with an injection molding machine IS-60B manufactured by Toshiba Machine Co., Ltd., which was set to each cylinder part and nozzle 275 ° C., screw rotation speed 100 rpm, injection time 10 seconds, and mold cooling water temperature 10 ° C. This preform was blow-molded with a BMB-3 machine manufactured by Corpoplast Co., Ltd., which was set at a preheating furnace of 90 ° C., a blow pressure of 20 kg / cm ² , and a molding cycle of 10 seconds, and the internal volume was 1
Got a bottle of. 370, 380 and 400 of 350μ thick part of this bottle
The UV transmittances in nm were 0.4%, 0% and 0%, respectively.

Comparative Example 1 A polyester having an intrinsic viscosity of 0.70 was obtained under the same conditions as in Example 1 except that the imide compound represented by the formula (VI) was not used. The 350 μm thick sheet molded in the same manner as in Example 1 had an ultraviolet transmittance of 68% at 370 nm and 69% at 380 nm. The light transmittance chart is shown in FIG.

Comparative Example 2 Polyethylene terephthalate having an intrinsic viscosity of 0.78 (RT-54
3C , Japan Unipet Co., Ltd. 5000 representative UV commercially available
Absorbent Tinuvin 326 [2 (2'-hydroxy-
3'-t-butyl-5'-methylphenyl) benzotri
Azole] 5.5 parts by dry blending, same as in Example 1
And a 350 μ thick sheet was molded. Light transmittance
The chart is shown in FIG.

The light transmittances of the sheet at 370 and 380 nm are respectively
It showed 2.8% and 8.0%.

When a 2 m / m plate was continuously injected in the same manner as in Example 1, a yellow powder substance adhered to the tip of the nozzle of the molding machine,
Yellow deposits were noticeable on the plate surface from the first sheet.

Example 10 The same polyethylene terephthalate resin as in Comparative Example 2 [RT
−543C , Nippon Unipet Co., Ltd.] per 100 parts by weight,
Add 0.2 parts of the imide compound represented by the formula (VI) to obtain V-type
After mixing well with a blender, vacuum drying and mixing with Example 1
Similarly, a 350 μ transparent sheet was obtained. 330 of the sheet,
The light transmittance at 370, 380 and 400 nm is 12.6 each.
%, 2.7%, 0.6%, 0.2% were shown.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing the light transmittances of the polyester resin compositions obtained in Examples 1 and 2 and Comparative Examples 1 and 2, where the vertical axis is the transmittance and the horizontal axis is the wavelength. Represents

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tetsuo Kasai 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryoh Chemical Industry Co., Ltd. (72) Inventor Takayuki Ota 1000 Kamoshida-cho, Midori-ku, Yokohama, Kanagawa Sanryo Kasei Co., Ltd. Research Institute (56) Reference JP-A-1-234456 (JP, A) JP-A-56-84747 (JP, A) JP-A-58-91757 (JP, A) JP-A-58 59-49257 (JP, A) JP-A-48-48536 (JP, A)

Claims (4)

[Claims] 1. A thermoplastic polyester resin containing at least one diimide compound represented by the general formula (I),
A thermoplastic polyester resin composition containing an effective amount for blocking ultraviolet rays. [In the formula (1), m and m'represent an integer of 0 to 4, and A or A'may be the same or different when m or m'is 2 or more, halogen, -COOH, or an ester thereof, -OH, -O-C (= O) CH 3, -NH 2, -CN, -NO 2, -
SO ₃ H or a metal salt thereof, a substituent selected from an optionally substituted alkoxy group, an aliphatic group or an aromatic group, and X is substituted with the substituent represented by A or A ′. Good Or And Z is And these aromatic nuclei may be substituted with the substituents represented by A or A ′. Further, Y is _{-CH 2 CH 2 -, - CH} = CH-, And these aromatic nuclei may be substituted with the substituent represented by A or A ′. ] 2. The composition further comprises the following general formula (II) or (II
The thermoplastic polyester resin composition according to claim 1, further comprising at least one of the naphthalene dicarboxylic acid compounds represented by I). [In the formulas (II) and (III), R ¹ and R ² may be the same or different and are hydrogen, an optionally substituted alkyl group, an aryl group, B: —O— or N—R ³ here. Wherein R ³ is hydrogen, an optionally substituted aliphatic group or aromatic group, D, E: may be the same or different, halogen, --COO
H or an ester, -OH, -O-C (= O) CH 3,,
_{-NH 2, -CN, -NO 2,} -SO 3 H or a metal salt thereof, an optionally substituted alkoxy group, a substituent selected from an aliphatic group or an aromatic group, 1, n: each 0-4 Indicates an integer. Further, the acid anhydride group or imide group of -C (= O) -BC (= O)-has a ring at any of 1,2-position, 1,8-position or 2,3-position of the naphthalene ring. Form. ] 3. An amount of at least one diimide compound represented by the general formula (1) effective for blocking ultraviolet rays, before starting or during polycondensation reaction of a thermoplastic polyester resin-forming substance. A thermoplastic polyester resin composition which is added to complete the polycondensation reaction. [In the formula (1), m and m'represent an integer of 0 to 4, and A or A'may be the same or different when m or m'is 2 or more, halogen, -COOH, or an ester thereof, -OH, -O-C (= O) CH 3, -NH 2, -CN, -NO
₂ , -SO ₃ H or a metal salt thereof, a substituent selected from an optionally substituted alkoxy group, an aliphatic group or an aromatic group, and X is substituted with the substituent represented by A or A ′. May have been Or And Z is And these aromatic nuclei may be substituted with the substituents represented by A or A ′. Further, Y is _{-CH 2 CH 2 -, - CH} = CH-, And these aromatic nuclei may be substituted with the substituent represented by A or A ′. ] 4. The composition further comprises the following general formula (II) or (II
The thermoplastic polyester resin composition according to claim (3), wherein at least one kind of the naphthalenedicarboxylic acid compound represented by I) is further added to complete the polycondensation reaction. [In the formulas (II) and (III), R ¹ and R ² may be the same or different and are hydrogen, an optionally substituted alkyl group, an aryl group, B: —O— or N—R ³ here. Wherein R ³ is hydrogen, an optionally substituted aliphatic group or aromatic group, D, E: may be the same or different, halogen, --COO
H or an ester, -OH, -O-C (= O) CH 3,,
_{-NH 2, -CN, -NO 2,} -SO 3 H or a metal salt thereof, an optionally substituted alkoxy group, a substituent selected from an aliphatic group or an aromatic group, 1, n: each 0-4 Indicates an integer. Further, the acid anhydride group or imide group of -C (= O) -BC (= O)-has a ring at any of 1,2-position, 1,8-position or 2,3-position of the naphthalene ring. Form.