JP2792111B2 - Method for producing polyester resin molded article - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a polyester resin molded article having excellent ultraviolet blocking properties.

[Conventional technology]

Polyester represented by polyethylene terephthalate has been widely used for fibers, films, etc. due to its excellent mechanical properties and chemical properties.In recent years, however, due to its excellent transparency, gas barrier properties, safety and health, etc., Attention has been drawn to its suitability as a container for carbonated drinks, fruit drinks, liquid seasonings, edible oils, sake and wine. As a new use of polyester films, window-attached films for the purpose of shielding heat rays and preventing glass scattering have been showing rapid growth in recent years from the viewpoint of energy saving and earthquake countermeasures. There is a strong demand for a transparent film that selectively blocks ultraviolet light in a specific wavelength range for the purpose of promoting the growth of rice and increasing the yield (for example, JP-A-53-98242).

However, these polyester containers and films are extremely excellent in blocking ultraviolet rays on the short wavelength side up to about 320 nm, but almost transmit ultraviolet rays and visible rays on the longer wavelength side. In such a polyester container, for example, an edible oil, mirin, and a liquid seasoning such as dressing are filled, and after a storage period of several months, depending on the filled food and storage conditions, there are specialities. Often, the contents gradually degrade, for example, subtle changes in color, taste, and aroma. The deterioration of the contents is caused by external factors such as oxygen, heat, light, especially ultraviolet rays, and microorganisms. In the case of a polyester container, the oxygen barrier properties are relatively excellent. Even below, it is possible to greatly prevent the deterioration of the contents.

In the case of a window-attached film, for example, the transmission of ultraviolet rays from sunlight causes discoloration of indoor equipment such as furniture, books, and furniture. In mulching cultivation in agriculture and horticulture, mulching with a transparent covering material that substantially blocks UV transmission of at least 370 nm or less promotes the growth of many useful plants and early It is also known that a large amount can be harvested (for example, JP-A-53-124556).

At present, ultraviolet absorbers and the like are generally used in the industry for the purpose. However, these ultraviolet absorbers are generally expensive, and the application step is complicated, and these compounds generally have high sublimability and are often inferior in thermal stability. When molding and processing often cause troubles, and when used in food containers and packaging, there is a risk of transfer to contents, which is not always preferable.

The present inventors have conducted intensive studies on a polyester resin composition meeting such an object, and as a result, added a naphthalenetetracarboxylic acid or a derivative thereof to a thermoplastic polyester resin mainly composed of polyethylene terephthalate, or By using a carboxylic acid or a derivative thereof in combination with a naphthalenedicarboxylic acid or a derivative thereof, the invention of a polyester resin composition capable of sufficiently blocking ultraviolet rays having a wavelength of 360 nm or more has been reached (Japanese Patent Application Laid-Open No. 63-225650). .

However, containers, sheets and films made of such a composition, although having sufficient UV-blocking properties, have a strong tendency to be colored yellow, and as a packaging material for contents such as colorless and transparent beverages and liquor, it is not always necessary. It was not satisfactory enough.

[Means for solving the problem]

The present inventors have further studied from such a viewpoint, and as a result, have found a method of manufacturing a thermoplastic polyester resin molded article that sufficiently blocks ultraviolet rays having a wavelength of 360 nm or more and has extremely low coloring properties. The invention has been reached.

That is, the gist of the present invention is that at least one of naphthalenetetracarboxylic acid or an acid anhydride, imide or ester thereof is added to the polyethylene terephthalate resin (A) in an amount effective for blocking ultraviolet rays to the entire polyester composition. A method for producing a polyester resin molded article, comprising molding a polyester resin composition obtained by blending a polybutylene terephthalate resin composition (B).

 Hereinafter, the present invention will be described in detail.

As the compound to be added to the polybutylene terephthalate resin, naphthalenetetracarboxylic acid or a compound having a naphthalenetetracarboxylic acid skeleton of an acid monoanhydride, an acid dianhydride, an imide, or an ester is used.

As naphthalenetetracarboxylic acid, naphthalene-
1,4,5,8-tetracarboxylic acid, naphthalene-1,3,5,7-tetracarboxylic acid, or similarly naphthalene-1,2,5,6
-, 2,3,6,7-, 1,3,6,8- and 1,4,6,7-, 1,2,4,5-,
1,3,4,5-, 1,2,3,4-tetracarboxylic acid and the like,
When a carboxylic acid group is present at the adjacent position, it may be an acid anhydride.

Of these, naphthalene-1,4,5,8-tetracarboxylic acid or its anhydride is preferred.

Various esters are used as the naphthalenetetracarboxylic acid ester, and alkyl esters such as methyl, ethyl, propyl, and butyl are preferable. For example, naphthalene-1,4,5,8-tetracarboxylic acid tetramethyl ester, naphthalene-1,4,5,8-tetracarboxylic acid tetraethyl ester, naphthalene-1,4,5,8-tetracarboxylic acid tetrapropyl ester Ester, naphthalene-1,
4,5,8-tetracarboxylic acid tetrabutyl ester, naphthalene-1,3,5,7-tetracarboxylic acid tetramethyl ester, naphthalene-1,3,6,8-tetracarboxylic acid tetramethyl ester, etc. .

Further, naphthalenetetracarboxylic acid 1,8-anhydro-3,6-
Compounds having both an anhydride ring and an ester bond, such as dimethyl ester, can also be used.

As the imide compound, any imide compound of naphthalenetetracarboxylic acid can be used.For example, naphthalene-1,4,5,8-tetracarboxylic acid or an acid derivative thereof and ammonia, glycine, alanine, valine, aminobutyric acid can be used. Aliphatic aminocarboxylic acids such as aminovaleric acid, aminocaproic acid, aminoundecanoic acid and aminododecanoic acid or esters thereof, amino alcohols, o-, m- or p-aminobenzoic acid or aromatic aminocarboxylic acids such as esters thereof It can be produced by reaction with acids or diaminos. An imidized compound, particularly a diimide compound, is particularly preferable because of its excellent heat resistance as compared with the above-mentioned tetracarboxylic acid, its acid anhydride or esterified compound.

Preferred as diimide compounds are naphthalene-1,
A diimide compound of 4,5,8-tetracarboxylic acid, having the following general formula (I) (In the formula (I), R ¹ and R ² may be the same or different,
Hydrogen, a halogen, a hydroxyl group or an optionally substituted alkyl group, an alkenyl group, an aryl group, an aralkyl group or an alkylaralkyl group, and Q represents a halogen, a hydroxyl group, an amino group, a nitro group, a cyano group, a carboxyl group, A sulfonic acid group or a salt thereof, an optionally substituted alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group or an alkylaralkyl group, and l is an integer of 0 to 4. ). In formula (I), the alkyl group of R ¹ , R ² and Q has 1 to 10 carbon atoms, the alkenyl group has 2 to 10 carbon atoms, and the aryl group has 6 to 10 carbon atoms. And an aralkyl group having 7 carbon atoms
~ 10, alkyl aralkyl groups having 8 to 8 carbon atoms
Twenty are usually used.

Specifically, N, N'-bis (carboxymethyl) -naphthalene-1,4,5,8-tetracarboxydiimide N, N'-bis (β-carboxyethyl) naphthalene-1,
4,5,8-tetracarboxydiimide N, N'-bis (γ-carboxypropyl) -naphthalene-1,4,5,8-tetracarboxydiimide N, N'-bis (11-carboxyundecyl) -naphthalene-1,4,5,8-tetracarboxydiimide N, N'-bis (β-hydroxyethyl) naphthalene-1,
4,5,8-tetracarboxydiimide N, N'-bis (γ-hydroxypropyl) -naphthalene-1,4,5,8-tetracarboxydiimide N, N'-bis (o-, m- or p-carboxyphenyl) -naphthalene-1,4,5,8-tetracarboxydiimide N, N'-bis (carboxytolyl) -naphthalene-1,4,
5,8-tetracarboxydiimide And their ester-forming functional derivatives, for example,
N, N'-bis (ethylcarboxyphenyl) naphthalene-1,4,5,8-tetracarboxydiimide Further, N, N'-bis-n-butyl-naphthalene-1,4,
5,8-tetracarboxydiimide Similarly, diimides having no ester-forming functional group are also preferably mentioned.

Further, in the present invention, in order to more effectively exhibit the ultraviolet ray blocking effect, the following general formula (II) or (II)
It is preferable to use the naphthalenedicarboxylic acid represented by I) or a derivative thereof in combination.

(In the formulas (II) and (III), X is O or NR ⁵ , and R ⁵ has the same meaning as R ¹ and R ² .

R ³ and R ⁴ may be the same or different and represent hydrogen, halogen or an optionally substituted alkyl group, alkoxy group, alkenyl group, aryl group, aralkyl group or alkylaralkyl group.

A and B may be the same or different, halogen, hydroxyl group, amino group, nitro group, cyano group, sulfonic acid group or a metal salt thereof, carboxyl group, optionally substituted alkyl group, alkenyl group, aryl Group, aralkyl group or alkylaralkyl group, m, n
Is an integer of 0 to 3, and m + n is 0 to 6.

Further, the acid anhydride group or imide group of —C (） O) —X—C (＝ O) — is a 1,8,2,3 or 3,3 position of the naphthalene ring.
Form a ring at any of the 4-positions. ) These compounds include 2,6-, 2,7-, 1,8-, 1,5-
Or a dicarboxylic acid structural isomer such as 2,3-naphthalenedicarboxylic acid, an ester thereof, or an acid anhydride thereof and a halogen thereof, NO ₂ , NH ₂ , CN, SO ₃ H and a metal salt or COO thereof.
Nuclear substituents by the H group and imides produced by the reaction of these naphthalenedicarboxylic acids with ammonia, amines, aminocarboxylic acids and amino alcohols are exemplified.

Specifically, when a 2,3-substituted product is described as a representative example, naphthalene-2,3-dicarboxylic acid and its dimethyl, diethyl, dipropyl, dibutyl ester, naphthalene-2,3-dicarboxylic anhydride, naphthalene- 2,3-dicarboximide, naphthalene-2,3-dicarboxy α-carboxymethyl) imide, similar β-carboxyethyl) imide, o- (m- or p-) carboxyphenyl) imide, α-bromomethyl) Imide, α
Naphthalene-2,3-dicarboxylic acid such as -hydroxymethyl) imide and derivatives thereof and 1,4-, 1,5-, 1,8-,
2,6-, 2,7-structural isomers as well as their hydroxyl, chloro, bromo, methoxy, ethoxy, cyano, amino, nitro, sulfonyl or carboxyl groups
Six or less nucleus-substituted products are mentioned, and it is important to have a naphthalenedicarboxylic acid skeleton in order to exhibit a 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 a dicarboxylic acid of these dicarboxylic acids. Esters, especially lower alkyl esters.

The naphthalenetetracarboxylic acid skeleton compound and the naphthalene dicarboxylic acid skeleton compound as described above can be added at any stage of the production of polybutylene terephthalate, or similarly, even when dry-blended with polybutylene terephthalate, the ultraviolet ray shielding effect is exhibited. However, when used as containers, sheets, and films for foods and beverages, it is most preferable to add them directly to the polybutylene terephthalate resin production tank and bind them to the polymer chains, considering dissolution into the contents. preferable.

Such a naphthalenetetracarboxylic acid-based compound and, if necessary, a naphthalenedicarboxylic acid-based compound are added to a polybutylene terephthalate resin in advance to form a uniform composition, and then mixed with the polyethylene terephthalate resin.

The blend ratio ((B) / (A)) of the polybutylene terephthalate resin composition (B) and the polyethylene terephthalate resin (A) is preferably 0.1 to 30 / 99.9 to 70,
It is better to blend in a ratio of 0.5 to 20 / 99.5 to 80, more preferably 1 to 10/99 to 90 weight percent. If the amount of the polybutylene terephthalate resin is more than 30% by weight, the transparency of the molded article is reduced. If the amount is less than 0.1% by weight, the ultraviolet ray blocking effect cannot be expected, which is not preferable.

Further, naphthalenetetracarboxylic acid contained in polybutylene terephthalate resin, its anhydride, ester,
Derivatives such as imide compounds and additives such as naphthalenedicarboxylic acid and derivatives thereof may be contained in the final polyester composition after blending with polyethylene terephthalate in amounts effective for blocking ultraviolet rays. ) And (B) may be determined in accordance with the blend amount ratio.

The preferred amount of the additive in the blend of (A) and (B) is 0.01% for naphthalenetetracarboxylic acid or a derivative thereof.
% By weight, and 0.01% by weight or more of naphthalenedicarboxylic acid or a derivative thereof, preferably about 0.05 to 20% by weight.

The preferable addition amount of naphthalenetetracarboxylic acid or a derivative thereof to the polybutylene terephthalate resin is 0.01 part by weight or more and 50 parts by weight or less per 100 parts by weight of the polybutylene terephthalate resin. When less than 0.01 parts by weight, naphthalenedicarboxylic acid or
Even when the derivative is used in an appropriate amount, it does not show sufficient ultraviolet shielding properties when blended with PET to form a container, sheet or film. On the other hand, if it is used in excess of 50 parts by weight, the melting point of polybutylene terephthalate will be too high, which may cause troubles during resin production or when molding and processing a blend composition with PET.

A particularly preferred addition amount is 0.05 to 30 parts by weight, more preferably 0.05 to 20 parts by weight.

When naphthalenedicarboxylic acid or its derivative is used in combination with the above-mentioned tetracarboxylic acid or its derivative, 0.01 part by weight or more is added per 100 parts by weight of the polybutylene terephthalate resin. If less than 0.01 parts by weight, PET
No further improvement in ultraviolet blocking properties is observed when blended with a mixture and formed into a container, sheet or film.

 Particularly, the preferable addition amount is 0.05 to 30 parts by weight.

The polybutylene terephthalate resin used in the present invention is obtained from terephthalic acid or a lower alkyl ester such as dimethyl terephthalate as a dicarboxylic acid component, and butylene glycol as a glycol component. Acids, phthalic acid, diphenyl ether dicarboxylic acid, aromatic dicarboxylic acids such as diphenylsulfone dicarboxylic acid and ester-forming derivatives thereof, alicyclic dicarboxylic acids which are nuclear hydrogenated compounds of aromatic dicarboxylic acids such as hexahydroterephthalic acid and the like; Ester-forming products, aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid and its ester-forming products, unsaturated dicarboxylic acids such as fumaric acid and 4-carboxycinnamic acid and its ester-forming products one The above dicarboxylic acids may be those obtained by copolymerizing 20 mol% of total dicarboxylic acid components.

As the glycol component, 1,4-butylene glycol is mainly used, but 1,2-, 1,3- or 2,3-
Aliphatic glycols such as butylene glycol, ethylene glycol, diethylene glycol, trimethylene glycol, tetramethylene glycol and neopentyl glycol; alicyclic glycols such as cyclohexanedimethanol; and 2,2-bis4'-β-hydroxyethoxyphenyl ) Propane, bisphenol derivatives such as bis- (4'-β-hydroxyethoxyphenyl) sulfone, and a compound of the general formula (CH _{2 n} O _m , wherein n is 1
≦ n ≦ 6, and m is an integer of m ≧ 4), such as polyethylene glycol, polytetramethylene glycol, or the like. A polyester obtained by copolymerizing an oxyacid component such as benzoic acid may be used.
In addition, as long as the polyester maintains a substantially linear shape, trifunctional or more polyfunctional compounds such as pentaerythritol, trimethylolpropane, trimellitic acid, trimesic acid, and pyromellitic acid, and monofunctional compounds such as o-benzoylbenzoic acid. A functional compound may be copolymerized.

The polybutylene terephthalate resin used in the present invention can be produced by any conventionally known polymerization method for polybutylene terephthalate.

For example, there is a method in which an esterification reaction is directly performed under pressure using terephthalic acid and 1,4-butylene glycol, and then the temperature is further raised and the pressure is gradually reduced to cause a polycondensation reaction. Alternatively, it can be produced by performing a transesterification reaction using an ester derivative of terephthalic acid, for example, dimethyl terephthalate and 1,4-butylene glycol, and then subjecting the obtained reaction product to polycondensation.

In the production of such polymers, an esterification catalyst,
It is preferable to use a transesterification catalyst, a polycondensation catalyst, a stabilizer and the like.

As the transesterification catalyst, known compounds, for example, one or more of titanium, calcium, manganese, zinc, sodium and lithium compounds can be used, but titanium and zinc compounds are particularly preferable from the viewpoint of reactivity and color tone. As the polymerization catalyst, one or more of known titanium, antimony, germanium, zinc, tin, and cobalt compounds can be used.
Antimony, germanium and zinc compounds are used.

The polybutylene terephthalate resin used in the present invention preferably has an intrinsic viscosity of 0.5 or more, more preferably 0.7 or more. The viscosity of the polyester is important, for example, when producing a hollow molded article, particularly in relation to the molding method. In particular, when obtaining a substantially non-oriented hollow molded article by extrusion blow molding, in order to prevent drawdown, it depends on the volume of the blow molded article, but it is necessary to maintain the fluidity of the molten polyester at a certain level or more, Generally 0.8
As described above, a polyester having an intrinsic viscosity of 1.0 or more is preferably used. In addition, in the extrusion molding method in which a film is formed by uniaxially or biaxially stretching after stretching hollow molding and sheeting, or in the injection molding method in which molded products of various forms are obtained, a polymer having a relatively low viscosity compared to the case of extrusion blow molding. In general, those having an intrinsic viscosity of 0.5 or more, preferably 0.7 or more are used. However, depending on the required physical properties of a molded article, a polyester having a higher viscosity is also used.

Further, in the present invention, conventionally known additives as a polybutylene terephthalate composition, for example, a stabilizer, a release agent, an antistatic agent, a coloring agent such as a dispersant or a dye or pigment, at any time during the production of polybutylene terephthalate. It may be added at a stage.

Preferred dyes and pigments in the present invention include titanium oxide, carbon black, phthalocyanine blue, phthalocyanine green, ultramarine, cobalt blue, titanium yellow, red iron oxide, baked amber, yellow oxide and the like, and heat resistance mainly in polycyclic systems. Oil-soluble dyes, specifically, oil-soluble dyes having a skeleton such as perinone-based, quinophthalone-based, anthrapyridone-based, and anthraquinone-based dyes, have a structure that reacts with a polyester functional group and bonds to a polyester chain. Are particularly preferred, and have good compatibility with polyester, exhibit sufficient heat stability and color tone stability even at the resin production and processing temperatures, and when used as packaging containers for foods, etc. The dyes and pigments having no problem are selected and added.

If necessary, the polybutylene terephthalate resin is further subjected to solid-state polymerization under high vacuum or under the flow of an inert gas to increase the degree of polymerization, reduce tetrahydrofuran, reduce oligomerization, or use xylene or chloroform. After adding post-treatment such as solvent oil removal, it may be blended with polyethylene terephthalate before use.

In addition, the above-mentioned stabilizers, release agents, antistatic agents, additives such as dispersants and dyes and pigments are several times or more than a predetermined concentration, 100 times,
Practically, a so-called masterbatch whose concentration is increased up to about 50 times is used, and this may be used by blending with a polyethylene terephthalate resin.

Further, the polyethylene terephthalate resin used in the present invention is obtained, for example, from a lower alkyl ester thereof such as terephthalic acid or dimethyl terephthalate and ethylene glycol, and as a dicarboxylic acid component, isophthalic acid, phthalic acid, diphenyl ether dicarboxylic acid. Acid, aromatic dicarboxylic acid such as diphenylsulfone dicarboxylic acid and its ester-forming derivative, alicyclic dicarboxylic acid which is a nucleated hydrogenated compound of the above aromatic dicarboxylic acid such as hexahydroterephthalic acid and its ester-forming product, succinic acid At least one dicarboxylic acid component represented by an aliphatic dicarboxylic acid such as adipic acid, sebacic acid, azelaic acid and its ester-former, unsaturated dicarboxylic acid such as fumaric acid and 4-carboxycinnamic acid and its ester-former To, 20 It may be those obtained by copolymerizing the following Le%.

As the glycol component, ethylene glycol is mainly used, but diethylene glycol, 1,4
-Or 1,3-butylene glycol, trimethylene glycol, tetramethylene glycol, aliphatic glycols such as neopentyl glycol, alicyclic glycols such as cyclohexanedimethanol, 2,2-bis4'-β- Bisphenol derivatives such as hydroxyethoxyphenyl) propane and bis- (4'-β-hydroxyethoxyphenyl) sulfone;
CH _{2 n} O _m (where n is an integer of 1 ≦ n ≦ 6, m is m
Polyethylene glycol, polytetramethylene glycol, etc., represented by the formula: (integral of ≧ 4) or less than 20 mol% of the total glycol components, or an oxyacid component such as hydroxybenzoic acid. It may be polyester. Also, as long as the polyester maintains substantially linear, pentaerythritol, trimethylolpropane, trimellitic acid, trimesic acid,
Trifunctional or more polyfunctional compounds such as pyromellitic acid, o
-A monofunctional compound such as benzoylbenzoic acid may be copolymerized.

The polyethylene terephthalate of the present invention can be produced by any conventionally known polymerization method for polyethylene terephthalate. For example, a direct esterification reaction is performed using terephthalic acid and ethylene glycol, or a transesterification reaction is performed using a lower alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol, and then, the obtained reaction product is used. Is further polycondensed. In the production of such a polymer, an esterification catalyst, a transesterification catalyst, a polycondensation catalyst, a stabilizer and the like may be used.

As the transesterification catalyst, one or more known compounds such as calcium, manganese, zinc, sodium and lithium compounds can be used, but manganese compounds are particularly preferred from the viewpoint of transparency. As the polymerization catalyst, one or more known antimony, germanium, titanium, and cobalt compounds can be used, but antimony, germanium, and a titanium compound are preferably used.

From the above viewpoint, the intrinsic viscosity of the polyethylene terephthalate resin is 0.5 or more, preferably 0.7 or more. Depending on the required physical properties of the molded product, a higher viscosity is also used. Further, the polyethylene terephthalate resin of the present invention is similar to the polybutylene terephthalate resin,
Lubricants such as the above-mentioned release agents, antistatic agents, dispersants, dyes and pigments, and slippery agents may be added. Alternatively, an additive in the form of a reaction in the system during the esterification, transesterification or polymerization reaction and precipitated on the polyethylene terephthalate resin may be used. These additives are
The concentration may be increased and used as a master batch.

This polyethylene terephthalate, after melt polymerization, as it is, may be blended with the above-mentioned polybutylene terephthalate resin composition to form a molded article, or, if necessary, further under a high vacuum or under an inert gas flow. After drying, solid-phase polymerization, and post-treatment such as increasing the degree of polymerization, lowering the aldehyde, lowering the oligomer, or extracting with a solvent, the mixture may be blended with the above-mentioned polybutylene terephthalate resin composition.

The polybutylene terephthalate resin thus obtained and a blend of polyethylene terephthalate resin are molded and processed by a conventional method, whereby the composition having a favorable color tone claimed in the present invention and having excellent ultraviolet shielding properties and a molded article made thereof are obtained. You can get it. At that time, all of the melt molding methods generally used for polyesters are applicable. More specifically, ordinary extrusion blowing method, injection blowing method, and blow molding such as cold parison method of biaxially stretching the preformed body after reheating, and the like, have ultraviolet shielding property, gas shielding property, toughness,
It is possible to obtain a hollow molded body with excellent chemical resistance and high-grade glass-like transparency, seasoning such as soy sauce, sauce, mirin, dressing, etc., cooking oil, carbonated beverage, It is particularly suitable for fruit juice drinks, liquor, wine and other cosmetic and pharmaceutical containers. Also, after extruded into sheets, it is used as a uniaxially or biaxially stretched film or as a laminated film with other resins for packaging of general foods, medicines, cosmetics, etc. It is particularly preferably used also as a molded product of various shapes by injection molding.

〔Example〕

 Hereinafter, the present invention will be described in detail with reference to examples.

In the examples, “parts” means “parts by weight”. The various measuring methods used in this example are shown below.

Intrinsic viscosity of polybutylene terephthalate and polyethylene terephthalate Phenol-tetrachloroethane (50/50 weight ratio)
It was measured at a medium temperature of 30 ° C. at a concentration of 1.0 g / dl.

Ultraviolet transmittance The transmittance was measured using a Hitachi Spectrophotometer Model 340 by an ordinary method.

Example 1 4400 parts of dimethyl terephthalate, 2500 parts of 1,4-butylene glycol, 7 parts of tetrabutyl titanate, N, N'-
Bis-4-ethylcarboxyphenyl) -naphthalene-
120 parts of 1,4,5,8-tetracarboxydiimide and 300 parts of dimethyl 2,6-naphthalenedicarboxylate were weighed into a reactor,
The content liquid was heated to 150 ° C. While distilling methanol, the temperature was gradually raised to 210 ° C., and a transesterification reaction was performed for a total of 2.5 hours. Subsequently, the polycondensation reaction was performed for a total of 3 hours at 245 ° C. and 1 torr while gradually increasing and decreasing the temperature.
The limiting viscosity of the obtained polybutylene terephthalate is 0.
78 was shown.

After crystallizing the chip surface at 120 ° C. in a stirring type crystallizer, the chip surface was dried at 120 to 160 ° C. for 3 hours.
The solid phase polymerization treatment was performed for a time.

 The intrinsic viscosity of the solid-phase polymerized product was 1.15. This chip
19 parts of polyethylene tere blow for 1 part
Tallate resin RT-543H (Nihon Unipet Co., Ltd.)
Dry blended, injection molding machine IS-60 manufactured by Toshiba Machine Co., Ltd.
A preform was molded in B. Homemade this preform
And a colorless transparent bottle having an inner volume of 1.5 L. This
Almost no coloration occurs even in the plug and bottom of the bottle
I was not able to admit. This bottle body 380μ thick part 370 and 38
The light transmittance at 0 nm is as good as 0.0% and 0.1%, respectively.
It showed good UV blocking properties.

Example 2 N, N'-bis (4-ethylcarboxyphenyl) -na
Instead of phthalene-1,4,5,8-tetracarboximide
Naphthalene-1,4,5,8-tetracarboxylic acid 50 parts
The polyethylene terephthalate resin (R
T-543H ) And blended as in Example 1
By operation, a bottle having an internal volume of 1.5 L was obtained. 380μ thick part of the bottle body
The light transmittance at 370 and 380 nm was 1.7% and 1%, respectively.
Showed 5.1%.

Example 3 Polybutylene terephthalate produced in the same manner as in Example 1
The melt polymerized product of the rate resin composition is subjected to a solid phase polymerization treatment.
1 part of the chip without any
Renterephthalate resin Diafoil H (Diahoy
Dry-blended at a ratio of 4 parts, according to a standard method.
After vacuum drying, the cylinder and nozzle are
40mmφ extruder (Modern Ma
chinery Ltd.) to form a 1200μ thick sheet.

The light transmittance at 370 and 380 nm of this extruded sheet was both 0.0%.

The sheet was simultaneously biaxially stretched 3 × 3 times with a long stretching machine (manufactured by TMLong Ltd., USA) set to an inner bath temperature of 90 ° C., then sandwiched between fixed frames, and placed in a geared oven at 200 ° C. for 60 hours.
Heat set for seconds. The light transmittance at 370 and 380 nm of the film was 4.2% and 7.5%, respectively.

Comparative Example 1 5000 parts of dimethyl terephthalate, ethylene glycol
3300 parts, N, N'-bis (4-ethylcarboxyphenyl
L) -Naphthalene-1,4,5,8-tetracarboximide 1
20 parts, dimethyl 2,6-naphthalenedicarboxylate 300 parts,
Weigh 0.7 parts of germanium oxide and 1 part of orthophosphoric acid into the reactor
Then, according to Example 1, the transesterification and polycondensation
went. The polycondensation reaction finally raises the temperature to 280 ° C,
Obtain polyethylene terephthalate resin with intrinsic viscosity of 0.60
Was. After crystallization of the chip surface, resin temperature 210 ° C at 15:00
In the meantime, solid-state polymerization is applied to obtain chips with intrinsic viscosity of 0.78
Was. One part of this chip was polyethylene resin in the same manner as in Example 1.
Terephthalate resin (RT-543H ) 19 copies and drilet
To obtain a bottle having an internal volume of 1.5 L. 380μ thick part of the bottle body
The light transmittance at 370 and 380 nm is the same as in Example 1.
In addition, 0.0% and 0.1%, respectively, were shown, especially the plug and
Orange yellow was conspicuous in the thick part at the bottom.

Comparative Example 2 Six parts of N, N'-bis (4-ethylcarboxyphenyl) -naphthalene-1,4,5,8-tetracarboximide,
The same operation as in Comparative Example 1 was carried out except that 300 parts of dimethyl 2,6-naphthalenedicarboxylate was used, and transesterification, polycondensation and solid-phase polymerization treatments were performed to obtain chips having an intrinsic viscosity of 0.78. This chip was made into a bottle having an internal volume of 1.5 L using the same device as in Example 1. The light transmittance of the body was the same as in Example 1, but orange-yellow coloring was noticeable in the thick portions such as the plug and the bottom.

Comparative Example 3 N, N'-bis (4-ethylcarboxyphenyl) -naphthalene-1,4,5,8-tetracarboximide and 1,6-
Except that dimethyl naphthalenedicarboxylate was not added, melt polymerization and solid state polymerization were performed in the same manner as in Example 1 to obtain a polybutylene terephthalate resin having an intrinsic viscosity of 1.18.

 This chip and polyethylene terephthalate resin (RT-
543H ) Is dry-blended in the same quantitative ratio as in Example 1,
A 1.5 L bottle was molded. 370 and 380n of the 380μ thick part of the bottle body
The light transmittance at m is 65.2% and 66.8%, respectively.
Was. No color is seen on the bottle stopper and the thick part at the bottom.
The condition was good, but the UV shielding effect was substantially recognized.
Did not.

Example 4 N, N'-bis- (4-ethylcarboxyphenyl) -naphthalene-1,4,5,8-tetracarboxylic acid diimide per 100 parts by weight of polybutylene terephthalate resin obtained by the same operation as in Comparative Example 3 3.6 parts and 9 parts of 2.6-naphthalenedicarboxylic acid are mixed well in a V-type blender, and then dried in vacuum,
A master batch chip was manufactured in the same manner as in Example 1.

 One part of this chip is polyethylene terephthalate
Fat (RT-543H ) Dry-blended at 29 parts
The mixture was made into a 1.5 L bottle in the same manner as in Example 1. The bottle body
Light transmittance at 370 and 380 nm of 380μ thick part is implemented
The values are the same as in Example 1, and the thickness of the plug and the bottom are slightly yellow.
The color exhibited a favorable color tone.

Comparative Example 4 The same polybutylene terephthalate used in Comparative Example 3
Tinuvin P, a commercially available typical UV absorber (T
inuvin P, manufactured by Ciba Geigy; 2 (2'-hydroxy-5 '
-Methylphenyl) benzotriazole) 110g dry
Blend and extruded 30mmφ manufactured by Tanabe Plastic Machinery Co., Ltd.
A masterbatch resin was manufactured on the machine.

 1 part of this masterbatch resin and polyethylene teref
Tallate resin (RT-543H ) For 19 parts
In the same manner as in Example 1, a 1.5 L bottle was formed. This bottle
Light transmittance at 370 and 380nm of 380μ thick body
Indicates 1.6% and 13.5%, respectively, and the UV blocking property is good.
Although it was good, the plug part and the bottom part showed a pale yellow color. Ma
In addition, during the above-mentioned masterbatch resin production and bottle molding
Near the nozzle of the molding machine
When drying the masterbatch resin,
There was a slight yellow sublimate deposit on top.

〔The invention's effect〕

As described above, according to the present invention, it is possible to obtain a polyester resin molded article having good ultraviolet blocking properties and good color tone.

[Brief description of the drawings]

FIG. 1 is a diagram showing the light transmittance of the polyester resin compositions obtained in Examples 1 and 2 and Comparative Examples 3 and 4, wherein the vertical axis represents the transmittance and the horizontal axis represents the wavelength.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ identification code FI C08K 5/3415 C08K 5/3415 (58) Investigation field (Int.Cl. ⁶ , DB name) C08L 67/02 C08K 5/092 , 5 / 15,5 / 3415,5 / 12 C08G 63/78

Claims (2)

(57) [Claims] 1. A polyethylene terephthalate resin (A)
To naphthalenetetracarboxylic acid or its anhydride,
A polyester resin composition is obtained by blending a polybutylene terephthalate resin composition (B) obtained by adding at least one kind of imide or ester to the entire polyester composition in an amount effective for blocking ultraviolet rays. A method for producing a polyester resin molded article. 2. The method for producing a polyester resin molded article according to claim 1, wherein naphthalenedicarboxylic acid or a derivative thereof is further added to the polybutylene terephthalate resin composition (B).