JPH01247451A - Thermoplastic polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in the property of screening ultraviolet rays, by adding a specified diimide compound to a thermoplastic polyester resin. CONSTITUTION:This resin composition is formed by adding at least one diimide compound of formula I in an amount effective in screening ultraviolet rays to a thermoplastic polyester resin, wherein m and m' are each 0-4, A and A', which may be the same or different from each other when m and m' are each >=2, are each a halogen atom, -COOH or its ester, -OH, -NH2, -CN, -NO2 or its metal salt, an alkoxy, an aliphatic group or an aromatic group or the like, X is a group of formula II or III or the like, and these aromatic nuclei may have substituents A or A'. Y is =SO2, -S-, =C=O, -O-, -CH2-, -CH2CH2-, -CH=CH-, formula IV, formula V or the like, and these aromatic nuclei may have substituents A or A'.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to thermoplastic polyester resin compositions.

More specifically, the present invention relates to a polyester resin composition having excellent ultraviolet blocking properties.

[Prior art] Polyester, represented by polyethylene terephthalate, has been widely used in fibers, films, etc. due to its excellent mechanical and chemical properties, but in recent years, its excellent transparency, gas barrier properties, and safety Due to their hygienic properties, they are being used as containers for carbonated drinks, fruit juice drinks, liquid seasonings, edible oils, alcoholic beverages, and wine. In addition, as a new use for polyester film, window film for the purpose of blocking heat rays and preventing glass from scattering has shown rapid growth in recent years from the viewpoint of energy saving and earthquake countermeasures. For the purpose of promoting growth and increasing yields,
There is a strong demand for a transparent film that selectively blocks ultraviolet rays in a specific wavelength range (for example, Japanese Patent Laid-Open No. 53-98242).

However, although these polyester containers and films are extremely good at blocking ultraviolet rays at short wavelengths up to about 320 r+m, they hardly transmit ultraviolet rays at longer wavelengths, developable light, etc. It ends up. For example, when a polyester container like this is filled with liquid seasonings such as edible oil, mirin, or dressing, and after a storage period of several months, there are specific characteristics depending on each filled food and storage conditions. , Gradual deterioration of contents,
For example, subtle changes in color, taste, and aroma often occur.

Deterioration of the contents is caused by external factors such as oxygen, heat, light, especially ultraviolet rays, and microorganisms, but polyester containers have relatively excellent oxygen blocking properties, so if the UV blocking properties can be further improved, it will last for a long time. Even during storage, it is possible to greatly prevent the contents from deteriorating.

In addition, with window films, for example, if ultraviolet rays from sunlight pass through, it will cause discoloration of furniture, books, furnishings, and other indoor fixtures, so it is necessary to minimize or completely block the penetration of ultraviolet rays. In mulching cultivation in agriculture and horticulture, mulching with a transparent covering material that substantially blocks the transmission of ultraviolet rays of at least 370 rv or less promotes the growth of many H plants and improves island quality. It is known that crops can be harvested early and in large quantities (for example, JP-A-53-124556).

Currently, ultraviolet absorbers and the like are generally added and used for this purpose in the industry. However, these ultraviolet absorbers are generally expensive, and the application process is complicated, and these compounds generally have high sublimation properties and many have poor thermal stability, so the application process is difficult. Sometimes troubles occur during molding or molding.
Furthermore, when used in food containers or packaging, there is a risk of migration to the contents, which is not necessarily preferable.

[Problems to be Solved by the Invention] In view of the above circumstances, the present invention has an excellent ultraviolet blocking property,
Moreover, it is an object of the present invention to provide a polyester resin composition that has good thermal stability, dispersion stability, etc., and does not cause troubles such as deposits on molded products during molding.

[Means for Solving the Problems] The present inventors have investigated a polyester resin composition that meets the above objectives, and have found that by incorporating a specific diimide compound into a polyester resin, it is possible to The present invention was achieved by discovering a polyester resin composition that can sufficiently block ultraviolet rays on the wavelength side.

That is, the gist of the first invention of the present invention is to provide a thermal nJ plastic polyester resin composition obtained by adding at least one diimide compound represented by general formula (1) in an amount effective for blocking ultraviolet rays to a thermal +J plastic polyester resin. Yes, −0−C(0)C1lp, −old+2, −CN, −
NO2, -8O311 or a metal salt thereof, an optionally substituted alkoxy group, an aliphatic group, or an aromatic group, and these aromatic nuclei are substituted with the substituent represented by A or A'' above. Good too.

In addition, Y is SQ2, -3-1〉~0, -0-1,
The gist of the second invention is that at least 1 fiI of the diimide compound represented by the general formula (1) is added to the thermoplastic polyester resin-forming substance before or during the polycondensation reaction of the substance! This is a thermoplastic polyester resin composition prepared by adding the above-mentioned polycondensation reaction in an amount effective for blocking ultraviolet rays to complete the polycondensation reaction.

The present invention will be explained in detail below.

In the present invention, a diimide compound represented by general formula (1) is used as a compound added to the thermoplastic polyester resin.

Specifically, the diamino compound inducing the X group in general formula (1) is 3,3'-dihydroxy-4,4
°-diaminobiphenyl, 3,3'-dimethyl-4,4
゛-Diaminobiphenyl, diaminodiamino diphenyl sulfide diaminodiphenylethanminophenoxy)benzene 9,9-bis(aminophenyl)anthracenephenoxyphenyl)propanyl)benzobisthiazolenzobistiazole, these Yoshitani nuclei are the above A or It may be substituted with a substituent represented by A'. Among these diamino compounds, 3,3"-dimethyl-4,4"-diaminobiphenyl, 9.10-bis(4-aminophenyl)anthracene, bis(3-aminophenyl)benzobisthiazole, bis(4- Particularly preferably used are aminophenyl)benzobisthiazole and bis(4-aminophenyl)3,4-diphenylthiophene.

In addition, a phthalic acid derivative is used as the dicarboxylic acid for inducing the imide compound of general formula (1), and ASA- is the same or different halogen, -C11, -COO11 or its ester, -0-C(-0)CIl ) , -N
112, -CN, -NO2, -3O311 or a metal salt thereof, an optionally substituted alkoxy group, an aliphatic group, or an aromatic group, and fl
lSm' is a fi number from 1 to 4. Specifically, phthalic acid, trimellitic acid (4-carboxyphthalic acid, 4-chlorophthalic acid, 4-hydroxyphthalic acid, 4-acetoxyphthalic acid, 4-nitrophthalic acid, 4-methoxyphthalic acid, 4-ethoxyphthalic acid) , 4-methyl phthalic acid, 4-ethyl phthalic acid, 4-aminophthalic acid, 4-sulfonylphthalic acid and its sulfonyl sodium salt, 4-phenylphthalic acid and their 5-16- or 3-nucleically substituted isomers. Of these, C00I+, 01
1 or their ester-forming derivatives are particularly preferably used.

More specifically, these imide compounds can be manufactured as follows by a known method (Bull, S.
oc, chim, France, 1951.727~
732).

For example, in the case of a diimide compound represented by formula (2) consisting of 9.10-bis(4-aminophenyl)anthracene and trimellitic anhydride, 9.10-bis(4-aminophenyl)anthracene and trimellitic anhydride are used in a flask equipped with a stirrer and a nitrogen gas introduction. Screw(
Add 4-aminophenyl)anthracene and dimethylacetamide and stir thoroughly to form a slurry mixture. Next, trimellitic anhydride and dimethylacetamide are added and the reaction is carried out while nitrogen gas is passed through the reaction solution to obtain an amic acid solution.

A reaction is carried out by adding dimethylaminopyridine as a catalyst and acetic anhydride as a dehydrating agent to this amic acid solution. The reaction solution thus obtained can be poured into a large amount of methanol and filtered to obtain the powdered imide compound of formula (2). These imide compounds may be synthesized by other methods, and the production method itself is not restricted in any way.

The amount of the imide compound added is at least o, ooi parts by weight per 100 mm parts of the thermoplastic polyester resin. 0
, 001 parts by weight, an effective ultraviolet blocking effect cannot be obtained. Particularly preferable addition amount is 0.01~
Weight in 10 layers and 2 parts.

These imide compounds may be added at any stage of polyester production, and even if they are added at any stage before or before molding, they can similarly exhibit the ultraviolet shielding effect.

That is, it may be added at any stage until the molding of the polyester is completed, for example, before the start of the polycondensation reaction, during the ffl condensation reaction, after the end of the polycondensation reaction, in the form of powder, in the molding stage, etc.

In the present invention, thermal rrJ 'ill polyesters include terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, diphenyl ether dicarboxylic acid,
Aromatic δ group dicarboxylic acids such as diphenylsulfone dicarboxylic acid and their ester formation products, alicyclic dicarboxylic acids and their ester formation products which are nuclear hydrogenated compounds of the aromatic dicarboxylic acids such as hexahydroterephthalic acid, succinic acid, One or more dicarboxylic acid components represented by aliphatic dicarboxylic acids such as adipic acid, sebacic acid, and azelaic acid and their esters, and unsaturated dicarboxylic acids and their esters such as fumaric acid and 4-carboxycinnamic acid. ,
It is a polyester obtained from a glycol component mainly composed of ethylene glycol, and its main target is polyethylene terephthalate, but these polyesters contain 20 mol% or less of the above dicarboxylic acids other than terephthalic acid as a third component. Also good.

In addition to ethylene glycol, this polyester also contains aliphatic glycols such as diethylene glycol, trimethylene glycol, tetramethylene glycol, and neopentyl glycol, and alicyclic glycols such as cyclohexanerimethanol.2.2
-bisphenol derivatives such as bis(4°-β-hydroxyethoxyphenyl)propane, bis-(4″-β-hydroxyethoxyphenyl)sulfone, and also general formula 110÷鵠I+ 2→−1−0±1 -11 (in the formula n
is an integer of 1≦n≦6, and m is an integer of m≧4. However, it may also be a polyester copolymerized with an oxyacid component such as glycolic acid or hydroxybenzoic acid. In addition, as long as the polyester remains substantially linear, polyfunctional compounds of trifunctional or higher functionality such as pentaerythritol, trimethylolpropane, trimellitic acid, trimesic acid, pyromellitic acid, etc. A monofunctional compound may be copolymerized. Further, in addition to the above-mentioned polyester, it may be a blend of other thermoplastic resins such as polybutylene terephthalate, polyethylene naphthalate, polyester elastomer, and polycarbonate.

The polyester used in the present invention has an intrinsic viscosity of 0.5 to
2.5 is preferred, more preferably 0.6 to 1.
2 are used. The viscosity of polyester is important, for example, when manufacturing blow molded bodies, especially in relation to the molding method. In particular, when a substantially non-oriented hollow molded body is obtained by extrusion blow molding, it is necessary to maintain the fluidity of the molten polyester above a certain level to prevent drawdown, although this depends on the capacity of the blow molded body. Yes, generally 0.7 or more,
Preferably polyesters with an intrinsic viscosity of 0.8 to 1.2 are used. In addition, after stretch blow molding and sheeting, −
In extrusion molding, which produces films through axial or biaxial stretching, and injection molding, which produces molded products in various forms, polymers with relatively low viscosity can be used compared to extrusion blow molding, and polymers with a generally low intrinsic viscosity can be used. 0.5 or more, preferably 0.6 to 1.2
However, depending on the required physical properties of the molded product, even higher viscosity polyesters may be used.

In addition, in the present invention, additives conventionally known as polyester compositions, such as stabilizers, mold release agents, antistatic agents,
Coloring agents such as dispersants and face washes may be added at any stage during polyester production, or may be added before molding 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, burnt umber, yellow oxides, and heat-resistant mainly polycyclic compounds. Oil-soluble dyes, specifically oil-soluble dyes with skeletons such as perinone, quinophthalone, anthrapyridone, and anthraquinone, have a structure that reacts with polyester functional groups to bond polyester chains. is particularly preferable, and has good compatibility with polyester, exhibits sufficient heat resistance stability and color stability even at the manufacturing and processing temperatures of polyester, and when used as packaging containers for foods, etc., from the viewpoint of safety and hygiene. Select and add dyes and pigments that do not cause any problems.

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

In addition, a so-called masterbatch is prepared which is colored with a desired color at a high concentration of several to 100 times, practically up to 50 times, the predetermined concentration, and this is diluted with uncolored polyester or polyester colored in another tone. Moreover, other new color tones can be developed and finally used as a desired color tone.

The polyester resin composition with excellent ultraviolet blocking properties obtained by the present invention is melt-molded to form a molded article. In this case, all melt-molding methods commonly used for polyesters are applicable. Specifically, blow molding methods such as the usual extrusion blowing method, injection blowing method, and cold parison method in which the preform is biaxially stretched after reheating produce excellent ultraviolet blocking properties, gas blocking properties, toughness, and chemical resistance. At the same time, it is possible to obtain a molded body with a luxurious glass-like transparency, and it can be used for seasonings such as soy sauce, sauces, mirin, and dressings, edible oil, carbonated drinks, fruit juice drinks, alcohol, and wine. It is particularly suitable as containers for other cosmetics and medicines. In addition, after being made into a sheet by extrusion molding, it can be used as a mulch or biaxially stretched film or a laminated film with other resins for packaging general foods, medicines, cosmetics, etc., as well as for window pasting and in agriculture and horticulture! It is particularly preferably used as l1jffl material, and also preferably used as molded products of various shapes by injection molding.

[Example] Hereinafter, the present invention will be explained in detail with reference to Examples.

In the examples, "part" means "part by weight".

Various measurement methods used in this example are shown below.

O intrinsic viscosity was measured in phenol-tetrachloroethane (50/50 weight ratio) at 30°C, l, at a concentration of Og/dI.

The ultraviolet transmittance was measured by a conventional method using a Hitachi Spectral Photometer Model 340.

After extracting O-acetaldehyde with water at 160°C for 2 hours, it was quantified using a high-sensitivity gas chromatograph.

0 Inert gas flow 2 Inert gas flow m is expressed as a volumetric amount (9,) calculated by converting the amount of gas flowing per unit time (hr) and unit resin weight (kg) at 1 atm and 25°C.

Synthesis Example 9. Synthesis of a diimide compound represented by formula (2) consisting of 10-bis(4-aminophenyl)anthracene and trimellitic anhydride.

Accurately weigh 7.21 g of 9,10-bis(4-aminophenyl)anthracene into a 30-hl four-eye flask equipped with a stirrer and nitrogen gas introduction, add 501 dimethylacetamide, and stir thoroughly to form a slurry. A mixed solution was prepared.

Next, 7.77g of trimellitic anhydride and 50Ill of dimethylacetamide were added to adjust the reaction solution to 15νt/Vo.
Adjust to 1%l agricultural level and heat to 30°C while flowing nitrogen gas.
The reaction was carried out for 5 hours, and the amic acid solution was diluted with i(?).

To this amic acid solution, 0.03 mol of dimethylaminopyridine as a catalyst per 1 mol of trimellitic acid and 1.5 mol of acetic anhydride as a dehydrating agent were added, and while stirring,
The temperature was raised to 0.degree. C. and maintained for 3 hours. The reaction solution thus obtained was poured into a large amount of methanol and filtered to obtain a powdery imide compound of formula (2).

Example 1 Bis(β-hydroxyethyl) terephthalate 4,00
0 parts, 0.4 parts of germanium dioxide, 0.4 parts of orthophosphoric acid, and 9°10-bis(4-
Add 5 ffll of diimide compound consisting of (aminophenyl)-anthracene and trimellitic anhydride, and heat at 260°C.
The temperature was gradually raised from 100 to 100, while the pressure within the polymerized amount was gradually reduced from normal pressure, and polyester with an intrinsic viscosity of 0.71 was produced at 280° C. and under a vacuum of 1 torr for a total polymerization time of 3.0 hours i)
Ta.

After drying the polyester in a normal vacuum, each part of the cylinder and nozzle was heated at 275°C and a screw rotation speed of 40 rpm.
, extrusion jilk 30iaφ set to 80g/min
A sheet with a wall thickness of 350 μm was molded using an extruder.

The light transmittance of the sheet at 370.380 and 400 parts m was 0.2%, 096 and 096, respectively. A light transmittance chart is shown in FIG.

Furthermore, apply this dry resin to each part of the cylinder and the nozzle.
5℃, screw rotation speed 100rpl, injection time 10 seconds, mold cooling water temperature set to 10℃.
2111/DI thick plates having a size of la were continuously injected, but no white powder or the like was observed on the thick plates even after 500 sheets were injected.

Examples 2 to 5 Same as Example 1 except that 15 parts of various imide compounds shown in the table below were added instead of the diimide consisting of 9, 1O-bis(4-aminophenyl)anthracene and trimellitic anhydride. Through this operation, various polyesters were obtained. The ultraviolet transmittances are summarized in Table 1.

Table 16 types of imide compounds and UV transmittance addition Imide compound addition amount equivalent to 0.4% (relative to polyester) Example 7 Except for adding copper phthalocyanine Q and OQS part, the same operation as in Example 1 was carried out, and the intrinsic viscosity A transparent polyester colored with a thin edge color having a coefficient of 0.60 was obtained.

The surface of the polyester chip was heated at a resin temperature of 165 in a solid air (Bapex, USA) type stirring crystallizer.
After crystallization at ℃, transferred to a stationary solid phase polymerization group, 305
After drying at 120 to IGO° C. for 3 hours under a flow of nitrogen gas at i/kg”hr, solid phase polymerization was performed at a resin temperature of 210° C. for 10 hours.

The solid phase polymer product had an intrinsic viscosity of 0.75 and contained 3.0 ppm of acetaldehyde in the chip material.

Each part of the cylinder and nozzle 27 are made from this polyester.
5℃, screw rotation speed 1100rp, Jul during injection
A preform was molded for 10 seconds using an injection molding machine 1s-60B manufactured by Toshiba Machine Corporation, which was set at a mold cooling water temperature of lO<0>C. This preform was heated in a preheating oven at 90°C and a blow pressure of 20kg/
cm' and a molding cycle of 10 seconds using a BMB-3 machine manufactured by Cohoblast ■ to obtain a bottle with an internal volume of 151 cm. The ultraviolet transmittance of 370.380 and 400tv of the 350μ thick part of this bottle is 0.2% and 0, respectively.
% and 0%.

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 diimide compound represented by formula (2) was not used. Wall thickness 35 molded in the same manner as in Example 1
The UV transmittance of the 0μ sheet is 68% at 370tv, 3
It showed 69% at 80ni. Light transmittance chart first
Shown in the figure.

Comparative Example 2 Polyethylene terephthalate CRT with intrinsic viscosity 0.78
-543C@, Nippon Unipet ■) 5000 copies of Tinuvln 32B', a typical commercially available UV absorber
35.5 parts of [2(2°-hydroxy-3°-t-butyl-5°-methylphenyl)benzotriazole] was triblended and operated in the same manner as in Example 1 to form a 350 μm thick sheet. A light transmittance chart is shown in FIG.

The light transmittance of the sheet at 370 and 380 nn+ was 2, 8% and 8.0%, respectively.

When 2IIllflll plates were continuously injected in the same manner as in Example 1, yellow powder adhered to the nozzle tip of the molding machine, and yellowing was noticeable on the plate surface from around the 200th plate.

Example 8 Polyethylene terephthalate resin [RT
-543C■, Nippon Unipet■] 0.4 part of the diimide compound represented by the above formula (2) was added per 100 parts by weight, mixed thoroughly with a V-type blender, and then vacuum dried,
A 350μ transparent sheet was obtained in the same manner as in Example 1. The light transmittance of the sheet at 370.380 rvl and 400 rvl was o, 3 qt, 0%, and 0%, respectively.

[Effects of the Invention] As is clear from the above description, the polyester resin composition of the present invention can sufficiently block not only short wavelength ultraviolet rays but also long wavelength ultraviolet rays, and the composition is uniform. It has excellent dispersion stability and thermal stability, and does not produce colored deposits on molded products during molding.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the light transmittance of the polyester resin compositions obtained in Example 1.3 and Comparative Example 1.2, where the vertical axis represents the transmittance and the horizontal axis represents the wavelength. Patent applicant Mitsubishi Chemical Industries, Ltd. agent Patent attorney Hidetake Komatsu

Claims (1)

[Scope of Claims] (1) A thermoplastic polyester resin composition obtained by adding at least one diimide compound represented by general formula (1) to a thermoplastic polyester resin in an amount effective for blocking ultraviolet rays. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) In the formula (1), m and m' represent integers from 0 to 4, and A or A' are the same if m or m' is 2 or more. or may be different, halogen, -COOH or its ester, -OH, -OC(=O)CH_3, -NH_
2, -CN, -NO_2, -SO_3H or a metal salt thereof, an optionally substituted alkoxy group, an aliphatic group, or an aromatic group; There are ▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ These aromatic nuclei may be substituted with the substituent shown by A or A' above. Also, Y is ■SO_2
, -S-, ■C=O, -O-, -CH_2-, -CH_
2CH_2-, -CH=CH-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and these aromatic nuclei are substituents indicated by A or A' above. may be replaced with . (2) Before or during the polycondensation reaction of the thermoplastic polyester resin-forming substance, the general formula (1
) A thermoplastic polyester resin composition comprising adding at least one diimide compound represented by formula 1 in an amount effective for blocking ultraviolet rays to complete the polycondensation reaction. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) In the formula (1), m and m' represent integers from 0 to 4, and A or A' are the same if m or m' is 2 or more. or may be different, halogen, -COOH or its ester, -OH, -OC(=O)CH_3, -NH_
2, -CN, -NO_2, -SH_3H or a metal salt thereof, an optionally substituted alkoxy group, an aliphatic group, or an aromatic group; There are ▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and these aromatic nuclei may be substituted with the substituent shown by A or A' above. Also, Y is ■SO_2
, -S-, ■C=O, -O-, -CH_2-, ▲ Formula,
There are chemical formulas, tables, etc.▼, -CH=CH-, ▲mathematical formulas,
There are chemical formulas, tables etc. It may be substituted with a substituent represented by A or A'.