JPH0480942B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to colored polyester resin compositions. Specifically, a colored polyester resin composition that can provide a transparent and colored hollow molded body, etc., and that contains one or more coloring compounds having a reactive functional group represented by the following general formula. It is related to. (In the above formula, A, B, C, D, E, F and G each represent a benzene ring, A may have a lower alkyl group or a lower alkoxy group, and B and C are a hydroxyl group, or It may form a lower hydroxyalkoxy group and/or an ester, but it has a carboxyl group, and D and E
are each substituted with a halogen atom, or

A ring may be formed using an ethylene group as shown in [Formula]. F may have a hydroxy group and/or an amino group, and G may have a hydroxy group, a lower hydroxyalkyl group, a lower hydroxyalkoxy group, a carboxyl group that may form an ester, and a carboxyl group that may form an ester. It may contain one or more of the lower carboxyl alkyl groups that may be used, and may further contain a lower alkyl group and/or a halogen atom. X is -O-(CH ₂ CH ₂ -O)-n or -(O-CH ₂
) _o+1 --O- (in the formula, m represents 0 or 1, and n represents an integer of 0 to 3), and R ¹ represents a hydrogen atom or a halogen atom. ) Polyesters, represented by polyethylene terephthalate, have excellent mechanical and chemical properties and are widely used in fibers, film molded bodies, hollow molded bodies, etc. In recent years, containers made by biaxial stretch blow molding of polyethylene terephthalate resin have been used for food, pharmaceuticals, cosmetics, etc. due to their excellent transparency, gas barrier properties, and safety and hygiene properties. It is attracting attention. In many of these applications, the commercial value is increased by coloring, and colored polyethylene terephthalate resins are actually used in some cosmetic containers and beverage containers. In order to obtain transparent and colored hollow containers, organic pigments or dyes are generally used as coloring agents, but since the above-mentioned coloring agents are insufficiently thermally stable. Currently, methods for incorporating colorants into resins are extremely limited. Specifically, a method is used in which a colorant and a polyester resin are mixed using a mixer such as a tumbler, and then melt-extruded using an extruder to form master batch chips. Even with this method, it is necessary to set the resin temperature as low as possible in order to prevent the colorant from fading or changing color. However, since polyester chips extruded at low temperatures tend to crystallize, precursor molded bodies for hollow containers molded using these masterbatch chips often turn white due to crystallization, resulting in poor transparency.
Therefore, the melt extrusion conditions for masterbatch chips have to be limited to a narrow temperature range. Therefore, in order to use normal extrusion temperatures, a coloring agent with excellent heat resistance is required, but even with heat-resistant compounds, when added during melt extrusion, the final colorant cannot be obtained. Since the problem of elution of compounds occurs in molded products, especially bottles for food, etc., it is necessary to use compounds that have a low elution property from the resin. One possible method for this purpose is to add a compound that has the property of reacting with polyester during the polyester manufacturing reaction, but in this case, the compound must be stable during the polyester reaction and during the melting process during molding. required. Furthermore, in bottle applications, in order to remove acetaldehyde and/or obtain polyester chips with a high degree of polymerization, solid phase polymerization is often carried out at a temperature of 190°C or higher and below the melting point for several hours or more. Therefore, the coloring compound added before the end of the polyester manufacturing reaction is exposed to high temperatures such as polymerization temperature, melt extrusion temperature, and solid state polymerization temperature for a long time, and it is difficult to develop a compound that can withstand such harsh conditions. You have to choose. In view of the current situation, the present inventors conducted intensive studies on various colorants and found that a specific coloring compound having an ester-forming functional group has heat resistance of 300°C or higher and does not deteriorate even over a long period of time. Because it chemically bonds with polyester without any
The inventors have discovered that colored polyester having extremely excellent properties can be provided, and have arrived at the present invention. That is, the present invention provides a colored polyester resin composition containing one or more colored compounds represented by the following general formula. (In the above formula, A, B, C, D, E, F and G each represent a benzene ring, A may have a lower alkyl group or a lower alkoxy group, and B and C are a hydroxyl group, or Although it may form a lower hydroxyalkoxy group and/or an ester, it has a carboxyl group, and D and E
are each substituted with a halogen atom, or

A ring may be formed using an ethylene group as shown in [Formula]. F may have a hydroxy group and/or an amino group, and G may have a hydroxy group, a lower hydroxyalkyl group, a lower hydroxyalkoxy group, a carboxyl group that may form an ester, and a carboxyl group that may form an ester. It may contain one or more of the lower carboxyl alkyl groups that may be used, and may further contain a lower alkyl group and/or a halogen atom. X is -O-(CH ₂ CH ₂ -O)-n or -(O-CH ₂
) _o+1 --O- (in the formula, m represents 0 or 1, and n represents an integer of 0 to 3), and R ¹ represents a hydrogen atom or a halogen atom. ). It is necessary that the substituents B, C and G have a group capable of reacting with the polyester reaction raw material.
The above-mentioned hydroxyl group, lower hydroxyalkoxy group, lower hydroxyalkyl group, carboxyl group that may form an ester, and lower carboxyalkyl group that may form an ester all have this ability. Examples of the carboxyl group or carboxyalkyl group forming the ester include a lower alkoxycarbonyl group, a lower alkoxy lower alkoxycarbonyl group, a lower hydroxyalkoxycarbonyl group, a lower alkoxycarbonylalkyl group, and a lower hydroxyalkoxycarbonylalkyl group. In the present invention, the term "lower" in the substituent names of the colored compound means that the number of carbon atoms is in the range of 1 to 4. In the present invention, polyester includes polyethylene terephthalate, polytetramethylene terephthalate, polyethylene-2,6-naphthalate, polyethylene isophthalate, neopentyl glycol copolymerized polyethylene terephthalate,
Mainly composed of polytetramethylene glycol copolymerized polyethylene terephthalate and copolymers thereof, these polyesters contain 10 mol% or less of phthalic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid, 1,
Aromatic dicarboxylic acids such as 4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, and 2,7-naphthalene dicarboxylic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, succinic acid, adipic acid, sebacic acid, azelain It may contain aliphatic dicarboxylic acids such as acids, unsaturated dicarboxylic acids such as fumaric acid, 4-carboxycinnamic acid, and the like.
In addition, as a glycol component, 15 mol% or less of diethylene glycol, 1,3-ropanediol,
Aliphatic glycols such as 1,2-propanediol, cycloaliphatic glycols such as cyclohexanedimethanol, 2,2-bis-(4-P-hydroxyethoxyphenyl)propane, bis-(4'-
Bisphenol derivatives such as P′-hydroxyethoxyphenyl) sulfone, as well as general formula [—
(CH ₂ )-aO]-b (where a is an integer of 1≦a≦6,
(b is an integer of b≧4), polyethylene glycol, polytetramethylene glycol, etc. may be contained. It may also contain 10 mol% or less of an oxyacid component such as hydroxybenzoic acid, and as long as the polyester remains substantially linear, it may contain oxyacids such as pentaerythritol, trimethylolpropane, trimellitic acid, trimesic acid, pyromellitic acid, etc. Trifunctional or higher polyfunctional compounds, o-
A monofunctional compound such as benzoylbenzoic acid may be copolymerized. As a method for producing polyester, a so-called two-step reaction is usually performed in which a well-known transesterification reaction or direct esterification reaction is performed to obtain a polyester oligomer, and then a melt polycondensation reaction is performed.
Furthermore, if necessary, a solid phase polycondensation reaction step may be added. The colored compound used in the present invention is represented by the general formula [], [], [],
All of these are known compounds or can be easily produced by those skilled in the art.
The compound of general formula [] has a yellowish hue,
The compound of general formula [] has an orange hue,
The compound of general formula [] exhibits a red or blue hue. In the preferred colored compound used in the present invention, the general formula [] can be represented by the following general formula [], the general formula [] can be represented by the following general formula [], and the general formula [] can be represented by the following general formula []. (In the above formula, R ¹ represents a hydrogen atom or a halogen atom, R ² and R ³ each represent a hydrogen atom, a hydroxyl group, or an amino group, and R ⁴ and R ⁵ each represent a hydroxyl group, a lower hydroxyalkoxy group, or an ester represents a carboxyl group that may form a hydrogen atom, a halogen atom, or a lower alkyl group, and R ⁷ is a hydroxyl group, a lower hydroxyalkyl group, a lower hydroxyalkoxy group, or a carboxyl group that may form an ester. or a lower carboxyalkyl group which may form an ester. X is -O-(CH ₂ CH ₂ -O)-n or -(O-CH ₂
) _o+1 --O- (In the formula, m represents 0 or 1, and n represents an integer of 0 to 3.) Specific examples of preferred colored compounds are listed below.

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[Table] Colored polyester resin containing the colored compound is colored and requires special treatment when melt processing is performed using an extruder, injection molding machine, etc. in order to obtain the desired molded product. do not. In other words, the colored polyester resin has excellent heat resistance that allows selection of optimal processing and molding conditions for the base polyester resin without paying attention to problems of fading or discoloration. The colored polyester resin exhibits excellent elution resistance because the colored compound is chemically bonded to the polyester. Since the colored polyester resin contains one or more types of colored compounds from the group of colored compounds including the three primary colors, the hue and tone can be arbitrarily controlled by selecting the combination and content of the colored compounds. The coloring compound used in the present invention can be incorporated into the polyester at any time and by any method as long as it exhibits the desired effect of the present invention. Specifically, methods include adding and dispersing it to polyester raw material monomers, adding it as a slurry of volatile solvent at the start of polycondensation of polyester, adding it as a slurry of raw material monomer liquid, and dry blending it to polyester chips and extruding it. Methods such as kneading and extrusion using a machine are possible.
In either method, in order to effectively bond the coloring compound to the polyester, the coloring compound is added to the polyester or its raw material in a solution or melt state so as to be as finely dispersed as possible. Should. A preferred method is a method in which the coloring compound is added at a stage before the end of the polyester production reaction, and a more preferred method is a method in which the coloring compound is added as a uniformly dispersed liquid to the raw material glycol component of the polyester in the above method. be. The total amount of coloring compounds contained in the polyester resin is 1.0~
A range of 20000ppm is recommended. Preferably it is in the range of 10 to 5000 ppm. If it is less than 1.0 ppm, the desired color tone cannot be obtained, and if it is more than 20,000 ppm, a polyester resin with a sufficiently high degree of polymerization cannot be obtained, so it is better to avoid it. If necessary, other coloring agents such as carbon black and phthalocyanine blue, and particles of titanium oxide, calcium carbonate, mica, etc. may be added depending on the purpose. The colored polyester resin of the present invention is used in melt-processed molded products and secondary processed molded products thereof. Specific examples include biaxially stretched blow bolts, injection blow bottles, direct blow bottles, injection molded products, biaxially stretched films, and extrusion molded sheets. As an example, a method for manufacturing a biaxially stretched blow bottle for soft drinks is as follows. A desired colored compound is added to a polyester oligomer, a catalyst and an auxiliary agent are added, and the mixture is reacted for several hours at a temperature above the melting point of the polyester under high vacuum to obtain a colored polyester resin. In order to increase the degree of polymerization and remove acetaldehyde, a solid phase polycondensation reaction is carried out at a temperature below the melting point of the colored polyester for several hours to more than ten hours under vacuum or inert gas flow. The obtained colored polyester containing low acetaldehyde is molded using an injection molding machine to obtain a preform. A biaxially stretched blow bottle is formed using a biaxially stretched blow molding machine. Examples are shown below, but the present invention is not limited to these examples unless the gist of the invention is exceeded. Note that "parts" in Examples and Comparative Examples indicate "parts by weight." Example 1 Coloring compound No. 6 was added to a polyester oligomer obtained by directly esterifying 86.5 parts of terephthalic acid and 40 parts of ethylene glycol using a conventional method. 0.01 part of was added and 0.015 part of germanium dioxide was used as a catalyst to react under reduced pressure at 280°C for 5 hours to obtain a transparent yellow colored polyester resin. At this time, no yellow colored substance was observed in the reaction distillate. This resin was dissolved in a mixed solution of 50/50 weight ratio of phenol/tetrachloroethane at a concentration of 1 g/100 ml, and the IV (intrinsic viscosity) measured at 30°C was 0.73. Using the obtained colored polyester resin
When a 0.5 mm thick sheet was formed and an elution test was conducted in accordance with Ministry of Health and Welfare Notification No. 20 (1982), it was found that distilled water, n-heptane, 40% ethanol, 4
% acetic acid, no coloration was observed in any of the eluates. Further, the obtained colored polyester resin was passed through an extruder with a cylinder temperature set at 280°C, and a residence time of 10 minutes was given to extrude the strands into chips. The color tone of the chips obtained was substantially the same as that of the colored polyester resin obtained by polycondensation reaction. Colored polyester resin obtained by melt polycondensation reaction is heated under vacuum.
Solid phase polycondensation reaction was performed at 215°C for 10 hours, IV = 0.80,
A colored polyester resin with an acetaldehyde content of 4 ppm was obtained by water extraction. At this time, no yellow coloring was observed in the distillate. Examples 2 to 53, Comparative Examples 1 to 2 Colored polyester resins using various coloring compounds were obtained under the same conditions as in Example 1. Display the results -
Shown in 1.

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Claims (1)

[Claims] 1. A colored polyester resin composition containing one or more colored compounds represented by the following general formula: (In the above formula, A, B, C, D, E, F and G each represent a benzene ring, A may have a lower alkyl group or a lower alkoxy group, and B and C are a hydroxyl group, or It has a lower hydroxyalkoxy group and/or a carboxyl group which may form an ester, and D and E are each substituted with a halogen atom, or a ring is formed with an ethylene group as shown in [Formula]. F may have a hydroxy group and/or an amino group, and G may have a hydroxyl group, a lower hydroxyalkyl group, a lower hydroxyalkoxy group, a carboxyl group that may form an ester, and an ester. It has one or more types of lower carboxyl alkyl groups that may be formed, and may further have a lower alkyl group and/or a halogen atom.X is -O-(CH ₂ CH ₂ -O)-
n or -(O-CH ₂ ) _o+1 --O- (in the formula, m is 0 or 1, n is an integer of 0 to 3), and R ¹ is a hydrogen atom or a halogen atom . ) 2. The colored polyester resin composition according to claim 1, wherein the colored compound represented by the general formula [] is a colored compound represented by the following general formula []. (In the above formula, R ² and R ³ each represent a hydrogen atom, a hydroxyl group, or an amino group.) 3. One or more of the coloring compounds represented by the above general formulas [] to [] are added at a stage before the end of the polyester production reaction. The colored polyester resin composition according to claim 1, wherein the colored polyester resin composition contains: 4. The colored polyester resin composition according to claim 3, wherein the colored compound represented by the general formula [] is a colored compound represented by the general formula []. 5 Claims 1 and 2 for hollow molded bodies
The colored polyester resin composition according to item 1, 3 or 4. 6. The colored polyester resin composition according to claim 5, wherein the hollow molded body is a biaxially stretched blow bottle.