JPS59232142A - Colored polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin compsn. capable of resisting heat at 300 deg.C or above and having excellent properties, by incorporating a specified colored compd. having reactive functional groups in a polyester resin. CONSTITUTION:A colored compd. of formula I , II or III [wherein A, B, C, D, E, F, G are each a benzene ring; X is a group of formula IV, V (wherein m is 0, 1 and n is 0-3); and R<1> is H, halogen] is incorporated in a polyester resin. The compd. of formula I has a yellowish tone, that of formula II has an orange tone and that of formula III has a reddish or bluish tone. Pref. examples of the compds. of formulas I , II and III are those of formulas IV, VI and VII (wherein R<2>, R<3> are each H, OH, amino; R<4>, R<5> are each OH, lower hydroxyalkoxy, carboxy which may form an ester; R<6> is H, halogen, etc; R<7> is OH, lower hydroxyalkyl, etc.), respectively.

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.

1 3- (In the above formula, A, B, O, D, B, F and G
each represents a benzene ring, A/ri may have a lower alkyl group, a lower alkoxy group, B and 0 represent a carboxyl group which may form a hydroxyl group or a lower hydroxyalkoxy group and/or an ester. D and E may each be substituted with a halogen atom, or may be substituted with a halogen atom.

4-F may have a hydroxyl group and/or an amino group, and G has one or more of a hydroxyl group, a lower hydroxyalkyl group, a lower hydroxyalkyl group, a lower carboxyalkyl group, and further a lower alkyl group. It may contain a group and/or a halogen atom. 1
X is 10 (-OH, OR, -0sn or +O-0Pb
-5TFO- (in the formula, m is θ or /, n is an integer of θ to 3, and t), and R1 is 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 obtained by two-wheel stretch blow molding of polyethylene terephthalate resin have been widely used in foods, pharmaceuticals,
It is used in cosmetics and other applications and 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, the colorant and polyester resin are mixed in a mixer such as a tumbler,
Thereafter, a method is used in which the masterbatch is melt-extruded using an extruder and turned into 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 had to be limited to a narrow temperature range.

Therefore, in order to use normal extrusion temperatures, colorants with excellent heat resistance are required, but even with heat-resistant compounds, when added during melt extrusion, the final shape Since the problem of elution of compounds occurs in products, especially bottles for food, etc., it is necessary to use compounds that have low elution properties from the resin. For this purpose,
One possible method is to add a compound that has the property of reacting with polyester during the polyester production reaction, but in this case, the compound is required to be stable during the reaction of the polyester and during the melting process during molding. Furthermore, in bottle applications, in order to remove acetaldehyde and/or obtain polyester chips with a high degree of polymerization, face-phase polymerization is often carried out at a temperature of usually 90° C. or above and below the melting point for several hours or more. Therefore, in polyester production 7- Coloring compounds added before the end of the reaction must be exposed to high temperatures for long periods of time, such as polymerization temperatures, melt extrusion temperatures, and solid state polymerization temperatures, and cannot withstand such harsh conditions. A compound must be selected.

In view of the current situation, the present inventors have conducted intensive studies on various colorants, and have found that they have heat resistance greater than Fi300'C, a specific coloring compound having an ester-forming functional group, and do not deteriorate even over a long period of time. The present invention was achieved based on the findings that the colored polyester is chemically bonded to the polyester, thereby providing a colored polyester with extremely excellent properties. That is, the present invention provides a colored polyester resin composition containing one or more colored compounds represented by the following general formula.

1 8- (In the above formula, A, B, O, D, B, F and G
each represents a benzene ring, A has a lower alkyl group or a lower alkoxy group and may also be b, and B and C represent a hydroxyl group or a lower hydroxyalkoxy group and/or a carboxyl group that may form an ester. D and E are each substituted with a halogen atom, but may also be substituted with a halogen atom.

F may have a hydroxyl 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 a carboxyl group that may form an ester. It may contain one or more of the lower carboxyalkyl groups that may be used, and may further contain a lower alkyl group and/or a halogen atom.

X is 10+OH* 0Ht-O-+n or +0-OH
, 0- (wherein, m is O or /, n is an integer of θ to 3), and RI represents a hydrogen atom or a halogen atom. ).

3% It is necessary that the C and G substituents 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, among the substituent names of the colored compound, one lower
The term means that the number of carbon atoms is in the range /~g.

In the present invention, polyester refers to polyethylene terephthalate, polytetramethylene terephthalate, polyethylene 1-1,6-nanthalate, polyethylene isophthalate, neopentyl glycol copolymerized polyethylene terephthalate, polytetramethylene glycol copolymerized polyethylene terephthalate, and copolymerized polyethylene terephthalate. Although mainly composed of polymers, these polyesters contain lO as an acid component.
7 Talic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic iLi+y-naphthalene dicarboxylic 11- acid, /,! - Aromatic dicarboxylic acids such as naphthalene dicarboxylic acid and Schiff-naphthalene dicarboxylic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, co-phosphoric acid,
It may contain aliphatic dicarboxylic acids such as adipic acid, sebacic acid and azelaic acid, unsaturated dicarboxylic acids such as fumaric acid and goocarboxycinnamic acid, and the like. In addition, as a glycol component, diethylene glycol of /& molar ratio or less, aliphatic glycol such as /, 3-propanediol, /9.2-propanediol, alicyclic glycol such as cyclohexane dimetatool, etc. 1-bis-(
Bisphenol derivatives such as lI-p-hydroxyethoxyphenyl)propane, bis-(y/p/-hydroxyethoxyphenyl)sulfone, as well as general formula f
(aH, aO-3-b (wherein, a is an integer of /≦a≦6, b is an integer of b≧g), even if it contains polyethylene glycol, polytetramethylene glycol, etc. Good. -! Yes, even if it contains oxyacid components such as hydroxybenzoic acid below 7θ molar ratio, it is good, as long as the polyester remains substantially linear. Pentaerythritol, trimethylolpropane, trimelit Acids, trifunctional or higher functional compounds such as trimesic acid and pyromellitic acid, and monofunctional compounds such as 0-benzoylbenzoic acid may be copolymerized.

The method for producing polyester usually involves a two-step reaction in which a well-known transesterification reaction or direct esterification reaction is performed to obtain a polyester oligomer, followed by a melt polycondensation reaction. A polycondensation reaction step may also be added.

The colored compound used in the present invention has the above general formula (i)
, [l), and [1ll), all of which are known compounds or can be easily produced by those skilled in the art. The compound of general formula [I) has a yellow hue, the compound of general formula [111] has an orange hue, and the compound of general formula [11D] has a red or blue hue.

Preferred colored compounds used in the present invention have the general formula [I
] is represented by the following general formula [V], and general formula [11] is represented by the following general formula [V].
, VI], the general formula [1111] can be represented by the following general formula [■].

1 (In the above formula, R' is a hydrogen atom or a halogen atom 1
R″ and R″ each represent a hydrogen atom, a hydroxyl group, or an amine group, R4 and R1 each represent a hydroxyl group, a lower hydroxyalkoxy group, or a carboxyl group that may form an ester, and R6 represents a hydrogen atom. atom, halogen atom or lower alkyl group,
R? represents a hydroxyl group, a lower hydroxyalkyl group, a lower hydroxyalkoxy group, a carboxyl group that may form an ester, or a lower carboxyalkyl group that may form an ester.

or -〇(-OHIOHl-0-)-, or +OOH
-Dinghe0 (where m id Oi or/, n is θ~
3). ) Specific examples of preferred colored compounds are listed below.

15- =16- When the colored polyester resin containing the colored compound is subjected to melt processing using an extruder, injection molding machine, etc., in order to obtain the desired molded product, special treatment is applied to the colored waste. do not need.

t',a The colored polyester resin has excellent heat resistance, allowing 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 in any manner as long as the desired effect of the present invention is achieved. Specifically, methods include adding and dispersing it to polyester raw material monomers, adding it as a slurry of volatile solvent at the start of polyester polycondensation, adding it as a slurry of raw material monomer liquid, and triblending it to polyester chips and extruding it. Methods such as cross-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 completion of the polyester production reaction, and a more preferred method is a method in which the coloring compound is added in the above method as a liquid in which the daglycol component of the DK material is uniformly dispersed. It's a method.

The total amount of colored compounds contained in the polyester resin is
For polyester resin, /, 0 to . 20000ppm
It is recommended that the

Preferably it is in the range of 0-3000 ppm.

/, Oppm or less, the desired color tone cannot be obtained;
0000 ppm IJ cannot produce a polyester resin with a sufficiently high degree of polymerization, 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 bottles, injection blow bottles, direct blow bottles, injection molded bodies, biaxially stretched films, and extrusion molded sheets. - As an example, the method for manufacturing a biaxially stretched blow bottle for soft drinks is as follows.

(2) A desired coloring compound is added to the polyester oligomer, a catalyst and an auxiliary agent are added, and the mixture is reacted for several hours under high vacuum at a temperature above the melting point of the polyester to obtain a colored polyester resin.

(2) 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 under vacuum or inert gas flow for several hours to several hours.

■ The resulting low acetaldehyde-containing colored polyester is molded using an injection molding machine to form a glycoform.

get ohm.

■Mold a biaxially stretched blow bottle using a biaxially stretched blow molding machine.

Examples are shown below, but the invention is not limited to these examples as long as they do not go beyond the gist of the present invention.

Note that "parts" in Examples and Comparative Examples indicate "parts by weight."

Example/ Terephthalic acid g 1. ! r part and 4t ethylene glycol
4. to a polyester oligomer obtained by directly esterifying part o by a conventional method. Color-enhancing compound 23 of A - Using 01015 parts of germanium dioxide as a catalyst, reaction was carried out under reduced pressure at 2 gO<0>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 mixed with phenol/tetrachloroethane, 5-0
/A; Dissolved in a mixed solution with a weight ratio of 0 at a concentration of /77/100 and measured at 30°C, the viscosity (intrinsic viscosity) is 3
Met. o Using the obtained colored polyester resin,
When a sheet with a thickness of smrR was formed and an elution test was conducted in accordance with Ministry of Health and Welfare Notification No. 1.20 (Showa S year),
No coloration was observed in any of the eluates of distilled water, n-hebutane, aoqb ethanol, and lI% acetic acid.

Further, the obtained colored polyester resin was passed through an extruder whose cylinder temperature was set to -gθ°C, and a residence time of 70 minutes was given to extrude the strands into chips. The color tone of the obtained chips was substantially different from the color tone of the colored polyester resin obtained by polycondensation reaction. Colored polyester 2 obtained by melt polycondensation reaction
4- The resin was subjected to a solid phase polycondensation reaction at 2/3° C. under vacuum for 10 hours to obtain a colored polyester resin having an acetaldehyde content of Q' ppm by a water extraction method. At this time, no yellow coloring was observed in the distillate.

Examples C to S3, Comparative Example 1 to C Colored polyester resins using various coloring compounds were obtained under the same conditions as in Example 1. The results are shown in Table 1.

Japanese Patent Publication No. 59-232142 (H)

Claims (1)

[Scope of 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, O, D, E, F and G are each Indicates a benzene ring, A is a lower alkyl group,
B and C may have a lower alkoxy group, B and C have a hydroxyl group, or 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. They may form a ring. F may have a hydroxyl group and/or an amino group, 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 at least one kind of lower carboxyalkyl groups which may be present, and may further have a lower alkyl group and/or a halogen atom. X represents 10-C-OHIOHI O+n or +OOL (in the formula, mid O or/, n represents an integer of θ to 3), and R1 represents a hydrogen atom or a halogen atom. ) (2) The colored polyester resin composition R'' OOH (3) according to claim 1, wherein the colored compound represented by the general formula [l] is a colored compound represented by the following general formula [■v]. Colored polyester resin composition-1 according to claim 1, characterized in that one or more of the colored compounds represented by the general formula [1] to [amount] is contained at a stage before the end of the polyester production reaction. (4) The colored polyester resin composition according to claim 3, wherein the colored compound represented by the general formula [l] is a colored compound represented by the general formula [IV] (5) Patent for a hollow molded body Gradual color polyester resin composition (6) according to claim 17, 3, or 3.Claim 3, wherein the hollow molded body is a biaxially stretched blow bottle. Colored polyester resin composition