JPH0572428B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a liquid colorant for molded polyester resins other than those for fibers.

Polyester resins, represented by polyethylene terephthalate (hereinafter referred to as PET), have traditionally been consumed in large quantities as fibers, but they are also used in film or sheet form for a variety of packaging applications including food applications, and recently for VTR tape applications. It is used in In addition, PET stretched blow bottles take advantage of their excellent transparency, glossy appearance, and excellent barrier properties against carbon dioxide, oxygen, water, etc.
They have started to be used as food bottles for edible oil, alcoholic beverages, soft drinks, etc., and are showing great progress.

Traditionally, master batches have been used to color PET films, sheets, and stretched blow bottles. The masterbatch used for this purpose is made by dispersing dyes and pigments in a high concentration in molded PET resin, and when used, a predetermined amount of masterbatch is mixed with uncolored PET and molded. The disadvantages of this coloring method using master batches are as follows.

1.Difficulties arise in dispersing pigments at high concentrations during the production of masterbatches.

2. When producing a masterbatch, it is necessary to dry the resin before processing, crystallize the masterbatch after processing, and sometimes further dry it, resulting in large energy consumption.

3 When molding, it is necessary to dry the masterbatch, and it is necessary to install special drying equipment for the masterbatch or to dry the mixture of natural resin and masterbatch in a dryer, so when changing colors, it is necessary to clean the line including the drying equipment. This makes it difficult to handle complicated color changes.

The present inventors focused on using a liquid coloring agent as a means to solve the above-mentioned drawbacks of the coloring method using a master batch. Liquid colorants are made by kneading pigments and dyes with a liquid dispersion medium (vehicle) at room temperature, and when coloring and molding, a diaphragm pump, plunger pump, gear pump, or rotary pump is used to pump the liquid colorant into the molding machine. A fixed amount is supplied directly to the screw section. Liquid coloring systems are commercially called liquid color systems and are widely used for general-purpose resins such as polyethylene and polypropylene.
It has been technically established as shown in Japanese Patent Application Laid-Open No. 54-34348. However, the reality is that colorants with excellent performance for polyester resins have not yet been developed, so they are hardly used commercially.

The present inventors have arrived at the present invention as a result of intensive studies on liquid colorants for molded polyester resins. That is, the present invention is a liquid coloring agent for molded polyester resins other than those for fibers, which is composed of 100 parts by weight of a pigment or dye and 30 to 5,000 parts by weight of liquid polyester, and is characterized by being a liquid of 1,500 poise or less at room temperature.

In the present invention, liquid polyesters include adipic acid, sebacic acid, azelaic acid, glutaric acid,
Fatty acids such as hydrogenated phthalic acid diracboxylic acid or terephthalic acid, isophthalic acid, orophthalic acid,
dibasic organic acids such as aromatic dicarboxylic acids such as phthalic anhydride, trimellitic acid, and pyromellitic acid, and ethylene glycol, propylene glycol, butylene glycol, pentyl glycol,
Dihydric alcohols such as hexylene glycol, neopentyl glycol, and diethylene glycol are used as main ingredients, and if necessary, aliphatic saturated or unsaturated monocarboxylic acids such as coconut oil fatty acids, soybean oil fatty acids, oleic acid, and lauric acid are used. ,n
- Monohydric alcohols such as octyl alcohol, isooctyl alcohol, 2-ethylhexyl alcohol, n-nonyl alcohol, and n-decyl alcohol, or polyhydric alcohols such as trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, and sorbitol. It is synthesized using

In order to obtain good measurement accuracy during use, the liquid colorant must exhibit fluidity at room temperature, and its viscosity must be 1500 poise or less at room temperature.
When it is less than 1500 poise, it can be supplied accurately using a gear pump, etc. Furthermore, when using a plunger pump or rotary pump, it is necessary to keep the viscosity to 100 poise or less, and from the viewpoint of ensuring versatility with various supply pumps, it is desirable that the viscosity of the liquid colorant be as low as possible. Therefore, it is desirable that the viscosity of the liquid polyester used as the liquid colorant be as low as possible. The viscosity of the liquid colorant is made higher than the viscosity of the liquid polyester used by dispersing the pigment or dye into the liquid polyester. Therefore, it is not possible to obtain a liquid colorant of 1500 poise or less by using a liquid polyester of 1500 poise or more. For this reason, the viscosity of liquid polyester is preferably 1500 poise or less at room temperature.
Must be less than 1000 poise. Furthermore, in order to obtain a liquid colorant in which pigments and dyes are dispersed at high concentrations, a liquid polyester having a particle size of 200 poise or less is desirable.
This is because if it exceeds 200 poise, the dispersibility of the pigment or dye may become poor.

Furthermore, although the liquid polyester of the present invention has a relatively high boiling point, depending on the conditions during molding, components in the liquid polyester may vaporize, causing poor appearance of the molded product. In such cases, especially when the vapor pressure at 200℃ is 10mm
Polyesters below Hg are selected.

Pigments or dyes that can be used in the present invention include azo-based, phthalocyanine-based, quinacridone-based, anthraquinone-based, dioxazine-based, perylene/perinone-based organic pigments, titanium oxide, iron oxide, ultramarine, titanium-mica pearl pigments, and carbon. Known pigments commonly used for polyester such as black, and azo, anthraquinone, perino, phthalocyanine, and heterocyclic dyes can be used, and it is also possible to use pigments and dyes together.

The liquid colorant for polyester of the present invention can be prepared by combining the above pigment or dye using a conventional dispersing machine such as a three-roll mill, a ball mill, a sand mill, or an attritor.
It can be manufactured by kneading liquid polyester.

The molded polyester resin to which the liquid colorant of the present invention is applied is a polyester resin that can be molded into films, blow bottles, injection molded products, etc., and is a resin obtained by an esterification reaction of terephthalic acid and ethylene glycol or a resin obtained by an esterification reaction of terephthalic acid and ethylene glycol. A homopolyester resin obtained by the transesterification reaction of a lower alkyl ester and ethylene glycol, and a homopolyester resin in which a part of the terephthalic acid component of the homopolyester resin is replaced with isophthalic acid, adipic acid, sebacic acid, trimellitic acid, pyromellitic acid, etc. Polyester resin and ethylene glycol components are replaced with propylene glycol, neopentyl glycol,
Examples include copolyester resins substituted with 1,4-butanediol, cyclohexanedimethanol, and the like. Also, terephthalic acid and 1,4
-obtained by esterification of butanediol
It may also be PBT resin.

Molding methods to which the colorant of the present invention can be applied include T-die extrusion for forming films and sheets, blow molding for forming blow bottles, and general injection molding. PET blow bottles are manufactured using the cold parison method, in which a cylindrical preform called a preform is first molded by injection molding, and then this preform is taken out and then reheated and then stretch blow molded, or the preform is not completely cooled. First, it is obtained by a hot parison method, etc., in which stretch blow molding is performed continuously in the same molding machine. The liquid colorant of the present invention is most suitable for molding these PET blow bottles. Conventionally, there are very few colored polyester films, but the liquid colorant of the present invention is sufficiently effective in film molding, and can also be effectively used in injection molding.

Furthermore, in addition to pigments and dyes, additives such as antistatic agents, ultraviolet absorbers, and antioxidants, and fillers such as calcium carbonate, silica, and talc may be added to the liquid colorant according to the present invention. Not only is it possible, but it also contains no pigments or dyes.
A composition consisting only of these additives and fillers and a dispersion medium can also be adjusted and used depending on the purpose.

The liquid polyester of the present invention does not decompose or change in quality even at the molding temperature of polyester resin (up to 320°C), exhibits fluidity at room temperature when pigments or dyes are dispersed to form a liquid colorant, and is compatible with polyester resin. The liquid colorant for molded polyester resin of the present invention has the desirable properties of (1) good pigment dispersion, and (2) good quantitative supply when using the colorant. Good (3) Does not impair the transparency of the polyester resin (4) There is almost no deterioration in the physical properties of the molded product (5) There is almost no elution of the colorant from the molded product (6) It does not harm the moldability. has.

The present invention will be described in more detail with reference to Examples below.

Liquid polyester preparation (1) Vehicle-1 452 parts of adipic acid and 348 parts of 1,3-butylene glycol were added to a reaction vessel equipped with a thermometer, stirring rod, nitrogen gas introduction tube, temperature control device, partial condenser, etc. After charging, the reaction temperature was gradually raised to 240°C while nitrogen gas was flowing, and the reaction was continued until the acid value reached 10. Next, remove the partial condenser from the reaction vessel and
Perform vacuum distillation for 1 hour at 60 mmHg, acid value 2.5,
A liquid polyester with a viscosity of 20 poise was obtained.

(2) Vehicle-2 Adipic acid 472
parts, 160 parts of ethylene glycol, and 168 parts of 2-ethylhexyl alcohol as raw materials, the acid value
A liquid polyester with a viscosity of 1.0 and a viscosity of 10 poise was obtained.

(3) Vehicle-3 In the same reaction vessel as in (1) above, add adipic acid 320
part, 2,2,4-trimethylpentane-1,3
- Charge 480 parts of diol, gradually raise the reaction temperature to 210℃ while flowing nitrogen, and increase the acid value.
The reaction was continued until 10 days. Next, the partial condenser was removed and vacuum distillation was carried out at 50 to 60 mmHg for 1 hour to obtain a liquid polyester having an acid value of 5.0 and a viscosity of 50 poise.

(4) Vehicle-4 Adipic acid 320
2-ethylhexane-1,3-diol
Using 480 parts as a raw material, a liquid polyester having an acid value of 2.0 and a viscosity of 40 poise was obtained.

(5) Vehicle-5 Adipic acid 423 was prepared using the same method as in (1) above.
part, n-pentanediol 302 parts, diethylene glycol 75 parts as raw materials, acid value 1.5, viscosity 60
Poise liquid polyester was obtained.

(6) Vehicle-6 Adipic acid 407 was prepared using the same method as in (1) above.
Polyester having an acid value of 10 and a viscosity of 200 poise was obtained using 103 parts of metal acid anhydride, 101 parts of trimethylolpropane, and 181 parts of ethylene glycol as raw materials (7) Vehicle-7 Anhydrous phthalic acid
A polyester having an acid value of 9 and a viscosity of 500 poise was obtained using 400 parts of coconut oil fatty acid, 142 parts of coconut oil fatty acid, and 258 parts of propylene glycol as raw materials.

(8) Vehicle-8 Phthalic anhydride was prepared using the same method as in (1) above.
Polyester having an acid value of 10 and a viscosity of 1000 poise was obtained from 491 parts of ethylene glycol, 180 parts of ethylene glycol, and 129 parts of neopentyl glycol.

Example 1 88.5 parts by weight of vehicle-1, 1.5 parts by weight of phthalocyanine blue (Nionol Blue BV (N) manufactured by Toyo Ink Manufacturing Co., Ltd.), and 10 parts by weight of monoazo yellow (Hosta Palm Yellow H4G, manufactured by Hoechst Co., Ltd.) were prepared in three rolls. The mixture was kneaded to obtain a liquid colorant. The viscosity of this colorant, measured using a Type B viscometer, is approximately
It was 100 poise (25℃). (Measurement conditions are the same for the following examples) Polyester resin (Mitsui PET) dried in a hot air dryer at 170°C for 4 hours
0.6 parts by weight of this coloring agent was added to 100 parts by weight of J125 (manufactured by Mitsui Petrochemicals, Inc.), and a stretched blown bottle with a colored edge was obtained by a cold parison method. This colored bottle was uniformly colored throughout, and no coarse pigment particles were found, indicating extremely good pigment dispersion. Furthermore, the transparency and gloss were also extremely good.

Example 2 80 parts by weight of Vehicle-2 and 20 parts by weight of transparent Hungara (Sicotransread L-2715, manufactured by Basf Corporation) were kneaded using three rolls to obtain a liquid colorant having a viscosity of about 120 poise. 1.25 parts by weight of this colorant was added to 100 parts by weight of a polyester resin treated in the same manner as in Example 1, and a stretched blow bottle colored brown was obtained by a cold parison method. This bottle was uniformly colored throughout, with no color unevenness, and had no pigment particles larger than 10 microns, showing good transparency.

Example 3 70 parts by weight of vehicle-3, 30 parts by weight of titanium white (Taipeke CR-80, manufactured by Ishihara Sangyo Co., Ltd.)
The mixture was kneaded using a main roll to obtain a liquid colorant. The viscosity of this colorant was approximately 200 poise.

Polyester resin treated in the same way as Example 1
3 parts by weight of this colorant was added to 100 parts by weight, and a white sheet was obtained by extrusion molding. This sheet was uniformly colored and showed extremely good dispersibility with no coarse pigment particles found.

Example 4 74 parts by weight of vehicle-4, 20 parts by weight of titanium mica pigment (Iriodin 100, manufactured by Merck & Co., Ltd.), 1 part by weight of carbon black (Mitsubishi Carbon MA100, manufactured by Mitsubishi Chemical Corporation), titanium white (Taipeke CR)
-80) 5 parts by weight were kneaded using three rolls to obtain a liquid colorant. The viscosity of this colorant was approximately 200 poise.

5 parts by weight of this colorant were added to 100 parts by weight of the same polyester resin used in Example 1, and a stretched blow bottle was molded by the cold parison method. This bottle was uniformly colored silver and had an extremely beautiful appearance.

Example 5 76.5 parts by weight of vehicle-5, 1.0 parts by weight of cyanine blue (Lionol Blue BV(N), 2.5 parts by weight of anthraquinone yellow (Firesta Yellow 2648A, manufactured by Ciba Geiger), ultraviolet absorber (Tinuvin P. manufactured by Ciba Geiger) A liquid coloring agent was obtained by kneading 20 parts by weight of the liquid coloring agent (manufactured by the company) with three rolls.The viscosity of the coloring agent was approximately 250 poise.

Polyester resin treated in the same way as Example 1
1.0 part by weight of this colorant was added to 100 parts by weight, and a stretched blow bottle was molded by the hot parison method. This bottle has a uniformly colored rim and excellent transparency.
It was rich in extremely clear color tones.

Example 6 Vehicle-6 95.22 parts by weight, anthraquinone dye (Estofil Yellow S5GL) 4.0 parts by weight, anthraquinone dye (Estofil Red)
0.5 parts by weight of SFBL) and 0.28 parts by weight of anthraquinone dye (Estofil Blue SRBL) were kneaded using three rolls to obtain a liquid colorant. The viscosity of this colorant was approximately 300 poise (25°C).

Three parts by weight of this colorant were added to 100 parts by weight of polyester resin (J125) treated in the same manner as in Example 1, and a stretched blow bottle was obtained by the hot parison method.
This bottle was colored in a uniform and highly transparent color tone.

Example 7 97.8 parts by weight of Vehictor-7, 1.0 parts by weight of cyanine blue (Lionor Blue BV(N)), and 1.2 parts by weight of quinoline dye yellow (Solvapalm Yellow R, manufactured by Hoechst) were kneaded with three rolls. ,
A liquid colorant was obtained. The viscosity of this colorant was approximately 600 poise (25°C).

0.7 parts by weight of this colorant was added to 100 parts by weight of polyester resin (J125) treated in the same manner as in Example 1, and a stretched blow bottle was obtained by the hot parison method. This bottle is colored with a uniform and clear edge color,
It showed excellent transparency.

Example 8 Vehicle-8 99.98 parts by weight, anthraquinone dye (Kayaset Blue A2R, manufactured by Nippon Kayaku Co., Ltd.)
Knead 0.02 parts by weight with 3 rolls to obtain a viscosity of approximately 1100.
Poise liquid coloring agent was obtained.

Add 1 of this colorant to 100 parts by weight of the same dry-treated polyester resin (RE-500, manufactured by Toyobo) as in Example 1.
Parts by weight were added and an unstretched film was obtained by T-die extrusion. This film is processed using a biaxial stretching machine.
The film was biaxially stretched 3.6 times to obtain a stretched film with a thickness of about 0.15 mm. This film was uniformly colored, and the present colorant showed an excellent masking effect.

Claims (1)

[Scope of Claims] 1. Consisting of 100 parts by weight of a pigment or dye and 30 to 5,000 parts by weight of a liquid polyester whose constituent components are mainly obtained by reacting a dibasic organic acid and a dihydric alcohol. A liquid coloring agent for polyester resins other than those for textiles, which is characterized by being liquid. 2. The liquid coloring agent for polyester resins other than those for fibers according to claim 1, wherein the dibasic organic acid is an aliphatic dicarboxylic acid. 3. A liquid colorant for polyester resins other than those for fibers according to claim 1, wherein the dibasic organic acid is an aromatic dicarboxylic acid. 4 The vapor pressure of liquid polyester at 200℃ is
A liquid colorant for polyester resins other than those for fibers according to claims 1 to 3, which is a liquid polyester having a temperature of 10 mmHg or less.