JP2811381B2 - Extrusion blow molding material and container composed of extrusion blow molding - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an extrusion blow molding material and a container formed by extrusion blow molding, and more particularly to an extrusion blow molding material having a pearly luster and a container formed by extrusion blow molding.

[0002]

2. Description of the Related Art In order to develop a pearl luster, a pearl pigment made of mica or the like is added to a thermoplastic resin, and a pearl luster obtained by melt-molding such a pearl pigment-added resin is exhibited. Containers and the like have been developed.
However, when using such a pearl pigment, there is a method of controlling the appearance only by changing the particle size and the amount of the pearl pigment, and a container having an excellent appearance that is more varied from the aspect of decorativeness. Despite being requested, this has not been answered. Also, pearl pigments have the disadvantage that they are expensive and costly.

On the other hand, there has been proposed a method utilizing a resin composition in which resins which are incompatible with each other are combined. For example, as shown in JP-B-61-39336, a resin composition comprising 10 to 99% by weight of a polyester resin and 1 to 90% by weight of a polyolefin resin, and a thin portion of a container is oriented in at least one direction. Has been proposed.

Further, as disclosed in JP-B-61-24253, a resin mixture comprising 99.5 to 90% by weight of a polyester resin and 0.5 to 10% by weight of a methacrylic resin is obtained by stretch blow molding. Plastic cosmetic bottles have been proposed.

[0005]

However, the above-mentioned technique is based on the premise that the resin composition is stretch-formed by some method, and since this stretching step is required, the construction of the container is extremely difficult. In addition, complicated molding machines are required. Therefore, the cost is high, and the demand for cost reduction is extremely strong.

[0006] The container thus obtained has a serious drawback in that a remarkable surface peeling occurs in a peeling test using an adhesive tape such as a cellophane tape, and the surface is fluffed. This means that when a label is attached or printed on the surface of a container, not only does it have an adverse effect on the adhesion fastness and printing fastness, but it is also significantly damaged by external factors such as slight rubbing and the appearance is impaired. become.

[0007] Further, in the case of containers whose appearance is important, an antistatic agent is added to the display at a store, since the display is very disliked by dirt or dust. However, even if these containers contain an antistatic agent, their antistatic effect is small, and therefore, it is required to add a large amount of the antistatic agent. If the antistatic agent is added to the resin composition in a large amount of, for example, 2% or more, more and more remarkable surface peeling occurs in a peeling test using an adhesive tape such as the above-mentioned cellophane tape, and it cannot be used. Therefore, the addition amount of the antistatic agent must be small, so that dust and dirt easily adhere to the display at the store, and there is a limit in preventing a reduction in commercial value.

Accordingly, a first object of the present invention is to provide an extrusion blow molding material which does not require an expensive molding apparatus, that is, can be formed by an extrusion blow molding apparatus. A second object of the present invention is to provide a technique for obtaining a product formed by an extrusion blow molding apparatus, which hardly causes surface peeling and which has a pearly luster and an excellent appearance.

A third object of the present invention is to prevent dust and dirt from adhering to a product formed by an extrusion blow molding apparatus, and
It is an object of the present invention to provide a technique for obtaining a product which is less likely to cause surface peeling and has a pearly luster and an excellent appearance.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a material used for extrusion blow molding, wherein the main constituent unit is terephthalic acid, ethylene glycol and cyclohexane dimethanol and has an intrinsic viscosity of 0.65 to 1%. .4
This is achieved by an extrusion blow molding material characterized by containing 60 to 95 parts by weight of a thermoplastic polyester resin of No. 0 and 5 to 40 parts by weight of a methacrylic resin.

A thermoplastic polyester resin 6 which is a material used for extrusion blow molding and whose main constituent unit is terephthalic acid, ethylene glycol and cyclohexanedimethanol and has an intrinsic viscosity of 0.65 to 1.40.
0 to 95 parts by weight, 5 to 40 parts by weight of the methacrylic resin, and 100 parts by weight of the resin, 0.0
And 5 to 1.7 parts by weight.

A container constituted by extrusion blow molding means, wherein the main constituent unit of the container is terephthalic acid, ethylene glycol and cyclohexanedimethanol and has an intrinsic viscosity of 0.65 to 1.4.
The composition is obtained by using a composition comprising 60 to 95 parts by weight of a thermoplastic polyester resin and 5 to 40 parts by weight of a methacrylic resin.

[0013] A container constituted by extrusion blow molding means, wherein the material of the container is mainly composed of terephthalic acid, ethylene glycol and cyclohexanedimethanol and has an intrinsic viscosity of 0.65 to 1.4.
0 to 60 parts by weight of a thermoplastic polyester resin, 5 to 40 parts by weight of a methacrylic resin, and a composition containing 0.05 to 1.7 parts by weight of an antistatic agent with respect to 100 parts by weight of the resin. This is achieved by a container formed by extrusion blow molding.

Hereinafter, the present invention will be described in detail. One of the reasons that the cost of containers has been high in the past is that it is premised that stretch molding is used, and in view of the high production equipment for this, extrusion that does not require stretch molding is required. We focused on adopting blow molding means. As a result of a detailed study of the characteristics required for the container constituent materials and the requirements based on the requirements of extrusion blow molding, the intrinsic viscosity of the main constituent unit consisting of terephthalic acid, ethylene glycol and cyclohexanedimethanol was 0.1%. 65-1.40 thermoplastic polyester resin 60-
It has been found that a resin composition containing 95 parts by weight and 5 to 40 parts by weight of a methacrylic resin satisfies the above requirements.

Further, it has been found that the use of extrusion blow molding means which does not require stretch molding is preferable in terms of antistatic effect. That is, an antistatic agent such as a nonionic, anionic, cationic or amphoteric surfactant is added to the resin composition as described above, and a product obtained by molding the same with an extrusion blow molding means is charged. It has been found that even with a small amount of the inhibitor, the antistatic effect is excellent. In the present invention, the reason why the antistatic agent works effectively is considered as follows. That is, in the extrusion blow molding process, during the time until the molten parison is extruded from the die, sandwiched by the mold and blown, the antistatic agent gradually bleeds out to the molten parison surface, It is presumed that the concentration of the antistatic agent on the parison surface increases, and the effect becomes remarkable also in the obtained molded article. On the other hand, in a stretch blow molding method such as injection blow, for example, first, a molten resin is fed into a mold in an injection step of a preform, and the surface of the preform sharply falls below the Tg (glass transition temperature) of the resin. It is presumed that the bleed-out does not occur as described above, the concentration of the antistatic agent on the surface does not increase, and the antistatic effect is less likely to be obtained because the temperature is cooled to the temperature. That is, since the main composition of the resin composition uses a thermoplastic polyester having a Tg higher than room temperature, an antistatic agent such as that found in a normal polyolefin resin bleeds out over time on the surface. That phenomenon cannot be expected, only the antistatic agent that appeared on the surface at the time of molding functions, and furthermore, the slight amount of the antistatic agent that appeared on the surface will be further reduced in density on the surface by stretch molding, and as a result It was imagined that the antistatic agent would be very difficult to work.

The thermoplastic polyester resin in the present invention has a main constituent unit of terephthalic acid, ethylene glycol and cyclohexanedimethanol and has an intrinsic viscosity in the range of 0.65 to 1.40. If the intrinsic viscosity is out of this range, it is not preferable because the resulting molded article has poor impact resistance and poor moldability.

The preferred copolymerization ratio of the thermoplastic polyester resin in the present invention is 50 to 98 mol of ethylene glycol and 2 to 50 mol of cyclohexanedimethanol, more preferably 100 mol of terephthalic acid, per 100 mol of terephthalic acid. 65 to 96 mol of ethylene glycol and 4 to 96 mol of cyclohexanedimethanol
35 mol. In addition, a small amount of another dicarboxylic acid or glycol may be copolymerized as long as the physical properties are not significantly affected. That is, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanoic acid and p-oxybenzoic acid are used as dicarboxylic acid components, and diethylene glycol, propylene glycol, butylene glycol, 1,6-hexanediol and neopentyl are used as glycol components. Glycol, polyethylene glycol, polytetramethylene glycol and the like may be contained as a copolymer component.

By using the thermoplastic polyester resin as described above, it is possible to use not the stretch molding,
The molding by the extrusion blow molding means can be easily performed. Methacrylic resin in the present invention,
For example, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate and other copolymerized methacrylates can be mentioned, and polymethyl methacrylate is most preferred. In order to improve performance such as impact resistance, a small amount of another monomer may be copolymerized, or another additive may be added.

Then, 60 to 95 parts by weight of the above-mentioned thermoplastic polyester resin and 40 to 5 parts by weight of the methacrylic resin, preferably 80 to 90 parts by weight of the thermoplastic polyester resin and 20 to 10 parts by weight of the methacrylic resin. For example, the resin composition is obtained by kneading and mixing with a biaxial kneader. The resin composition thus obtained is blow-molded with a normal extrusion blow molding machine (direct blow molding machine) to obtain a container having a pearly luster. In this case, there is no need to perform stretch blow under a special temperature condition equal to or higher than the Tg of the thermoplastic polyester resin as in stretch blow molding, and air, nitrogen, or other gas is blown into the molten parison to perform normal molding. The result is a container with a pearly luster.

In order to prevent the adhesion of dust and dirt, that is, to provide an antistatic effect to the obtained container,
It is preferable to add an antistatic agent to the resin composition in a range of 0.05 to 1.7% by weight before molding. Examples of the antistatic agent include nonionic, anionic, cationic, and amphoteric surfactants. For example, non-ionic compounds include polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, glycerin fatty acid ester, sorbitan fatty acid ester, and the like. Examples of the anionic type include alkyl sulfonates, alkyl benzene sulfonates, alkyl sulfates, and alkyl phosphates. Quaternary ammonium chloride, quaternary ammonium sulfate and the like are used for cationic ones, and alkyl betaines, alkylimidazolines, and alkylalanines are used for amphoteric ones.

Preferred among the above-mentioned antistatic agents are alkyl sulfonates, glycerin monofatty acid esters, and polyoxyethylene alkylamines. Specific examples of the alkyl sulfonate include C ₈ -C ₈ , such as sodium dodecyl sulfonate and sodium stearyl sulfonate.
_And sodium sulfonate having ₂₀ alkyl groups. Specific examples of glycerin monofatty acid ester include dodecyl glyceride, stearyl glyceride, and the like.
Alkyl monoglyceride of ₈ -C ₂₀ and the like.
Further, specific examples of polyoxyethylene alkyl amine, stearyl monoethanolamine, stearyl diethanolamine, lauryl monoethanolamine, alkyl ethanolamine of C ₈ -C _20, such as lauryl diethanolamine. These can be used alone or 2
More than one kind may be mixed and used, and a small amount of additives such as silica, fatty acid metal salt and higher alcohol may be contained.

Of these, alkyl sulfonate-based antistatic agents are most preferred. The container thus obtained has a very uniform surface gloss, a fine-grained pearly luster, and has no surface peeling even in a cellophane tape peeling test, and furthermore has a good antistatic effect. It has something. And the container of the present invention obtained in this manner is a skin lotion such as a moisturizing lotion, a massage lotion, a skin lotion, a cleansing lotion, an emollient lotion, various kinds of skin lotions such as baby oil, a cream under makeup, a burnishing cream, and an emollient cream. Various face care such as cream, liquid foundation, etc., skin care, body care, makeup cosmetics, shampoo, rinse, hair conditioner, perm blowing agent, hair care products such as hair coloring, body care such as whole body cleaning, liquid hand soap, hand care products , Liquid clothing detergent, mold remover, glass cleaner, bleach, softener, paste,
It is suitable as a container for filling things that generally require an excellent appearance, such as dishwashing detergents, cleansers, various household detergents, foodstuffs, and pharmaceuticals.

[0023]

The present invention will be specifically described below with reference to examples.
The present invention is not limited only to these examples. Example 1 Terephthalic acid 10 having an intrinsic viscosity of 0.75
72 moles of ethylene glycol and 1,4-
A cocondensation polymer (PETG6763, manufactured by Eastman Kodak Co., Ltd .; hereinafter abbreviated as PETG) consisting of 28 mol of cyclohexanedimethanol was obtained at 66 ° C. and 760 mmHg.
In addition, polythymel methacrylate [Delpet 560
F (manufactured by Asahi Kasei Corporation, hereinafter abbreviated as PMMA) at 70 ° C.
After drying under reduced pressure overnight at 60 mmHg, the weight ratio was 9%.
The mixture was mixed at a ratio of 0:10, and the mixture was biaxially kneaded at a resin temperature of 250 ° C. (using a PCM45II-30 extruder manufactured by Ikegai Iron Works Co., Ltd. having a diameter of 45 mm), extruded into strands, and cooled. Cutting was performed with a cutter to obtain pellets. The pellet was dried under reduced pressure at 760 mmHg and 66 ° C. overnight, and then subjected to direct blow molding at a resin temperature of 215 ° C. and a screw rotation speed of 22 rpm (φ50 mm, L
TZ5 made by Tahara Co., Ltd. equipped with a screw with a / D of 24
Using a 033M direct blow molding machine) to obtain a cylindrical bottle according to the present invention having a bottle weight of 38 g and a pearly luster having a capacity of 300 ml.

Embodiment 2 PETG and PM of Embodiment 1
MA was dried under reduced pressure, mixed at a weight ratio of 80:20, melt-kneaded, and directly blow-molded to obtain a cylindrical bottle having a pearly luster of 300 ml in capacity according to the present invention. Example 3 Terephthalic acid 10 having an intrinsic viscosity of 1.05
96 mol of ethylene glycol, 1,4-
A co-condensation polymer consisting of 4 mol of cyclohexanedimethanol was dried under reduced pressure, mixed at a weight ratio of 90:10, melt-kneaded and subjected to direct blow molding in the same manner as in Example 1 to obtain a pearl gloss having a capacity of 300 ml. Was obtained.

Comparative Example 1 PETG and PM of Example 1
MA was dried under reduced pressure, mixed at a weight ratio of 97: 3, melt-kneaded, and directly blow-molded to obtain a cylindrical bottle having a capacity of 300 ml. [Comparative Example 2] After drying PETG and PMMA of Example 1 under reduced pressure, they were mixed at a weight ratio of 50:50,
Similarly, melt kneading, direct blow molding and capacity of 300
ml of cylindrical bottle was obtained.

Comparative Example 3 PETG of Example 1 and low-density polyethylene (Mirason 50, manufactured by Mitsui Petrochemical Industries, Ltd.) were mixed at a weight ratio of 90:10,
Melt kneading and direct blow molding were performed in the same manner as in Example 1 to obtain a cylindrical bottle having a capacity of 300 ml. [Comparative Example 4] Polyethylene terephthalate having an intrinsic viscosity of 0.77 [Mitsui PET J125, Mitsui Pet Resin Co., Ltd.]
Was dried in a hot air at 120 ° C. overnight, and PMMA was dried in the same manner as in Example 1, mixed at a weight ratio of 90:10, and kneaded biaxially at a resin temperature of 280 ° C. The pellets obtained were subjected to direct blow molding at a resin temperature of 260 ° C., but the drawdown was severe, and no practical bottle was obtained.

Example 4 Resin composition 100 of Example 1
2 parts by weight of a composition obtained by adding 0.5 parts by weight of an alkyl sulfonate-based antistatic agent (Erest PC, manufactured by Kao Corporation) to 100 parts by weight and dried under reduced pressure at 760 mmHg overnight at 100 ° C. After kneading the shaft, it was subjected to direct blow molding at a resin temperature of 215 ° C. to obtain a cylindrical bottle of the present invention having a pearl luster of 38 g in bottle weight and 300 ml in capacity.

Example 5 Resin composition 100 of Example 1
Using a composition containing 1.0 part by weight of an alkylsulfonate-based antistatic agent [Erest PC, manufactured by Kao Corporation], dried at 100 ° C. and 760 mmHg under reduced pressure overnight, 2 parts by weight was used. After kneading the shaft, it was subjected to direct blow molding at a resin temperature of 215 ° C. to obtain a cylindrical bottle of the present invention having a pearl luster of 38 g in bottle weight and 300 ml in capacity.

Comparative Example 5 Polyethylene terephthalate having an intrinsic viscosity of 0.77 (Mitsui PET J125, manufactured by Mitsui Pet Resins Co., Ltd.) was decompressed at 120 ° C. and 760 mmHg overnight, and PMMA was treated in the same manner as in Example 1. After drying, 100 parts by weight of the resin composition mixed at a weight ratio of 90:10 was dried under reduced pressure at 100 ° C. and 760 mmHg overnight under reduced pressure. (Kao Co., Ltd.) was added in a similar manner to obtain a pellet.

The pellets were formed into a biaxial stretch molding machine (Nissei AS
Resin temperature 290 using a biaxial stretch blow molding machine manufactured by Company B)
Injection molding of a test tubular preform at 45 ° C. and an injection pressure of 45 kg / cm ² , then controlling the temperature of the preform at about 110 ° C. at a preheating station of the molding machine, and further at a blow pressure of 20 kg / cm at a blow station. Compressed air was blown into the preform at a pressure of ² cm ^{2 and} the area magnification was 4.5.
Thus, a cylindrical bottle having a capacity of 300 ml and a bottle weight of 32 g was obtained.

Comparative Example 6 The same procedure as in Comparative Example 5 was carried out except that the amount of the antistatic agent added was 1.7 parts by weight.
ml of cylindrical bottle was obtained. Comparative Example 7 The procedure of Comparative Example 5 was repeated except that the amount of the antistatic agent added was 2.5 parts by weight to obtain a cylindrical bottle having a capacity of 300 ml.

[0032]

[Characteristics] The appearance, impact resistance and surface peeling characteristics of the cylindrical bottles of Examples 1 to 3 and Comparative Examples 1 to 3 were examined. The results are shown in Table 1. Table 1 Bottle appearance Appearance Impact resistance Surface peelability 5 times 10 times Example 1 ◎ 0% 20% ○ Example 2 ◎ 0% 30% ○ Example 3 ◎ 0% 20% ○ Comparative example 1 △ 0% 10 % ○ Comparative Example 2 ○ 70% 100% △ Comparative Example 3 × 0% 10% △ Appearance ◎; Brilliant pearl gloss with strong surface gloss; Pearl gloss with strong internal reflection △; Large amount of transmitted light, reflected light Poor pearl luster ×; No pearl luster Impact The bottle was filled with tap water, a predetermined cap was closed, and the bottle conditioned at 5 ° C. for 24 hours was dropped from a height of 1 m. Prepare 10 sample bottles under the same conditions, and repeat this process until breakage occurs in each bottle. However, the maximum is 10 times. The evaluation result is
Displayed by the ratio of the number of pieces broken by 5 and 10 times.

Surface Peelability The cellophane tape adhered in the longitudinal direction of the bottle surface was instantaneously separated under a constant load, and the surface condition of the bottle to which the cellophane tape adhered was observed and evaluated. No peeling at the surface △: Peeling at a part of the surface ×: Peeling over the entire surface As can be understood from Table 1, in the case where the resin composition is a thermoplastic polyester to which low-density polyethylene is added, pearl is used. If the resin composition of the present invention does not show gloss and the amount of PMMA is out of the range of the resin composition of the present invention, the impact resistance is poor and the pearl gloss property is reduced, and the pearl gloss property is low if the amount of PMMA is small. bad.

The appearance, antistatic properties and surface peeling properties of Examples 4 and 5 and Comparative Examples 5, 6 and 7 were examined. The results are shown in Table 2. Table 2 External appearance of bottle Antistatic ability Surface peeling property Example 4 ○ ○ ○ Example 5 ○ ○ ○ Comparative example 5 ○ × △ Comparative example 6 △ △ △ Comparative example 7 × ○ × Antistatic ability Sample at 25 ° C, 50 After conditioning for 24 hours at% RH, the sample was sprayed with oily smoke for 5 minutes in a dirt chamber apparatus placed under the same conditions, and the antistatic ability was evaluated based on the degree of dirt.

No oil fumes adhered to the bottle △: Oil fumes adhered to a part of the bottle ×: Oil fumes adhered to the entire bottle As can be understood from Table 2, the container obtained by biaxial stretching blow molding has a surface It is easily peeled, has a low commercial value, and requires a large amount of an antistatic agent to be effectively prevented from adhering dust and dirt. However, if a large amount of the antistatic agent is added, the pearl luster will be lost, and the surface will be easily peeled off, and the commercial value will be lost.

On the other hand, the present invention obtained by extrusion blow molding has a pearly luster, is excellent in appearance, has excellent antistatic properties, and is hardly adhered to dust and dirt. Yes, and furthermore, surface peeling is unlikely to occur.

Claims (6)

(57) [Claims] 1. A thermoplastic polyester resin 60 which is a material used for extrusion blow molding and whose main constituent unit is terephthalic acid, ethylene glycol and cyclohexanedimethanol and has an intrinsic viscosity of 0.65 to 1.40.
An extruded blow-molded material comprising about 95 parts by weight and 5 to 40 parts by weight of a methacrylic resin. 2. A thermoplastic polyester resin 60 which is a material used for extrusion blow molding and whose main constituent unit is terephthalic acid, ethylene glycol and cyclohexanedimethanol and has an intrinsic viscosity of 0.65 to 1.40.
~ 95 parts by weight, and 5-40 parts by weight of a methacrylic resin,
Antistatic agent 0.05 to 100 parts by weight of the resin
Extrusion blow molding material characterized by containing 1.7 parts by weight. 3. The thermoplastic polyester resin contains 50 moles of ethylene glycol per 100 moles of terephthalic acid.
The extrusion blow-molded material according to claim 1 or 2, wherein the molar ratio of the cyclohexanedimethanol is 2 to 50 mol. 4. A container constituted by extrusion blow molding means, wherein the material of the container is composed of terephthalic acid, ethylene glycol and cyclohexane dimethanol with an intrinsic viscosity of 0.65 to 1.40.
A container comprising 60 to 95 parts by weight of a thermoplastic polyester resin and 5 to 40 parts by weight of a methacrylic resin. 5. A container constituted by extrusion blow molding means, wherein the material of the container is composed of terephthalic acid, ethylene glycol and cyclohexane dimethanol and has an intrinsic viscosity of 0.65 to 1.40.
A composition containing 60 to 95 parts by weight of a thermoplastic polyester resin, 5 to 40 parts by weight of a methacrylic resin, and 0.05 to 1.7 parts by weight of an antistatic agent with respect to 100 parts by weight of the resin. A container formed by extrusion blow molding. 6. The thermoplastic polyester resin contains 50 moles of ethylene glycol per 100 moles of terephthalic acid.
The container formed by extrusion blow molding according to claim 4 or 5, characterized in that the container comprises up to 98 mol of cyclohexanedimethanol and 2 to 50 mol of cyclohexanedimethanol.