JPH05339508A - Matte hollow container and production thereof - Google Patents

Abstract

PURPOSE:To more easily obtain a hollow container having a more beautiful matte appearance than the conventional ones. CONSTITUTION:The title container is made from a resin composition comprising, as the main component (a), a polyethylene, polypropylene, poly(vinyl chloride), or polyester resin and an additive component (b) which is at least one thermoset resin powder having an average particle diameter of 0.3-200mum, the ratio of the components (a) to (b) being 99.5/0.5 to 75/25 by weight. It has projections on the surface due to the component (b).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hollow container having a good moldability and a matte appearance, and a method for producing the hollow container.

[0002]

2. Description of the Related Art At present, polyethylene, polypropylene, polyvinyl chloride and polyester resins are mainly used as materials for plastic containers.
It has a wide range of applications such as cosmetics, household products, and pharmaceuticals, and is used in various fields. The function of the container is mainly to protect the contents, but recently, the molding work is easier, the cost is as low as possible, and the appearance is beautiful.
Functions that satisfy various conditions such as being useful for sales promotion have been required. Particularly in cosmetic containers, the quality of the appearance of the container affects the commercial value, so not only is it a transparent container with strong luster, but it also has an elegant appearance and a high-grade matte appearance with a solid feeling. Excellent containers are required.

[0003] As a method for obtaining a matting container which has been carried out so far in order to meet this demand, it is roughly classified into a method of blending an inorganic powder with a resin (JP-A-57-70154).
No. 63, Unexamined Japanese Patent Publication No. Sho 63-22338), a method of processing the container surface with a die with a diaphragm or sandblasting, and a method of applying a matting agent (Japanese Patent Publication No. Sho 43-20391).

Of these methods, the method of adding inorganic powder to a resin is suitable for obtaining an opaque matt container, and it is not possible to obtain a transparent container or to color only the inorganic powder. The appearance of the resulting container is difficult and it is difficult to obtain a unique one. It is difficult and costly to process the surface of the container with a squeezed die, and even if it is possible, injection biaxial stretch blow molding of polypropylene and polyester has a low temperature of around 120 ° C during the blow process. The resin is in a rubber state, and it is difficult to sufficiently transfer the die pattern of the mold. Further, the processing by sand blast or the like can obtain good matteness, but has a drawback that the obtained molded product has a low surface hardness and is easily scratched. Furthermore, the coating method has a problem that there are few coating materials having good adhesiveness to the resin, and the operation is multi-step, which is troublesome.

[0005]

Means for Solving the Problems As a result of intensive studies in view of the present situation, the present inventors have found that polyethylene resin, polypropylene resin, polyvinyl chloride resin or polyester resin having a specific composition range and an average particle diameter of 0.3 to
A resin composition consisting of 200 μm thermosetting resin powder,
The inventors have found that a direct and blow injection biaxial stretch blow molding can easily provide an elegant and heavy matte hollow container, and thus reached the present invention.

That is, the present invention is mainly composed of polyethylene resin, polypropylene resin, polyvinyl chloride resin or polyester resin and has an average particle size of 0.3 to
A resin composition containing at least one kind of auxiliary material containing 200 μm thermosetting resin powder, and the mixing ratio of the main material and the auxiliary material is 99.5 / 0.5 to 75/25 ,
The present invention provides a matte hollow container having a surface structure having protrusions by an auxiliary material on the surface of the container.

Further, the present invention comprises a polyethylene resin or a polyvinyl chloride resin as a main material and at least one kind of a thermosetting resin powder having an average particle diameter of 0.3 to 200 μm as a sub material. Direct blow molding of a resin composition in which the blending ratio with is a main material / auxiliary material (weight ratio) = 99.5 / 0.5 to 75/25, or polypropylene resin or polyester resin is the main material, and the average particle diameter is Resin containing 0.3 to 200 μm of thermosetting resin powder as at least one auxiliary material, and the mixing ratio of the main material and the auxiliary material is main material / auxiliary material (weight ratio) = 99.5 / 0.5 to 75/25 The present invention provides a method for producing a matte hollow container, which comprises subjecting the composition to direct blow molding or injection biaxial stretch blow molding.

In the present invention, a polyethylene resin, a polypropylene resin, a polyvinyl chloride resin or a polyester resin is used as the main material, and at least one kind of the auxiliary material is a thermosetting resin having an average particle size of 0.3 to 200 μm. Resin powder, main material / secondary material (weight ratio) = 99.5 / 0.5
A resin composition prepared by blending in a proportion of 75 to 25 is prepared, and the polyethylene or polyvinyl chloride resin composition is subjected to direct blow molding, and the polypropylene or polyester resin composition is subjected to direct blow molding or injection biaxial stretch blow molding. This makes it possible to produce a matte hollow container that is elegant and has good moldability.

In the present invention, the matte container is defined as follows. That is, when the gloss of the container wall is measured with a digital gloss meter GM-3D manufactured by Murakami Color Research Laboratory at an incident angle and an acceptance angle of 45 °, the gloss of the sample is 40 or less, preferably It is shown below 30. When the center line average roughness (Ra) was measured according to JIS (B0601) using the surface roughness measuring instrument SE-30H made by Kosaka Laboratory Ltd., the value of 0.07 μm was obtained. Or more, preferably 0.14 μm or more.

The polyethylene-based resin used as the main material in the present invention is one in which 70 mol% or more of the repeating units constituting the main resin is composed of ethylene, and basically, regardless of low density and high density polyethylene, basically, More preferably, polyethylene alone can be used for direct blow molding. The polypropylene-based resin is one in which 70 mol% or more of the repeating units constituting the polypropylene resin is composed of propylene, and basically, polypropylene alone is more preferable as long as it is capable of direct blow molding and injection biaxial stretch blow molding. In particular, PP6216E manufactured by Mitsubishi Kasei Co., Ltd. is preferably used for injection biaxial stretch blow molding. A polyvinyl chloride resin is a repeating unit that constitutes it.
70 mol% or more consists of vinyl chloride,
Basically, it is more preferable if polyvinyl chloride alone can be used for direct blow molding. As the polyester resin, it is preferable that 70 mol% or more of the repeating units constituting the polyester resin is composed of ethylene terephthalate, and the copolymerization component is isophthalic acid, adipic acid,
Dicarboxylic acid components such as sebacic acid, p-β-oxyethoxybenzoic acid, diphenylether-4,4'-dicarboxylic acid, diphenoxyethane-4,4'-dicarboxylic acid or their alkyl ester derivatives, propylene glycol, butanediol Glycols such as hexamethylene glycol, neopentyl glycol and cyclohexanedimethanol are used. Basically, it is more preferable if the polyester alone can be used for direct blow molding and injection biaxial stretch blow molding.

In the resin composition used in the present invention, the auxiliary material used as one component thereof has an average particle diameter of 0.3 to 200 μm.
m is a thermosetting resin powder selected from phenol-based, xylene-based, amino-based, epoxy-based, unsaturated polyester-based, or diallylphthalate-based thermosetting resin powders, or these containing a filler. The resin powders may be used alone or in various combinations.

As the phenolic resin, generally known ones and commercially available ones can be used. For example, phenol,
Cresol, xylenol, p-alkylphenol,
Examples thereof include resins obtained by adding and condensing aldehydes such as formalin and furfural to those having a phenolic hydroxyl group such as chlorophenol, bisphenol A, phenolsulfonic acid, resorcin and various modified phenols. As the xylene-based resin, generally known resins and commercially available resins can be used, and examples thereof include resins obtained by adding and condensing aldehydes such as formalin and furfural to xylene and modified xylene.

As the amino resin, generally known resins and commercially available resins can be used. For example, resins obtained by adding and condensing amino compounds such as urea, melamine, benzoguanamine and acetoguanamine and aldehydes such as formalin and furfural. Can be mentioned. As the epoxy resin, generally known ones and commercially available ones can be used. For example, bisphenol A and bisphenol F
Alternatively, a bisphenol AD type epoxy resin, a bromine-containing epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, etc. may be mentioned. Examples of unsaturated polyester resins include resins containing unsaturated acids such as maleic anhydride and fumaric acid in polyester, and diallyl phthalate resins include diallyl orthophthalate resin, diallyl isophthalate resin and diallyl chlorophthalate resin. Examples thereof include rendate resin, and generally known ones and commercially available ones can be used.

One of the auxiliary materials used in the present invention or a mixture thereof provides an excellent matting container when the average particle size is 0.3 to 200 μm. If it is less than 0.3 μm, a distinct matte appearance cannot be obtained, and if it exceeds 200 μm, the surface is rough and a refined appearance cannot be obtained, which is not preferable. The mixing ratio of the main material and the sub material in the resin composition used in the present invention is as follows: main material / sub material (weight ratio) = 99.5 / 0.5 to 75/25
The range is. When the amount of the sub-material blended is less than this range, the matte state is not uniformly developed on the entire surface of the container, which is not preferable. On the other hand, if the compounding amount of the auxiliary material exceeds this range, blow molding is not possible, or even if blow molding is possible, there is a drawback that impact resistance is poor, which is not preferable.

In the present invention, a low molecular weight substance is added to the resin composition for the purpose of promoting crystallization, improving processability, etc. within a range that does not impair the object of the present invention, and an antistatic agent and a colorant are added. There is no limitation on the addition of the above. When the colorant is added only to the main material or only to the auxiliary material, the decorative property is further increased and a container having a good appearance can be obtained.

The method for obtaining the resin composition of the present invention includes:
After dry blending the powdered main material and auxiliary material, knead and pelletize at the temperature at which the main material melts, or feed pelletized main material and powdered auxiliary material from separate feeders to the kneading machine in specified amounts Examples of the method include, but are not limited to, methods such as kneading and pelletizing at a temperature at which the main material melts, or using a well-dispersed dry blend product for direct molding. As a method for producing a container, a polyethylene-based or polyvinyl chloride-based resin composition is used in a direct blow molding machine, and a polypropylene-based or polyester-based resin composition is used in a direct blow molding machine or an injection biaxial stretch blow molding machine. A matte hollow container can be obtained by molding the preform (1) (parison or preform), adjusting each preform to an appropriate blow temperature range, and then blow molding.

[0017]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

Examples 1 to 6, Comparative Examples 1 to 4 Polyethylene 300P manufactured by Showa Denko KK (hereinafter abbreviated as PE) crushed to an average particle size of about 20 μm and an average particle size of about 0.2,
Phenol resin PL-2211 (hereinafter abbreviated as PL) manufactured by Koriei Chemical Industry Co., Ltd., which was pulverized to 2, 14, 58, 115, and 224 μm, was mixed in a ratio shown in Table 1 and dry-blended.
A 45 mmφ twin screw extruder (PCM-45) manufactured by Ikegai Tekko KK was used for melt kneading to obtain pellets having an average size of 3 mmφ × 3 mm. At this time, the cylinder temperature was 180 to 220 ° C., the screw rotation speed was 100 rpm, and the extrusion rate was 30 kg / hr. The pellets of each of these resin compositions were manufactured by Tahara Shoei Kiko Co., Ltd. TZ
Supply to a -5033M molding machine and use an extrusion screw of 50 mmφ, cylinder temperature 210-240 ℃, mold temperature 10-30 ℃, capacity 300 ml, body width about 43 mm, body depth about 25 mm,
A flat container with a height of 180 mm and a mouth diameter of 25 mm was directly blow molded. With respect to the obtained container, the appearance of the container was visually evaluated, the glossiness was evaluated, and the surface roughness of the container was evaluated. The results are shown in Table 1.

[0019]

[Table 1]

The indications in Table 1 are as follows (common to the following Examples and Comparative Examples). * 1 Evaluation criteria ◎ ・ ・ ・ The matte feeling is very strong. ○: Matte feeling is quite strong. Fair: Some matte feeling is observed. X: Almost no matte feeling is observed. * 2 Measured with a digital gloss meter GM-3D manufactured by Murakami Color Research Laboratory, using black glass as a standard plate at an incident angle and an acceptance angle of 45 °. * 3 The center line average roughness was measured according to JIS (B0601) using a surface roughness measuring instrument SE-30H manufactured by Kosaka Laboratory Ltd.

Examples 7 to 12 and Comparative Examples 5 to 7 Polypropylene B278 (hereinafter abbreviated as PPB278) manufactured by Mitsui Petrochemical Co., Ltd., crushed to an average particle size of about 24 μm, and an average particle size of 1, 8, 48, 76, Xylene resin Nikanol PR-1440M manufactured by Mitsubishi Gas Chemical Co., Ltd., pulverized to 218 μm (hereinafter
(Abbreviated as PX) was blended in a ratio shown in Table 2, and dry-blended was biaxially kneaded and subjected to direct blow molding under the same conditions as in Example 1. With respect to the obtained container, the appearance of the container was visually evaluated, the glossiness was evaluated, and the surface roughness of the container was evaluated.
The results are shown in Table 2.

[0022]

[Table 2]

Examples 13 to 17 and Comparative Examples 8 to 10 Polypropylene 6216E (hereinafter abbreviated as PP6216E) manufactured by Mitsubishi Kasei Co., Ltd. pulverized to an average particle size of about 18 μm and an average particle size of 1.
Amino resin U-VAN 120 (hereinafter abbreviated as PA) manufactured by Mitsui Toatsu Co., Ltd., which was pulverized to 5, 7, 29, and 231 μm, was blended in a ratio shown in Table 3 and dry-blended under the same conditions as in Example 1. It was kneaded biaxially. Then, using a Nissei ASB injection biaxial stretching machine, the resin temperature is 230 to 260 ℃, the mold temperature is 5 to 30 ℃, the total length is 125 mm, the body outer diameter is 28 mm (wall thickness 3.5 mm), and the mouth screw outer diameter is 30.
mm (thickness 2 mm) and weighted about 45 g of threaded preforms were molded. Then, these were subjected to biaxial stretch blow molding, and the surface temperature of the preform was 110 to 140 ° C in 5 to 30 seconds with a temperature controller heating the preform to 300 ° C.
After being heated to a temperature of 20 ° C., biaxial stretch blow molding was performed at a blow pressure of 20 kg / cm ² to obtain a container having a body thickness of 0.7 mm. With respect to this product, the visual appearance of the container, the glossiness, and the roughness of the container surface were evaluated. The results are shown in Table 3.

[0024]

[Table 3]

Examples 18 to 21 and Comparative Examples 11 to 13 Polyvinyl chloride manufactured by Toa Gosei Co., Ltd., Aron Compound BL-2S-6G2-P (hereinafter abbreviated as PVC), and average particles crushed to an average particle size of about 15 μm Unsaturated polyester resin Atrac 382 manufactured by Kao Corporation, crushed to diameters of 3, 12 and 220 μm
(Hereinafter abbreviated as PES) was blended in the proportions shown in Table 4, and dry blended was biaxially kneaded and direct blow molded under the same conditions as in Example 1. The cylinder temperature during biaxial kneading and direct blow molding was 130 to 220 ° C. With respect to the obtained container, the appearance of the container was visually evaluated, the glossiness was evaluated, and the surface roughness of the container was evaluated. The results are shown in Table 4.

[0026]

[Table 4]

Examples 22 to 26, Comparative Examples 14 to 16 Amorphous polyester PETG6763 (hereinafter abbreviated as PETG) manufactured by Eastman Kodak Co., pulverized to an average particle size of about 13 μm and an average particle size of 5, 26, 89, 220 μm Epoxy resin Epicoat 1001 (hereinafter abbreviated as PER) manufactured by Shell Chemical Co., Ltd., which was crushed into a mixture, was blended in a ratio shown in Table 5 and was dry-blended under the same conditions as in Example 1 under biaxial kneading and direct blow molding. did. The cylinder temperature during biaxial kneading and direct blow molding was 190-280 ° C. With respect to the obtained container, the appearance of the container was visually evaluated, the glossiness was evaluated, and the surface roughness of the container was evaluated. The results are shown in Table 5.

[0028]

[Table 5]

Examples 27 to 31, Comparative Examples 17 to 19 Polyethylene terephthalate J125 (hereinafter abbreviated as PET) manufactured by Mitsui Pet Co., Ltd. crushed to an average particle size of about 18 μm and PER used in Examples 22 to 26 are shown in the table. Biaxial kneading was carried out according to Example 1 at a cylinder temperature of 260 to 290 ° C. by blending in a ratio shown in 6 and dry blending. Then Example 13
The resin composition was injection-molded at a cylinder temperature of 270 to 300 ° C. by the injection biaxial stretch blow molding machine used in 1., and then biaxial stretch blow was performed to mold the container. With respect to the obtained container, the appearance of the container was visually evaluated, the glossiness was evaluated, and the surface roughness of the container was evaluated. The results are shown in Table 6.

[0030]

[Table 6]

[0031]

According to the present invention, by combining the thermosetting resin powder having an average particle size of 0.3 to 200 μm as described above with the main material of the container, a matte appearance that is easier and more beautiful than conventional ones can be obtained. It is possible to obtain a hollow container exhibiting the following, and it can be used as a container for cosmetics, shampoo, conditioner, food, medicine, daily sundries and the like.

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Claims (4)

[Claims] 1. A polyethylene resin, a polypropylene resin, a polyvinyl chloride resin, or a polyester resin as a main material, and a thermosetting resin powder having an average particle diameter of 0.3 to 200 μm as at least one auxiliary material. The mixing ratio of the main material and the auxiliary material (weight ratio) = 99.5 / 0.5
A matte hollow container, characterized in that it has a surface structure having a protrusion by an auxiliary material on the surface of the container, which is made of a resin composition of 75/25. 2. The thermosetting resin powder as an auxiliary material has an average particle size of 0.3 to 200 selected from phenolic, xylene-based, amino-based, epoxy-based, unsaturated polyester-based or diallylphthalate-based thermosetting resins. The matte hollow container according to claim 1, which is a resin powder of μm. 3. A polyethylene resin or polyvinyl chloride resin as a main material, having an average particle size of 0.3 to 200 μm.
At least one kind of secondary material contains at least one thermosetting resin powder, and the mixing ratio of the primary material and the secondary material is main material / secondary material (weight ratio) =
The method for producing a matte hollow container according to claim 1 or 2, characterized in that the resin composition of 99.5 / 0.5 to 75/25 is subjected to direct blow molding. 4. A polypropylene-based resin or a polyester-based resin as a main material, thermosetting resin powder having an average particle size of 0.3 to 200 μm as at least one auxiliary material, and a mixing ratio of the main material and the auxiliary material. Main material / sub material (weight ratio) = 99.5 / 0.
The method for producing a matte hollow container according to claim 1 or 2, wherein the resin composition of 5 to 75/25 is subjected to direct blow molding or injection biaxial stretch blow molding.