JPS5820443A - Plastic multilayer vessel - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

The present invention relates to a plastic multi-layered container, and more particularly to a plastic multi-layer container that does not have a high-grade caniglas-like appearance and has an excellent #41 container. The present invention relates to a plastic multilayer container that has elasticity, adhesiveness, heat shrinkage resistance, and mechanical strength. A plastic container? 11 For example, polyvinyl chloride. Containers made of thermoplastic resins such as polycarbonate, polystyrene, polyacrylonitrile, polyester, and polyolefin resins are widely used as containers for foods, beverages, cosmetics, medicines, and the like. Especially polyester 4i1 resin represented by polyethylene terephthalate? ÷ is transparency. Durability: Due to its excellent permeability, water vapor permeability, safety, and mechanical properties, it is suitable for carbonated beverages, edible oils, sauces,
In recent years, it has been used in a variety of applications, including containers for show oil, RI'1 seasonings, pharmaceuticals, chemical products, alcoholic beverages, etc. Polyester resin (Most typical plastic containers have excellent transparency, but such transparent containers are unsatisfactory in terms of the high-class appearance received from the container. Examples of methods for achieving this include, for example, creating fine irregularities on the outer surface of the container as seen in glass containers to give it a so-called frosted glass appearance, or adding many striped patterns to the outer surface. There are ways to give plastic containers a similar appearance.
Generally, a method is used in which a blow molding mold is processed so as to exhibit a pattern. However, the method of transferring the molded metal i9 by performing the processing (iij) has the disadvantage that the pattern is transferred only to the outer surface of the container, resulting in a lack of depth in appearance;
During molding, air exists between the surface of the mold and the outer surface of the container, and the pattern of the mold is not transferred to the light because it cannot be removed by light. Inconveniences occur during molding, such as the container sticking to the surface of the mold, and solids such as low offshore solids accumulate in one finely carved part of the mold, and this is transferred to the outer surface of the container, resulting in poor appearance. In addition, as a method for manufacturing containers with a frosted-glass-like or black-and-white glass-like appearance using polyester resin, a polyester container or a parison with a bottom, which is an intermediate material thereof, is sanded/rusted and its surface is polished. There have been proposals for methods such as roughening the parison, or biaxially orienting the bottomed parison, which is an intermediate material, by solvent treatment and then biaxially orienting it. Since the product is not subjected to any chemical or physical changes during or after manufacture, productivity is poor and it is difficult to impart a modified effect under certain circumstances. A method of blow molding after crystallizing a parison with a bottom by heating, or a method of blow molding using a parison that is crystallized by cooling the thread during injection molding. However, the crystallization rate of the bottomed parison is rectangular, and a parison with too much crystallization will not be stretched to the shape of the blowing mold during blow molding, and will not be completely stretched. It has the disadvantage of not being able to form a good product.Furthermore, inorganic inert particles such as talc or clay are added to a polyester resin, and an attempt is made to obtain a glass-like container by blow molding. Attempts have also been made to add inorganic inert particles, while particles added by blow molding have been shown to improve the production of polyester.
Because it acts as a so-called crystallization nucleating agent,
If the flesh fj'+j-sllζ of the parison crystallizes, or the injection L1 part during 111 injection molding becomes noticeably white, and the injection port becomes the bottom of the container, the container However, it has not yet been possible to obtain a satisfactory carnivorous-like container by adding inert particles. As a result of extensive research to obtain a container that has improved heat shrinkability and mechanical strength compared to containers that would otherwise be damaged by molding, we have found that glass granules with a specific shape have been improved. By stretching a multi-layered preformed body containing a thermal pJ'i resin layer mixed in a specific ratio in layers other than the innermost layer, it has a high-class appearance, and has excellent hygiene and heat shrinkage resistance. , and seating force (strength, pressure deformation resistance, castle deformation resistance, etc.).
We have arrived at the present invention. 5- That is, the present invention is a multilayer container having two or more thermoplastic resin layers, and at least one layer other than the innermost 1f1] A thermoplastic 111- containing 01 to 30% by weight of PFi in the form of glass particles.
It is a bluff multilayer container having a layer of wood Jl) and a portion extending in at least one direction. The thermoplastic resin referred to in the present invention refers to blow molding. It is a thermoplastic resin that can be molded into containers using molding methods that involve hard elongation, such as vacuum forming and pressure forming. Such thermoplastic #i
Table 1 shows preferred fats. Among these, those having a light transparency of 70 degrees or more are more preferable because they form a good frosty appearance, and polyester resins are particularly preferable because the effects of the present invention are particularly exhibited. Table-1 Note) 1) A: Good transparency, B: Slightly cloudy C: Translucent, D = Opaque 2) Measured according to ASTM D-1003 Among the thermoplastic resins mentioned above, a particularly preferable polyester resin is terephthalic acid. The main target is polyethylene terephthalate, which is produced by the reaction of ethylene glycol or its lower alkyl ester with ethylene glyfur, but fi1 of the terephthalic acid component! (usually 20 molar or less), aromatic dicarboxylic acids such as isofucric acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenoxyethane dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid, etc.: hexahydroprephthal acids, alicyclic dicarboxylic acids such as hexahydroisofucuric acid; aliphatic dicarboxylic acids such as adipic acid, sepatic acid, azelaic acid, etc.; A portion of other difunctional carboxylic acids such as oxyacids, esters, esters, and/or a portion of the ethylene glycol component (usually not more than 20 mol%) can be added to, for example, tri-r-thinsogelicol, tetramethylene. Glycol, hexamethylene glycol, decamethylene glycol, neopentyl glycol, diethylene glycol, triethylene glycol. +51-cyclohexane dimethylol, 1,4-cyclohexane dimethylp-rol, 2,2-bis(4'-β-hydroxyethoxyphenyl)propane. glycols such as bis(4'-β-human p-xyethoxyfugonyl)sulfonic acid and their mediators [
substituting with one or more polyfunctional compounds such as J conductors,
A copolymerized one may also be used. Among such polyester resins, a homopolymer of polyethylene terephthalate is most preferable, but the polyethylene terephthalate has an intrinsic viscosity of 0.5 or more, more preferably 0.
．． It is preferable that it is 60 or more. Also, the softening point of polyethylene terephthalate is 220°C to 270°C.
is preferred, particularly preferably 250 to 265°C. 9- Other polyester #t! jj'? It is also desirable that the polyester resin has the same elasticity as described above.The polyester resin may also be manufactured by any method known to a person having the relevant knowledge. The container of the present invention is a multilayer container made of such a thermoplastic resin, and one of the layers contains a polyamide resin and an ethylene-vinyl alcohol copolymer having good gas barrier properties, particularly oxygen barrier properties.Ethylene -Saponified vinyl acetate copolymer, Hini)-lyl resin, etc., or polycarbonate I with good heat resistance
X! It is preferable to select from among these resins, polyarylate resins, polyarylate resins, polyethylene naphthalate resins, heat-resistant polystyrene resins, etc., since the performance of the container will be improved. Furthermore, inorganic or organic colorants, antistatic +1- agents, antioxidants, ultraviolet absorbers, and stabilizers. A thermoplastic resin layer mixed with a lubricant, a plasticizer, etc. may be interposed in layers other than the innermost layer. As such a technique, for example, Japanese Patent Application Laid-Open No. 54-115981 σ
Although the technology is unknown, the technology is an excellent multi-layer container, and the high-class appearance according to the present invention is similar to that of V4G.
do not have. 1. Containing the glass particles of the present invention. - A plastic multilayer container including a laminated layer has the effect of improving interlayer adhesion due to the presence of surface irregularities of the layer. The glass particles used in the present invention are, for example, cylindrical (glass j
2) Spherical (glass 7, beads), plate-shaped (glass flakes), irregular shape (glass powder), etc.1. The appearance differs depending on the type of granules used, but

In the case of [, it also presents a high-class crabgrass style evening view. For example, glass fibers give a fine cut glass look, glass peas give a frosty H'l look, glass flakes give a coarse ground glass look, and glass flakes give a fine ground glass look. The dimensions of the glass particles vary depending on the container molding method, stretching ratio, shape, wall thickness, etc.
The upper limit of the dimensions is determined by the stretchability such as breakage of the thermoplastic resin (thermoplastic resin) Ilt film during stretching, or the feel when it comes into contact (A = rough feel if it is large).In the case of glass-fed fibers, the length is 3. Tone. In the case of glass heather, the average particle size is 10 (11μ), and in the case of glass flakes and glass powder, the average particle size is about 10 mesh.The lower limit of the size of glass particles is:
If the particles become too thin, the appearance will become cloudy and the sense of luxury will be poor, but the lower limit is preferably about 1 μm. These glass granules are contained in a thermoplastic resin layer in which the glass granules are mixed at least (1
The effects of the present invention can be exhibited by dispersing a single ivL, preferably 0.5 weight factor or more, but if the amount added exceeds 30 weight factor, stretching becomes difficult and it is difficult to obtain a desired container. In order to obtain a high-grade glass-like appearance, it is preferable to keep the weight of glass particles to 5 or less. Although such glass particles can be used untreated, it is preferable to treat them with a treatment agent such as a conventional coupling agent such as a silane-based, chromium-based, or poran-based coupling agent. Examples of the plastic multilayer container of the present invention include bottles,
An example is a container that is formed by a molding method that involves stretching, such as a copper. By stretching during the molding process, a glass-like appearance, which is a feature of the present invention, is achieved, but if the container is formed by simply injection molding, for example, no peeling appearance is obtained. The container of the present invention can be obtained by such a molding method, and the container of the present invention is a container having two or more thermoplastic resin layers, and the thermoplastic resin layer containing the glass particles is not included in any layer other than the innermost layer. It is something that has been intervened. A container having a layer containing glass granules as the innermost layer is not preferred because a portion of the glass granules may migrate into the contents of the container when the container is severely and repeatedly deformed. As a method for obtaining a container having the features of the present invention, for example, in the case of a bottle, conventionally known multilayer injection blow molding methods, multilayer extrusion blow molding methods, multilayer biaxially oriented blow molding methods, etc. are advantageously used. In the case of injection blow molding, a multi-layer closed-ended parison is formed by direct injection molding of the expandable geometry, which is then transferred into a bottle mold and blow expanded. At this time, when injection molding the parison, it is preferable to control the temperature of the core mold and the injection mold using a heating medium, a cooling medium, air cooling, etc. to a temperature that allows stretching. In addition, when molding a container by extrusion blow molding, first extrude heat-molten thermoplastic resin into a multi-layered tube shape, then cut the pipe-shaped extrudate into a desired length and cut out the bottom. The parison is then transferred to a mold having the shape of a desired container, and a compressed fluid such as compressed air is blown into the parison to expand it to the shape of the container. In addition, when molding a container by multilayer biaxially oriented blow molding using polyester resin, etc., first, the thermoplastic resin is heated and melted to a temperature above the melting point using an injection molding machine, and then injected in multiple layers into a preform mold. A multilayer parison with a bottom is formed by molding, and then the temperature of the parison is adjusted to a temperature range that allows stretching, and the parison is transferred into a mold having the shape of the desired container, and then stretched in the axial direction with a stretching rod (14-). At the same time, compressed air is blown into the compressed fluid to expand the container to the desired shape. When the bottomed parison is stretched or expanded by blowing, the stretching ratio of the body of the bottle is at least 2 times, preferably at least 2 times, in terms of area magnification. Further, as a method for obtaining a container such as a pot, for example, a method such as vacuum forming of a multilayer structure sheet having a layer containing glass particles under pressure is applied. When a container having a layer containing glass granules is produced by blow molding, pressure forming, vacuum forming, etc., as described above, the container may consist of a single layer of thermoplastic outer layer containing glass granules. It's good, and depending on the use, it's f? It has a multi-layered structure of il- or semi-resin. The above information! : Dyeing when molding ¥-1. Fρ grains, ultraviolet absorbers, inorganic inert particles, stabilizers, etc. can be added within the range that does not impair the purpose of the present invention. In the present invention, any method can be selected for adding the glass particles to the thermoplastic resin layer containing the glass particles. For example, a method of adding it when polymerizing a thermoplastic resin,
A method in which master pellets containing glass particles at a high concentration are separately manufactured and blended with additive-free pellets during molding and then added, or a method in which glass particles are sprinkled onto additive-free pellets and directly molded, etc. There is, but
In order to closely disperse it in the thermoplastic resin in the form of glass particles, it is preferable to add it during polymerization of the thermoplastic resin or to use mastic pellets. If the glass particles are poorly dispersed in the film, not only will the commercial value of the hollow container be significantly impaired, but the effect of improving heat absorption and mechanical strength will not be achieved. The crab glass-like container according to the present invention 1 can be produced by mixing glass granules in the thermoplastic resin material, and does not require any post-processing such as sandblasting, and is economically superior. It not only has the advantage of being able to be manufactured under constant conditions and has excellent reproducibility.It also has the advantage of being able to be manufactured under constant conditions and having excellent reproducibility. Excellent gas permeability,
Maintains mechanical strength. Furthermore, since the cylindrical container and the parison with a bottom that is intermediate in shape have excellent slip properties, the productivity during manufacturing the container and filling the container with contents can be improved to 11]. The thus obtained plastic multilayer container has excellent heat shrinkage resistance and mechanical strength, and is useful as a variety of industrial containers.In addition, the caniglas-like container, which has a decorative appearance, is particularly popular. Useful as containers for cosmetics and alcoholic beverages. The present invention will be described in detail below with reference to Examples, but the present invention is not limited to the following Examples unless it deviates from the gist thereof. The methods for measuring the main characteristics measured in the examples are shown below. Hot water shrinkage rate: After filling a bottle with hot water at a predetermined temperature, the bottle was tightly stoppered and allowed to stand. The bottle was opened for 24 hours and the internal volume of the bottle was measured. The shrinkage rate was determined by the following formula. -17= Vo -V Shrinkage rate = -X 100 (g) O Buckling strength: Toyo Sokki TENSILO'N/UTM-
W-so. Using a machine, a load was applied to an empty bottle from the vertical direction at a head speed of 5 mm/min, and the load at which the bottle deformed was determined. Pressure resistance strength: 10 to 9/10 by using a water pressure machine in a bottle filled with water.
Water pressure was applied at a speed of iG/min, and the pressure at which the bottle burst was determined. Light transmittance: Integrating sphere type light transmittance measuring device (measured at a thickness of 0.3 m/m) JISK-67
According to 14. When this light transmittance takes a value of 2096 or more, a crab glass tone appears. Examples-1 to 4 and Comparative Example-1 18- A polyester multilayer oriented container having the inner layer and outer layer compositions shown in Table 2 was made using a Nissei ASB (manufactured by Flame Machinery Co., Ltd. 150 D > 1+7 multi-j tin oriented plue molding machine). It is molded.The polyester resin contains polyethylene terephthalate resin with an intrinsic viscosity of 075, 20wt glass particles, phthalocyanine blue, and Kino 7 resin.Intrinsic viscosity 07
0 polyethylene tere V7 talate master pellet was dried in a hot air dryer. The expansion ratio of the body of the multilayer container is approximately 2 times in the vertical direction and 4 times in the horizontal direction, and the dimensions of the container are approximately 200 r.
rrm, trunk diameter approximately 701. The wall thickness of the body is between outer layer 02 and 03. Inner layer 02-03 fin, approximately 500 yd in volume. From Table 2, it can be seen that a multilayer container having a layer made of polyester containing glass granules of 0.5 to 1 layer or more has a higher hot water shrinkage rate and a higher shrinkage rate than a container that does not have a layer containing glass granules. It can be seen that mechanical strength such as bending strength, pressure resistance strength, and adhesive strength between two layers deteriorated significantly, indicating that the improvement effect of the present invention is remarkable. Examples 5 to 6 and Comparative Examples 2 to 3 Sumitomo 1″Kisei Kogyo C; 1) 31r, -51/BA-2
3ft high-speed blow molding deflection! A container with a three-layer structure shown in Table 3 was molded using a forging machine capable of molding a three-layer container. The conditions of molding and the results of evaluating the obtained bottle are shown in G-3. Table 3 Notes: *marked with an asterisk (diameter 10μ, length 1000μσ) contains 3 subbonds that are glassy. For PET, use polyethylene terephthalate with an intrinsic viscosity of 081. For PE, use low-density polyethylene terephthalate with a melt index of 1.0. Note 2: Bottle body wall thickness is 0 layer theory or higher...○ is 0.21
11111 or less... marked as ×. Note 3: Approximately 1 volume of 50% ethyl alcohol aqueous solution
/2 was filled and a migration test was conducted after capping, and the results were rated as × if there was migration into the aqueous solution even on the machine, and ○ if there was no migration. In Token-1, the container was rotated for 4 hours at a rotation speed of 30 rpm centering on the middle part of the container. Condition-2 is that buckling deformation is applied repeatedly from the lateral direction at a rate of about 30 times per minute, once every 2 hours, so that the amount of deformation is about 115 times the diameter of the body of the container. . Patent Applicant Teijin Ltd. Agent Patent Attorney Former 1) Jun Hiroshi 22-

Claims (1)

[Claims] 1. A multilayer container having two or more thermoplastic GJ fat layers, in which at least one layer outside the innermost layer has glass particles 1. A plastic multilayer container having a resin layer and a portion stretched in at least one direction.2 Claims fl in which at least one layer is a polyester resin whose main constituent is ethylene terephthalate.
! 'G The plastic multilayer container described in item 1. The plastic multilayer container according to claim 1 or 2, wherein the λ container is a bottle produced by a biaxial stretch blow molding method.