CN115551787A - Extrusion molded article for tube container, and tube container - Google Patents
Extrusion molded article for tube container, and tube container Download PDFInfo
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- CN115551787A CN115551787A CN202180035104.4A CN202180035104A CN115551787A CN 115551787 A CN115551787 A CN 115551787A CN 202180035104 A CN202180035104 A CN 202180035104A CN 115551787 A CN115551787 A CN 115551787A
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- extrusion
- polyethylene resin
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- molded article
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D35/00—Pliable tubular containers adapted to be permanently or temporarily deformed to expel contents, e.g. collapsible tubes for toothpaste or other plastic or semi-liquid material; Holders therefor
- B65D35/02—Body construction
- B65D35/10—Body construction made by uniting or interconnecting two or more components
Abstract
The extrusion-molded article for a tube container of the present invention has a 3-layer structure having a tube shape as a whole, and having an inner layer, an outer layer, and an intermediate layer interposed therebetween, the inner layer and the outer layer each containing an acid-modified polyethylene resin derived from petroleum and a linear low-density polyethylene resin derived from a plant.
Description
Technical Field
The present invention relates to an extrusion-molded article for a tube container and a tube container.
Background
As a tube container for containing toothpaste, cosmetics, and the like, a laminate tube is known. The laminated tube is produced using, as a raw material, a laminated sheet obtained by laminating polyethylene resin, special paper, aluminum foil, or the like. Generally, a laminated tube is manufactured by: the laminate sheet is rolled into a cylindrical shape, both end portions of the sheet are overlapped, the overlapped portions are welded, and the lid fitting portion is joined to the obtained container body.
This laminated tube has the following problems, for example. Since the laminate tube is manufactured by overlapping both end portions, a difference in level occurs in the overlapped portion, which causes a problem in appearance. Since the end faces of the laminated sheet are exposed at the overlapping portions, the contained contents permeate into the interior of the laminate from the end faces, and the physical properties of the laminated sheet are degraded. Further, since the laminate tube is difficult to be thickened and it is difficult to maintain sufficient strength when a tube having a large diameter is used, the laminate tube includes a step of winding the laminate tube into a cylindrical shape and the height difference is desired to be made inconspicuous.
In order to solve the above-described problem of the laminate tube, a container body for manufacturing a tube container by extrusion molding is proposed (patent documents 1 and 2). The tube container produced by extrusion molding is called an extrusion molded tube. The extrusion molded tube was manufactured by: the molten resin is continuously extruded into a tube shape by an extruder, and then cut into an appropriate length, and the cap fitting portion is joined to the obtained container body. In the case of a multilayer extrusion molded tube, the tube is manufactured by extruding a plurality of kinds of molten resins into one die in different extruders to form a tube shape of a multilayer structure in the die.
Currently, a mainstream of a pipe container to be circulated is a pipe container formed using a petroleum-derived resin.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 11-309406
Patent document 2: japanese patent laid-open publication No. 11-309785
Disclosure of Invention
Technical problem to be solved by the invention
The present inventors have made an effort to develop an extrusion-molded tube containing a plant-derived polyethylene resin from the viewpoint of the above-mentioned problems of the laminate tube and environmental protection, and as a result, have newly found the following problems.
When a plant-derived polyethylene resin is blended in place of a petroleum-derived polyethylene resin, stress cracking is likely to occur in an extrusion-molded pipe. Further, when a multilayer extrusion molded tube including a resin layer containing a plant-derived polyethylene resin and a resin layer having a gas barrier property is produced, interlayer peeling is likely to occur. Further, when such a multilayer extrusion molded tube is continuously molded, deformation occurs after extrusion into a tubular shape.
The object of the invention is therefore: provided is a technique relating to an extrusion-molded tube which contains a plant-derived polyethylene resin and is excellent in stress cracking resistance, interlayer adhesion strength, and production stability.
Means for solving the problems
According to one aspect of the present invention, there is provided an extrusion-molded article for a tube container, which has a 3-layer structure having a tube shape as a whole, and including an inner layer, an outer layer, and an intermediate layer interposed therebetween, the inner layer and the outer layer each containing a petroleum-derived acid-modified polyethylene resin and a plant-derived linear low-density polyethylene resin.
According to another aspect of the present invention, there is provided a tube container including:
a container body including the extrusion-molded article having one end heat-sealed; and
and a lid fitting portion joined to the other end of the extrusion-molded product having the one end heat-sealed.
Effects of the invention
The present invention can provide an extrusion-molded tube which contains a plant-derived polyethylene resin and is excellent in stress cracking resistance, interlayer adhesion strength, and production stability.
Drawings
FIG. 1 is a cross-sectional view showing a 3-layer structure of an extrusion-molded article according to an embodiment of the present invention.
FIG. 2 is a plan view showing the structure of a tube container according to an embodiment of the present invention.
Detailed Description
The present invention will be described below, but the following description is intended to describe the present invention in detail and is not intended to limit the present invention.
1. Extrusion molded article for tube container
The extrusion molded product for a tubular container has a 3-layer structure having a tubular shape as a whole, and having an inner layer, an outer layer, and an intermediate layer interposed therebetween, the inner layer and the outer layer each containing an acid-modified polyethylene resin derived from petroleum and a linear low-density polyethylene resin derived from a plant. In the following description, the extrusion molded article for a tube container is simply referred to as "extrusion molded article".
1-1. Structure
The extrusion molded article has a tubular shape as a whole, and has a 3-layer structure of an inner layer, an outer layer, and an intermediate layer interposed therebetween. Fig. 1 is a sectional view showing a 3-layer structure of an extrusion molded article according to an embodiment of the present invention. As shown in fig. 1, the extrusion molded article 1 has a 3-layer structure of an inner layer 1a, an outer layer 1c, and an intermediate layer 1b interposed therebetween. When the extrusion molded product 1 shown in fig. 1 is used as a container body of a tube container, the surface on the inner layer 1a side is adjacent to the inner space of the tube container, and the surface on the outer layer 1c side is adjacent to the outer space of the tube container.
The extrusion-molded article 1 may have a cylindrical shape or an elliptical tube shape. The extrusion-molded article 1 has a circumferential length of, for example, 30 to 190 mm. The extrusion molded article 1 preferably has a thickness of 40 to 160mm. The circumferential length is the length of the outer periphery of the tubular extrusion-molded article 1. The extrusion-molded article 1 has a thickness of, for example, 0.19 to 0.55mm, preferably 0.24 to 0.5 mm. The thickness is the thickness of the wall of the tubular extrusion molded article 1, and is an average value of the thicknesses measured at 3 positions of the extrusion molded article 1 set at substantially equal intervals in the longitudinal direction. The inner layer 1a has a thickness of, for example, 0.12 to 0.25mm, preferably 0.14 to 0.24mm, the intermediate layer 1b has a thickness of, for example, 0.01 to 0.1mm, preferably 0.02 to 0.08mm, and the outer layer 1c has a thickness of, for example, 0.06 to 0.2mm, preferably 0.08 to 0.18 mm.
The extrusion-molded product 1 may have any length, may have a length longer than the container body of the tube container, or may have the same length as the container body of the tube container. In the former case, the extrusion molded product 1 is cut into a length of the container body of the tube container and then used as the container body of the tube container.
1-2. Resin
The resins constituting the inner layer 1a, the intermediate layer 1b, and the outer layer 1c will be described below.
(inner layer 1 a)
The inner layer 1a includes: "petroleum-derived acid-modified polyethylene resin" and "plant-derived linear low-density polyethylene resin".
"acid-modified polyethylene resin derived from petroleum"
The "petroleum-derived acid-modified polyethylene resin" is a resin obtained by modifying petroleum-derived polyethylene with an unsaturated carboxylic acid or an anhydride thereof. This resin is modified with an acid to impart adhesiveness, and is therefore known as an adhesive resin. Examples of the unsaturated carboxylic acid or anhydride thereof include: acrylic acid, methacrylic acid, α -ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, chloromaleic acid, butenylsuccinic acid, and anhydrides of these.
The "petroleum-derived acid-modified polyethylene resin" is preferably a petroleum-derived maleic anhydride-modified polyethylene resin. More preferably, the "petroleum-derived acid-modified polyethylene resin" is a petroleum-derived maleic anhydride-modified low-density polyethylene resin (MA-modified LDPE), a petroleum-derived maleic anhydride-modified linear low-density polyethylene resin (MA-modified L-LDPE), or a mixture of these resins.
"maleic anhydride-modified low-density polyethylene resin derived from petroleum (MA-modified LDPE)" is a resin obtained by modifying a homopolymer of ethylene produced using petroleum as a raw material with maleic anhydride.
The density of the "maleic anhydride-modified low-density polyethylene resin derived from petroleum (MA-modified LDPE)" is preferably 0.91g/cm 3 ～0.93g/cm 3 More preferably 0.915g/cm 3 ～0.93g/cm 3 In the presence of a surfactant. The density of the resin described in the present specification is a measured value obtained by a method based on JIS K7112: 1999.
Further, the "maleic anhydride-modified low density polyethylene resin derived from petroleum (MA-modified LDPE)" preferably has a melt index (MFR) in the range of 0.1g/10 min to 10g/10 min, more preferably in the range of 1g/10 min to 5g/10 min. The Melt Flow Rate (MFR) of the resin described in the present specification is a measured value obtained by a method according to JIS K7210: 1999. Specifically, the melt index is a measurement of the weight of a resin discharged within 10 minutes when a load of 21.18N (2.16 kgf) was applied to the resin at 190 ℃.
As the "maleic anhydride-modified low-density polyethylene resin derived from petroleum (MA-modified LDPE)", for example, a resin sold under the trade name "MODIC" (registered trademark) by MITSUBISHI CHEMICAL corporation, a resin sold under the trade name "ADMER" (registered trademark) by mitsui CHEMICAL corporation, and the like can be used.
"petroleum-derived maleic anhydride-modified linear low-density polyethylene resin (MA-modified L-LDP E)" is a resin produced by using petroleum as a raw material and obtained by modifying a copolymer of ethylene and α -olefin with maleic anhydride. The "α -olefin" is at least one compound selected from α -olefins having 3 to 20 carbon atoms, and examples thereof include: 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, etc.
The density of the "petroleum-derived maleic anhydride-modified linear low-density polyethylene resin (MA-modified L-LDP E)" is preferably 0.91g/cm 3 ～0.93g/cm 3 More preferably 0.915g/cm 3 ～0.93g/cm 3 Within the range of (1). The "petroleum-derived maleic anhydride-modified linear low-density polyethylene resin (MA-modified L-LDPE)" preferably has a melt index (MFR) in the range of 0.1g/10 min to 10g/10 min, more preferably in the range of 1g/10 min to 5g/10 min.
As the "petroleum-derived maleic anhydride-modified linear low-density polyethylene resin (MA-modified L-LDP E)", for example, a resin sold under the trade name of "ADMER" (registered trademark) by MITSUBISHI CHEMICAL corporation, a resin sold under the trade name of "MODIC" (registered trademark) by MITSUBISHI CHEMICAL corporation, a resin sold under the trade name of "OREVAC" (registered trademark) by ARKEMA corporation, or the like can be used.
"straight-chain low-density polyethylene resin derived from plant"
"plant-derived linear low-density polyethylene resin (Bio) L-LDPE)" is a copolymer of ethylene and α -olefin produced using a plant as a raw material. The "plant-derived linear low-density polyethylene resin (bio L-LDPE)" is preferably a linear low-density polyethylene resin derived from sugar cane. The linear low-density polyethylene resin derived from sugar cane is a copolymer of ethylene and α -olefin produced using sugar cane as a raw material.
The "α -olefin" is at least one compound selected from α -olefins having 3 to 20 carbon atoms, and examples thereof include: 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, etc.
The density of the "plant-derived linear low-density polyethylene resin (bio L-LDPE)" is preferably 0.91g/cm 3 ～0.93g/cm 3 More preferably 0.915g/cm 3 ～0.93g/cm 3 Within the range of (1). The "plant-derived linear low-density polyethylene resin (biol L-LDPE)" preferably has a melt index (MFR) in the range of 0.1g/10 min to 10g/10 min, more preferably in the range of 1g/10 min to 5g/10 min.
As the "plant-derived linear low-density polyethylene resin (bio L-LDPE)", for example, plant-derived linear low-density polyethylene sold from Br askem can be used, and examples thereof include: resins sold under the trade names SLL118, SLL118/21, SLL218/21, SLL318, SLH118, SLH218, SLH0820/30 AF.
The inner layer 1a may contain "petroleum-derived acid-modified polyethylene resin" and "plant-derived linear low-density polyethylene resin" at a mass ratio of 9:1 to 4:6, for example. The inner layer 1a may preferably contain "petroleum-derived acid-modified polyethylene resin" and "plant-derived linear low-density polyethylene resin" at a mass ratio of 9:1 to 5:5.
(intermediate layer 1 b)
The intermediate layer 1b preferably contains a resin having gas barrier properties. As the resin constituting the intermediate layer 1b, a resin known as a resin having a gas barrier property can be used. Examples of the resin constituting the intermediate layer 1b include ethylene-vinyl alcohol copolymer resin (EVOH), nylon (NY), polyvinyl alcohol (PVA), polyacrylonitrile (PAN), and polyvinylidene chloride (PVDC), and ethylene-vinyl alcohol copolymer resin (EVOH) is preferable.
As the ethylene-vinyl alcohol copolymer resin (EVOH), for example, a resin sold under the trade name "SOARNOL" (registered trademark) by MITSUBISHI CHEMICAL, a resin sold under the trade name "EVAL" (registered trademark) by KURARAY, K.K., and the like can be used.
(outer layer 1 c)
The outer layer 1c contains "an acid-modified polyethylene resin derived from petroleum" and "a linear low-density polyethylene resin derived from a plant". The "petroleum-derived acid-modified polyethylene resin" contained in the outer layer 1c is as described for the inner layer 1 a. The "plant-derived linear low-density polyethylene resin" contained in the outer layer 1c is as described for the inner layer 1 a.
The outer layer 1c may contain "petroleum-derived acid-modified polyethylene resin" and "plant-derived linear low-density polyethylene resin" at a mass ratio of 9:1 to 4:6, for example. The outer layer 1c may preferably contain "petroleum-derived acid-modified polyethylene resin" and "plant-derived linear low-density polyethylene resin" at a mass ratio of 9:1 to 5:5.
The outer layer 1c may have the same resin composition as the inner layer 1a, or may have a different resin composition from the inner layer 1 a.
(additives)
The inner layer 1a, the intermediate layer 1b, and the outer layer 1c are mainly composed of a resin, but may contain a known additive other than the resin as needed. As the additive, various additives known as additives for resins can be used. Examples of the additives include: antioxidants, ultraviolet absorbers, weather-resistant agents, antistatic agents, fillers, crystal nucleating agents, coloring pigments, delustering agents, anti-coloring agents, antifogging agents, flame retardants, antiblocking agents, lubricants (including slip agents, mold release agents), and the like. The total content of the additives may be set to, for example, 0.01 to 10 parts by mass with respect to 100 parts by mass of the resin of each layer.
1-3. Method of manufacture
The extrusion molded article 1 can be produced by a known coextrusion molding method. That is, the resin constituting the inner layer 1a, the resin constituting the intermediate layer 1b, and the resin constituting the outer layer 1c are extruded into one die by different extruders, and a tube shape having a 3-layer structure is formed in the die.
2. Pipe container
The tube container is provided with:
a container body including the extrusion-molded article having one end heat-sealed; and
and a lid fitting portion joined to the other end of the extrusion-molded product having the one end heat-sealed.
Hereinafter, a tube container according to an embodiment of the present invention will be described with reference to fig. 2. Fig. 2 is a plan view showing the structure of a tube container according to an embodiment of the present invention.
As shown in fig. 2, the tube container 1 includes: a container body 11, and a lid fitting portion 12 joined to the container body 11. The tube container 1 is used by filling the container body 11 with contents and fitting the lid to the lid fitting portion 12. Here, the content may be a highly viscous liquid or a semi-solid. The contents are daily necessities such as facial cleanser, cosmetics, toothpaste, hand cream and the like, and foods such as jam, butter and the like.
The container body 11 is obtained by heat-sealing one end of the extrusion molded article 1 described above. In the extrusion molded product 1, a printed layer may be provided on the outer surface before one end is heat-sealed. That is, the container body 11 may further include a printed layer.
As shown in fig. 2, the container body 11 includes a body portion 21 and a seal portion 22 provided at one end of the body portion 21.
The body portion 21 is a portion of the extrusion molded article 1 that is not heat-sealed. The end of the body 21 not provided with the seal 22 has a circular or elliptical cylindrical shape when having a peep opening.
The seal portion 22 is a portion formed by thermally welding one end portion of the extrusion molded product 1. The sealing portion 22 has a flat shape, and opposite inner surfaces thereof are heat-sealed to each other. The sealing portion 22 closes one end of the container body 11.
A cover fitting portion 12 is provided at an end portion of the body portion 21 opposite to the end portion provided with the seal portion 22. The lid fitting portion 12 includes: a shoulder portion 31 integrally connected to an end portion of the body portion 21 where the seal portion 22 is not provided, and a cylindrical mouth portion 32 provided at the center of the shoulder portion 31. The lid fitting portion 12 and the body portion 21 are manufactured by injection molding and compression molding, respectively, and joined to the body portion 21.
As for the shoulder 31, an outer surface facing the outer space of the tube container 10 and an inner surface facing the inner space of the tube container 10 respectively have a truncated cone shape tapering from the inner space toward the tip of the outer space. The peripheral edge of the shoulder portion 31 is connected to the trunk portion 21. The mouth portion 32 is provided to protrude outward from the center of the shoulder portion 31.
3. Effect
The extrusion-molded article and the pipe container comprising the extrusion-molded article of the present invention contain a combination of a "petroleum-derived acid-modified polyethylene resin" and a "plant-derived linear low-density polyethylene resin" in the inner layer and the outer layer of a 3-layer structure, respectively. In the present invention, by using such a combination of specific resins, even when a plant-derived polyethylene resin is blended, excellent stress cracking resistance, excellent interlayer adhesion strength, and excellent production stability can be achieved (see examples described later).
The extrusion-molded article of the present invention and the tube container including the extrusion-molded article have the following advantages. The extrusion-molded article and the pipe container comprising the extrusion-molded article of the present invention contain the plant-derived polyethylene resin, and therefore can contribute to CO compared with the case of the petroleum-derived polyethylene resin 2 And (4) reduction of discharge amount. Further, since the extrusion-molded article of the present invention and the tube container including the extrusion-molded article are manufactured by extrusion molding, such overlapping portions (i.e., seams) as seen in a laminated tube are not present, and a seamless appearance can be realized. Further, the extrusion-molded article and the bag of the present inventionSince a tube container including the extrusion-molded product is manufactured by extrusion molding, the tube container is more likely to be thicker than a laminated tube, and can maintain sufficient strength even in a tube container having a large diameter.
4. Preferred mode of carrying out the invention
Hereinafter, preferred modes are summarized.
[1] An extrusion-molded article for a tubular container having a 3-layer structure comprising an inner layer, an outer layer and an intermediate layer interposed therebetween, the inner layer and the outer layer each comprising a petroleum-derived acid-modified polyethylene resin and a plant-derived linear low-density polyethylene resin.
[2] The extrusion-molded article according to item [1], wherein the linear low-density polyethylene resin is a linear low-density polyethylene resin derived from sugarcane.
[3]According to [1]Or [2]]The extrusion-molded article of, wherein the linear low-density polyethylene resin has a density of 0.91g/cm 3 ～0.93g/cm 3 Preferably 0.915g/cm 3 ～0.93g/cm 3 The density of (c).
[4] The extrusion-molded article according to any one of [1] to [3], wherein the linear low-density polyethylene resin has a melt index of 0.1g/10 min to 10g/10 min, preferably 1g/10 min to 5g/10 min.
[5] The extrusion-molded article according to any one of [1] to [4], wherein the acid-modified polyethylene resin is a polyethylene resin modified with an unsaturated carboxylic acid or an anhydride thereof.
[6] The extrusion-molded article according to [5], wherein the unsaturated carboxylic acid or an anhydride thereof is selected from acrylic acid, methacrylic acid, α -ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, chloromaleic acid, butenylsuccinic acid, and anhydrides thereof.
[7] The extrusion-molded article according to any one of [1] to [6], wherein the acid-modified polyethylene resin is a maleic anhydride-modified polyethylene resin derived from petroleum.
[8] The extrusion-molded article according to any one of [1] to [7], wherein the acid-modified polyethylene resin is a petroleum-derived maleic anhydride-modified low-density polyethylene resin, a petroleum-derived maleic anhydride-modified linear low-density polyethylene resin, or a mixture thereof.
[9]According to [8]The extrusion-molded article of (A), wherein the maleic anhydride-modified low-density polyethylene resin has a density of 0.91g/cm 3 ～0.93g/cm 3 Preferably 0.915g/cm 3 ～0.93g/cm 3 The maleic anhydride-modified linear low-density polyethylene resin has a density of 0.91g/cm 3 ～0.93g/cm 3 Preferably 0.915g/cm 3 ～0.93g/cm 3 The density of (c).
[10] The extrusion-molded article according to [8] or [9], wherein the maleic anhydride-modified low-density polyethylene resin has a melt index of 0.1g/10 min to 10g/10 min, preferably 1g/10 min to 5g/10min, and the maleic anhydride-modified linear low-density polyethylene resin has a melt index of 0.1g/10 min to 10g/10 min, preferably 1g/10 min to 5g/10 min.
[11] The extrusion-molded article according to any one of [1] to [10], wherein the intermediate layer contains a resin having a gas barrier property.
[12] The extrusion-molded article according to [11], wherein the resin having a gas barrier property is an ethylene-vinyl alcohol copolymer resin (EVOH), nylon (NY), polyvinyl alcohol (PVA), polyacrylonitrile (PAN), or polyvinylidene chloride (PVDC), and is preferably an ethylene-vinyl alcohol copolymer resin (EVOH).
[13] The extrusion-molded article according to any one of [1] to [12], wherein the inner layer and the outer layer each contain an acid-modified polyethylene resin derived from petroleum and a linear low-density polyethylene resin derived from a plant at a mass ratio of 9:1 to 4:6, preferably 9:1 to 5:5.
[14] The extrusion-molded article according to any one of [1] to [13], which has a cylindrical shape or an elliptic cylindrical shape.
[15] The extrusion-molded article according to any one of [1] to [14], wherein the extrusion-molded article has a circumferential length of 30 to 190mm, preferably 40 to 160mm.
[16] The extrusion-molded article according to any one of [1] to [15], wherein the extrusion-molded article has a thickness of 0.19 to 0.55mm, preferably 0.24 to 0.5 mm.
[17] The extrusion-molded article according to any one of [1] to [16], wherein the inner layer has a thickness of 0.12 to 0.25mm, preferably 0.14 to 0.24mm, the intermediate layer has a thickness of 0.01 to 0.1mm, preferably 0.02 to 0.08mm, and the outer layer has a thickness of 0.06 to 0.2mm, preferably 0.08 to 0.18 mm.
[18] A tube container, comprising: a container body including the extrusion-molded article according to any one of [1] to [17] in which one end is heat-sealed; and
and a lid fitting portion joined to the other end of the extrusion-molded product having one end heat-sealed.
Examples
[ example 1]
[1-1] production of extrusion molded article
As resins for the inner layer and the outer layer, the following resins a to E were prepared.
Resin A: petroleum-derived maleic anhydride-modified Low Density polyethylene (Density: 0.93 g/cm) 3 MFR:1.0g/10min (190 ℃,2.16kg load)) (hereinafter also referred to as "MA-modified LDPE-1");
resin B: petroleum-derived maleic anhydride-modified Low Density polyethylene (Density: 0.92 g/cm) 3 MFR:1.5g/10min (190 ℃,2.16kg load)) (hereinafter also referred to as "MA-modified LDPE-2");
resin C: petroleum-derived maleic anhydride-modified straight-chain low-density polyethylene (density: 0.926 g/cm) 3 MFR:1.2g/10min (190 ℃,2.16kg load)) (hereinafter also referred to as "MA-modified L-LDPE");
resin D: low-density polyethylene (density: 0.923 g/cm) derived from plants 3 MFR:2.7g/10 min (190 ℃,2.16kg load)) (hereinafter also referred to as "bioLDPE");
resin E: plant-derived linear low-density polyethylene (density: 0.916 g/cm) 3 MFR:1.0g/10min (190 ℃,2.16kg load)) (hereinafter also referred to as "organism")L-LDPE”)。
As a resin for the intermediate layer (barrier layer), an ethylene-vinyl alcohol copolymer (density: 1.14 g/cm) was prepared 3 MFR:12.0g/10min (210 ℃,2.16kg load)) (hereinafter also referred to as "EVOH").
< example 1A >
As the resins constituting the inner layer and the outer layer, a mixed resin obtained by dry-blending MA-modified LDPE-1 and bioldp E at a mass ratio of 50. To 100 parts by mass of the mixed resin, 0.1 part by mass of an antioxidant and 2.5 parts by mass of titanium oxide as a coloring pigment were added to obtain a mixture. The pellets of the mixture and the pellets of the ethylene-vinyl alcohol copolymer were charged into two hoppers of a single-shaft tube extruder, respectively. The set temperatures of the extruder and the die were set to 170 to 200 ℃ and a tube having a 3-layer structure of outer layer/intermediate layer/inner layer was formed under forming conditions of a production rate of 60 pieces/min and a drawing rate of 6.1 m/min. The obtained tube (i.e., extrusion-molded article) had a circumferential length of 93.2mm, a length of 100mm and an average wall thickness of 0.46mm.
< example 1B >
A pipe was produced in the same manner as in example 1A, except that a mixed resin obtained by dry-blending MA-modified LDPE-1, MA-modified L-LDPE and bio-LDPE at a mass ratio of 50.
< example 1C >
Pipes were produced in the same manner as in example 1A, except that a mixed resin obtained by dry-blending MA-modified LDPE-1 and bio L-LD PE at a mass ratio of 50.
< example 1D >
Pipes were produced in the same manner as in example 1A, except that a mixed resin obtained by dry blending MA-modified LDPE-1, MA-modified L-LDPE and bio-L-LDPE at a mass ratio of 50.
< example 1E >
Pipes were produced in the same manner as in example 1A, except that a mixed resin obtained by dry-blending MA-modified LDPE-1, MA-modified LDPE-2, and bio L-LDPE at a mass ratio of 50.
< example 1F >
A pipe was produced in the same manner as in example 1A, except that a mixed resin obtained by dry-blending MA-modified LDPE-1, MA-modified L-LDPE and bio-LDPE at a mass ratio of 60.
[1-2] evaluation method
The physical properties of the pipes of examples 1A to 1F were evaluated by the following methods.
< stress cracking resistance (ESCR resistance) >
After one end of the tube obtained was heat-sealed, a 5cm portion was cut from the end portion to obtain a test piece. The test piece was immersed in a 10% Igepal aqueous solution and stored at 65 ℃ for 168 hours in a thermostatic bath. After storage, the presence or absence of cracks was determined by visual observation.
Evaluation criteria
O: without cracking
And (delta): minute cracks were observed
X: major cracking (resulting in leakage of contents) was observed
< interlayer adhesion Strength >
The resulting tube was cut into a 15mm wide strip as a test piece. The test piece was partially peeled between the inner layer and the intermediate layer, and the non-peeled portion of the test piece was placed at the center, opened 180 degrees, and mounted on a grip plate of a tensile testing machine (manufactured by Shimadzu corporation, under the trade name AUTOGRAPH AGS-X). A T-type tensile test was conducted at a tensile rate of 50mm/min, and the stability value was defined as the interlaminar adhesion strength.
Evaluation criteria
O: 1.0kgf or more
And (delta): 0.4kgf or more and less than 1.0kgf
X: less than 0.4kgf
< continuous Molding Property >
When the tube was continuously formed, it was confirmed by visual observation whether or not the formed product was not deformed.
Evaluation criteria
O: without deformation
X: with deformation
[1-3] evaluation results
The resin compositions and evaluation results of the respective layers of the tubes of examples 1A to 1F are shown in tables 1 and 2 below. The numbers in the table indicate parts by mass.
In examples 1A, 1B, 1F, the inner and outer layers of the pipe respectively comprise a combination of "petroleum-derived acid-modified polyethylene resin" and "plant-derived low-density polyethylene resin (bio-LDPE)". In these examples, when the amount of the plant-derived polyethylene resin added was increased, the stress cracking resistance was reduced, the interlayer adhesion strength was slightly reduced, and deformation was observed in the molded article after continuous molding.
On the other hand, in examples 1C, 1D, and 1E, the inner layer and the outer layer of the pipe each contained a combination of "petroleum-derived acid-modified polyethylene resin" and "plant-derived linear low-density polyethylene resin (bio L-LDP E)". In these examples, even if the amount of the plant-derived polyethylene resin added was increased, the resulting molded article showed excellent stress cracking resistance and interlayer adhesion strength (0.4 kgf or more) without any problem in quality, and no deformation was observed in the molded article after continuous molding.
[ example 2]
Various pipes were produced by changing the amount of linear low-density polyethylene resin (biol L-LDPE) derived from plants and the circumferential length of the pipe, and the effects of the amount of biol L-LDPE and the circumferential length of the pipe on stress cracking resistance, interlayer adhesion strength and continuous moldability were examined.
[2-1] production of pipes
< example 2A >
As the resins constituting the inner layer and the outer layer, a mixed resin obtained by dry blending MA-modified LDPE-1, MA-modified LDPE-2, and bio L-LDPE at a mass ratio of 60. The circumferential length of the tube (i.e., extrusion-molded article) was 20mm, 60mm, 100mm, 160mm, 180mm, and 200mm. The tube had a length of 100mm and an average wall thickness of 0.46mm.
< example 2B >
As the resins constituting the inner layer and the outer layer, a mixed resin obtained by dry blending MA-modified LDPE-1, MA-modified LDPE-2, and bio L-LDPE at a mass ratio of 50. The circumferential length of the tube (i.e., extrusion-molded article) was 20mm, 60mm, 100mm, 160mm, 180mm, and 200mm. The tube had a length of 100mm and an average wall thickness of 0.46mm.
< example 2C >
As the resins constituting the inner layer and the outer layer, a mixed resin obtained by dry blending MA-modified LDPE-1, MA-modified LDPE-2, and bio L-LDPE at a mass ratio of 40. The circumferential length of the tube (i.e., extrusion-molded article) was 20mm, 60mm, 100mm, 160mm, 180mm, and 200mm. The length of the tube was 100mm and the average wall thickness was 0.46mm.
[2-2] evaluation method
As described in column [1-2], stress cracking resistance, interlaminar peeling adhesion strength and continuous moldability were evaluated.
[2-3] evaluation results
Example 2A (in the case where the amount of the plant-derived polyethylene resin was 10% by mass)
In example 2A, no cracks were observed in the stress cracking resistance test in any of the tube circumferences. In example 2A, the interlayer adhesion strength was not problematic in terms of quality in any tube circumference. In example 2A, in the case where the tube has any circumference, no deformation was observed in the formed product after the continuous forming.
Example 2B (in the case where the amount of the plant-derived polyethylene resin was 30% by mass)
In example 2B, no cracks were observed in the stress cracking resistance test in any of the tube circumferences. In example 2B, the interlayer adhesion strength tended to decrease in the pipe having a small circumference, but the interlayer adhesion strength was not problematic in terms of quality in any circumference of the pipe. In example 2B, in any case of the tube having any circumference, no deformation was observed in the molded article after the continuous molding.
Example 2C (when the amount of the plant-derived polyethylene resin was 50% by mass)
In example 2C, no cracks were observed in the stress cracking resistance test in the case of tubes having any circumference. In example 2C, the interlayer adhesion strength tended to decrease in the pipes having a small circumferential length and a large circumferential length, but the interlayer adhesion strength was not problematic in terms of quality in any of the pipes having the circumferential lengths. In example 2C, in the case where the tube has any circumference, no deformation was observed in the formed product after the continuous forming.
These results show that even when the amount of the plant-derived polyethylene resin and the circumferential length of the pipe are changed, excellent stress cracking resistance, excellent interlayer adhesion strength, and excellent production stability can be achieved.
Description of the symbols
1 … extrusion molded product, 1a … inner layer, 1b … intermediate layer, 1c … outer layer, 10 … tube container, 11 … container body, 12 … lid fitting portion, 21 … trunk, 22 … sealing portion, 31 … shoulder, 32 … mouth.
Claims (7)
1. An extrusion-molded article for a tube container, which has a 3-layer structure comprising an inner layer, an outer layer, and an intermediate layer interposed therebetween, the inner layer and the outer layer each comprising a petroleum-derived acid-modified polyethylene resin and a plant-derived linear low-density polyethylene resin.
2. The extrusion-molded article according to claim 1,
the linear low-density polyethylene resin is derived from sugarcane.
3. The extrusion-molded article according to claim 1 or 2,
the acid-modified polyethylene resin is a petroleum-derived maleic anhydride-modified low-density polyethylene resin, a petroleum-derived maleic anhydride-modified linear low-density polyethylene resin, or a mixture thereof.
4. The extrusion-molded article according to any one of claims 1 to 3,
the intermediate layer contains a resin having gas barrier properties.
5. The extrusion-molded article according to any one of claims 1 to 4,
the inner layer and the outer layer each contain an acid-modified polyethylene resin derived from petroleum and a linear low-density polyethylene resin derived from a plant at a mass ratio of 9:1 to 4:6.
6. The extrusion-molded article according to any one of claims 1 to 5, which has a circumferential length of 30 to 190 mm.
7. A tube container is provided with:
a container body comprising the extrusion-molded article according to any one of claims 1 to 6, one end of which is heat-sealed; and
and a lid fitting portion joined to the other end of the extrusion-molded product having the one end heat-sealed.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020102146A JP2021195149A (en) | 2020-06-12 | 2020-06-12 | Extruded product for tube container and tube container |
| JP2020-102146 | 2020-06-12 | ||
| PCT/JP2021/019229 WO2021251101A1 (en) | 2020-06-12 | 2021-05-20 | Extrusion-molded article for tube container and tube container |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115551787A true CN115551787A (en) | 2022-12-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202180035104.4A Pending CN115551787A (en) | 2020-06-12 | 2021-05-20 | Extrusion molded article for tube container, and tube container |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2021195149A (en) |
| CN (1) | CN115551787A (en) |
| WO (1) | WO2021251101A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7166656B2 (en) | 2020-11-13 | 2022-11-08 | 株式会社ベッセル・ジャパン | multi-layer extruded tube container |
| JP2022144924A (en) * | 2021-03-19 | 2022-10-03 | 大和製罐株式会社 | Tube container extrusion molding article and tube container |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006240666A (en) * | 2005-03-03 | 2006-09-14 | Takeuchi Press Ind Co Ltd | Multi-layer tubular container |
| JP6413231B2 (en) * | 2013-11-15 | 2018-10-31 | 大日本印刷株式会社 | Tube container |
-
2020
- 2020-06-12 JP JP2020102146A patent/JP2021195149A/en active Pending
-
2021
- 2021-05-20 CN CN202180035104.4A patent/CN115551787A/en active Pending
- 2021-05-20 WO PCT/JP2021/019229 patent/WO2021251101A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| JP2021195149A (en) | 2021-12-27 |
| WO2021251101A1 (en) | 2021-12-16 |
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