JP2537000C - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION   [0001]   [Industrial applications]   This application is related to U.S. Pat. Based on a continuation-in-part application of 07 / 721,813
US Patent Application, which is incorporated herein by reference.   [0002]   The present invention relates to paperboard laminates, especially for dry products that are not liquid.
Can be used to manufacture containers for products such as fruits, citrus juices and beverages
Non-foil paperboard laminate and its manufacturing method
The laminate is the essential oils and flavors of the product packed inside.
It also has excellent oxygen barrier properties in addition to the function to prevent loss of vitamins.   [0003]   [Prior art]   Conventionally, paperboard coated with low-density polyethylene (LDPE) is used for beverage containers.
Used for production, but satisfactory containers have not yet been produced.
In particular, paperboard coated with LDPE has a relatively high permeability to oxygen.
For this reason, oxidation was performed and the fragrance component and vitamins were sometimes damaged. Incense
Loss is not only due to oxidation, but scent components may migrate into the LDPE layer
Or even if absorbed, this kind of fragrance loss is called "scalping
"(Scalping) is called. For this reason, additional blocking to get the ideal container
Materials research has been done.   [0004]   Such oxidation loss of vitamin C, metal hull as a liner inside the container
It is possible to greatly reduce the amount by using a laminate having a metal layer. I
However, using metal foil is expensive and impractical
Was. Research into more economical foil alternatives has resulted in polypropylene and polyvinyl chloride.
Co-extruded poly such as Nilidene (PVdC), ethylene alcohol vinyl copolymer (EVOH)
Laminate structures using plywood have been developed as barriers. For example, Tan
U.S. Pat. 4,988,546; Gibbons et al.
U.S. Pat. 4,789,575 and 4,701,360 and Thomp
son et al. U.S. Pat. 4,513,036 from Huffman
U.S. Pat. 5.059,459 discloses these barrier materials.   [0005]   Not only does it cost less than a structure with foil, but also has a low level of LD
Since PE is used for the contact layer with the product, the paperboard containing the above-mentioned barrier material is not It is also excellent in terms of loss characteristics. Traditional commercial for juices and similar products
Many structural components for paperboard cartons are screened against oxygen and flavor oils.
Using a laminate containing ethylene alcohol vinyl copolymer as the shear
ing.   [0006]   Alternatively, for plastic bottles (Plastics World, 1986)
February pp. 36-38) Blocking polymer, plastic packaging material (Asep
tipak84, pp. 119-148), an alternative to cellophane (Platic
s World, July 1984, pp. 139-143. Niro proposed as 42-47)
Is used. However, plastic bottles or packaging barriers
Characteristics are completely different from those required for paperboard containers.
Useful barriers for bottles or packaging are not available for paperboard containers
In some cases. For paperboard containers, see US Pat.
l. No. 3,972,467 laminated with low density polyethylene layer to paperboard support
Nylon film with low density polyethylene product contact layer disclosed
Have been. In this case, the tensile yield strength of the nylon film is 218.2 kg / c.
m^Two(4,000 psi) or more and the elongation at break is about 200% or more. This
Such a laminated film structure is expensive and requires a complicated laminating apparatus. Also
For materials with such high tensile strength, cut the container blank from the cut-off paperboard material
Or difficult to mold containers.   [0007]   Thompson et al. U.S. Pat. At 4,777,088,
Shielding paperboard construction for flavored oils and oxygen retention in juice carton
A body is disclosed, on one or both sides of the structure, molding material and physical properties
Is an unspecified extruded nylon layer and trade name Surlyn from duPont
A special ionic copolymer material combination sold is applied. The above features
Permit No. No. 4,777,088, the nylon barrier paperboard wrapper described above.
In the minate structure, Surlyn is an essential component.   [0008]   Brown et al. U.S. Pat. 4,753,832 contains glyco
Modified polyethylene terephth
alate) (PET-G), and nylon oxygen barrier
Although a structural member using a barrier material as a support material that can also include a layer is disclosed,
The U.S. patent does not specify the type of nylon and the nylon material
Is not limited. U.S. Pat. Open to 4,753,832
As shown, PET-G is an essential component of the barrier paperboard laminate structure.
is there.   [0009]   Gibbons et al. U.S. Pat. 4,921,733
Is a crystalline material with a tensile strength of 703 kg / cm^Two(10,000 psi
Nylon 6, Nylon 11, and Nylon 12 polymers are Surly
n Caulking polymers such as ionomer resins and aluminum foil for paperboard containers
Abuse-resistent layer that can be used in combination with any oxygen barrier
s).   [0010]   [Problems to be solved by the invention]   However, conventional nylon films and the like are expensive and require complicated laminating equipment.
Semi-finished product for container due to its high cost
That it is difficult to cut paper from paperboard and form containers
There is.   [0011]   The present invention has been made in view of the above-mentioned problems of the prior art, and has an object of juice.
Improved heat-sealable laminate material for citrus and other juices
Do not permeate odorous / odorous components, have substantial blocking properties against vitamin C loss,
Equivalent to or better than currently used polymer barrier laminates
To provide a paperboard laminate that is easy to manufacture without sacrificing economics.
It is to be.   [0012]   [Means for Solving the Problems]   In order to achieve the above object, the present invention relates to the present invention having a barrier property against oxygen and odor.
A paperboard laminate is formed on a paperboard support and one side of the paperboard support,
A heat-sealable olefin polymer layer that forms the outer surface of the antenna;
A first tie layer, higher oxygen permeability than ethylene vinyl alcohol
An amorphous nylon layer and a second bonding layer are sequentially formed, and the other of the paperboard support
The inner sandwich layer formed on the surface of, the tensile yield strength is about 281.2k
g / cm^Two(Approximately 4,000 psi) or less and an inner sand with an elongation at break of about 200% or less
A sandwich layer, formed on the paperboard support on the same side as the inner sandwich layer.
A heat-sealable olefin that forms a product contact surface inside the container.
And a polymer layer.   [0013]   In a preferred embodiment of the present invention, preferably, the outer surface of the container is structured.
About 9.75-29.26 g / m of the resulting olefin polymer layer^Two(About 6
-18 lbs / ream) of the low-density polyethylene;
The sandwich layer is about 3.25-13.00 g / m.^Two(2-8 lbs / ream)
Low density polyethylene, about 3.25-9.75 g / m^Two(2-6 lbs / re
am), the first bonding layer of about 6.50-19.50 g / m;^Two(4-12 lbs
/ Ream) amorphous nylon, about 3.25-9.75 g / m^Two(2-6 lb
s / ream) and about 3.25-13.00 g / m2.^Two(2-8
  lbs / ream) of low density polyethylene. here,
The first and second tie layers are ethylene-based anhydride modified copolymers (anhydri
It is preferable to use a modified ethylene-based copolymer). Furthermore, before
The inner product contact surface polymer layer is about 8.13-24.38 g / m.^Two(About 5-15
  (lbs / ream) of low density polyethylene. This time,
The tensile yield strength of the inner sandwich layer is about 281.2 kg / cm^Two(About 4,
000 psi), and the elongation at break is preferably about 200% or less.
New   [0014]   In addition, it has excellent gas barrier properties and heat to prevent migration of essential oils, flavors and vitamins.
Method for producing a paperboard laminate of the present invention relating to the production of the above sealable paperboard laminate
The method uses a heat-sealable olefin polymer layer that constitutes the outer surface of the laminate.
Selecting a support material comprising a paperboard support formed on one side of the paperboard
And the first adhesive bonding layer, and amorphous, which has higher oxygen permeability than ethylene vinyl alcohol
A sandwich layer comprising a nylon layer and a second adhesive bonding layer, wherein the sandwich layer has a tensile yield strength.
Saga about 281.2kg / cm^Two(Approx. 4,000 psi) and elongation at break
Co-extruding a sandwich layer onto the other surface of the paperboard layer;
Heat sealing to the surface of the sandwich layer so that the other outer surface is formed
Extruding a possible olefin polymer layer.
I do.   [0015]   In a preferred embodiment of the present invention, the support material is provided on a surface of the paperboard support.
A flame-treated low heat-sealable paperboard support surface that has been subjected to the flame treatment.
Desirably, the density polyethylene polymer layer is formed by extrusion. Further, the plate
The low-density polyethylene polymer layer forming the outer surface of the paper has a coating weight of about 9.
75-13.0 g / m^Two(About 6-18 lbs / ream)
No. The sandwich layer has a thickness of about 3.25-13.00 g / m.^Two(About 2-8 lb
s / ream), the first adhesive bonding layer, and the amorphous
The iron layer, the second adhesive bonding layer, and about 3.25-13.00 g / m.^Two(About 2-
8 lbs / ream) of the first and second joints.
The layer is preferably composed of an ethylene-based anhydrous modified copolymer.   [0016]   [Action and effect]   Not only for dried products that are not liquid, but also for fruits, citrus juices and beverages,
The present invention is easy to manufacture, easy to manufacture, and reliable on site.
Such an improved non-foil laminate comprises an amorphous nylon
It consists of a laminated polymer sandwich coated with a mer barrier layer.   [0017]   Amorphous nylon is a relatively low-strength polymer material,
What is high-strength crystalline nylon material such as nylon 6 material conventionally used
Although they differ in physical properties, they are equivalent in their oxygen barrier properties. Surprisingly, high strength
Amorphous nylon with such low strength without additional polymer or oxygen barrier
It has been found that can be used as a barrier for a paperboard support.   [0018]   Thus, in one embodiment of the present invention, a heat sealable polio is used as the support material.
Uses a paperboard coated with a refining outer layer, preferably low density polyethylene
. Polyolefin / bonding layer / amorphous nylon / bonding layer / poly
A 5-layer sandwich structure composed of olefins is co-extruded to form a laminate layer.
ing. The laminate layer is applied in order from the outside of the container to the inside of the container.
/ Paperboard / polyolefin / bonding layer / amorphous nylon / bonding layer / polyolefin
It is composed of   [0019]   The polyolefin used for the sandwich layer is low density polyethylene
It is desirable. If necessary, to increase the thickness to increase the bending rigidity of the product
Made of heat-sealable polyolefin, preferably of low density polyethylene
Further extruding the article contact layer onto the inner surface of the coextruded sandwich layer.
Both are possible. Apply the co-extruded sandwich layer to the opposite side of the paperboard
The other side of the flame treated paperboard with polyolefin before
The entire paperboard can be manufactured in a single pass line.   [0020]   The final structure is a heat-sealable polyolefin on the inner and outer surfaces,
A barrier paperboard laminate preferably having polyethylene is obtained, the most desirable
As well as having a heat sealing property, the same blocking property as the conventional one is secured. In addition,
Processing into container blanks and containers compared to conventional structural members
It will be easier.   [0021]   In another embodiment of the present invention, a wrapper for a paperboard carton or container is provided. The mineralized structural member is made of paperboard, and the outer surface of the paperboard is made of polyolefin.
, Preferably coated with LDPE, the outer surface of the carton is heat sealable
It has become. Thus, in a single manufacturing step, the bonding layer / amorphous nylon / bonding layer
The laminated three-layer sandwich structure is co-extruded onto the inner surface of the paperboard, and then further extruded.
Extrude a polyolefin layer on the exposed bonding layer to form a product contact layer
You. Here, the polyolefin used as the product contact layer is a low-density polyethylene.
Is desirable.   [0022]   Use of the laminate of the present invention facilitates the assembly of the carton,
Carton is a good gas for liquids, dried products and flavor oils
It has a blocking property, holds vitamin C of citrus juice contained therein,
Prevent loss and extend the shelf life of these products. Furthermore, it is made with the laminate of the present invention.
In the case of manufactured carton semi-finished products, lamination with ethylene alcohol vinyl barrier layer
Weave bending for carton blanks compared to carton blanks made of minate
The advantage is that the runnability of the device is improved and the manufacturing process can be simplified.
.   [0023]   【Example】   Hereinafter, preferred embodiments of the paperboard container according to the present invention will be described with reference to the drawings.
You.   [0024]   Referring to FIGS. 1 and 2, a paperboard according to a first embodiment of the present invention will be described.
This will be described below.   [0025]   First, one surface of the paperboard support 1 is subjected to a flame or corona treatment. Next, low density
Polyethylene (hereinafter referred to as LDPE) layer 2 at about 315.56 ° C. (about 600 °
Extrude and coat onto the treated surface of the paperboard 1 at the temperature of F). 282.22 ° C-32
Desirable temperature is 6.67 ° C (540 ° F-620 ° F) and good adhesion to paperboard
The outer surface of the laminate is configured. If necessary,
Since the LDPE coating layer is formed on the uncoated paperboard support in one step, Instead, a paperboard support previously coated with LDPE may be used.   [0026]   The other inner surface of the paperboard support is subjected to a flame or corona treatment to provide two layers of vinyl.
Sandwiched between tie layers 32 and 32 'and two LDPE coating layers 33 and 33'
Co-extrusion of the inner surface directly with five sandwich layers 3 containing amorphous nylon 31
Cover. The temperature of the extrusion coating is determined by the amorphous nylon 31 and the bonding layers 32, 32 '.
To prevent polymer deterioration and maintain good polymer extrusion coating characteristics.
I have to control. In three experimental examples relating to the production of this laminate,
The supply temperature of each material of the sandwich structure to the extruder is shown below.   [0027]   Finally, the product contact layer 4 made of low-density polyethylene is applied to the five-layer sandwich 3
Extruded onto the inner surface of the The total weight of polymer extruded onto the paperboard inner surface is about 8
9.40 g / m^Two(55 lbs / ream) or less. (here
The size of Ream is 278.7m^Two(3,000 sq. Feet)
. ) The laminate is easily creased and cut into semi-finished products. After this,
Bend these semi-processed crystals by the conventional method and perform side seam and heat seal treatment.
You. The semi-finished product produced in this way is always filled with conventional equipment in the usual way.
Filling and sealing can be performed.   [0028]   According to a second embodiment of the present invention, as shown in FIG.
An amorphous nylon layer 51 is provided at the center so that either one of them is in contact with the paperboard support 1.
And a three-layer sandwich structure in which both ends are sandwiched between two vinyl bonding layers 52 and 52 '.
The structure 5 is co-extruded on the surface of the paperboard support 1. Next, the polyolefin layer 4
The surface of the bonding layer 52 'is coated to form a product contact surface.   [0029]   In another embodiment of FIG. 3b, a coated layer of LDPE is formed on both sides of the paperboard in advance.
The sandwich layer is co-extruded directly onto the surface of the formed support material. In FIG. 3a
If the co-extruded sandwich is three layers as shown, the final
The structure is substantially the same as that described above, but further between the paperboard and the co-extruded layer.
A layer of polyolefin is sandwiched.   [0030]   In the case of such a coating treatment, a symmetric layer structure is generally most easily coextruded.
Preferably, the co-extruded sandwich layer has a symmetric structure. However,
If necessary, perform asymmetric coextrusion
Part of the co-extruded sandwich structure can be the product contact layer.   [0031]   Olefin polymers suitable for the present invention are heat sealable, polypropylene
, High density polyethylene, medium density polyethylene, low density polyethylene, low linear density
(linear low density)
However, low density polyethylene is particularly preferred. Commercially available extruded paint level polyolefin
Can be used in the present invention. Olefin polymers contain additives
The desired fluidity, tackiness, or heat sealing properties.   [0032]   The paperboard used in the present invention may be any suitable high-quality paperboard material (pap
evboard stock). The basis weight of the paperboard is about 243.81-487
. 62g / m^Two(About 150-300 lbs / ream), preferably about
422.60 g / m^Two(260 lbs / ream). Any one of paperboard
Flame on one or both sides to facilitate adhesion to the next polymer layer, or
Corona treatment and / or undercoat treatment has been performed. As a primer used
Is composed of polyethylene amine (PEI) or ethylene vinyl acetate
There is   [0033]   The amorphous nylon used in the present invention is suitable for co-extruding onto the surface of a paperboard support.
It is suitable. To simplify the manufacturing process, the coextruded polymer and The elongation at break of the sandwich layer composed of amorphous nylon is about 200% or less.
And the tensile yield strength is about 281.2 kg / cm^Two(About 4,000 psi) or less
is there. The tensile yield strength of amorphous nylon itself is 703 kg / cm^Two(10,000
psi) and the elongation at break is most preferably 200% or less. preferable
As amorphous nylon, from DuPont Corporation of the United States
There is Selar PA3426 available for sale. Nylon 6 or nylon 6-6
For example, in the case of nylon having substantially crystallinity, the yield point is 703 kg / cm^Two(
It has a tensile strength of 10,000 psi or more and an elongation at break of 20 psi.
0% or more, the effect of the present invention cannot be obtained with this material.   [0034]   The bonding layer resin according to the present invention, which is suitable for co-extrusion with amorphous nylon, comprises an amorphous nylon.
It is made of a resin that has excellent adhesion to iron and polyolefin. Proper bonding
Bonding layer resins having properties include anhydride modified copolymers, especially anhydride modified ethylene.
Those containing a copolymer as a component are preferred. In addition, anhydride modified low linear density / low density
Tylene copolymer (anhydride modified linear low / low density ethylene copo
lymers). Suitable as a bonding layer material in the present invention
Anhydrous modified low linear density / low density ethylene copolymers include US DuPon
There is Vinyl E388 available from t Corporation. Also,
Other DuPont products include anhydrous modified ethylene acrylate copolymer.
-(Vinyl E369) can also be used as the bonding layer. In addition, the United States
Patent No. 4,087,587 and 4,087,588 have a bonding layer material
Suitable materials are disclosed, both patents being incorporated herein by reference.
Is quoted. The materials disclosed in these patents are trade names Plexar.
Sold.   [0035]   The barrier laminate produced according to the present invention has excellent barrier properties,
United States Food and Drug Administration (FDA) on food contact packaging
Conforms to the requirements of For example, the present invention comprising a five-layer sandwich structure
Of about 9.75-29.26 g / m^Two(6-18 lbs / rea m) an outer covering made of LDPE, a paperboard whose thickness is determined by the size of the carton,
And a sandwich layer coextruded on the inner surface of the paperboard.
The sandwich layer further comprises about 3.25 to 13.00 g / m^Two(About 2-8 lbs
/ Ream) LDPE and about 3.25-9.75 g / m^Two(2-6 lbs /
Ream) adhesive bonding layer (vinyl E388) and about 6.50-19.50 g / m
^Two(4-12 lbs / ream) of amorphous nylon (Selar PA 34)
26) and about 3.25-9.75 g / m^Two(2-6 lbs / ream)
Layer (vinyl E388) and about 3.25-13.00 g / m^Two(2-8 lbs /
(ream) LDPE and about 8.13-24.38 g / m^Two(5-15 lbs
/ Ream) LDPE. Lamine of the present invention
Approximately 19.50 g / m^Two(12 lbs / ream) LDPE external coating
Layer and about 422.60 g / m^Two(260 lbs / ream) paperboard and about 4.
88 g / m^Two(3 lbs / ream) LDPE and about 6.50 g / m^Two(4
lbs / ream) of vinyl E388 and about 9.75 g / m^Two(6 lbs / r
eam) Selar PA and about 6.50 g / m^Two(4 lbs / ream)
Of vinyl E388 and about 4.88 g / m^TwoLDPE of (3 lbs / ream)
And about 11.38 g / m^Two(7 lbs / ream) LDPE product contact layer
Preferably, the laminate comprises about 19.50 g / m2.^Two(12
  lbs / ream) of LDPE outer coating layer and about 422.60 g / m^Two(26
0 lbs / ream) and about 9.75 g / m^Two(6 lbs / ream
) And about 6.50 g / m^Two(4 lbs / ream) vinyl E38
8 and about 9.75 g / m^Two(6 lbs / realm) Selar PA and about
6.50 g / m^Two(4 lbs / ream) vinyl E388 and about 9.75 g
/ M^Two(6 lbs / ream) LDPE and about 11.38 g / m^Two(7 lb
Most preferably, it comprises a product contact layer comprising LDPE (s / ream).
No. Here, the size of the Ream is 278.7 m.^Two(3,000 ft^Two).   [0036]   The laminate of the present invention having a four-layer sandwich has a thickness of a carton.
About 9.75-29.26 g / m formed on the surface of the determined paperboard^Two(About 6-1 8 lbs / ream) LDPE coating layer and applied on the inner surface of the paperboard
A co-extruded sandwich layer, the sandwich layer comprising about 3.
25-9.75 g / m^Two(About 2-6 lbs / ream) ethylene as base
About 6.50 to 19.50 g / m^Two(4-12
lbs / ream) of amorphous nylon and about 3.25-9.75 g / m2.^Two(2-
6 lbs / ream) ethylene-based anhydrous modified copolymer tie layer;
About 8.13-24.38 g / m^Two(5-15 lbs / ream) LDPE layer
It is composed of   [0037]   Surprisingly, the laminate of the present invention is an ethylene alcohol vinyl copolymer.
It was confirmed that the laminate had the same barrier properties as a laminate made of As shown in FIG.
As noted, refrigerated packaged juice containers are usually exposed to humid environments.
Yes, even in such a state, compared to ethylene alcohol vinyl copolymer,
Such properties are usually not expected because of the high oxygen permeability of crystalline nylon.
It is.   [0038]   First experimental example   A laminate according to the present invention is produced on an extrusion line in which three extruders are arranged in series.
. First, using the first extruder, apply about 1 mm to the left side of the flame treated paperboard support.
9.50 g / m^TwoApply (12 lbs / ream) LDPE. Next, before
The other side of the support is flame treated and primed with PEI. Second extrusion position
Then, from three extruders, LDPE, Selar PA amorphous nylon, vinyl E
388 into one extrusion mold and LDPE / vinyl E388 / Selar PA
/ Copolymer E388 / LDPE to form a five-layer co-extruded sandwich layer
. Finally, at the position of the third extruder, a table of said co-extruded sandwich layers
Extrude about 3.17 kg (7 lbs) of LDPE layer on the face. For shielding paperboard structural members
There was no problem in the production of semi-finished containers and containers.   [0039]   Second experimental example   Comparative study on vitamin C, filling volume and decomposition oxygen characteristics
The test was performed using a container made of wood. The laminated structural member is made of an amorphous metal.
Ron barrier layer and conventional ethylene alcohol vinyl copolymer, PET and LDP
It is composed of an E blocking layer structural member. The laminate has the structure shown in Table 1
It is manufactured to become.   [0040] [Table 1]   [0041] Plexar 177 is the Quantum Chemical Corporation
This is a bonding layer material sold by Tion. PET is polyethylene
Abbreviation of phthalate. FIGS. 5, 6, and 7 relate to the four laminate structures.
4 shows the results of each of vitamin C, filling space, and decomposed oxygen. Made with the present invention
The oxygen permeability of the laminated structural member and the EVOH lamine shown in Table 2
Compare the oxygen permeability of the sheet and PET laminate.   [0042] [Table 2]   [0043]   Vitamin C retention capacity, oxygen level at filling volume, and decomposed oxygen level were examined.
Inject the refrigerated juice into the paperboard container made by laminating
Stored at a temperature of 5 ° C. for 8 weeks. Cartons were removed weekly for analysis. Vita
The measurement of Min C was performed by AOAC (Association of Official Agricultural Chemists, Ch. (icago). Take 3 aliquots of juice and for each aliquot
A titration was performed. Filling empty volume is based on Macon HS-750 headspace analysis.
It was measured using a laser. 10 ml of gas in the filling space is discharged through the airtight bulkhead.
, Injected into the analyzer. The analyzer is a standard gas containing 0.5% oxygen.
Calibrated with air mix and room air. Decomposed oxygen is Yellow Spring
gs Instruments, Inc. Model 5739 Decomposition oxygen probe
The measurement was performed using a model 58 decomposition oxygen meter equipped with a probe. The juice container
Stir and pour 125 ml into a 250 ml beaker. When the reading is constant
The juice was agitated with the probe until a bell was reached. This probe is
Placed in an airtight container together with the sponge soaked in air with 100% relative humidity
Calibrated.   [0044]   Tables 3 and 4 show the experimental results.   [0045] [Table 3]   [0046] [Table 4]   [0047] [Table 5]  [0048] [Table 6]   [0049] From the experimental results in Table 4, the high oxygen permeation characteristics shown in the above-mentioned data (FIG. 4) were measured.
Despite the fixed results (Table 2), the amorphous nylon barrier laminate structure of the present invention
The vitamin C retention properties of the resulting carton (Structure 5) are surprisingly EVOH shielding. Exactly equivalent to the holding characteristics of a carton consisting of a sheared laminate structure (Structures 2-4)
.   [0050]   Thus, the barrier properties of the barrier paperboard laminates of the present invention are among the most currently available.
The desired product, that is, the product containing the ethylene alcohol vinyl copolymer
It turns out to be equal. Further, in the case of the barrier board laminate of the present invention, the high strength polymer
Cutting, weaving and heat-sealing compared to insulation board laminates
Easy to process in the equipment for the production of durable carton
.   [0051]   Third experimental example   Amorphous nylon, nylon 6, nylon 6 film material with PVDC coating layer,
Comparative study of tensile strength and elongation characteristics of the co-extruded sandwich structure of Fig. 1
Was performed according to ASTM method D882. Table 5 shows the results.   [0052] [Table 7]  [0053] As can be seen from Table 5, compared to nylon 6 and nylon 6 with a PVDC coating layer,
Amorphous nylon has low elongation at break, and the coextruded sand of the present invention. The switch structure has a low tensile strength in addition to a low elongation at the breaking point.
Manufacturing characteristics can be obtained.   [0054]   Hereinafter, embodiments of the present invention will be described in sections.   Embodiment 1 (a) Paperboard support;   (B) formed on one side of the paperboard support and constituting the outer surface of the container;
A heat sealable olefin polymer layer;   (C) sequentially, a first tie layer, ethylene vinyl alcohol (
(EVOH) composed of an amorphous nylon layer having a higher oxygen permeability and a second bonding layer.
An inner sandwich layer formed on the other side of the paperboard support,
, Tensile yield strength is about 281.2kg / cm^Two(Approximately 4,000 psi) or less and elongation at break is approximately 200
 % Or less of the inner sandwich layer,   (D) formed on the paperboard support on the same side as the inner sandwich layer;
A heat-sealable olefin port forming a product contact surface inside the container.
And a product contact surface on the inside and outside, characterized in that the product contact surface
Paperboard container.   Embodiment 2 The inner sandwich layer comprises, in order, a first polyolefin layer,
The first bonding layer, the amorphous nylon layer, the second bonding layer, the second polyolefin
2. The paperboard container of claim 1, wherein the paperboard container is comprised of layers.   Embodiment 3 The inner sandwich layer is a low-density polyethylene polymer layer.
And the first bonding layer, the amorphous nylon layer, the second bonding layer,
3. The paperboard container according to claim 2, wherein the paperboard container comprises a polyethylene layer.
-   [Embodiment 4] The first and second bonding layers are made of an anhydride modified based on ethylene.
Containing an amorphous modified ethylene-based copolymer
2. The paperboard container according to claim 1, wherein:   Embodiment 5 The first and second bonding layers are made of an ethylene-based anhydride layer.
4. The paperboard container according to claim 3, characterized in that the paperboard container comprises a high quality copolymer.   Embodiment 6 The inner sandwich layer has a thickness of about 3.25 to 13.00 g / m^Two(2-8 lbs / ream) low density polyethylene, about 3.25-9.7
5g / m^Two(2-6 lbs / ream) of the first bonding layer, about 6.50-19
. 50g / m^Two(4-12 lbs / ream) amorphous nylon, about 3.25
-9.75 g / m^Two(2-6 lbs / ream) of the second bonding layer;
25-13.00 g / m^Two(2-8 lbs / ream) low density polyethylene
3. The paperboard container according to claim 3, wherein the paperboard container comprises:   Embodiment 7 The sandwich layer is co-extruded, and
The inner product contact surface is about 8.13-24.3 formed on the surface of the sandwich layer.
8g / m^Two(5-15 lbs / ream) low density polyethylene
Olefin polymer which is a coated layer and constitutes the outer surface of the container
The layer is about 9.75-29.26 g / m^Two(6-18 lbs / ream) low density
7. The paperboard container according to claim 6, wherein the paperboard container is made of polyethylene.
Ner.   Embodiment 8 The first and second bonding layers are made of an anhydride based on ethylene.
8. The paperboard container of claim 7, wherein the paperboard container is made of a porous copolymer.   Embodiment 9 The coating amount of the amorphous nylon is about 6.50 to 19.50 g /
m^Two(4-12 lbs / ream).
Paperboard container.   Embodiment 10 The inner product contact surface polymer layer is about 8.13-24.3.
8g / m^Two(About 5-15 lbs / ream) low density polyethylene
2. The paperboard container of claim 1, wherein   Embodiment 11 The olefin resin forming the outer surface of the container
The rimer layer is about 9.75-29.26 g / m^Two(About 6-18 lbs / ream
2. The plate according to claim 1, wherein the plate is made of low-density polyethylene according to (1).
Paper container.   Embodiment 12 The inner sandwich layer has a weight of about 6.50-19.50 g /
m^Two(About 4-12 lbs / ream) of amorphous nylon-containing layer.
2. The paperboard container according to claim 1, wherein the paperboard container is a paperboard container.   Embodiment 13 The inner sandwich layer has a weight of about 3.25-9.75 g / m^Two(2-6 lbs / ream) of said first tie layer and about 6.50-19.5
0 g / m^Two(4-12 lbs / ream) of amorphous nylon and about (3.25 lbs / ream)
-9.75 g / m^Two(2-6 lbs / ream) of the second bonding layer;
13-24.38 g / m^Two(5-15 lbs / ream) low density polyethylene
2. The paperboard container according to claim 1, wherein the paperboard container is formed of a paperboard container.   Embodiment 14 The first and second bonding layers are made of an ethylene-based anhydride.
14. The paperboard container according to embodiment 13, comprising a modified copolymer as a component.
-   Embodiment 15 The outer surface layer is about 19.50 g / m^Two(12 lbs / rea
m) low-density polyethylene with an inner sandwich layer of about 9.75 g / m^Two
(6 lbs / ream) low density polyethylene and about 6.50 g / m^Two(4
lbs / ream) ethylene-based anhydrous modified copolymer tie layer and about 9
. 75 g / m^Two(6 lbs / ream) of amorphous nylon and about 6.50 g /
m^Two(4 lbs / ream) ethylene-based anhydrous modified copolymer bonding
Layer and about 9.75 g / m^Two(6 lbs / ream) low density polyethylene
The product contact layer is about 11.38 g / m^Two(7 lbs / ream) low density poly
The inner sandwich layer has a tensile yield strength of slightly
About 281.2 kg / cm^Two(About 4,000 psi) and an elongation at break of about 20
The paperboard container of claim 1 wherein the paperboard container is 0% or less.   Embodiment 16 The outer surface layer is about 19.50 g / m^Two(12 lbs / rea
m) low-density polyethylene with an inner sandwich layer of about 4.88 g / m^Two
(3 lbs / ream) low density polyethylene and about 6.50 g / m^Two(4
lbs / ream) ethylene-based anhydrous modified copolymer tie layer and about 9
. 75 g / m^Two(6 lbs / ream) of amorphous nylon and about 6.50 g /
m^Two(4 lbs / ream) ethylene-based anhydrous modified copolymer bonding
Layer and about 4.88 g / m^Two(3 lbs / ream) low density polyethylene
The product contact layer is about 11.38 g / m^Two(7 lbs / ream) low density poly
The inner sandwich layer has a tensile yield strength of slightly
About 281.2 kg / cm^Two(About 4,000 psi) and an elongation at break of about 2 2. The paperboard container according to claim 1, which is less than or equal to 00%.
.   Embodiment 17 (a) Heat Sealable Forming Outer Surface of Laminate
A support comprising a paperboard support having an olefin polymer layer formed on one side of the paperboard.
Selecting materials to have,   (B) Oxygen permeability from the first adhesive bonding layer and ethylene vinyl alcohol (EVOH)
A sandwich layer consisting of a highly transient amorphous nylon layer and a second adhesive bonding layer.
The tensile yield strength is about 281.2kg / cm^Two(Approx. 4,000psi) and the elongation at break
Co-extruding less than about 200% of a sandwich layer onto the other surface of the paperboard layer
When,   (C) the sandwich layer so that the other outer surface of the laminate is formed;
Extruding a heat-sealable olefin polymer layer on the surface of
It has excellent gas barrier properties, and prevents migration of essential oils, flavors and vitamins.
For producing a heat-sealable paperboard laminate with improved resistance.   Embodiment 18 The step of flame-treating the surface of the paperboard support comprises the steps of:
Low density polyethylene polymer heat-sealable on the coated paperboard support surface
Forming the support material through extrusion coating with a layer.
18. The method for producing a paperboard laminate according to item 17.   Embodiment 19 The low density polyethylene forming the outer surface of the paperboard
The polymer layer has a coating amount of about 9.75 to 13.00 g / m.^Two(About 6-18 lbs
/ Ream), which comprises a heat-sealable layer.
A method for producing a paperboard laminate according to aspect 17.   Embodiment 20 The sandwich layer comprises a first polyolefin layer and the first polyolefin layer.
One bonding layer, the amorphous nylon layer, the second bonding layer, and a second polyolefin
18. A paperboard laminate according to embodiment 17, characterized in that the paperboard laminate is composed of layers in sequence
Construction method.   Embodiment 21 The sandwich layer has a thickness of about 3.25-13.00 g / m.^Two
(About 2-8 lbs / ream) low density polyethylene and the first adhesive bonding layer
And the amorphous nylon layer, the second adhesive bonding layer, and about 3.25-13.00.
g / m^Two(About 2-8 lbs / ream) low density polyethylene
21. The method for producing a paperboard laminate according to embodiment 20, wherein   Embodiment 22 The sandwich layer has a thickness of about 3.25-13.00 g / m.^Two
(About 2-8 lbs / ream) low density polyethylene and about 3.25-9.7
5g / m^Two(About 2-6 lbs / ream) of said first adhesive bonding layer and said amorphous
Quality nylon layer and about 3.25-9.75 g / m^Two(About 2-6 lbs / ream
)) And about 3.25-13.00 g / m.^Two(About 2-8 lb
(s / ream) low-density polyethylene.
22. The method for producing a paperboard laminate according to item 21.   Embodiment 23 The first and second bonding layers are made of an ethylene-based anhydrous modification.
23. A paperboard laminate according to claim 22, comprising a porous copolymer as a component.
Production method.   Embodiment 24 On one side of the paperboard support is about 9.75-29.26 g.
/ M^Two(About 6-18 lbs / ream) heat-sealable low density polyethylene
A renpolymer layer is applied and the inner sandwich layer is about 3.25
-13.00 g / m^Two(About 2-8 lbs / ream) low density polyethylene
, About 3.25-9.75 g / m^Two(2-6 lbs / ream) of the first adhesion
Bonding layer and about 6.50-19.50 g / m^Two(4-12 lbs / ream)
Amorphous nylon and about 3.25-9.75 g / m^Two(2-6 lbs / ream
) And the second adhesive bonding layer, and the other surface of the paperboard support is
About 3.25 to 13.00 g / m^Two(2-8 lbs / ream) low density polye
The product contact layer is about 8.13-24.38 g / m
^Two(5-15 lbs / ream) low density polyethylene
21. The method for producing a paperboard laminate according to embodiment 20, wherein:   Embodiment 25 The inner sandwich layer is an ethylene-based anhydrous modification.
Bonding layer of a porous copolymer, an amorphous nylon layer, and an ethylene-based anhydrous
A second bonding layer of a modified copolymer, and the polyolefin layer
Is about 8.13-24.38 g / m^Two(5-15 lbs / ream)
19. The paperboard lamine according to embodiment 18, wherein the paperboard lamine is composed of a polyolefin.
Sheet manufacturing method.   Embodiment 26 The inner sandwich layer has a thickness of about 3.25-9.75 g / m^Two(2-6 lbs / ream) anhydrous modified copolymer bonding layer
Layer and about 3.25-9.75 g / m^Two(2-6 lbs / ream) anhydrous
The plate of embodiment 25, comprising a modified copolymer tie layer.
Paper laminate manufacturing method.   Embodiment 27 On one side of the paperboard is about 9.75-29.26 g / m^Two
(About 6-18 lbs / ream) heat-sealable low-density polyethylene
A rimer layer is applied and the inner sandwich layer is about 3.25-9.
75 g / m^Two(2-6 lbs / ream) ethylene-based anhydrous modified copolymer
Said first tie layer of polymer and about 6.50-19.50 g / m^Two(4-12 l
bs / ream) amorphous nylon and about 3.25-9.75 g / m^Two(2-6
  lbs / ream) of the ethylene-based anhydrous modified copolymer.
Embodiment 25. The paperboard laminate production according to Embodiment 25, which is constituted by laminated layers.
Method.   Twenty-eighth Embodiment A heat-sealable male paperboard formed on one side of the paperboard
Refin is about 19.50 g / m^Two(12 lbs / ream) low density polyethylene
And the inner sandwich layer is about 9.75 g / m^Two(6 lbs / re
am) low density polyethylene and about 6.50 g / m^Two(4 lbs / ream)
An ethylene-based anhydrous modified copolymer tie layer and about 9.75 g / m^Two(6
  lbs / ream) of amorphous nylon and about 6.50 g / m^Two(4 lbs /
a) an ethylene-based anhydrous modified copolymer tie layer of about 9.75 g.
/ M^Two(6 lbs / ream) of low density polyethylene,
Heat sealable olefin polymer formed on the surface of the sandwich layer
The layer is about 11.38 g / m^Two(7 lbs / ream) low density polyethylene
And the inner sandwich layer has a tensile yield strength of only about 281.2 kg / cm.^Two
(About 4,000 psi) and elongation at break is about 200% or less
21. The method for manufacturing a paperboard laminate according to embodiment 20, wherein   Embodiment 29 A heat-sealable unit formed on one side of the paperboard.
Refin is about 19.50 g / m^Two(12 lbs / ream) low density polyethylene
And the inner sandwich layer is about 4.88 g / m^Two(3 lbs / r eam) low density polyethylene and about 6.50 g / m^Two(4 lbs / ream
A) an ethylene-based anhydrous modified copolymer tie layer of about 9.75 g / m2;^Two(
6 lbs / ream) of amorphous nylon and about 6.50 g / m^Two(4 lbs
/ Ream) ethylene-based anhydrous modified copolymer tie layer and about 4.88
g / m^Two(3 lbs / ream) low density polyethylene
Heat sealable olefin polymer formed on the surface of the sandwich layer
ー is about 11.38 g / m^Two(7 lbs / ream) low density polyethylene
And the inner sandwich layer has a tensile yield strength of only about 281.2 kg / cm.^Two
(About 4,000 psi) and elongation at break is about 200% or less
21. The method for manufacturing a paperboard laminate according to embodiment 20, wherein

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view showing the structure of a barrier paperboard laminate according to the present invention. FIG. 2 is a block diagram showing a general manufacturing process of the barrier paperboard laminate according to the present invention. FIG. 3B is a cross-sectional view showing a shielding paperboard laminate according to another embodiment of the present invention.
FIG. 4 is a cross-sectional view showing a barrier paperboard laminate according to another embodiment of the present invention. FIG. 4 is a graph showing changes in humidity and oxygen permeability of amorphous nylon and ethylene alcohol vinyl copolymer. FIG. FIG. 6 is a graph showing the amount of oxygen in the headspace of the carton tested in the second experimental example. FIG. 7 is a graph showing the amount of oxygen in the headspace of the carton tested in the second experimental example. Graph showing the amount of decomposed oxygen in the juice contained in the filled carton [Description of symbols] 1 Paperboard support 2 LDPE layer 3 Sandwich layer 4 Product contact layer 5 Three-layer sandwich layer 31 Amorphous nylon 32, 32 ' Vinyl bonding layer 33, 33 'LDPE coating layer 51 Amorphous nylon 52, 52' Vinyl bonding layer

Claims (1)

Claims: 1. A (a) paperboard support; and (b) a heat-sealable olefin polymer layer formed on one side of the paperboard support and constituting an outer surface of a container. (C) sequentially comprising a first tie layer, an amorphous nylon layer having a higher oxygen permeability than ethylene vinyl alcohol, and a second tie layer, on the other surface of the paperboard support. An inner sandwich layer having a tensile yield strength of about 281.2 kg / cm ² (about 4,000 psi) or less and an elongation at break of about 200% or less; An outer surface formed on the paperboard support on the same side as the inner sandwich layer and comprising a heat-sealable olefin polymer layer constituting a product contact surface inside the container. Product contact inside Paperboard container with surface. 2. The method according to claim 1, wherein the inner sandwich layer comprises a first polyolefin layer, the first bonding layer, the amorphous nylon layer, the second bonding layer, and a second polyolefin layer in this order. The paperboard container of claim 1 wherein 3. The inner sandwich layer is composed of a low density polyethylene polymer layer, the first bonding layer, the amorphous nylon layer, the second bonding layer, and a low density polyethylene layer. The paperboard container according to claim 2, characterized in that: 4. The inner sandwich layer has a thickness of about 3.25 to 13.00 g / m ^2.
(2-8 lbs / ream) low density polyethylene, about 3.25-9.75 g
/ M ² (2-6 lbs / ream) of the first bonding layer, about 6.50-19. 50 g / m ² (4-12 lbs / ream) of amorphous nylon, about 3.25-
9.75 g / m ² (2-6 lbs / ream) of the second bonding layer and about 3.2
4. The paperboard container according to claim 3, wherein the paperboard container is composed of low density polyethylene of 5-13.00 g / m < ² > (2-8 lbs / ream). 5. The sandwich layer is co-extruded, and the inner product contact surface is formed between about 8.13-24.38 formed on the surface of the sandwich layer.
g / m ² (5-15 lbs / ream) of low density polyethylene, a separate coating layer comprising the outer surface of the container, the olefin polymer layer comprising about 9.75-29.26 g / m 2. 5. The paperboard container according to claim 4, wherein the paperboard container is composed of ² (6-18 lbs / ream) low density polyethylene. 6. The inner sandwich layer has a thickness of about 3.25-9.75 g / m ² (
2-6 lbs / ream) of the first tie layer and about 6.50-19.50 g /
and amorphous nylon m ² (4 over 12 lbs / ream), about (3.25-9.
75 g / m ² (2-6 lbs / ream) of the second bonding layer;
2. The paperboard container according to claim 1, wherein the paperboard container is composed of low density polyethylene at 24.38 g / m < ² > (5-15 lbs / ream). 7. A method comprising: (a) selecting a support material comprising a paperboard support having a heat-sealable olefin polymer layer constituting the outer surface of the laminate formed on one side of the paperboard; A sandwich layer comprising an adhesive bonding layer, an amorphous nylon layer having higher oxygen permeability than ethylene vinyl alcohol, and a second adhesive bonding layer, and having a tensile yield strength of about 281.2 kg / cm ² (about 4,000 (c) co-extruding a sandwich layer having an elongation at break of less than about 200% onto the other surface of the paperboard layer; and (c) forming said other outer surface of the laminate to form said other outer surface of the laminate. The heat-sealed olefin polymer layer is extruded on the surface of the sandwich layer, and has excellent gas barrier properties. A method of manufacturing a paperboard laminate that can be controlled. 8. The method according to claim 1, wherein the sandwich layer includes a first polyolefin layer, the first bonding layer, the amorphous nylon layer, the second bonding layer, and a second polyolefin layer. The method for producing a paperboard laminate according to claim 7, characterized in that: 9. The one side of the paperboard support has about 9.75-29.26 g / m2.
² (approximately 6-18 lbs / ream) of a heat-sealable low density polyethylene polymer layer, wherein the inner sandwich layer comprises approximately 3.25-1.
About 3.00 g / m ² (about 2-8 lbs / ream) of the low density polyethylene, about 3.25-9.75 g / m ² (2-6 lbs / ream) of the first adhesive bonding layer; 4.50-19.50 g / m ² (4-12 lbs / ream) of amorphous nylon and about 3.25-9.75 g / m ² (2-6 lbs / ream) of the second adhesive joint. And the other side of the paperboard support has about 3
. 25-13.00g / m ² low-density polyethylene has been applied, also the product contact layer of (2-8 lbs / ream) is about 8.13-24.38g / m ² (
9. The method for producing a paperboard laminate according to claim 8, comprising a low-density polyethylene of 5-15 lbs / ream). 10. One side of the paperboard has about 9.75-29.26 g / m ² (
About 6-18 lbs / ream) of a heat-sealable low density polyethylene polymer layer, wherein the inner sandwich layer is about 3.25-9.7.
5 g / m ² (2-6 lbs / ream) of the ethylene-based anhydride modified copolymer said first tie layer and about 6.50-19.50 g / m ² (4-12 l)
bs / ream) amorphous nylon and about 3.25-9.75 g / m ² (2-6
8. The method of claim 7, wherein said second bonding layer comprises an anhydride-modified copolymer based on ethylene (lbs / ream).