CN1891756B - Easy-split stretched film, easy-split laminated film, easy-split bag, and manufacturing method for easy-split stretched film - Google Patents

Easy-split stretched film, easy-split laminated film, easy-split bag, and manufacturing method for easy-split stretched film Download PDF

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CN1891756B
CN1891756B CN2006101000396A CN200610100039A CN1891756B CN 1891756 B CN1891756 B CN 1891756B CN 2006101000396 A CN2006101000396 A CN 2006101000396A CN 200610100039 A CN200610100039 A CN 200610100039A CN 1891756 B CN1891756 B CN 1891756B
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tearability
film
thermal history
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CN1891756A (en
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高重真男
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Idemitsu Unitech Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Laminated Bodies (AREA)
  • Bag Frames (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

The easily tearable oriented film is made of a raw material containing a virgin raw material comprising of 60 to 85 pts.mass of Ny6 and 15 to 40 pts.mass of MXD6, and a heat history article which is prepared by melt-kneading Ny6 and MXD6, the MXD6 having a melting point of from 233 to 238[deg.]C, wherein the content of the heat history article is from 5 to 40 mass% based on the total amount of the raw material.

Description

The manufacture method of tearability oriented film, tearability laminated film, tearability sack and tearability oriented film
TECHNICAL FIELD OF THE INVENTION
The present invention relates to the manufacture method of tearability oriented film, tearability laminated film, tearability sack and tearability oriented film.
Background technology
In Japan, helpful for arrival to aging society, make the elderly or Disabled persons spend comfortable social life with youngster or healthy normal people, " accessible " notion of remove obstacles in every field (barrier) begins to be attracted attention.
On the other hand, as sealing ground (sealing ply) film of the packing bag of food, medicine etc., use the film of straight-chain low density polyethylene (L-LDPE) etc. more.This L-LDPE diaphragm seal excellent strength, thereby be safe, but its anti tear resistance is big, therefore in use, has and can not tear as the crow flies along cut, the problem that is difficult to break a seal.
So, even also very high at packaging field, particularly, higher with the requirement of the easily openable (tearability) of wrapping material, medical wrapping material to various food to the requirement of " accessible ".
Therefore, have tearability, particularly have straight cuts, proposed various schemes in order to make the film that constitutes sack.
For example, known have single axle drawn membrane as the such formation of the laminated film in middle layer (document 1: special public clear 58-38302 communique), uses the example (document 2: spy open flat 5-220837 communique, document 3: spy open flat 5-200958 communique) of the biaxially oriented film of the hybrid resin that contains nylon 6 (below be called Ny6) and m xylylene adipamide (below be called MXD6) as surperficial substrate film.
For the related formation of document 1, make single axle drawn membrane between the middle layer, thus the straight cuts excellence, but this single axle drawn membrane not too can play a role aspect intensity.
On the other hand, the surperficial ground that document 2, document 3 related formations have the straight cuts excellence, thus even when forming laminated film, also can keep its excellent straight cuts, therefore, as the practical value height of tearability sack.But the biaxially oriented film that contains the hybrid resin of Ny6 and MXD6 constitutes behind the laminated film as is placed under the exacting terms, then in the layer of biaxially oriented film, might cause in the so-called layer and peel off.If take place to peel off in such layer, it is unstable that the laminated thin film strength can become, thereby when constituting sack, produced the problem in the practicality.
Therefore, main purpose of the present invention is to provide: the tearability film of have excellent straight cuts, not peeling off simultaneously at the oriented film layer in the genetic horizon, use the tearability laminated film of this film, tearability sack, and the manufacture method of tearability oriented film.
Summary of the invention
Tearability oriented film of the present invention is the tearability oriented film of the m xylylene adipamide (below be called MXD6) (both totals are 100 mass parts) of the nylon 6 that contains 60～85 mass parts (below be called Ny6) and 15～40 mass parts as raw material, it is characterized in that, the tear strength of MD direction of this tearability oriented film (travel direction of film) and/or TD direction (width of film) is 70N/cm or following, the laminated film that this tearability oriented film of lamination and straight-chain low density polyethylene made membrane are formed is at 40 ℃ down after aging 3 days, when it is carried out the splitting test, do not find to peel off in the layer in the inside of this tearability oriented film.
According to tearability oriented film of the present invention, cooperation ratio as raw material, Ny6 is 60～85 mass parts, MXD6 is 15～40 mass parts, therefore, stretch along MD direction and/or TD direction by the base material film that will not stretch (former anti-Off イ Le system), obtain the tearability oriented film that equidirectional tear strength becomes 70N/cm or following and straight cuts excellence.In addition, biaxial stretch-formed if the base material film that will not stretch carries out, can form the also excellent tearability oriented film of shock-resistance.
In addition, the laminated film that lamination tearability oriented film of the present invention and straight-chain low density polyethylene made membrane are formed is at 40 ℃ down after aging 3 days, when it is carried out the splitting test, do not find to peel off in the layer in the inside of this tearability oriented film, so, also be very stable aspect intensity.Therefore, as Practical Performance (easily openable) excellence of packing the finished product such as sack.
To peel off in order not producing in the layer, to cooperate in raw material that Ny6 and MXD6 both sides are had the solvation mutually of affinity is effective.For example, preferably in raw material, cooperate thermal history thing described later.
In addition, if the cooperation ratio of raw material has departed from above-mentioned scope, then the straight cuts of tearability oriented film, shock-resistance reduce, thereby lack Practical Performance as the finished product such as packing sacks.In addition, if stretching conditions such as stretching ratio are poor, then the tear strength of tearability oriented film surpasses 70N/cm, the straight cuts reduction, thus lack Practical Performance as the finished product such as packing sacks.
The value of tear strength is based on that Elmendorf tear strength test (JIS K 7128) obtains.
Tearability oriented film of the present invention is to contain Ny6 and the MXD6 tearability oriented film as raw material, it is characterized in that, described raw material contains: the virgin material that contains 60～85 mass parts Ny6,15～40 mass parts MXD6, with with Ny6 and MXD6 melting mixing, the fusing point of MXD6 is 233～238 ℃ a thermal history thing, total amount with described raw material is a benchmark, and the content of described thermal history thing is 5～40 quality %.
Here, the chemical formula of described Ny6 is shown in following formula 1, and the chemical formula of MXD6 is shown in following formula 2 in addition.
[formula 1]
H-〔NH-(CH 2) 5-CO〕 n-OH
[formula 2]
Figure A20061010003900061
Above-mentioned virgin material is often referred to the raw material that is not the such state of following mixing raw material, that is, described mixing raw material has Ny6 and MXD6 are mixed and the course of melting mixing mutually.For example, be melted mixing course (for example recycle) separately separately, but,, remain virgin material for this situation as long as they do not have the mixed melting mixing that carries out even Ny6, MXD6 have.But the least possible virgin material of cycle index is preferably used in the rerum natura aspect during from formation tearability film.Even Ny6 and MXD6 have mutual the mixing and the course of melting mixing, if because a little less than should be mixing, and the fusing point of MXD6 is not almost reduced, above 238 ℃, these Ny6 and MXD6 also still constitute virgin material so, and do not constitute the thermal history thing.
That is, in the present invention, in Ny6 that constitutes virgin material and MXD6, add the thermal history thing, this three (perhaps both) is carried out so-called dry mixed after, carry out melting mixing again, thereby constitute the tearability oriented film.
Above-mentioned thermal history thing is meant the title complex of Ny6 and MXD6, and by a forcing machine, and in the present invention, the MXD6 melting point resin that uses differential scanning calorimeter (DSC) to measure remains on 233～238 ℃ of scopes.
According to tearability oriented film of the present invention, in virgin material, Ny6 is that Ny6 is 60～85 mass parts with the ratio that cooperates of MXD6, and MXD6 is 15～40 mass parts, therefore, and the straight cuts excellence.With respect to whole raw materials, contain Ny6 and MXD6 are carried out thermal history thing 5～40 quality % that melting mixing forms, therefore,, also be difficult to peel off in the genetic horizon even under exacting terms, use the tearability oriented film.
Here, peel off in the so-called layer, be meant, when under exacting terms, using, in tearability oriented film (nylon layer), cause the phenomenon of peeling off behind tearability oriented film and the suitable seal layer film lamination.The mechanism peeled off also is not very clear and definite in the layer, thinks that Ny6 and MXD6 are orientated to stratiform in the tearability oriented film, peels off at its interface.
If take place to peel off in such layer, then the laminated thin film strength becomes unstable, thereby when the formation sack, under the working conditions of harshness, might produce the problem of bag breakage etc.The working conditions of such harshness can for example be passed through, and the test of measuring the lamination strength (stripping strength) of laminated film reappears.
In addition, the fusing point of the MXD6 in the thermal history thing is 233～238 ℃, preferably 235～237 ℃.If the fusing point of the MXD6 in the thermal history thing is less than 233 ℃, then the straight cuts of tearability oriented film and shock strength reduce.In addition, if, then preventing the effect of peeling off in the layer more than 238 ℃, reduces the fusing point of the MXD6 in the thermal history thing.
And in the process of making the thermal history thing, if temperature, pressure height when mixing, then the fusing point of the MXD6 in the thermal history thing descends more.
Here, the fusing point of the MXD6 in the thermal history thing is meant the fusing point of measuring under the state before carrying out melting mixing with virgin material.
When this tearability oriented film uses as the surperficial ground of lamination bag, consider from improving the shock-resistance this point, preferably carry out it biaxial stretch-formed.In addition, from the strength balance this point consideration of direction in length and breadth, biaxial stretch-formed preferably by utilizing tubular process (チ ユ one Block ラ one method) to carry out biaxial stretch-formed simultaneously.
In addition, consider that from the tearability this point preferably for the either direction of MD direction and TD direction, tear strength all is 70N/cm or following.
In the present invention, the Ny6 in the preferred described thermal history thing is Ny6: MXD6=60～85 mass parts with the ratio that cooperates of MXD6: 15～40 mass parts.
According to the present invention, the Ny6 in the thermal history thing is Ny6: MXD6=60～85 mass parts with the ratio that cooperates of MXD6: therefore 15～40 mass parts, can form in straight cuts, shock strength and the layer and peel off the tearability oriented film that prevents the effect excellence.
If the content of the MXD6 in the thermal history thing when being made into the tearability oriented film, prevents the effect step-down of peeling off in the layer less than 15 quality % (content of Ny6 be 85 quality % or more than).If the content of the MXD6 in the thermal history thing is at 40 quality % or above (content of Ny6 is less than 60 quality %), then the straight cuts of tearability oriented film, shock strength reduce.
Tearability laminated film of the present invention is characterised in that, above-mentioned tearability oriented film is formed as the one deck at least in the multilayer.
According to tearability laminated film of the present invention, owing to being forms above-mentioned tearability oriented film as the one deck at least in the multilayer, therefore, even as laminated film, also have excellent straight cuts, shock strength, in addition, even under exacting terms, use, in nylon layer, can not peel off in the genetic horizon yet.
Tearability sack of the present invention is characterised in that, has used above-mentioned tearability laminated film.
Tearability sack of the present invention is owing to use above-mentioned tearability laminated film to constitute, therefore has excellent Kaifeng property (straight cuts), do not peel off in the genetic horizon simultaneously, so be the tearability sack stable, that practicality is high aspect intensity even be at polyamide laminate film yet.
The manufacture method of tearability oriented film of the present invention is to contain Ny6 and the MXD6 manufacture method as the tearability oriented film of raw material, it is characterized in that, described raw material contains: contain 60～85 mass parts Ny6, the virgin material of 15～40 mass parts MXD69 (both totals are 100 mass parts), with with Ny6 and MXD6 melting mixing and the thermal history thing that forms, in described thermal history thing, the fusing point of MXD6 is 233～238 ℃, and, total amount with described raw material is a benchmark, the content of described thermal history thing is 5～40 quality %, all carries out biaxial stretch-formed with 2.8 times or above stretching ratio along MD direction (travel direction of film) and TD direction (width of film).
Manufacture method according to tearability oriented film of the present invention, owing to contain Ny6 and MXD6 as raw material, and stretch, so the straight cuts excellence of the film after making with the stretching ratio of regulation, even when constituting laminated film, also can keep its good straight cuts.In addition, if carry out biaxial stretch-formedly along MD direction and TD direction, then shock-resistance is also excellent.And then, owing to contain the thermal history thing of regulation in the raw material, so even handle laminated film (bag) under exacting terms, nylon layer can not peeled off in the genetic horizon yet.
In addition, along the stretching ratio of MD direction and/or TD direction be decided to be 2.8 times or more than, preferably be decided to be 3.0 times or more than.For stretching ratio than 2.8 times of littler situations, straight cuts variation.Even carry out biaxial stretch-formedly in addition, shock-resistance also reduces, thereby has problems aspect practicality.And it is biaxial stretch-formed by utilizing tubular process to carry out simultaneously to stretch, and this strength balance this point from MD direction and TD direction considers it is preferred.
Description of drawings
Fig. 1 is the sketch chart of the biaxial stretch-formed device that uses in the manufacture method of the related tearability oriented film of the present invention's the 1st embodiment.
Fig. 2 is the sectional view of the related routine tearability laminated film of expression the 2nd embodiment of the present invention.
Fig. 3 is the sectional view of the routine tearability laminated film in the above-mentioned embodiment of expression.
Fig. 4 is the sectional view of the routine tearability laminated film in the above-mentioned embodiment of expression.
Fig. 5 is the front elevation of the tearability sack in the above-mentioned embodiment of expression.
Fig. 6 is the figure of the evaluation method of the related straight cuts of expression embodiments of the invention.
Embodiment
As mentioned above, tearability oriented film of the present invention, as long as satisfy the conditions such as use level of Ny6 and MXD6 in the raw material, there is no particular limitation on manufacture method, below, describe in detail for implementing best mode of the present invention.
[the 1st embodiment]
The tearability oriented film of present embodiment contains Ny6 and MXD6 as raw material, this raw material contains: the virgin material that contains 60～85 mass parts Ny6,15～40 mass parts MXD6, with with Ny6 and MXD6 melting mixing and the thermal history thing that forms, the fusing point of MXD6 in the thermal history thing is 233～238 ℃, and, total amount with raw material is a benchmark, and the content of thermal history thing is 5～40 quality %.Here, the chemical formula of Ny6 is shown in formula 3, and the chemical formula of MXD6 is shown in formula 4.
[formula 3]
H-〔NH-(CH 2) 5-CO〕 n-OH
[formula 4]
From the straight cuts of system film rear film and the viewpoint of shock strength, in virgin material, Ny6 must be that Ny6 is that 60～85 mass parts, MXD6 are 15～40 mass parts with the ratio that cooperates of MXD6.When in virgin material, MXD6 than 15 mass parts after a little while, the straight cuts variation.In addition, when MXD6 than 40 mass parts for a long time, shock strength reduces significantly, thereby lacks practicality.
Ny6 that preferred virgin material contains and MXD6 carry out dry mixed with the form of partical to be used.
In raw material, need contain the thermal history thing that Ny6 and MXD6 is carried out melting mixing and form.In addition, the fusing point of the MXD6 in the thermal history thing is 233～238 ℃, preferably 235～237 ℃.If the fusing point of the MXD6 in the thermal history thing is less than 233 ℃, then the straight cuts of tearability oriented film and shock strength reduce.In addition, if the fusing point of the MXD6 in the thermal history thing more than 238 ℃, then prevents the effect step-down of peeling off in the layer.
And then, with respect to whole raw materials, need contain thermal history thing 5～40 quality % that Ny6 and MXD6 carried out melting mixing and form.When thermal history thing during less than 5 quality %, the tearability oriented film made laminated film after, if under exacting terms, use, peel off in the genetic horizon easily.In addition, if the thermal history thing surpasses 40 quality %, the straight cuts of tearability oriented film, shock strength reduce.
Ny6 in the preferred thermal history thing is Ny6 with the ratio that cooperates of MXD6: MXD6=60～85 mass parts: 15～40 mass parts.
Because Ny6 is that Ny6 is that 60～85 mass parts, MXD6 are 15～40 mass parts with the ratio that cooperates of MXD6 in the thermal history thing, so can be made into straight cuts, shock strength and prevent to peel off in the layer tearability oriented film of effect excellence.
If the content of the MXD6 in the thermal history thing when being made into the tearability oriented film, prevents the effect step-down of peeling off in the layer less than 15 quality % (content of Ny6 be 85 quality % or more than).If the content of the MXD6 in the thermal history thing is 40 quality % or above (content of Ny6 is less than 60 quality %), then the straight cuts of tearability oriented film, shock strength reduce.
This thermal history thing also can be the tearability oriented film that recycle obtains according to present embodiment.In addition, for the pellet of thermal history thing and Ny6 and the pellet of MXD6 are carried out dry mixed fully, preferably the shape with the thermal history thing is processed into the partical use.For example, also can be the shape that the tearability oriented film shreds, compression obtains that present embodiment obtains.
This tearability oriented film when the surperficial ground as lamination bag utilizes, preferably carries out it biaxial stretch-formed.From the strength balance this point consideration of direction in length and breadth, biaxial stretch-formed preferably biaxial stretch-formed by utilizing tubular process to carry out simultaneously.In addition, the tear strength of the either direction of MD direction and TD direction all is 70N/cm or following, and this considers it is preferred from improving the straight cuts this point.
And, can in the tearability oriented film, suitably add necessary additive.As such additive, can list for example anti (mineral filler etc.), water-resisting agent (two stearic acid ethyls etc.), lubricant (calcium stearate etc.).
Such tearability oriented film can use the biaxial stretch-formed device manufacturing of tubulose mode for example shown in Figure 1.For example, can be by following method manufacturing, that is, the pellet of the pellet of Ny6, MXD6 and thermal history thing are carried out after mixture that dry mixed obtains melt extrudes, all with 2.8 times or above multiplying power carry out biaxial stretch-formed along MD direction and TD direction chilled base material film.
According to such embodiment, in virgin material, Ny6 is that Ny6 is that 60～85 mass parts, MXD6 are 15～40 mass parts with the ratio that cooperates of MXD6, wherein contain the thermal history thing that Ny6 and MXD6 is carried out melting mixing and form, the fusing point of MXD6 in this thermal history thing is 233～238 ℃, and, total amount with raw material is a benchmark, the content of thermal history thing is 5～40 quality %, therefore, have excellent straight cuts and shock strength, a while and under exacting terms, use and also be difficult to the tearability oriented film peeled off in the genetic horizon even can access.
[the 2nd embodiment]
Tearability laminated film of the present invention contains at least 1 layer tearability oriented film, and containing 2 layers, 3 layers etc., which floor is also passable.In Fig. 2～Fig. 4, show the tearability laminated film 100,200,300 of present embodiment.Here, for example, as shown in Figure 2, the 1st layer is that tearability oriented film 18, the 2nd layer are 2 layers of structure of various sealing ply films 19; As shown in Figure 2, the 1st layer to be the 20, the 2nd layer of various substrate film be the 3-tier architecture of various sealing ply films 19 for tearability oriented film 18, the 3rd layer; As shown in Figure 3; The 1st layer is that tearability oriented film 18, the 2nd layer are the 3-tier architecture of various sealing ply films 19 for the 20, the 3rd layer for various substrate films.
As the material of substrate film 20, for example can use PET (polyethylene terephthalate), EVOH (ethylene-acetidin copolymer saponification material), PVA (polyvinyl alcohol), PP (polypropylene), PVDC (polyvinylidene chloride), HDPE (high density polyethylene(HDPE)), PS twin shaft or single axle drawn membranes such as (polystyrene) or not have oriented film.And, except such resene film, also can use the such metallic film of aluminium foil.
As the material of sealing ply film 19, can use L-LDPE (straight-chain low density polyethylene), LDPE (new LDPE (film grade)), HDPE (high density polyethylene(HDPE)), EVA (vinyl-vinyl acetate copolymer), PB (polybutene-1), CPP (un-stretched polypropylene), ionomer, PMMA (polymethylmethacrylate) etc. and their mixture.As the laminated mode of described tearability laminated film, extrusion laminate is for example arranged, hot melt is laminated, dry type is laminated, wet type is laminated etc.
According to present embodiment, tearability laminated film the 100,200, the 300th, with above-mentioned tearability oriented film 18 be multiwalled at least the mode of one deck form, therefore, even as laminated film, also have excellent tearability, straight cuts, shock strength, in addition, even use under exacting terms, nylon layer can not peeled off in the genetic horizon yet.That is, as use this tearability laminated film 100,200,300 to make sack, can be used as the tearability sack 400 (Fig. 5) of having brought into play its characteristic and utilize.
Above record discloses and has been used to implement optimum structure of the present invention etc., but the present invention is not limited to this.Promptly, the present invention mainly is illustrated for specific embodiment, but under the condition that does not break away from the technology of the present invention thinking and purpose scope, to above-mentioned embodiment, those skilled in the art can carry out various conversion to material, quantity, other detailed structure.
Therefore, the record of above-mentioned disclosed qualification material, layer structure etc. is the exemplary record in order to make understanding of the present invention become and carry out easily, it does not limit the present invention, so, use the record of the title beyond limiting or all limiting such as the part of those material characters etc. to be also contained among the present invention.
For example, in the present embodiment,, made biaxially oriented film, but also can make single axle drawn membrane as the tearability oriented film.For example, for the tearability sack of Fig. 5, also can use single axle drawn membrane along TD direction orientation as surperficial substrate film.Be preferred under the situation that straight cuts is much accounted of especially.
In addition, in the present embodiment, as biaxial stretch-formed method, employing be the tubulose mode, but also can adopt the tentering mode.And then, as drawing process, can carry out biaxial stretch-formedly simultaneously, also can carry out biaxial stretch-formed one by one.
Embodiment
Below, the present invention will be described in more detail by embodiment and comparative example.But the present invention is not subjected to any qualification of these examples.
[embodiment 1]
(manufacturing of tearability oriented film)
The relative mixture that Ny6 pellet and MXD6 pellet are obtained by the mixed of 70 mass parts and 30 mass parts respectively, cooperate 15 quality % once and the thermal history thing (fusing point of MXD6 is 236 ℃) of pelletization by this proportioning melting mixing.This dry blend carried out melting mixing in forcing machine, under 270 ℃ after, melts is extruded into film cylindraceous from mould, then water quenching, thus make ejection material film.
In addition, the fusing point of MXD6 uses the differential scanning calorimetry device (DSC) of パ one キ Application エ Le マ one society's system, is warming up to 280 ℃ with the heat-up rate of 10 ℃/min from 50 ℃ and measures.All be as fusing point with the most at the beginning value.
As Ny6, use nylon 6[UBE Na イ ロ Application 1023FD (trade(brand)name), the relative viscosity η r=3.6 of the emerging product of space portion (strain) system], as MXD6, use the m xylylene adipamide [MX Na イ ロ Application 6007 (trade(brand)names), relative viscosity η r=2.7] of the ガ ス of Mitsubishi chemistry (strain) system.
In addition, the cooperation ratio of My6 and MXD6 is respectively 70 mass parts and 30 mass parts, extrudes at 270 ℃ with 40 φ EX, single screw extrusion machine (Yamaguchi Seisakusho K.K.'s system), as the thermal history thing.
Then, as shown in Figure 1, after passing this base material film 11 between a pair of nip rolls 12, on one side to wherein being pressed into air, on one side with well heater 13 heating, simultaneously, blow air 15 from air ring 14 to the stretching initiation site, make to be expanded to bubble 16, and derive, thereby utilize tubular process to carry out biaxial stretch-formed simultaneously along MD direction and TD direction from a pair of nip rolls 17 in downstream side.Multiplying power during this stretching all is 3.0 times in MD direction and TD direction.
Then, this oriented film is imported in tentering formula heat treatment furnace (not diagram), implement heat setting down, thereby obtain the tearability oriented film 18 (below be also referred to as oriented film 18) of present embodiment at 210 ℃.
(manufacturing of tearability laminated film)
Then, with this oriented film 18 (thickness 15 μ m) as surperficial substrate film, with L-LDPE film [the unified science and technology of ユ ニ ラ Star Network ス LS-711C (trade(brand)name), bright dipping (strain) system, thickness 50 μ m] as the sealing ply film, it is laminated that both are carried out dry type, thereby obtain the tearability laminated film (below be also referred to as laminated film) of present embodiment.And,, use the title complex (proportioning 16/1) of the タ ケ ラ Star Network A-615/ タ ケ ネ one ト A-65 of Mitsui タ ケ ダ ケ ミ カ Le system as the tackiness agent of the laminated usefulness of dry type.In addition, the laminated film of dry type after laminated 40 ℃ aging 3 days down.
[evaluation method]
(drawing and forming)
The stability of making the bubble of oriented film 18 is estimated as drawing and forming.Specifically, the drawing and forming during with bubble stabilizes is evaluated as A, and the waving of bubble, unsettled drawing and forming are evaluated as C.And bubble waves in the time of will beginning, but can make the drawing and forming of bubble stabilizes be evaluated as B through fine setting.
(shock strength)
The mensuration of shock strength is carried out at oriented film 18.
Shock strength is measured following carrying out: use the film impact tester of the smart machine of Japan (strain) system, the annular membrane that hemispheric oscillator (1/2 inch of diameter) bump has been fixed is measured the needed shock strength of film breakdown.With shock strength is 45, and 000J/m or be evaluated as A when above less than 45, is evaluated as C during 000J/m.If this shock strength is less than 45,000J/m, low as the performance of surperficial ground, so lack practicality as the liquid packing ground.
(straight cuts)
The evaluation of straight cuts is carried out at oriented film 18.
As shown in Figure 6, be that the interval Ws (for example interval of 2cm) with regulation introduces cut 21 on the film 18 of 20cm at width, after along these cuts 21 film 18 being torn, measure the width W e of the other end 22 of diaphragm 18A, obtain deviation α with original interval Ws by following formula 5.
[formula 5]
α＝[|Ws-We|/Ws]×100
10 diaphragm 18A are carried out this mensuration, when its mean value α (%) less than ± 10% the time, be evaluated as A +(straight cuts is very good) when ± 10%≤α≤± 30%, is evaluated as A (straight cuts is good), when α (%) surpasses ± 30%, is evaluated as C (straight cuts is bad).If α (%) surpasses ± 30%, then film 18 is torn as the crow flies the difficulty that becomes.
(peeling off in the layer)
Cut out the strip test film of wide 15mm from above-mentioned laminated film, interface peel about cm counted in its end with hand, make surperficial substrate film (oriented film 18) and sealing ply divided thin film from.Afterwards, each diaphragm is fixed on the tensile testing machine (イ Application ス ト ロ Application universal testing machine 1123 types), carries out the stripping test (90 degree are peeled off) of laminated part with the speed of 300mm/min.
Can carry out in the process in stripping test, if peel off inner the generation in the layer of surperficial substrate film, stripping strength can sharply reduce, so can judge to have or not and peel off generation in the layer with observing such behavior.For example, if stripping strength is about 7N/m when stripping test is initial, but in the stripping test process as sharply be reduced to about 1～2N/m, then can judges and take place to peel off in the layer.
When not showing the behavior of peeling off in the layer in surperficial substrate film inside, be evaluated as A, show the behavior of peeling off in the layer, be evaluated as C.
(tear strength)
Oriented film 18 is carried out the mensuration of tear strength.
According to Elmendovf tear strength test (JIS K 7128), measure the tear strength of stretched film 18MD direction and TD direction.And tear strength is 70N/cm or the following A that is evaluated as, and is evaluated as C for 71N/cm or when above.Consider that from improving the straight cuts aspect preferably this tear strength is 70N/cm or following.But, if tear strength be 71N/cm or more than, then straight cuts reduction lacks the practicality as the liquid packaging ground.
(comprehensive evaluation)
For peeling off these 5 in above-mentioned drawing and forming, shock strength, straight cuts and the layer all is that comprehensive evaluation more than the A is A.In above-mentioned 5, as long as there is 1 to be C, comprehensive evaluation is C so.
[embodiment 2～6, comparative example 1～6]
In the foregoing description 1, change the combined amount of Ny6 pellet, MXD6 pellet and thermal history thing, and then the fusing point of the MXD6 in the change thermal history thing utilizes manufacturing process similarly to Example 1 to make film.Evaluation test is also carried out similarly to Example 1.In table 1, list creating conditions of embodiment, in table 2, listed creating conditions of comparative example.
Formability
[table 1]
? Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
Ny6 (mass parts) 70? 70? 70? 70? 70? 80?
MXD6 (mass parts) 30? 30? 30? 30? 30? 20?
Thermal history thing (quality %) 15? 30? 15? 5? 10? 20?
Fusing point 1) (℃) 236? 236? 234? 237? 235? 237?
Drawing and forming A? A? A? A? A? A?
Shock strength (J/m) measured value 70000? 58000? 62000? 72000? 70000? 75000?
Shock strength A? A? A? A? A? A?
Straight cuts A+? A+? A+? A+? A+? A?
Peel off in the layer A? A? A? A? A? A?
Tear strength (N/cm) measured value 60? 65? 58? 55? 60? 65?
Tear strength A? A? A? A? A? A?
Comprehensive evaluation A? A? A? A? A? A?
1) fusing point of the MXD6 in the thermal history thing
[table 2]
? Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6
Ny6 (mass parts) 70? 70? 70? 70? 70? 90?
MXD6 (mass parts) 30? 30? 30? 30? 30? 10?
Thermal history thing (quality %) 0? 45? 15? 3? 30? 20?
Fusing point 1) (℃) -? 234? 232? 236? 210? 237?
Drawing and forming A? B? B? A? C? A?
Shock strength (J/m) measured value 70000? 44000? 60000? 70000? 40000? 78000?
Shock strength A? C? A? A? C? A?
Straight cuts A+? C? C? A+? C? C?
Peel off in the layer C? A? A? C? A? A?
Tear strength (N/cm) measured value 60? 72? 75? 62? 80? 80?
Tear strength A? C? C? A? C? C?
Comprehensive evaluation C? C? C? C? C? C?
1) fusing point of the MXD6 in the thermal history thing
[evaluation result]
Shown in table 1, table 2, the oriented film 18 of present embodiment contains Ny6 and MXD6 as raw material, this raw material contains: the virgin material that contains 60～85 mass parts Ny6,15～40 mass parts MXD6, with with Ny6 and MXD6 melting mixing and the thermal history thing that forms, the fusing point of MXD6 in the thermal history thing is 233～238 ℃, and, total amount with described raw material is a benchmark, the content of thermal history thing is in the scope of 5～40 quality %, so drawing and forming, shock strength, straight cuts, prevent that effect and the tear strength peeled off in the layer are all excellent.
On the other hand, because comparative example does not satisfy above-mentioned condition, so the rerum natura of oriented film 18 all has problems.Specifically, comparative example 1 does not contain the thermal history thing as raw material, so peel off in the polyamide laminate film genetic horizon.In addition, comparative example 2 is 45 quality %, so shock strength, straight cuts and tear strength are poor because the content of thermal history thing is mostly.For comparative example 3,, it is 232 ℃, so straight cuts and tear strength are poor because the fusing point of the MXD6 in the thermal history thing is low.The content of the thermal history thing of comparative example 4 is few, thus identical with comparative example 1, peel off in the polyamide laminate film genetic horizon.In comparative example 5, the fusing point of thermal history thing is 210 ℃, and is quite low, so shock strength, straight cuts and tear strength are poor.In addition, drawing and forming is also bad.In comparative example 6, the content of Ny6 is too many, so straight cuts and tear strength are poor.

Claims (5)

1. tearability oriented film, it is to contain nylon 6 and m xylylene adipamide as the tearability oriented film of raw material, it is characterized in that,
Described raw material contains: contain 60～85 mass parts nylon, 6,15～40 mass parts m xylylene adipamides virgin material and
With nylon 6 and m xylylene adipamide melting mixing and the thermal history thing that forms,
The fusing point of m xylylene adipamide is 233～238 ℃ in the described thermal history thing,
The cooperation ratio of nylon 6 and m xylylene adipamide is a nylon 6 in the described thermal history thing: m xylylene adipamide=60～85 mass parts: 15～40 mass parts,
Total amount with described raw material is a benchmark, and the content of described thermal history thing is 5～40 quality %.
2. the described tearability oriented film of claim 1, it is characterized in that, the tear strength of the travel direction of this tearability oriented film and/or the width of film is below the 70N/cm, and described tear strength is based on that Elmendorf tear strength test JIS K 7128 obtains.
3. a tearability laminated film is characterized in that, is claim 1 or 2 described tearability oriented films are formed as the one deck at least in the multilayer.
4. a tearability sack is characterized in that, has used the described tearability laminated film of claim 3.
5. the manufacture method of a tearability oriented film, it is to contain nylon 6 and m xylylene adipamide as the manufacture method of the tearability oriented film of raw material, it is characterized in that,
Described raw material contains: contain 60～85 mass parts nylon, 6,15～40 mass parts m xylylene adipamides virgin material and
With nylon 6 and m xylylene adipamide melting mixing and the thermal history thing that forms,
The total of nylon 6 and m xylylene adipamide is 100 mass parts in the described virgin material,
The fusing point of the m xylylene adipamide in the described thermal history thing is 233～238 ℃, and,
The cooperation ratio of nylon 6 and m xylylene adipamide is a nylon 6 in the described thermal history thing: m xylylene adipamide=60～85 mass parts: 15～40 mass parts,
Total amount with described raw material is a benchmark, and the content of described thermal history thing is 5～40 quality %,
Stretch with the stretching ratio more than 2.8 times along the travel direction of film and/or the width of film.
CN2006101000396A 2005-06-27 2006-06-27 Easy-split stretched film, easy-split laminated film, easy-split bag, and manufacturing method for easy-split stretched film Active CN1891756B (en)

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