CN100572047C - Laminated material and container - Google Patents
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- CN100572047C CN100572047C CNB2005101146247A CN200510114624A CN100572047C CN 100572047 C CN100572047 C CN 100572047C CN B2005101146247 A CNB2005101146247 A CN B2005101146247A CN 200510114624 A CN200510114624 A CN 200510114624A CN 100572047 C CN100572047 C CN 100572047C
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Abstract
The present invention relates to a kind of have internal layer, intermediate layer and outer field laminated material at least, wherein said internal layer comprises the resin material (A) that contains high density polyethylene (HDPE), described intermediate layer comprises the resin material (B) that mainly contains polyethylene resin I, described polyethylene resin I be by make ethene and the alpha-olefin with 3-20 carbon atom carry out the ethylene/alpha-olefin copolymer of copolymerization acquisition and have as the described physical property of specification (a)-(d) and as described in skin comprise the resin material (C) that contains high density polyethylene (HDPE).Compare with conventional laminated material, laminated material of the present invention has excellent performance at the transparency, resistance to blocking, aspect such as flexible, and showing is enough to tolerate the high-fire resistance of 121 ℃ of sterilizations, and is being improved aspect the impact strength of seal member.
Description
The application is that application number is dividing an application of 02803617.4 patent application, and the applying date of original application is on January 5th, 2002, and denomination of invention is " laminated material and a container ".
The cross reference of related application
The application is based on the Japanese patent application Nos2001-5858 that submits in Japan and 2001-382096 and the temporary patent application No.US60/282871 that submits in the U.S. according to 35USC § 119 (e).
Invention field
The present invention relates to a kind of laminated material and container, it has excellent resistance to blocking, the transparency and flexible, and show high seal member impact strength, and be suitable as the containers for medical use that can fill blood, liquid medicine etc., or as the container of canned food.The example of containers for medical use comprises blood bag, blood platelet reservoir bag, infusion bag (liquid drug), multicell containers for medical use, and (wherein two or more liquid drugs are stored in the separate chambers of bonded property parts separation, mix by strip off adhesive means in use under air-tight state with these multiple liquid drugs) and artificial dialysis bag.
Background technology
The containers for medical use that is used to fill blood, liquid medicine etc. need have the transparency so that observe the troubled water of foreign substance or confirm to mix the variation that causes by medicine, need have the hear resistance that the tolerance of being high enough to is disinfected, and can discharge the flexible of liquid contents easily.
For containers for medical use that satisfies these performances or canning food container, used the flexible vinyl chloride resin in the past; Polyethylene material, for example hp-ldpe, linear low density polyethylene (LLDPE), high density polyethylene (HDPE) and vinyl-vinyl acetate copolymer; And based on the material of propylene.But these materials existing problems, more particularly, the hear resistance of vinyl-vinyl acetate copolymer is low, and the shortcoming of vinyl chloride resin is plasticizer stripping and entering in the liquid drug, propylene flexible poor, the intensity of hp-ldpe is relatively poor.The density of linear low density polyethylene (LLDPE) must reduce so that satisfy the transparency or flexible, but the reduction of density has caused the problem such as hear resistance deficiency or lower-molecular-weight component ooze out from resin.
In recent years, developed and used single-point type Hi-fax material Preparation of Catalyst and that have impact and excellent transparency, and begin to be applied to these materials medical or canning food container in.In addition, proposed with two-layer or three press the form of material to be used in combination the method (referring to JP-A-8-309939, JP-A-7-125738 and JP-A-8-244791) (term used herein " JP-A " refers to " examining open Japanese patent application ") of these materials layer by layer.
But even in the material of these suggestions, the transparency is still not enough, and the impact strength of heat-sealing parts is unsatisfactory, and the heat-sealing parts may break when bag drops.So, needed to improve these performances.In addition, if form this material by water-cooled inflation method, T-modulus method etc., then the film of gained or sheet material have smooth especially surface, cause film or sheet material to stick to each other, sometimes the branch defection of these films or sheet material produces muddy defective from the teeth outwards, grievous injury outward appearance.
At present, needing day by day can be at 121 ℃ of following container of sterilization, and in order to satisfy these requirements, needs higher hear resistance.
The purpose of this invention is to provide the resin laminated material of a kind of polyethylene, compare with conventional laminated material, this material has excellent performance at the transparency, resistance to blocking, aspect such as flexible, show be enough to tolerate 121 ℃ of sterilizations high-fire resistance, and be significantly improved aspect the impact strength of seal member.Purpose of the present invention comprises provides the containers for medical use that contains this resin laminated material, food containers etc.
DISCLOSURE OF INVENTION
Through deep research, the inventor has been found that above-mentioned purpose can realize by a kind of laminated material, and this laminated material comprises internal layer, intermediate layer and the outer field combination that each free specific resin material is formed.Finished the present invention based on this discovery.
More particularly, the invention provides a kind of have internal layer, intermediate layer and outer field laminated material at least, wherein:
Internal layer comprises the resin material (A) that contains high density polyethylene (HDPE);
The intermediate layer comprises the resin material (B) that mainly contains polyethylene resin I, described polyethylene resin I is by making ethene and the alpha-olefin with 3-20 carbon atom carry out the ethylene/alpha-olefin copolymer of copolymerization acquisition, and has following physical property (a)-(d);
(a) density is less than 0.920g/cm
3,
(b) MFR is 0.1-50g/10 minute,
(c) in 25 ℃ of amount X (% quality), density d (g/cm that dissolve in the fraction of o-dichlorohenzene
3) and the satisfied following relation of MFR (g/10 minute):
X＜9.8×10
3×(0.9300-d+0.008logMFR)
2+2.0
(d) forming distributed constant Cb is 1.08-2.00; With
Described skin is made up of the resin material that contains high density polyethylene (HDPE) (C), and the containers for medical use that is made of this laminated material is provided.
The resin material (A) that the preferred feature of laminated material of the present invention is to constitute internal layer only comprises high density polyethylene (HDPE).
The resin material (A) that laminated material preferable feature of the present invention is to constitute internal layer is a kind of by the resin combination with high density polyethylene (HDPE) and polyethylene resin II blend acquisition, wherein said polyethylene resin II carries out the ethylene/alpha-olefin copolymer that copolymerization obtains by ethene and the alpha-olefin with 3-20 carbon atom, and has following physical property (e)-(h);
(e) density is to less than 0.960g/cm from 0.920
3,
(f) MFR is 0.1-50g/10 minute,
(g) in 25 ℃ of amount X (% quality), density d (g/cm that dissolve in the fraction of o-dichlorohenzene
3) and the satisfied following relation of MFR (g/10 minute):
I) under the situation of d-0.008logMFR 〉=0.93, X＜2.0;
Ii) under the situation of d-0.008logMFR＜0.93,
X＜9.8 * 10
3* (0.9300-d+0.008logMFR)
2+ 2.0 and
(h) form distributed constant Cb less than 2.00.
The preferred feature of laminated material of the present invention is when the resin material (A) that constitutes internal layer when being high density polyethylene (HDPE) with the blend of the ethylene/alpha-olefin copolymer that is carried out the copolymerization acquisition by ethene and alpha-olefin with 3-20 carbon atom, and alpha-olefin is to be selected from propylene, butene-1,4-methylpentene-1, hexene-1, octene-1, decylene-1 and the dodecylene-1 one or more.
The preferred feature of laminated material of the present invention is that the alpha-olefin content in the copolymer is to be less than or equal to 30 moles of % in the ethylene/alpha-olefin copolymer that constitutes polyethylene resin II.
The resin material (A) that the preferred feature of laminated material of the present invention is to constitute internal layer is a kind of by with the high density polyethylene (HDPE) of 40-99% quality and the resin combination of the polyethylene resin II blend acquisition of 60-1% quality.
The preferred feature of laminated material of the present invention is MFR and the 0.940-0.970g/cm that the high density polyethylene (HDPE) of resin material (A) had 0.1-20g/10 minute
3Density.
The resin material (B) that the preferred feature of laminated material of the present invention is to constitute the intermediate layer only comprises polyethylene resin I.
The preferred feature of laminated material of the present invention be when the intermediate layer be when carrying out the ethylene/alpha-olefin copolymer of copolymerization acquisition by ethene and alpha-olefin with 3-20 carbon atom, alpha-olefin is to be selected from propylene, butene-1,4-methylpentene-1, hexene-1, octene-1, decylene-1 and the dodecylene-1 one or more.
The preferred feature of laminated material of the present invention is that polyethylene resin I satisfies above-mentioned physical property (a)-(d) and has following physical property (i) and (j) simultaneously:
(i) Mw/Mn is 1.5-3.5,
(j) on the eluting temperature that obtains by continuous intensification elution fractionation (TREF)-elution amount curve, there are a plurality of peaks.
The resin material (B) that the preferred feature of laminated material of the present invention is to constitute the intermediate layer is the resin combination that obtains by polyethylene resin I and polyethylene resin II blend.
The resin material (B) that the preferred feature of laminated material of the present invention is to constitute the intermediate layer is the resin combination that the polyethylene resin II blend by the polyethylene resin I of 50-99% quality and 50-1% quality obtains.
The resin material (B) that the preferred feature of laminated material of the present invention is to constitute the intermediate layer is by polyethylene resin I and the resin combination that is selected from least a material blend acquisition in the following substances: high density polyethylene (HDPE), medium density polyethylene, hp-ldpe, linear low density polyethylene (LLDPE), polypropylene, ethylene-propylene random copolymer and Ethylene-Propylene Block Copolymer.
The resin material (B) that the preferred feature of laminated material of the present invention is to constitute the intermediate layer is to be equal to or greater than 0.935g/cm by polyethylene resin I and a kind of density
3The resin combination that obtains of resin alloy.
The preferred feature of laminated material of the present invention is to constitute outer field resin material (C) and only contains high density polyethylene (HDPE).
It is the resin combination that obtains by high density polyethylene (HDPE) and polyethylene resin II blend that the preferred feature of laminated material of the present invention is to constitute outer field resin material (C).
It is the resin combination that the polyethylene resin II blend of high density polyethylene (HDPE) by the 95-5% quality and 5-95% quality obtains that the preferred feature of laminated material of the present invention is to constitute outer field resin material (C).
The preferred feature of laminated material of the present invention is that skin comprises by having the fusing point peak temperature and is equal to or higher than the resin material (D) that 130 ℃ heat-resistant resin material is formed that this temperature detects by differential scanning calorimetry (DSC).
The heat-resistant resin material that the preferred feature of laminated material of the present invention is to constitute resin material (D) is that blend therein has the resin combination that is selected from least a material in the following material: medium density polyethylene, polypropylene, ethylene-propylene random copolymer, Ethylene-Propylene Block Copolymer, ethylene-vinyl alcohol copolymer (EVOH), polyamide is nylon-6 and nylon-6 for example, and 6, polyester is PET and polybutylene terephthalate for example.
The preferred feature of laminated material of the present invention is that the thickness of whole laminated material is 0.01-1mm.
The preferred feature of laminated material of the present invention is that the thickness proportion between each layer is internal layer/intermediate/outer layer=30-1/40-98/30-1 (the supposition summation is 100).
The preferred feature of laminated material of the present invention is that laminated material forms by water-cooled coextruded multilayer inflation method or the coextruded multilayer T-die casting method of moulding.
Container of the present invention comprises any above-mentioned laminated material.
The preferred feature of container of the present invention is that at least a portion of laminated material internal layer is heat-sealed as hot sealing layer.
The preferred feature of container of the present invention is that the internal layer of laminated material is processed to a bag shape by sealing as internal layer four limits of hot sealing layer.
Embodiments of the present invention
Laminated material of the present invention has following at least internal layer, intermediate layer and skin.
I. internal layer
Internal layer in the laminated material of the present invention comprises the resin material (A) that contains high density polyethylene (HDPE).Resin material (A) can only comprise high density polyethylene (HDPE), but also can be the resin combination that obtains by high density polyethylene (HDPE) and the polyethylene resin II blend with pre-defined physical properties.
(1) high density polyethylene (HDPE)
The high density polyethylene (HDPE) that is used for internal layer is by the conventional method Alathon of slurry process, solwution method or vapor phase method preparation for example, ethene and the copolymer with alpha-olefin of 3-12 carbon atom, or their mixture.The object lesson of alpha-olefin comprises propylene, butene-1,4-methylpentene-1, hexene-1, octene-1, decylene-1 and dodecylene-1.
Normally about 0.1-20g/10 minute of the MFR of high density polyethylene (HDPE), preferred 0.1-10g/10 minute.When MFR was in this scope, said composition can have suitable melt tension and help film forming.The normally about 0.940-0.970g/cm of density
3, preferred 0.945-0.970g/cm
3When density is in this scope, can advantageously keep hear resistance.
(2) polyethylene resin II
Be used for polyethylene resin II of the present invention and have following physical property (e)-(h).
(e) density
The density of polyethylene resin II is to less than 0.960g/cm from 0.920
3If density less than this scope, then adhesion can occur unfriendly, and if density surpasses this scope, then flexible reduction, this is not preferred.Density is more preferably 0.920-0.950g/cm
3, further more preferably 0.920-0.945g/cm
3
(f)MFR
The MFR of polyethylene resin II is 0.1-50g/10 minute.If MFR less than this scope, then can reduce mouldability unfriendly, and if MFR surpasses this scope, then intensity reduces, this is not preferred.MFR is more preferably 0.1-20g/10 minute.
(g) in 25 ℃ of fractions that dissolve in o-dichlorohenzene
In polyethylene resin II, dissolve in amount X (% quality), the density d (g/cm of the fraction of o-dichlorohenzene (hereinafter referred is " ODCB ")
3) and the satisfied predetermined relation of MFR (g/10 minute).
Here, detect by the following method in 25 ℃ of fractions that dissolve in ODCB.In the ODCB of 20ml, the 0.5g sample in 135 ℃ of heating 2 hours, after sample dissolves fully, is cooled to 25 ℃ with solution.Make this solution leave standstill a night in 25 ℃, the filter with the Teflon system filters then.To the filtrate sampling, use this filtrate, use determination of infrared spectroscopy at 2925cm
-1Near the wave number absworption peak area is the asymmetric stretching vibration of methylene herein.Based on the value that is obtained, from the calibration curve calculation sample concentration that obtained in the past.Can be determined at 25 ℃ of fractions that dissolve in ODCB by this value.
In polyethylene resin II, in 25 ℃ of amount X (% quality), density d (g/cm that dissolve in the fraction of ODCB
3) and the satisfied following relation of MFR (g/10 minute):
I) under the situation of d-0.008logMFR 〉=0.93, X is less than 2% quality, preferably less than 1% quality; With
Ii) under the situation of d-0.008logMFR＜0.93, X has following relation: X＜9.8 * 10
3* (0.9300-d+0.008logMFR)
2+ 2.0, preferred X＜7.4 * 10
3* (0.9300-d+0.008logMFR)
2+ 1.0, more preferably X＜5.6 * 10
3* (0.9300-d+0.008logMFR)
2+ 0.5.Here, density d and MFR in above-mentioned inequality right side are numerical value, do not have unit.Therefore, must be in 25 ℃ of amounts (% quality) that dissolve in the fraction of ODCB less than the value that under only with the situation in the formula on the density d of polyethylene resin II and this inequality right side of MFR substitution, obtains.
Be included in main contained high degree of branching component and lower-molecular-weight component in the polyethylene resin in 25 ℃ of fractions that dissolve in ODCB.This fraction causes the problem of adhesion on health or moulded products inner surface, so the content of this fraction is preferably little.The amount that dissolves in the fraction of ODCB is subjected to the influence of the content and the molecular weight of comonomer.Therefore, when satisfying above-mentioned relation, this means and in whole resin, contain less copolymerization component (alpha-olefin) as density, the MFR of index and the amount that dissolves in the fraction of ODCB.In the present invention, when polyethylene resin II satisfies above-mentionedly during about the concerning of the fraction that dissolves in ODCB, hear resistance, sanitation performance and resistance to blocking are improved, so this is preferred.
(h)Cb
In polyethylene resin II, form distributed constant Cb less than 2.00.
The detection method of forming distributed constant Cb is as follows.In the o-dichlorohenzene that adds antioxidant (ODCB), sample dissolution under 135 ℃ of heating, thus sample concentration is 0.2% quality.This solution is transferred in the post that diatomite (Celite 545) are housed, and be cooled to 25 ℃, thereby make sample deposition on the Celite surface with 1 ℃/minute speed.When ODCB flowed into this post with constant flow rate, column temperature progressively was elevated to 130 ℃ carrying out wash-out with 5 ℃ increment, thereby with sample classification.Subsequently, methyl alcohol is mixed with eluate,, obtain the classification sample under each eluting temperature reppd sample filtering, drying.The mass fraction of elution samples at each temperature and the degree of branching (by the side chain number of per 1000 carbon atoms) by isotope nuclear magnetic resonance of carbon spectrum (
13C-NMR) detect.
The following correction of the degree of branching of 30-90 ℃ of fraction.Map with respect to eluting temperature with the degree of branching that detects, be in line with least square fitting, thereby obtain calibration curve.Coefficient correlation in this match is enough big.Be designed to the degree of branching of each fraction by the value of this calibrating curve determining.As for each component under 95 ℃ or higher eluting temperature, not to set up linear relationship between the eluting temperature and the degree of branching, so do not need to carry out this correction when using detected value.
Subsequently, with the mass fraction w of each fraction
iDivided by degree of branching b
iVariable (b by per 5 ℃ of eluting temperatures
i-b
I-1), obtain relative concentration C
i, map with respect to the degree of branching with this relative concentration, obtain component distribution curve.This component distribution curve is divided into fixing width, calculates according to following formula and form distributed constant Cb:
C wherein
jAnd b
jRepresent the relative concentration and the degree of branching of j fraction independently of one another.Form at sample under the situation of homogeneous, forming distributed constant Cb is 1.0.It is wide more to form distribution, and this value is just big more.
The composition distributed constant Cb that is used for polyethylene resin II of the present invention is preferably 1.04-2.00 less than 2.00.If Cb is equal to or greater than 2.00, then resistance to blocking is low, and heat sealability is bad.In addition, lower-molecular-weight component etc. also takes place easily be exuded to phenomenon on the resin surface, this causes hygienic issues.
The example of polyethylene resin II comprises ethylene/alpha-olefin copolymer.Alpha-olefin is the alpha-olefin with individual, preferred 3-12 the carbon atom of 3-20.Object lesson comprises propylene, butene-1,4-methylpentene-1, hexene-1, octene-1, decylene-1 and dodecylene-1.Can use in these alpha-olefins one or more.The content of the alpha-olefin in copolymer is 30 moles of % or lower normally, preferred 20 moles of % or lower.
The preparation method of polyethylene resin II
Preparation method to polyethylene resin II has no particular limits, this resin can prepare by any method, as long as can satisfy above-mentioned physical property, but polyethylene resin II preferably by having the part of cyclopentadienyi skeleton and contain in the presence of the catalyst of transistion metal compound as solvent of period of element Table IV family containing 0,1 or 2, makes ethene carry out copolymerization with the alpha-olefin with 3-20 carbon atom and obtains.
Polyethylene resin II more preferably uses following catalyst to prepare, but the invention is not restricted to this.
For example, can use such catalyst system, it contains and has the transition metal that is selected from period of element Table IV family and contain 0,1 or 2 organic transition catalyst with cyclopentadienyl derivative, with a kind of compound that can form ionic complex with organic transition catalyst reaction, and/or the Organoaluminoxy based compound.In this catalyst system, if necessary, also can use organo-aluminum compound.In addition, if necessary, also can use by organic transition catalyst is fixed on inorganic compound, the fine grained etc.
Disclosed catalyst can be used to produce this resin in following patent publications, but the invention is not restricted to this.The example of operable catalyst is included in those disclosed among JP-A-11-293054, JP-A-11-310607, JP-A-8-309939, the JP-A-10-77370 etc.
(3) resin material (A)
Resin material (A) contains the above-specified high density polyethylene.Resin material (A) can only contain high density polyethylene (HDPE), maybe can be the resin combination that contains high density polyethylene (HDPE) and polyethylene resin II.
Under the situation of resin combination, in resin material (A), the ratio between high density polyethylene (HDPE) and the polyethylene resin II makes that high density polyethylene (HDPE) is the 40-99% quality, preferred 50-99% quality, more preferably 60-99% quality.If the ratio of the high density polyethylene (HDPE) of blend is less than above-mentioned scope, then the impact strength of seal member reduces, and this is not preferred, and if this blend ratio surpasses above-mentioned scope, then intensity reduces unfriendly.
In the present invention, particularly when internal layer forms by the resin material of 50% quality or more high density polyethylene (HDPE) by blend wherein and so when mainly comprising high density polyethylene (HDPE), surprisingly, compare with the situation that internal layer is made up of the resin material that mainly contains the ethylene/alpha-olefin copolymer with above-mentioned physical property (e)-(h), not only hear resistance is improved, and the impact strength of heat sealability, particularly seal member is significantly improved.
In resin material (A), when needed, blend known additive commonly used suitably, its consumption is in the scope of not serious infringement effect of the present invention, and described additive for example is antistatic additive, antioxidant, lubricant, antiblocking agent, antifoggant, organic or inorganic pigment, ultra-violet absorber and dispersant.
II. intermediate layer
In laminated material of the present invention, the intermediate layer is made up of resin material (B), and this resin mainly contains the polyethylene resin I with following physical property (a)-(d).
(1) polyethylene resin I
(a) density
The density of polyethylene resin I is less than 0.920g/cm
3If density surpasses this scope, the then transparency and flexible reduction unfriendly.Density is more preferably 0.880-0.920g/cm
3, further more preferably 0.890-0.918g/cm
3
(b)MFR
The MFR of polyethylene resin I is 0.1-50g/10 minute.If MFR less than this scope, then can reduce mouldability unfriendly, and if MFR surpasses this scope, then intensity reduction.MFR is more preferably 0.1-10g/10 minute.
(c) dissolve in the fraction of ODCB
In polyethylene resin I, satisfy predetermined relation in 25 ℃ of amount X (% quality), density d and MFR that dissolve in the fraction of ODCB.Measure by above-mentioned detection method in 25 ℃ of fractions that dissolve in ODCB.In 25 ℃ of amount (% quality), density d (g/cm that dissolve in the fraction of ODCB
3) and MFR (g/10 minute) between relation as follows.Their relation satisfies X＜9.8 * 10
3* (0.9300-d+0.008logMFR)
2+ 2.0, preferred X＜7.4 * 10
3* (0.9300-d+0.008logMFR)
2+ 1.0, more preferably X＜5.6 * 10
3* (0.9300-d+0.008logMFR)
2+ 0.5.Here, density d and MFR in above-mentioned inequality right side are numerical value, do not have unit.Therefore, must be in 25 ℃ of amount X (% quality) that dissolve in the fraction of ODCB less than the value that under only with the situation in the formula on the density d of polyethylene resin I and this inequality right side of MFR substitution, obtains.In the present invention, when polyethylene resin I satisfies above-mentionedly during about the concerning of the fraction that dissolves in ODCB, obtaining good result aspect patience, sanitation performance and the resistance to blocking.
(d)Cb
The composition distributed constant Cb of polyethylene resin I is preferably 1.08-2.00 less than 2.00.Under the situation in Cb is in above-mentioned scope, reached high resistance to blocking and excellent heat sealability.If Cb is equal to or greater than 2.00, then resistance to blocking is low, and heat sealability is bad.In addition, lower-molecular-weight component etc. also takes place easily be exuded to phenomenon on the resin surface, this causes hygienic issues.The detection method of composition distributed constant Cb as mentioned above.
The example of polyethylene resin I comprises ethylene/alpha-olefin copolymer.Alpha-olefin is the alpha-olefin with individual, preferred 3-12 the carbon atom of 3-20.Object lesson comprises propylene, butene-1,4-methylpentene-1, hexene-1, octene-1, decylene-1 and dodecylene-1.Can use in these alpha-olefins one or more.The content of the alpha-olefin in copolymer is 30 moles of % or lower normally, preferred 20 moles of % or lower.
(2) preferred polyethylene resin I
The preferred example that is used for polyethylene resin I of the present invention comprises and can satisfy above-mentioned physical property (a)-(d) and satisfy following physical property (i) and (j) those in addition.
(i)Mw/Mn
The molecular weight distribution (Mw/Mn) of preferred polyethylene resin I is 1.5-3.5 among the present invention, preferred 2.0-3.0.As for the method for calculating Mw/Mn, weight average molecular weight (Mw) and number-average molecular weight (Mn) detect by gel permeation chromatography (GPC), and obtain ratio Mw/Mn from detected value.If Mw/Mn is less than above-mentioned scope, insufficient formability then, and if Mw/Mn surpasses above-mentioned scope, then impact resistance is poor.
(j) peak on TREF method eluting temperature-elution amount curve
On the eluting temperature that obtains by continuous intensification elution fractionation method (TREF)-elution amount curve, the preferred polyethylene resin of the present invention I has a plurality of peaks.More preferably, at least one in these peaks is preferably between 85-100 ℃.Because the existence at this peak, the hear resistance of moulded products is improved.
Undertaken by the detection of TREF is following.In the ODCB that adds antioxidant,, obtain the sample that concentration is 0.05% quality in 135 ℃ of heating for dissolving samples.Then, this sample solution of 5ml is poured in the post that bead is housed, and is cooled to 25 ℃ with 0.1 ℃/minute cooldown rate, thus on the bead surface deposited samples.Subsequently, when ODCB flow through this post with constant flow rate, column temperature progressively raise with 50 ℃/hour constant rate of speed, thus elution samples successively.At this moment, use the infrared spectrometer METHOD FOR CONTINUOUS DETERMINATION in 2925cm
-1There is the wash-out of absorption to go into the concentration of the sample in the solvent, 2925cm
-1It is the wave number of the asymmetric stretching vibration of methylene.Based on this detected value, the concentration of ethylene/alpha-olefin copolymer in solution is quantitative, and obtain relation between eluting temperature and the elution rate thus.In TREF analyzes, can analyze continuously with the sample of trace with respect to the elution rate variation of variations in temperature, can not be thereby can detect by the thinner peak of hierarchical detection.
(3) preparation method of polyethylene resin I
Preparation method to polyethylene resin I has no particular limits, this resin can prepare by any method, as long as can satisfy above-mentioned physical property, but polyethylene resin I preferably by having the part of cyclopentadienyi skeleton and contain in the presence of the catalyst of transistion metal compound as solvent of period of element Table IV family containing 0,1 or 2, makes ethene carry out copolymerization with the alpha-olefin with 3-20 carbon atom and obtains.
Polyethylene resin I more preferably uses following catalyst to prepare, but the invention is not restricted to this.
For example, can use such catalyst system, it contains the organic transition catalyst that has the transition metal that is selected from period of element Table IV family and contain 0,1 or 2 cyclopentadienyl derivative, with a kind of compound that can form ionic complex with organic transition catalyst reaction, and/or the Organoaluminoxy based compound.In this catalyst system, if necessary, can use organo-aluminum compound.In addition, if necessary, also can use by organic transition catalyst is fixed on inorganic compound, the fine grained etc.
For example disclosed catalyst can be used for production polyethylene resin I in above-mentioned patent publications, but the invention is not restricted to this.
Polymerisation can use any gas phase process, slurry process and solution methods to carry out.Polymerisation also can be single-step method or multistep processes.
(4) resin material (B)
Resin material (B) mainly contains polyethylene resin I, preferably only contains polyethylene resin I, but is that the resin of non-polyethylene resin I can blend in the scope of not damaging effect of the present invention.The example of other resin comprises polyethylene resin II, high density polyethylene (HDPE), medium density polyethylene, hp-ldpe, linear low density polyethylene (LLDPE), polypropylene, ethylene-propylene random copolymer and Ethylene-Propylene Block Copolymer.Under the situation of other resin of blend, the percentage of polyethylene resin I is 50% quality or bigger aptly, preferred 60% quality or bigger.If the percentage of polyethylene resin I is lower than 50% quality, intensity reduces unfriendly.In addition, in other resin, preferred density is equal to or greater than 0.935g/cm
3Resin and more preferably density be equal to or greater than 0.940g/cm
3Resin.These resins are preferred, because they have improved hear resistance.The example of these resins comprises the resin that is selected from polyethylene resin II, linear low density polyethylene (LLDPE) and the high density polyethylene (HDPE), and it has the 0.935g/cm of being equal to or greater than
3Density.Particularly, preferred density is equal to or greater than 0.935g/cm
3High density polyethylene (HDPE).
In resin material (B), when needed, blend known additive commonly used suitably, its consumption is in the scope of not serious infringement effect of the present invention, and described additive for example is antistatic additive, antioxidant, lubricant, antiblocking agent, antifoggant, organic or inorganic pigment, ultra-violet absorber and dispersant.
III. outer
Skin in laminated material of the present invention comprises the resin material (C) that contains high density polyethylene (HDPE).Resin material (C) can only contain high density polyethylene (HDPE), perhaps can contain by high density polyethylene (HDPE) and/or hp-ldpe and formation internal layer and has the resin combination that the polyethylene resin II blend of physical property (e)-(h) is obtained.
These high density polyethylene (HDPE)s and polyethylene resin II are selected from above-mentioned can be used for the constituting high density polyethylene (HDPE) of internal layer and those resins of polyethylene resin II.
Resin combination that use contains high density polyethylene (HDPE) and polyethylene resin II as outer field situation under, blend percentage makes that polyethylene resin II is the 5-95% quality, preferred 15-85% quality, more preferably 30-70% quality.If the blend percentage of polyethylene resin II is less than above-mentioned scope, then intensity reduces unfriendly, and if blend percentage surpasses above-mentioned scope, then may stick together unfriendly.
When skin contained the resin combination that obtains by high density polyethylene (HDPE) and hp-ldpe blend, the percentage of hp-ldpe was 5-95% weight aptly, preferred 15-85% weight, more preferably 30-75% weight.If the percentage of hp-ldpe is in above-mentioned scope, then mouldability is improved, and bad outward appearance can occur hardly, and is for example wrinkling.Thereby skin has good surface appearance.
Outer can also be equal to or higher than 130 ℃ hear resistance material (D) by the fusing point peak temperature and form, this temperature is by differential scanning calorimetry (DSC) detection.Exist under the situation at a plurality of peaks, the highest temperature peak is to be equal to or higher than 130 ℃.The example of resin material (D) comprises medium density polyethylene, polypropylene, ethylene-propylene random copolymer, Ethylene-Propylene Block Copolymer, ethylene-vinyl alcohol copolymer (EVOH), polyamide is nylon-6 and nylon 6 for example, 6, polyester is PET and polybutylene terephthalate for example.
IV. laminated material
(1) layer structure
Layer structure in the laminated material of the present invention had no particular limits, as long as this laminated material has internal layer, intermediate layer and skin (internal layer is a hot sealing layer) successively.As for the number of layer, most preferably the three-decker that is made of skin/intermediate layer/internal layer still the invention is not restricted to this.Can use the layer of additional layer structure wherein is provided in the intermediate layer of skin/intermediate layer/endothecium structure, promptly, skin/intermediate layer/middle layer/intermediate layer/internal layer perhaps when needed, is providing another layer aptly between skin and the intermediate layer or between intermediate layer and internal layer.The example of these other layers comprises adhesive layer, gas barrier layer and UV-absorbing layer.For example, also can use five-layer structure, for example skin/gas barrier layer/intermediate layer/adhesive layer/internal layer.In addition, can provide one deck again in outer field outside.
The example that constitutes the adhesive of adhesive layer comprises polyolefin and the ionomer resin that polyurethane-type adhesive, vinyl acetate ester adhesive, PUR and adhesive resin are for example maleic anhydride modified.Under situation about adhesive layer being introduced in the layer structure, this layer can be by coming out laminated with the adhesive co-extrusion necessary component layers (for example internal layer and intermediate layer).
Of the present invention layer structure most preferably is the structure of internal layer/intermediate/outer layer, just high density polyethylene (HDPE)/by having the resin combination of physical property (a)-(d) and (i) and the resin combination that obtains of polyethylene resin I (j) and the polyethylene resin II blend with physical property (e)-(h)/by high density polyethylene (HDPE) and the polyethylene resin II blend with physical property (e)-(h) are obtained.
By using this layer structure, improved the impact strength of hear resistance and seal member astoundingly.This is the effect that particularly obtains when using this certain layer structure, can not obtain this effect when the polyethylene resin II with physical property (e)-(h) is used alone as the resin material that constitutes internal layer.The reason that obtains this effect is not must be fully aware of, but thinks when internal layer seals each other, not only the physical property in internal layer but also intermediate layer (intensity) and according to circumstances in addition outer field performance all can influence the intensity of seal member.In routine techniques, do not have to describe or layer the effect that combination obtain of hint by forming by the specific resin material yet.
(2) thickness of each layer
Whole thickness to laminated material of the present invention has no particular limits, and can suitably select thickness according to final use, but whole thickness preferably 0.01-1mm, more preferably 0.1-0.5mm.Whole thickness in above-mentioned scope is favourable, because obtained the flexible of the high transparency and excellence.
Thickness ratio between each layer is had no particular limits, and density is equal to or less than 0.920g/cm but the structure optimization of laminated material makes use
3The low-density layer (intermediate layer) of resin material become main layer with regard to thickness.Thickness ratio between these layers more preferably approximately is an internal layer: intermediate layer: skin=1-30: 40-98: 1-30 (thickness ratio) (prerequisite is that the gross thickness of all layers is 100).
(3) preparation method of laminated material
Preparation method to laminated material of the present invention has no particular limits, but its example comprise by water-cooled or air-cooled coextruded multilayer inflation, coextruded multilayer T die casting mould, dry lamination or extrude the method that lamination forms laminated film or sheet material.Wherein, preferably method is moulded in water-cooled coextruded multilayer inflation method and coextruded multilayer T die casting.Specifically, with regard to many aspects such as the transparency and health aspect etc. for example, advantageously use water-cooled coextruded multilayer inflation method.In addition, the multilayer blow moulding product can also form by the multilayer blow moulding method.
Laminated film or sheet material can further be processed into bag by heat-sealing, or the multilayer blow moulding product can be used as it is or can be used as container after fixed cover etc.Particularly, laminated material of the present invention is preferably by using internal layer as hot sealing layer at least a portion laminated film or sheet material heat-sealing to be processed to a bag shape.
V. purposes
Particularly when laminated material of the present invention preferably when internal layer being sealed into hot sealing layer and is processed into bag shape, the impact strength of the heat-sealing parts after 155 ℃ of temperature sealing heat-sealing parts can be up to 700kJ/m
2Or bigger, preferred 800kJ/m
2Or bigger, more preferably 900kJ/m
2Or it is bigger.
Equally, even after carrying out for example sterilizing for the heat treatment of necessity such as medical or food containers, laminated material of the present invention also can keep high seal member impact strength.More particularly, for example when disinfection (121 ℃, 20 minutes), the seal member impact strength after disinfecting is up to 500kJ/m
2Or bigger, preferred 600kJ/m
2Or bigger, more preferably 700kJ/m
2Or it is bigger.
Here used seal member impact strength is when making that seal temperature is that 155 ℃, sealing time are that 5 seconds and sealing load are the value when sealing under the heat seal condition of 0.4MPa.
So, even after heat treatment is for example sterilized, the container that contains laminated material of the present invention also can keep high seal member intensity.Therefore, this container is suitable for containers for medical use, and food containers is jar box etc. for example, and they need also have high seal member intensity after disinfecting.Particularly, this container is suitable for containers for medical use, medical infusion bags for example, more especially (wherein two or more liquid drugs are stored in the separate chambers of bonded property parts separation for blood bag, blood platelet reservoir bag, infusion bag (liquid drug), multicell containers for medical use, mix by strip off adhesive means in use under air-tight state with these multiple liquid drugs) and artificial dialysis bag etc.
Embodiment
Describe the present invention in detail below by embodiment, but the invention is not restricted to these embodiment.In embodiment and Comparative Examples, physical property is estimated by the following method.
(1) MFR: detect MFR according to JIS-K6760.
(2) density: detect density according to JIS-K6760.
(3) dissolve in the fraction of ODCB
In the ODCB of 20ml, the 0.5g sample in 135 ℃ of heating 2 hours, after sample dissolves fully, is cooled to 25 ℃ with solution.Make this solution leave standstill a night in 25 ℃, the filter with the Teflon system filters then.To the filtrate sampling, use this filtrate, use determination of infrared spectroscopy at 2925cm
-1Near the wave number absworption peak area is the asymmetric stretching vibration of methylene herein.Based on the value that is obtained, from the calibration curve calculation sample concentration that obtained in the past.Can be determined at 25 ℃ of fractions that dissolve in ODCB by this value.
(4)Cb
In the o-dichlorohenzene (ODCB) that adds antioxidant (2,6-BHT, 0.1% weight), sample dissolution under 135 ℃ of heating, thus sample concentration is 0.2% quality.This solution is transferred in the post that diatomite (Celite 545) are housed, and be cooled to 25 ℃, thereby make sample deposition on the Celite surface with 1 ℃/minute speed.When ODCB flowed into this post with 1ml/ minute speed, column temperature progressively was elevated to 120 ℃ carrying out wash-out with 5 ℃ increment, thereby with sample classification.Subsequently, methyl alcohol is mixed with eluate,, obtain the classification sample under each eluting temperature reppd sample filtering, drying.In that the mass fraction and the degree of branching (by the side chain number of per 1000 carbon atoms) of elution samples are passed through at each temperature
13C-NMR detects.Subsequently, with the mass fraction w of each fraction
iDivided by degree of branching b
iVariable (b by per 5 ℃ of eluting temperatures
i-b
I-1), obtain relative concentration C
i, map with respect to the degree of branching with this relative concentration, obtain component distribution curve.This component distribution curve is divided into fixing width, calculates according to the formula of front and form distributed constant Cb.
(5)Mw/Mn
Weight average molecular weight (Mw) and number-average molecular weight (Mn) detect by gel permeation chromatography (GPC), and obtain ratio Mw/Mn from detected value.Detailed condition is as follows.
GPC:Model 150 types are produced by Waters.
Eluting solvent: ODCB
Column temperature: 135 ℃
Post: GMMHR-H (S) is produced by Tosoh Corporation.
(6) the TREF method is measured the peak number order
In the ODCB that adds antioxidant (2,6-BHT, 0.1% weight),, obtain the sample that concentration is 0.05% quality in 135 ℃ of heating for dissolving samples.Then, this sample solution of 5ml is poured in the post that bead is housed, and is cooled to 25 ℃ with 0.1 ℃/minute cooldown rate, thus on the bead surface deposited samples.Subsequently, when ODCB crossed this post with 1ml/ minute data rate stream, column temperature progressively raise with 50 ℃/hour constant rate of speed, thus elution samples successively.At this moment, use the infrared spectrometer METHOD FOR CONTINUOUS DETERMINATION at 2925cm
-1There is the wash-out of absorption to go into sample concentration in the solvent, 2925cm
-1It is the wave number of the asymmetric stretching vibration of methylene.Based on this detected value, the concentration of ethylene/alpha-olefin copolymer in solution is quantitative, and obtain relation between eluting temperature and the elution rate thus.Make the curve of eluting temperature and elution amount by the value that obtains, and calculate the number at peak.
(7) impact strength of seal member
Using internal layer as hot sealing layer, is that 0.4MPa, seal temperature are 155 ℃ and sealing time to be to seal under 5 seconds the condition at pressure.The seal member of gained is struck out the s type sample that uses in tension impact experimental technique (ASTM-D1822), so that the seal interface reaches the center.Afterwards, seal member is separated by the seal interface disinfecting (121 ℃, 20 minutes), resemble to open the T type, and with the tension impact experimental machine in 23 ℃ of detections.
(8) resistance to blocking
Two films are cut into the wide bar of 20mm separately, and the counterweight of 10kg is placed in only overlapping placement on 5cm length in the above.Make these diaphragms in baking oven, after 48 hours, condition is adjusted to 23 ℃, two films are peeled away each other in 50 ℃ of maintenances.The surface that range estimation is peeled away.
Zero: the surface does not have muddy.
*: external haze.
(9) hear resistance
Cut out the film of long 20cm and wide 20cm, seal three, pour water into its inside, seal a remaining side, obtain the sack that all four limits all seal.Be 121 ℃ of sterilizations after 20 minutes, the visual assessment outward appearance.
◎: do not have distortion and no wrinkle.
Zero: nothing is out of shape but fold is arranged slightly.
*: be out of shape and many fold are arranged.
Embodiment 1-12 and Comparative Examples 1-3:
Contain internal layer, intermediate layer and the outer field laminated film formed by resin shown in the table 1 respectively and pass through the production of water-cooled coextruded multilayer inflation method.Each layer is 10 microns/225 microns/15 microns apart from the thickness setting of internal layer.The testing result of hear resistance, resistance to blocking and seal member impact strength is listed in the table 2.
In embodiment and Comparative Examples, use following resin.
(1) s-LL1: ethylene/hexene-1 copolymer (density: 0.898g/cm
3, MFR:1.0g/10 minute, Mw/Mn:2.7), use single-point type Catalyst Production.
(2) s-LL2: ethylene/hexene-1 copolymer (density: 0.905g/cm
3, MFR:1.2g/10 minute, Mw/Mn:2.8), use single-point type Catalyst Production.
(3) s-LL3: ethylene/hexene-1 copolymer (density: 0.901g/cm
3, MFR:0.8g/10 minute, Mw/Mn:2.3), use single-point type Catalyst Production.
(4) s-LL4: ethylene/hexene-1 copolymer (density: 0.924g/cm
3, MFR:2.1g/10 minute, Mw/Mn:2.6), use single-point type Catalyst Production.
(5) s-LL5: ethylene/hexene-1 copolymer (density: 0.942g/cm
3, MFR:1.2g/10 minute, Mw/Mn:2.2), use single-point type Catalyst Production.
(6) HD1: high density polyethylene (HDPE) (density: 0.945g/cm
3, MFR:2.8g/10 minute)
(7) HD2: high density polyethylene (HDPE) (density: 0.952g/cm
3, MFR:3.5g/10 minute)
(8) LD1: hp-ldpe (density: 0.927g/cm
3, MFR:1.5g/10 minute)
(9) PP1: propylene-ethylene random copolymer (density: 0.900g/cm
3, MFR:4.0g/10 minute)
(10) PP2: propylene-ethylene block copolymer (density: 0.900g/cm
3, MFR:2.5g/10 minute).
Table 1
| MFR (g/10 minute) | Density g/cm 3 | Dissolve in the fraction (% quality) of ODCB | (c) 1) | (g) 2) | Cb | Mw/Mn | TREF peak number order | |
| S-LL1 | 1.0 | 0.898 | 11.6 | 12.0 | 12.0 | 1.40 | 2.7 | Multimodal |
| S-LL2 | 1.2 | 0.905 | 3.4 | 8.4 | 8.4 | 1.35 | 2.8 | Multimodal |
| S-LL3 | 0.8 | 0.901 | 3.1 | 9.8 | 9.8 | 1.10 | 2.3 | Unimodal |
| S-LL4 | 2.1 | 0.924 | 0.8 | 2.7 | 2.7 | 1.20 | 2.4 | Multimodal |
| S-LL5 | 1.2 | 0.942 | 0.4 | 3.3 | 2.0 | 1.15 | 2.5 | Unimodal |
| HD1 | 2.8 | 0.945 | - | - | - | - | ||
| HD2 | 3.5 | 0.952 | - | - | - | - | ||
| LD1 | 1.5 | 0.927 | - | - | - | - | ||
| PP1 | 4.0 | 0.900 | - | - | - | - | ||
| PP2 | 2.5 | 0.900 | - | - | - | - |
In table 1,
1) represent the X value that is expressed from the next:
X＝9.8×10
3×(0.9300-d+0.008logMFR)
2+2.0，
Wherein density is by d (g/cm
3) expression, MFR by MFR (g/10 minute) expression and
2) represent the X value that is expressed from the next:
Under the situation of d-0.008logMFR 〉=0.93, X＜2.0 and
Under the situation of d-0.008logMFR＜0.93, X＜9.8 * 10
3* (0.9300-d+0.008logMFR)
2+ 2.0,
Wherein density is by d (g/cm
3) expression, MFR is represented by MFR (g/10 minute).
Film thickness: 250 μ m
Internal layer/intermediate/outer layer=10 μ m/225 μ m/15 μ m
Industrial applicability
As previously mentioned, even laminated material of the present invention also keeps high seal member intensity after heat treatment is for example sterilized. Therefore, even being adapted at requiring also to have after disinfecting in containers for medical use, food containers such as the tank box of high seal member intensity, it uses. Particularly, laminated material of the present invention is suitable as containers for medical use, medical infusion bags for example, more especially (wherein two or more liquid drugs are stored in the separate chambers of bonded property parts separation for blood bag, blood platelet reservoir bag, infusion bag (liquid drug), multicell containers for medical use, mix by strip off bonding part in use under air-tight state with these plurality of liquid medicines), and artificial dialysis bag etc.
Claims (5)
1. one kind has internal layer, intermediate layer and outer field laminated material at least, wherein
Described internal layer comprises the resin material (A) that contains high density polyethylene (HDPE),
Described intermediate layer comprises the resin material (B) that contains 50% quality or more polyethylene resin I, described polyethylene resin I is by making ethene and the alpha-olefin with 3-20 carbon atom carry out the ethylene/alpha-olefin copolymer of copolymerization acquisition and have following physical property (a)-(d), and
Described skin comprises resin material (D), this resin material (D) is that blend therein has the resin combination that is selected from least a material in the following material: medium density polyethylene, polypropylene, ethylene-propylene random copolymer, Ethylene-Propylene Block Copolymer, ethylene-vinyl alcohol copolymer, polyamide and polyester
(a) density is less than 0.920g/cm
3,
(b) MFR is 0.1-50g/10 minute,
(c) in 25 ℃ of amount X (% quality), density d (g/cm that dissolve in the fraction of o-dichlorohenzene
3) and the satisfied following relation of MFR (g/10 minute):
X＜9.8×10
3×(0.9300-d+0.008logMFR)
2+2.0
(d) forming distributed constant Cb is 1.08-2.00,
And
The described resin material (A) that constitutes described internal layer only contains high density polyethylene (HDPE); Perhaps
The described resin material (A) that constitutes described internal layer is the resin combination that comprises the polyethylene resin II of the high density polyethylene (HDPE) of 60-99% quality and 1-40% quality, described polyethylene resin II carries out the ethylene/alpha-olefin copolymer that copolymerization obtains by ethene and the alpha-olefin with 3-20 carbon atom, and has following physical property (e)-(h);
(e) density is to less than 0.960g/cm from 0.920
3,
(f) MFR is 0.1-50g/10 minute,
(g) in 25 ℃ of amount X (% quality), density d (g/cm that dissolve in the fraction of o-dichlorohenzene
3) and the satisfied following relation of MFR (g/10 minute):
I) under the situation of d-0.008logMFR 〉=0.93, X＜2.0 and
Ii) under the situation of d-0.008logMFR＜0.93,
X＜9.8 * 10
3* (0.9300-d+0.008logMFR)
2+ 2.0 and
(h) form distributed constant Cb less than 2.00.
2. according to the laminated material of claim 1, wherein constituting described outer field described resin material (D) is that blend therein has the resin combination that is selected from least a material in the following material: ethylene-propylene random copolymer and Ethylene-Propylene Block Copolymer.
3. according to the laminated material of claim 1 or 2, the described resin material (B) that wherein constitutes described intermediate layer is the resin combination that comprises described polyethylene resin I and be selected from least a material in the following substances: high density polyethylene (HDPE), medium density polyethylene, hp-ldpe, linear low density polyethylene (LLDPE), polypropylene, ethylene-propylene random copolymer and Ethylene-Propylene Block Copolymer.
4. according to the laminated material of claim 1 or 2, the described resin material (B) that wherein constitutes described intermediate layer is the resin combination that comprises described polyethylene resin I and high density polyethylene (HDPE).
5. comprise container according to the laminated material of claim 1 or 2.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001005858 | 2001-01-15 | ||
| JP5858/2001 | 2001-01-15 | ||
| US60/282,871 | 2001-04-11 | ||
| JP382096/2001 | 2001-12-14 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028036174A Division CN100425442C (en) | 2001-01-15 | 2002-01-15 | Laminate and container |
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| Publication Number | Publication Date |
|---|---|
| CN1765629A CN1765629A (en) | 2006-05-03 |
| CN100572047C true CN100572047C (en) | 2009-12-23 |
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| TWI444291B (en) * | 2009-10-20 | 2014-07-11 | Hosokawa Yoko Kk | Plastic film and infusion bag |
| WO2019142809A1 (en) * | 2018-01-22 | 2019-07-25 | 三井・ダウポリケミカル株式会社 | Sealable resin composition, seal material, packaging material, packaging container and package |
| CN109927358B (en) * | 2019-04-12 | 2019-10-25 | 广东超维塑料薄膜有限公司 | A kind of high-barrier anti-extrusion all-plastic flexible sheet material and preparation method thereof |
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