CN109328167A

CN109328167A - The chemical resistance blow molding stacked containers that the transparency is excellent and contaminant particles the amount of dissolution is few

Info

Publication number: CN109328167A
Application number: CN201680086859.6A
Authority: CN
Inventors: 小林玄明; 松尾初夫
Original assignee: Eryu Resin Industry Co Ltd
Current assignee: Eryu Resin Industry Co Ltd; Kodama Plastics Co Ltd
Priority date: 2016-06-17
Filing date: 2016-06-17
Publication date: 2019-02-12
Anticipated expiration: 2036-06-17
Also published as: JP6518839B2; KR20190020077A; WO2017216826A1; CN109328167B; JPWO2017216826A1; KR102191634B1

Abstract

The present invention provides a kind of chemical resistance blow molding stacked containers, it is sequentially laminated with internal layer 1 from container inside to outside and (does not have adhesiveness functional group, loss on heating is 0.20 mass % fluororesin below), internal layer 2 (has adhesiveness functional group, loss on heating is 0.40 mass % fluororesin below), stop simultaneous bonding resin layer (polyamide without containing additive), adhesiveness layer (maleic anhydride modified polyolefin resin), barrier layer (ethylene-vinyl alcohol copolymer resin) and outer layer 1 (contain maleic anhydride modified polyolefin resin, ultraviolet transmittance is 1% super high molecular weight high-density polyethylene resin below), each layer is transparent, contaminant particles the amount of dissolution (number/ml) after the container is stored 30 days at 23 DEG C and at 40 DEG C is respectively 5 or less and 10 or less , and ultraviolet-shielding type, oxygen barrier etc. are excellent, the dissolution of contaminant particles is few, has visibility identical with Clear glass bottles and jars.

Description

The chemical resistance blow molding layer that the transparency is excellent and contaminant particles the amount of dissolution is few Folded container

Technical field

A kind of chemical resistance blow molding stacking excellent the present invention relates to transparency and that contaminant particles the amount of dissolution is few Container is further specifically related to the chemical resistance that a kind of following transparency is excellent and contaminant particles the amount of dissolution is few Blow molding stacked containers: chemical resistance and mechanical strength etc. are excellent, such as contaminant particles are stored 30 days at 40 DEG C Drug or fragrance etc. in the amount of dissolution (number/ml) be 10 hereinafter, considerably less, the i.e. good blow molding (blow of cleanliness Molding) stacked containers, visibilities with the storage liquid that can confirm storage from external visual, comparable to Clear glass bottles and jars, And ultraviolet-shielding type, oxygen barrier are also excellent, can be used as ultra-high purity chemicals container.

Background technique

Usually as the container for saving chemicals or fragrance etc., using having glass container or air-tight bottle (commercially available fragrance Container) etc. the plastic container of chemical resistances or carried out the container of coating treatment in the inner face of canister.

In semiconductor field, it is desirable to be able to directly save stored high-purity chemical drug class with high-purity.Glass Container is not easy to operate since container itself is heavier, can also rupture sometimes because dropping.

On the other hand, the container molding being made of polythylene resin, which has, to be not easily broken in operation, is light-weight excellent Point.However, in semiconductor fabrication, to high-purity chemical drug, such as sulfuric acid, nitric acid, the dioxygen for etching or cleaning Water etc., and solvent resist or retarder thinner, example for the high-purity in semiconductor technology use, liquid crystal display use etc. Such as methanol, ethyl alcohol, isopropanol, isobutanol, ethylene glycol, acetone, ethyl acetate, toluene, dimethylformamide, ethylene glycol acetic acid Ester, Methoxypropylacetate, butyl cellosolve etc., and for sterilizing, sterilizing, high-purity that preparation raw material etc. is pharmaceutical it is molten Agent carries out keeping when storing such as methanol, ethyl alcohol, isopropanol, there are contaminant particles from the resin combination for forming container or The problem of being oozed out into additive in the chemicals of storage, destroying the purity of chemicals, therefore exist to semiconductor, liquid crystal Quality and yield cause the problem of storage life of significant adverse effect or chemicals shortens.

When by chemicals long-term storage in container, contaminant particles ooze out into work from the resin combination for forming container In chemicals for the object accommodated, as indicate the contaminant particles make the object accommodated generate impurity degree index, Call it as cleanliness.

Cleanliness is found out in the following manner: first making to check container formation, certain period (23 is stored in the inspection container At DEG C, 30 days) ultrapure water after, calculating in the 1ml water stored in the container of resin there are how many partial size is 0.2 μm or more Particle.

(measuring methods of previous contaminant particles (particle))

1. measurement device: using RION CO., particle collector " KL-26 " the RION KL-26 of LTD. manufacture.

2. a measurement specimen: ultrapure water is filled in molding container, after storing 30 days at 23 DEG C, from upright state It has stood and has taken measurement sample in 20 minutes containers, as a measurement specimen.

3. after cleaning (purge) particle collector with ultrapure water before the assay, using 25ml ultrapure water to measurement device into Row 2 times cleanings.

4. 10ml ultrapure water after cleaning, is injected particle collector, granule number is measured.Carry out 2 operations, confirmation 0.2 μm or more of granule number is 0 (A).

5. carrying out 2 cleanings to measurement device with a measurement specimen of 25ml.

6. after cleaning, taking out 10ml from the container (bottle) of ultrapure water for filling a measurement specimen, being injected into particle meter Number device, measures granule number.2 operations are carried out, the average value (B) of 0.2 μm or more of granule number is found out.

7. calculating the grain value in 1ml by measured value by following formula.

10ml=/ml of (B (a)) ÷

In the past, if cleanliness is less than 500/ml, it is considered as can be improved semiconductor, the quality of liquid crystal and yield.It is existing Become it is more stringent it is more and more in the case where require to be 5/ml or less.

However, recently, the requirement of cleanliness is further got higher, it is desirable that as follows: making to check container formation, in the inspection container In fill ultrapure water, in the 1ml ultrapure water after being stored 30 days at 23 DEG C partial size be 0.2 μm or more contaminant particles the amount of dissolution (number/ml) is 5 hereinafter, and partial size is 0.2 μm or more in the 1ml ultrapure water after storing 30 days at 40 DEG C contaminant particles The amount of dissolution (number/ml) is 10 or less.

As the container used in field of perfumery, uses be coated with tank or the sealing of fluorine in metal can inner face on the market Bottle, but there are problems that being recessed and getting rusty when for metal can, fragrance component is rotten frequent occurrence when for air-tight bottle, fragrance The problem of quality variation.

In this regard, being easy as mechanical strength, operation, contaminant particles seldom ooze out into the chemicals of keeping storage , high-purity chemical drug light-shielding container with light-proofness, propose and be made of polyethylene or ethene-alpha-olefin copolymer Material resin weight average molecular weight in a certain range, the content of light-proofness pigment and dispersing agent in resin combination exists In certain range, make the polymer of the low molecular weight in resin combination, the content of additive be less than constant weight, by gathering The molding container of resin combination (referring to patent document 1) of ethylene or ethene-alpha-olefin copolymer composition.

However, according to previous measuring method, although the cleanliness of the container meets less than 500/ml, cleanliness without Method reach 5/ml hereinafter, and there is also the oxygen barrier etc. not having for preventing the storage liquid of storage from going bad etc. ask Topic.

Furthermore, it is also proposed that a kind of high-purity solvent is with container (referring to patent document 2), for storage methanol, ethyl alcohol, different Propyl alcohol, isobutanol, ethylene glycol, acetone, ethyl acetate, toluene, dimethylformamide, Ethylene glycol acetate, methoxy-propyl second The container of the high-purity solvent of acid esters or butyl cellosolve, at least inner surface of the container are 940~970Kg/ by density The polyethylene of m3 or the resin composition of ethene-alpha-olefin copolymer, it is legal by liquid chromatogram relative to the total weight of the resin The content of neutralizer, antioxidant in the resin of amount and resistance to light stabilizer is 0.01 weight % hereinafter, being seeped by gel The weight average molecular weight of the resin of saturating chromatography determination is 120,000~260,000, relative to the total weight of the resin, the resin In molecular weight be 1,000 polymer below less than 2.5 weight %.

However, according to previous measuring method although the cleanliness of the high-purity solvent container of patent document 2 meets small In 500/ml, but cleanliness is unable to reach 5/ml hereinafter, and ultraviolet there is also that can prevent the storage liquid of storage from going bad The poor problem such as line shielding.

Furthermore, it is also proposed that a kind of high-purity chemical drug with container (referring to patent document 3), to density be 940 At least it is added to 0.01 weight of weight %~5 %'s in the polyethylene of~970Kg/m3 or the resin of ethene-alpha-olefin copolymer The resin combination of the liquid or gas barrier resin of the light-proofness such as titanium oxide or carbon black pigment and 4 weight of weight %~25 % Composition, the weight average molecular weight of the resin measured by gel permeation chromatography are 120,000~260,000, weight average molecular weight 1,000 Polymer below be less than the resin 5 weight %, the alpha-olefin be selected from propylene, 1- butylene, 4-methyl-1-pentene, 1- oneself At least one of alkene, 1- octene.

However, the high-purity chemical drug of patent document 3 still has following problems with container, i.e., according to previous measurement Method, although cleanliness meets less than 500/ml, cleanliness is unable to reach 5/ml or less.

Further it is proposed that a kind of high-purity chemical medical fluid is with container (referring to patent document 4), which is characterized in that it is served as reasons Internal layer, solvent block resin middle layer and outer layer blow molding made of container, the internal layer is made of high-purity resin, The high-purity resin contains the alkene selected from ethylene, propylene, 1- butylene, 4-methyl-1-pentene, 1- hexene or 1- octene Polymer and ethylene and at least one of the copolymer of alkene in addition to ethylene, and by neutralizer, antioxidant and fast light The respective content maximum of stabilizer is set as 0.01 weight %, and the middle layer contains poly- (ethylene-vinyl alcohol), the outer layer by Resin combination composition containing light-proofness substance, all layers of the wavelength by the container of spectrophotometric determination are 400nm Minimum absorbance when following is 2.0 or more, and obtained from absorbance of all layers of the thickness divided by all layers of container Absorptivity when wavelength 400nm is 1.5mm-1 or more, and similarly absorptivity when wavelength 600nm is 1.5mm-1 or less.

However, the high-purity chemical medical fluid of patent document 4 is had the following problems with container: according to previous measuring method, Cleanliness meets less than 100/ml, but cleanliness is unable to reach 5/ml or less.

A kind of chemical resistance blow molding stacked containers (reference patent document has been proposed in present inventor 5), by stacking gradually following internal layers, blocking and bonding resin layer from container inside to outside, adhesive layer, barrier layer, gluing It closing layer and outer layer forms, each layer has the transparency, and the transparency is excellent,

Internal layer: fluororesin,

Stop simultaneous bonding resin layer: polyamide,

Adhesive layer: maleic anhydride modified polyolefin resin

Barrier layer: ethylene-vinyl alcohol copolymer resin,

Adhesive layer: maleic anhydride modified polyolefin resin,

Outer layer: super high molecular weight high-density polyethylene resin.

Existing technical literature

Patent document

Patent document 1: No. 2805723 bulletins of Japanese Patent No.

Patent document 2: No. 2749513 bulletins of Japanese Patent No.

Patent document 3: No. 2805188 bulletins of Japanese Patent No.

Patent document 4: No. 4167745 bulletins of Japanese Patent No.

Patent document 5: No. 5706512 bulletins of Japanese Patent No.

Summary of the invention

The technical problem to be solved in the present invention

As described above, further increasing to the requirement of cleanliness recently, it is desirable that as follows: making to check container formation, in the inspection It looks into and fills ultrapure water in container, the contaminant particles that partial size is 0.2 μm or more in the 1ml ultrapure water after storing 30 days at 23 DEG C The amount of dissolution (number/ml) is 5 hereinafter, and partial size is 0.2 μm or more in the 1ml ultrapure water after storing 30 days at 40 DEG C impurity The amount of dissolution (number/ml) of particle is 10 or less.

The excellent chemical resistance blow molding stacked containers (reference of the transparency that present inventor has proposed Patent document 5) chemical resistance and mechanical strength etc. it is excellent, impurity particle is to chemicals of keeping storage or fragrance etc. In exudation it is few, in the 1ml ultrapure water after being stored 30 days at 23 DEG C partial size be 0.2 μm or more contaminant particles the amount of dissolution (with Under, sometimes referred to as cleanliness) (number/ml) be 5 hereinafter, have the storage liquid that storage can be confirmed from external visual, comparable to The visibility of Clear glass bottles and jars, and ultraviolet-shielding type, oxygen barrier are also excellent, but in the presence of after storing 30 days at 40 DEG C The problem of the amount of dissolution (number/ml) for the contaminant particles that partial size is 0.2 μm or more in 1ml ultrapure water is more than 10, and there is also The problem of cost increase, this is because, in order to outer layer super high molecular weight high-density polyethylene resin assign wavelength 500~ The transmissivity of the visible light of 800nm is 35% or more, the ultraviolet transmittance of 200~400nm of wavelength is 1% characteristic below, Need to add the nucleating agent or resistance to light stabilizer of high price.

A kind of chemical resistance excellent the purpose of the present invention is to provide transparency and that contaminant particles the amount of dissolution is few is blown Type stacked containers are moulded into, chemical resistance and mechanical strength etc. are excellent, take care of storage as indicating to ooze out into from container side Ultra-high purity chemicals etc. in contaminant particles number index cleanliness, after being stored 30 days at 23 DEG C for 5 with Under, and after being stored 30 days at 40 DEG C for 10 hereinafter, have the storage liquid that storage can be confirmed from external visual, comparable to transparent The visibility of vial, and ultraviolet-shielding type, oxygen barrier are also excellent, and do not have to addition for the superelevation point of external layer Son amount high-density polyethylene resin assign 500~800nm of wavelength visible light transmissivity be 35% or more, wavelength 200~ The ultraviolet transmittance of 400nm is the high price nucleating agent or resistance to light stabilizer of 1% characteristic below, compared with the existing product At low cost and economy is excellent, can be used as the ultra-high purity chemicals container of fragrance or photoresist liquid etc..

Solve the technological means of technical problem

Present inventor is carefully studied to solve existing issue, as a result, it has been found that in the following manner can A kind of chemical resistance blow molding stacked containers that contaminant particles the amount of dissolution is few are obtained, so as to complete the present invention: the appearance Device for example by from container inside to outside stack gradually following internal layers 1, internal layer 2, stop and bonding resin layer, adhesiveness layer, Barrier layer and outer layer form, and each layer has the transparency, which has the visibility comparable to Clear glass bottles and jars, by using not having Adhesive functional group has adhesiveness to the fluororesin of internal layer 2 but does not have an adhesiveness to other layers, and it is additive-free plus Heat loss is 0.20 mass % specific fluororesin below as the internal layer 1, using with adhesiveness functional group, to internal layer 1 fluororesin and blocking and bonding resin layer have adhesiveness, and additive-free loss on heating is that 0.40 mass % is below Specific fluororesin is as the internal layer 2, using poly- without containing the additive comprising the additive or lubricant that intentionally add Amide resin as stop and bonding resin layer, can reach the contaminant particles the amount of dissolution after being stored 30 days at 23 DEG C (number/ Ml the contaminant particles the amount of dissolution (number/ml) after being) 5 or less and storing 30 days at 40 DEG C is 10 cleanliness below, is passed through Use ethylene-vinyl alcohol copolymer resin as barrier layer, can be improved gas barrier, adds high price by using not outer layers Nucleating agent or the super high molecular weight excellent, that melting tension is big such as resistance to light stabilizer, ultraviolet-shielding type and the transparency it is highly dense Polyvinyl resin is spent, drawdown etc. can not occur, mouldability and mechanical strength etc. are improved, therefore one kind can be obtained and also can be used as The container of the high price such as fragrance or photoresist liquid and the high chemical substance of risk also more ultra-high purity chemicals.

In order to solve the technical problem, the invention of claim 1 of the invention is that a kind of transparency is excellent and impurity is micro- The few chemical resistance blow molding stacked containers of grain the amount of dissolution, by being stacked gradually in following from container inside to outside Layer 1, internal layer 2 stop simultaneous bonding resin layer, adhesiveness layer, barrier layer and outer layer 1 to form, and each layer has the transparency, special Sign is that the contaminant particles the amount of dissolution (number/ml) after storing 30 days at 23 DEG C is 5 hereinafter, and storing 30 days at 40 DEG C Contaminant particles the amount of dissolution (number/ml) afterwards is 10 or less.

Internal layer 1: to there is adhesiveness to the fluororesin of internal layer 2 but do not have to other layers without adhesiveness functional group The additive-free fluororesin of adhesiveness, loss on heating be 0.20 mass % hereinafter,

Internal layer 2: for adhesiveness functional group, fluororesin and blocking and bonding resin layer to internal layer 1 have adhesiveness Additive-free fluororesin, loss on heating be 0.40 mass % hereinafter,

Stop and bonding resin layer: for it is without containing the additive comprising the additive or lubricant that intentionally add, be selected from The polyamide of at least one of the group that the polyamide obtained from the open loop polycondensation as caprolactam forms,

Adhesiveness layer: for maleic anhydride modified polyolefin resin,

Barrier layer: for ethylene-vinyl alcohol copolymer resin,

Outer layer 1: for super high molecular weight high-density polyethylene resin, containing maleic anhydride modified polyolefin resin, with institute The adhesiveness for stating barrier layer is excellent, and the ultraviolet transmittance of 200~400nm of wavelength is 1% or less.

The invention of claim 2 of the invention is the chemical-resistant resistance that a kind of transparency is excellent and contaminant particles the amount of dissolution is few Property blow molding stacked containers, by from container inside to outside stack gradually following internal layers 1, internal layer 2, stop and bonding tree Rouge layer, adhesiveness layer, barrier layer, adhesiveness layer and outer layer 2 form, and each layer has the transparency, which is characterized in that at 23 DEG C Contaminant particles the amount of dissolution (number/ml) after lower storage 30 days be 5 hereinafter, and contaminant particles after being stored 30 days at 40 DEG C it is molten Output (number/ml) is 10 or less.

Adhesiveness layer: for maleic anhydride modified polyolefin resin,

Barrier layer: for ethylene-vinyl alcohol copolymer resin,

Adhesiveness layer: for maleic anhydride modified polyolefin resin,

Outer layer 2: the ultraviolet transmittance for 200~400nm of wavelength is 1% super high molecular weight high density polyethylene (HDPE) below Resin.

The invention of claim 3 of the invention is characterized in that, the chemically-resistant described in claim 1 or claim 2 In drug blow molding stacked containers, fluororesin used in the internal layer 2 is selected from by tetrafluoroethylene/hexafluoropropylene/mono- Body (α) copolymer, tetrafluoroethylene/perfluoro (alkyl vinyl ether)/monomer (α) copolymer, ethylene/tetrafluoroethylene/monomer (α) are altogether Polymers, ethylene/tetrafluoroethylene/hexafluoropropene/monomer (α) copolymer, chlorotrifluoroethylene/monomer (α) copolymer, chlorine trifluoro second At least one in alkene/tetrafluoroethene/monomer (α) copolymer and ethylene/chlorotrifluoroethylene/monomer (α) copolymer composition group Kind, the monomer (α) indicates the monomer with adhesiveness functional group, and the fluororesin has following characteristics.

(characteristic)

MFR (265 DEG C, 5Kg load g/10min): 10~40

Specific gravity: 1.7~1.9

Fusing point (DEG C): 150~220

The invention of claim 4 of the invention is characterized in that, in chemically-resistant according to any one of claims 1 to 3 In drug blow molding stacked containers, fluororesin used in the internal layer 1 is without the adhesiveness functional group, tool There is the fluororesin of following characteristics.

(characteristic)

MFR (297 DEG C, 5Kg load g/10min): 9~35

Specific gravity: 1.7~2.0

Fusing point (DEG C): 200~240

The invention of claim 5 of the invention is characterized in that, in chemically-resistant according to any one of claims 1 to 4 In drug blow molding stacked containers, the polyamide has following characteristics.

(characteristic)

Fusing point (DEG C): 170~250

Density (Kg/m3): 1.0~1.2

The invention of claim 6 of the invention is characterized in that, in chemically-resistant according to any one of claims 1 to 5 In drug blow molding stacked containers, the barrier layer is the excellent ethylene-second of the oxygen barrier with following characteristics Enol copolymer resins.

(characteristic)

MFR (210 DEG C, 2.16Kg load g/10min): 2~5

Density (Kg/m3): 1.1~1.3

Fusing point (DEG C): 170~200

The invention of claim 7 of the invention is characterized in that chemical resistance described in claim 1 is blow molded into In type stacked containers, the outer layer 1 is by the superelevation being made of polyethylene or ethene-alpha-olefin copolymer with following characteristics point Son amount high-density polyethylene resin and composition 1 are constituted, and the composition 1 is containing 0.01~0.04 mass % for assigning purple Outside line shielding and the transparency, selected from by selected from the organics shading such as quinacridine ketone, phthalocyanines, Anthraquinones, monoazo class In the property inorganics light-proofness pigment such as pigment or carbon black, iron oxide, zinc oxide, ultramarine, chromium oxide, titanium oxide, silica At least one of the group of at least one light-proofness pigment composition light-proofness pigment, 0.05~0.30 mass % antioxidant, The maleic anhydride modified polyolefin resin of 25~65 mass %, the transmission of visible light of 500~800nm of wavelength be 35% with On, the ultraviolet transmittance of 200~400nm of wavelength is 1% or less.

(characteristic)

Density: 940~962Kg/m3

Weight average molecular weight: 220,000~260,000

12 or less molecular weight distribution (Mw/Mn):

Melt tension: 18~30g

The invention of claim 8 of the invention is characterized in that, is blow molded into chemical resistance as claimed in claim 2 In type stacked containers, the outer layer 2 is by the superelevation being made of polyethylene or ethene-alpha-olefin copolymer with following characteristics point Son amount high-density polyethylene resin and composition 2 are constituted, and the composition 2 is containing 0.01~0.04 mass % for assigning purple Outside line shielding and the transparency, selected from by selected from the organics shading such as quinacridine ketone, phthalocyanines, Anthraquinones, monoazo class In the property inorganics light-proofness pigment such as pigment or carbon black, iron oxide, zinc oxide, ultramarine, chromium oxide, titanium oxide, silica The antioxidant of at least one of the group of at least one light-proofness pigment composition light-proofness pigment, 0.05~0.30 mass %, The transmission of visible light of 500~800nm of its wavelength is 35% or more, the ultraviolet transmittance of 200~400nm of wavelength be 1% with Under.

(characteristic)

Density: 940~962Kg/m3

Weight average molecular weight: 220,000~260,000

12 or less molecular weight distribution (Mw/Mn):

Melt tension: 18~30g

Invention effect

The invention of claim 1 of the invention is the chemical-resistant resistance that a kind of transparency is excellent and contaminant particles the amount of dissolution is few Property blow molding stacked containers, by from container inside to outside stack gradually the internal layer 1, internal layer 2, stop and bonding tree Rouge layer, adhesiveness layer, barrier layer and outer layer 1 form, and each layer has the transparency, which is characterized in that stores 30 at 23 DEG C Contaminant particles the amount of dissolution (number/ml) after it be 5 hereinafter, and contaminant particles the amount of dissolution after being stored 30 days at 40 DEG C it is (a Number/ml) it is 10 or less.

By using not having adhesiveness functional group, do not have with adhesiveness but to the fluororesin of internal layer 2 to other layers Adhesiveness, additive-free and loss on heating are 0.20 mass % specific fluororesin below as the internal layer 1, using having Adhesiveness functional group, fluororesin and blocking and bonding resin layer to internal layer 1 have adhesiveness, and additive-free and loss on heating is 0.40 mass % specific fluororesin below includes the additive intentionally added or profit as the internal layer 2, using not containing As simultaneous bonding resin layer is stopped, cleanliness after storing 30 days at 23 DEG C can be obtained is the polyamide of the additive of lubrication prescription 5 hereinafter, and cleanliness is 10 cleanliness that are below, being equivalent to vial after storing 30 days at 40 DEG C, performance can be improved Chemical resistance simultaneously can strongly reduce the rotten remarkable result of odour component.

In addition, by the way that the excellent barrier layer being made of ethylene-vinyl alcohol copolymer resin of oxygen barrier, Neng Gougai is arranged Kind oxygen barrier, on the other hand, after melting due to fluororesin, polyamide and resin of binding property, melting tension is once It reduces, therefore in blow molding the problems such as generation drawdown, such as in the presence of the container that can not be shaped to uniform wall thickness or generates not The problems such as non-defective unit, yield are deteriorated, by using big melting tension, ultraviolet-shielding type and the transparency and mechanical strength to outer layer 1 Etc. excellent super high molecular weight high-density polyethylene resin, mouldability and ultraviolet-shielding type can be improved, therefore played following Remarkable result, can provide a kind of also can be used as the high price such as fragrance or photoresist liquid and the high chemical substance of risk The container of more ultra-high purity chemicals, the blow molding of the transparency is excellent and contaminant particles the amount of dissolution is few chemical resistance Form stacked containers.

Further, since chemical resistance blow molding stacked containers of the invention contain maleic anhydride modified polyolefin tree Rouge has used the outer layer excellent with the adhesiveness on the barrier layer as outer layer 1, therefore is not required in outer layer 1 and the barrier layer Between adhesiveness layer (maleic anhydride modified polyolefin resin) is set, play workability and economy further and become and is good aobvious Write effect.

In addition, with heavier, cracky, lack safety vial compared with, chemical resistance of the invention is blow molded into Type stacked containers are difficult to breakage, have excellent mechanical strength, by setting barrier layer so as to improve oxygen barrier, therefore have There is the performance that can be used as apothecary jar etc., play remarkable result below: can be as can also be into other various objects accommodated The omnipotent plastic containers of enforcement, the sense of taste or in terms of can carry out safely and securely using.

Due to chemical resistance blow molding stacked containers of the invention have characteristic as described above, play with Under remarkable result: it is environmentally friendly and healthy, facilitate environmental problem and health problem, and due to going back cutback of spending therefore It is economical.

The invention of claim 2 of the invention is the chemical-resistant resistance that a kind of transparency is excellent and contaminant particles the amount of dissolution is few Property blow molding stacked containers, by from container inside to outside stack gradually the internal layer 1, internal layer 2, stop and bonding tree Rouge layer, adhesiveness layer, barrier layer, adhesiveness layer and outer layer 2 form, and each layer has the transparency, which is characterized in that at 23 DEG C Contaminant particles the amount of dissolution (number/ml) after lower storage 30 days be 5 hereinafter, and contaminant particles after being stored 30 days at 40 DEG C it is molten Output (number/ml) is 10 or less.

The chemical resistance blow molding stacked containers of claim 2 of the invention pass through in outer layer 2 and the blocking Adhesiveness layer (maleic anhydride modified polyolefin resin) is set between layer, although economy is in a slight decrease within the allowable range, The adhesiveness of the two becomes really, thus can depending on the application or purpose carry out using, in addition to this, have and power of the invention Benefit requires the 1 identical composition of chemical resistance blow molding stacked containers, play a role and effect also with power of the invention Benefit requires 1 this identical remarkable result of chemical resistance blow molding stacked containers.

The invention of claim 3 of the invention is characterized in that, the chemically-resistant described in claim 1 or claim 2 In drug blow molding stacked containers, fluororesin used in the internal layer 2 is selected from by tetrafluoroethylene/hexafluoropropylene/mono- Body (α) copolymer, tetrafluoroethylene/perfluoro (alkyl vinyl ether)/monomer (α) copolymer, ethylene/tetrafluoroethylene/monomer (α) are altogether Polymers, ethylene/tetrafluoroethylene/hexafluoropropene/monomer (α) copolymer, chlorotrifluoroethylene/monomer (α) copolymer, chlorine trifluoro second At least one in alkene/tetrafluoroethene/monomer (α) copolymer and ethylene/chlorotrifluoroethylene/monomer (α) copolymer composition group Kind, the monomer (α) indicates the monomer with adhesiveness functional group, and the fluororesin has the characteristic.

The fluororesin of the monomer (α) with adhesiveness functional group is copolymerized by using the internal layer 2, to internal layer 1 Fluororesin and blocking and bonding resin layer (polyamide) have excellent adhesiveness, and playing can be with identical with polyolefin Forming temperature carries out co-extrusion modling, this more significant effect.

The invention of claim 4 of the invention is characterized in that, in chemically-resistant according to any one of claims 1 to 3 In drug blow molding stacked containers, fluororesin used in the internal layer 1 is without the adhesiveness functional group, tool Have the fluororesin of the characteristic, there is excellent adhesiveness to the fluororesin of internal layer 2, play can with it is identical with polyolefin at Type temperature carries out co-extrusion modling, this more significant effect.

By improving the adhesiveness with the fluororesin of internal layer 2, and be set as additive-free or lubricant, play it is below more Significant effect: impurity particle the amount of dissolution caused by capable of being greatly reduced because of the additive obtains being equivalent to the clean of vial Cleanliness.

The invention of claim 6 of the invention is characterized in that, in chemically-resistant according to any one of claims 1 to 5 In drug blow molding stacked containers, the barrier layer is the excellent ethylene-vinyl of the oxygen barrier with the characteristic Alcohol copolymer resins.

Play oxygen barrier is certainly further improved, this more significant effect.

The invention of claim 7 of the invention is characterized in that chemical resistance described in claim 1 is blow molded into In type stacked containers,

The outer layer 1 is by the super high molecular weight being made of polyethylene or ethene-alpha-olefin copolymer with the characteristic High-density polyethylene resin and composition 1 are constituted, and the composition 1 is containing 0.01~0.04 mass % for assigning ultraviolet light Shielding and the transparency, selected from by selected from the organics light-proofness face such as quinacridine ketone, phthalocyanines, Anthraquinones, monoazo class In the inorganics light-proofness pigment such as material or carbon black, iron oxide, zinc oxide, ultramarine, chromium oxide, titanium oxide, silica at least A kind of at least one of the group of light-proofness pigment composition light-proofness pigment, the antioxidant of 0.05~0.30 mass %, 25~ The maleic anhydride modified polyolefin resin of 65 mass %, the transmission of visible light of 500~800nm of wavelength are 35% or more, wave The ultraviolet transmittance of long 200~400nm is 1% or less.

After melting, melting tension once reduces, therefore in blow molding for fluororesin, polyamide and resin of binding property The problems such as middle generation drawdown, for example, in the presence of can not be shaped to uniform wall thickness container or generate defective products, yield be deteriorated the problems such as, But by using weight average molecular weight and melting the big super high molecular weight high-density polyethylene resin of tension to outer layer 1, to not deposit The drawdown the problems such as, mouldability and mechanical strength etc. are improved.

By using light-proofness pigment with the range, the transparency and ultraviolet-shielding type are certainly improved, can be true The transmissivity for reaching the visible light of 500~800nm of wavelength on the spot is the ultraviolet transmittance of 35% or more, 200~400nm of wavelength For 1% hereinafter, therefore can more reliably provide a kind of chemistry that can be used as fragrance or photoresist liquid etc. at high price and risk is high Substance also the container of more ultra-high purity chemicals, the transparency is excellent and contaminant particles the amount of dissolution is few chemical-resistant resistance Property blow molding stacked containers, by with the range use antioxidant, play more significant effect below: Neng Goufang Only the scaling loss of resin, prevent because of scaling loss resin caused by physical property reduce or appearance be deteriorated etc..

Further, since chemical resistance blow molding stacked containers of the invention contain maleic anhydride modified polyolefin tree Rouge has used the outer layer excellent with the adhesiveness on the barrier layer as outer layer 1, therefore is not required in outer layer 1 and the barrier layer Between adhesiveness layer (maleic anhydride modified polyolefin resin) is set, play workability and economy further and become it is good this One more significant effect.

In addition, with heavier, cracky, lack safety vial compared with, chemical resistance of the invention is blow molded into Type stacked containers are difficult to breakage, have excellent mechanical strength, by setting barrier layer so as to improve oxygen barrier, therefore have There is the performance that can be used as apothecary jar etc., play more significant effect below: can be as to other various objects accommodated The omnipotent plastic containers that can also be used, the sense of taste and in terms of can use safely and securely.

The invention of claim 8 of the invention is characterized in that, is blow molded into chemical resistance as claimed in claim 2 In type stacked containers,

The outer layer 2 is by the super high molecular weight being made of polyethylene or ethene-alpha-olefin copolymer with the characteristic High-density polyethylene resin and composition 2 are constituted, and the composition 2 is containing 0.01~0.04 mass % for assigning ultraviolet light Shielding and the transparency, selected from by selected from the organics light-proofness face such as quinacridine ketone, phthalocyanines, Anthraquinones, monoazo class In the inorganics light-proofness pigment such as material or carbon black, iron oxide, zinc oxide, ultramarine, chromium oxide, titanium oxide, silica at least The antioxidant of a kind of at least one of the group of light-proofness pigment composition light-proofness pigment, 0.05~0.30 mass %, wave The transmission of visible light of long 500~800nm is 35% or more, and the ultraviolet transmittance of 200~400nm of wavelength is 1% or less.

After melting, melting tension once reduces, therefore in blow molding for fluororesin, polyamide and binder resin The problems such as drawdown occurs, such as there is a problem of that the container of uniform wall thickness or generation defective products, yield variation etc. can not be shaped to, But by using weight average molecular weight and melting the big super high molecular weight high-density polyethylene resin of tension to outer layer 2, there is no hang down The problem stretched etc., mouldability and mechanical strength etc. are improved, and by using light-proofness pigment with the range, can certainly be changed The kind transparency and ultraviolet-shielding type, the transmissivity for certainly reaching the visible light of 500~800nm of wavelength is 35% or more, wave The ultraviolet transmittance of long 200~400nm is 1% hereinafter, therefore can more reliably provide one kind can be used as fragrance or photic anti- Lose the high price of liquid etc. and the high chemical substance of risk also the container of more ultra-high purity chemicals, the transparency it is excellent and The few chemical resistance blow molding stacked containers of contaminant particles the amount of dissolution are risen by using antioxidant with the range To more significant effect below: the scaling loss of resin can be prevented, physical property reduction or appearance caused by preventing because of scaling loss resin Be deteriorated etc..

By the way that adhesiveness layer (maleic anhydride modified polyolefin resin) is arranged between outer layer 2 and the barrier layer, although Economy is in a slight decrease within the allowable range, but the adhesiveness of the two becomes really, therefore can depending on the application or purpose is made With, in addition to this, there is composition identical with outer layer 1, play a role and effect also with used the of the invention resistance to of outer layer 1 Chemicals blow molding stacked containers are identical, this more significant effect.

That is, with heavier, cracky, lack safety vial compared with, chemical resistance blow molding of the invention Stacked containers are difficult to breakage, have excellent mechanical strength, by setting barrier layer so as to improve oxygen barrier, therefore have The performance that can be used as apothecary jar etc. plays more significant effect below: can be as to other various objects accommodated Workable omnipotent plastic containers, the sense of taste and in terms of can carry out safely and securely using.

Detailed description of the invention

Fig. 1 is the wall section for schematically illustrating an example of chemical resistance blow molding stacked containers of the invention Explanatory diagram.

Fig. 2 is to schematically illustrate the wall of another example of chemical resistance blow molding stacked containers of the invention to cut open The explanatory diagram in face.

Fig. 3 is the knot for indicating the infrared spectroscopic analysis of internal layer 1 of chemical resistance blow molding stacked containers of the present invention The chart of fruit.

Fig. 4 is the infrared spectroscopic analysis for indicating the internal layer 2 of chemical resistance blow molding stacked containers of the invention As a result chart.

Specific embodiment

The present invention is described in detail for attached drawing used below.

The explanation of the wall section of one example of the chemical resistance blow molding stacked containers of Fig. 1 to illustrate the invention Figure.

In Fig. 1, the 1A of chemical resistance blow molding stacked containers 8A of the invention is indicated by not having adhesiveness The internal layer 1 of the fluororesin composition of functional group, 1B indicate the internal layer being made of the fluororesin with adhesiveness functional group 2, also, 2 indicate the blocking being made of the polyamide and bonding resin layer, 3 indicate by maleic anhydride modified polyolefin The adhesiveness layer of resin composition, 4 indicate the barrier layer being made of ethylene-vinyl alcohol copolymer resin, and 5 indicate by maleic anhydride modified The adhesiveness layer of polyolefin resin composition, 6A indicate that by the transmissivity of the visible light of 500~800nm of wavelength be 35% or more, wave The ultraviolet transmittance of long 200~400nm is the outer layer 2 of 1% super high molecular weight high-density polyethylene resin composition below.Institute It states each layer and is respectively provided with the excellent transparency.7 indicate the ultra-high purity chemicals as the object accommodated.

The explanation of the section of another example of the chemical resistance blow molding stacked containers of Fig. 2 to illustrate the invention Figure.

In Fig. 2, the 1A of chemical resistance blow molding stacked containers 8B of the invention is indicated by not having adhesiveness Functional group the fluororesin composition internal layer 1,1B indicate by do not have adhesiveness functional group the fluororesin form in Layer 2, also, 2 indicate the blocking being made of the polyamide and bonding resin layer, 3 indicate by maleic anhydride modified polyene The adhesiveness layer of hydrocarbon resin composition, 4 indicate the barrier layer being made of ethylene-vinyl alcohol copolymer resin, and 6B expression contains maleic acid The transmission of anhydride modified polyolefin resin and the barrier layer 4 excellent, by 500~800nm of wavelength the visible light of adhesiveness Rate is 35% or more, the ultraviolet transmittance of 200~400nm of wavelength is 1% super high molecular weight high density polyethylene (HDPE) tree below The outer layer 1 of rouge composition.Each layer is respectively provided with the excellent transparency.7 indicate the ultra-high purity chemistry as the object accommodated Drug.

Maleic anhydride modified polyolefin resin of the outer layer 1 containing 25~65 mass %, therefore the outer layer 1 and blocking The problems such as adhesiveness of layer 4 is excellent, and there is no drawdowns, mouldability and mechanical strength etc. are excellent.However, if maleic anhydride modified Then there is the outer layer 1 and a possibility that the adhesiveness on barrier layer 4 becomes inadequate less than 25 mass % in polyolefin resin, if Maleic anhydride modified polyolefin resin is more than 65 mass %, then there is a possibility that the problems such as drawdown occurs.

Fluororesin used in internal layer 2 is not particularly limited, specifically, being, for example, selected from by tetrafluoroethene/hexafluoro third Alkene/monomer (α) copolymer, tetrafluoroethylene/perfluoro (alkyl vinyl ether)/monomer (α) copolymer, ethylene/tetrafluoroethylene/monomer (α) copolymer, ethylene/tetrafluoroethylene/hexafluoropropene/monomer (α) copolymer, chlorotrifluoroethylene/monomer (α) copolymer, chlorine three In vinyl fluoride/tetrafluoroethene/monomer (α) copolymer and ethylene/chlorotrifluoroethylene/monomer (α) copolymer composition group at least One kind, if fluororesin made of monomer (α) copolymerization with the characteristic with adhesiveness functional group, then the fluorine of internal layer 1 Resin and stop and bonding resin layer (polyamide) have excellent adhesiveness, can with it is identical with polyolefin at Type temperature carries out co-extrusion modling, so preferably use.

In the present invention, it is preferable to use additive-free no added grade fluororesin for fluororesin used in internal layer 2.

In the present invention, fluororesin used in internal layer 1 be not copolymerized the monomer (α) with adhesiveness functional group, Fluororesin without the adhesiveness functional group is, it is preferable to use additive-free no added grade fluororesin.

Also, in present invention, it is desirable to make fluororesin used in internal layer 1 by following (loss on heating measuring methods) The loss on heating of measurement is for 0.20 mass % hereinafter, preferably 0.15 hereinafter, fluororesin used in internal layer 2 passes through same measured The loss on heating of method measurement is 0.40 mass % hereinafter, preferably 0.30 or less.If respectively in the range, cleanliness energy Enough reaching is 5 or less and be 10 after storing 30 days at 40 DEG C hereinafter, if outside the range after storing 30 days at 23 DEG C, Then in the presence of a possibility that can not reaching the cleanliness.

(loss on heating measuring method)

Accurate weighing (W0), quality accurate weighing to 0.1mg are carried out to aluminium cup with balance.

5.00 ± 0.01g sample is put into aluminium cup, accurate weighing, accurate weighing to 0.1mg are carried out to gross mass.

After the temperature of electric furnace is adjusted to 260 DEG C ± 1 DEG C, sample is heated 240 minutes.

After heating, sample is taken out, it is cooling in drier, accurate weighing (W1) is carried out to sample, accurate weighing is extremely 0.1mg。

Then, loss on heating is calculated by following formula.

Loss on heating (quality %)=[(W-W1)/(W-W0)] × 100

(preferred characteristics about internal layer 2)

MFR (265 DEG C, 5Kg load g/10min) (measuring method: 265 DEG C, ASTM D1238) it is preferably 10~40, into one There is blow molding melt-moldability and be deteriorated in step preferably 20~30, what driving energy also increased if melting sticky height less than 10 Possibility, if more than 40, exist melting tension it is low, in blow molding occur drawdown the problems such as a possibility that.

Specific gravity (measuring method: ASTM D-792) is the specific gravity 1.7~1.9 of usual commercially available commercially available product, further Preferably 1.72~1.76.When specific gravity is less than 1.7, there are problems that a possibility that adhesiveness reduces occurs, if more than 1.9, A possibility that insufficient there are the intensity of generation container.

Fusing point (DEG C) (measuring method: ASTM D792) changes according to the amount or type for the monomer (α) being copolymerized, but It is usually 150~200 DEG C of fusing point of commercially available commercially available product, further preferably 190~200.When fusing point is less than 150 DEG C, It is poor with the fusing point of other resins to generate, and there are problems that a possibility that adhesive strength or mouldability occurs, if fusing point is more than 200 DEG C, then exist and is difficult to a possibility that being laminated with other resins.

The monomer (α) being copolymerized does not have as long as having the monomer for being able to carry out copolymerization of adhesiveness functional group It is particularly limited to, considers melt molding and control amount or type, thus make the fluororesin of internal layer 2 in fusing point (DEG C) range, And fluororesin to internal layer 1 and stop and bonding resin layer (polyamide) has superior adhesiveness.

As the concrete example of adhesiveness functional group, such as epoxy group, hydroxyl, carboxylic anhydride residue, carboxylic acid group, third can be enumerated Olefin(e) acid ester group, carbonate group, amino etc..As the concrete example of the copolymer, ethylene-used in embodiment 1 can be enumerated Hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinyl carbonate copolymer EFEP (for example, DAIKIN INDUSTRIES, LTD. manufacture RP5000)。

(preferred characteristics about internal layer 1)

MFR (297 DEG C, 5Kg load g/10min) (measuring method: 265 DEG C, ASTM D1238) it is preferably 9~35, into one Step is preferably 15~25, when less than 9, melts viscosity height, there is blow molding melt-moldability variation, the possibility that driving energy also increases Property, if more than 35, exist melting tension it is low, in blow molding occur drawdown the problems such as a possibility that.

Specific gravity (measuring method: ASTM D-792) is the specific gravity 1.7~1.9 of usual commercially available commercially available product, further preferably It is 1.83~1.89.When specific gravity is less than 1.7, there are problems that a possibility that adhesiveness reduces occurs, if existing more than 1.9 A possibility that intensity of generation container is insufficient.

Fusing point (DEG C) (measuring method: ASTM D792) is 200~240 DEG C of fusing point of usual commercially available commercially available product, into One step is preferably 208~228 DEG C.When fusing point is less than 200 DEG C, it is poor with the fusing point of other resins to generate, and there are generation adhesive strengths Or a possibility that the problem of mouldability, if fusing point is more than 240, generation is difficult to a possibility that being laminated with other resins.

The polyamide of blocking and bonding resin layer used in the present invention, which refers to, to be typically free of comprising intentional The additive of the additive or lubricant of addition, no added grade polyamide, with following characteristics, specifically, example The Z4887 of Daicel-Evonik Ltd. manufacture can such as be enumerated.

It wherein, is that nylon 6, nylon 11, nylon 12, nylon66 fiber are selected from as obtained from the open loop polycondensation of caprolactam Deng at least one of polyamide, it is preferable to use do not contain the additive comprising additive or lubricant polyamide.

(characteristic)

Fusing point (DEG C) (is based on ISO11357): preferably 170~250,

Density (Kg/m3) (is based on ASTM D1250-80): preferably 1.0~1.2.

Fusing point (DEG C) is more preferably 175~190, and density (Kg/m3) is more preferably 1.00~1.03.

Fusing point be less than lower limit value when, it is insufficient there are adhesiveness a possibility that, if be more than upper limit value, there are mouldability variation A possibility that.

Density be less than lower limit value when, it is insufficient there are adhesiveness a possibility that, if be more than upper limit value, there are mouldability variation A possibility that.

As long as the maleic anhydride modified polyolefin resin of adhesiveness layer used in the present invention is to blocking and bonding resin layer (polyamide) and barrier layer (ethylene-vinyl alcohol copolymer resin) has excellent adhesiveness, further, adhesiveness layer Maleic anhydride modified polyolefin resin as long as to barrier layer (ethylene-vinyl alcohol copolymer resin) and outer layer, (super high molecular weight is high Density Polyethylene Resin) have excellent adhesiveness, by the two bond and form adhesiveness layer, can melt molding, can Using usually carrying out commercially available commercially available product.

It can be into the maleic anhydride modified polyolefin resin for the adhesiveness layer for bonding the barrier layer and outer layer, not It damages in the range of its adhesiveness, blends containing internal layer 1,2 (fluororesin), stops the simultaneous bonding resin layer (polyamide resin Rouge), adhesiveness layer (maleic anhydride modified polyolefin resin), barrier layer (ethylene-vinyl alcohol copolymer resin), adhesiveness layer (horse Carry out anhydride modified polyolefin resin) and outer layer (super high molecular weight high-density polyethylene resin) regenerant.

This is because, being blended with the maleic anhydride modified polyolefin resin of the regenerant of the adhesiveness layer far from work For connect liquid level internal layer 1 fluororesin, therefore on practicability there is no damage cleanliness a possibility that.

It is excellent to stopping simultaneous bonding resin layer (polyamide) and barrier layer (ethylene-vinyl alcohol copolymer resin) to have The maleic anhydride modified polyolefin resin of different adhesiveness and to barrier layer (ethylene-vinyl alcohol copolymer resin) and outer layer (superelevation point Son amount high-density polyethylene resin) the maleic anhydride modified polyolefin resin with excellent adhesiveness can be identical or not Together, test is preferably first passed through in advance and determine.

The ethylene-vinyl alcohol copolymer resin (ethylene 24~44 moles % copolymerization) on barrier layer used in the present invention refers to, The resin for being hydrolyzed to ethylene vinyl alcohol copolymer and being almost saponified has the excellent gas barriers such as fragrance protectiveness is excellent Property, therefore in the container packages material such as be widely used in chemicals, cosmetics, it is high to the repellence of oils, organic solvent etc., Especially oxygen barrier can be ensured by using the ethylene-vinyl alcohol copolymer resin with following characteristics, and MFR, Fusing point etc. is close with super high molecular weight high-density polyethylene resin, and stable molding is excellent, so preferably use.As blocking The example of the ethylene-vinyl alcohol copolymer resin of layer, specifically, KURARAY CO. can be for example enumerated, the F171B of LTD manufacture (32 moles of % copolymerization of ethylene, 183 DEG C of fusing point, saponification rate 99.99%).

(characteristic)

MFR (210 DEG C, 2.16Kg load g/10min): 2~5

Density (Kg/m3): (being based on ISO1183) 1.1~1.3

Fusing point (DEG C): (being based on ISO1346): 170~200

MFR is preferably 2~5, and further preferably 3~5, density is preferably 1.1~1.3, further preferably 1.2~ 1.3, fusing point (DEG C) is preferably 170~200, and further preferably 190~200.If MFR, density, fusing point in the range, Then gas barrier, intensity, stable molding etc. are excellent, if there are at least one in these characteristics outside the range A a possibility that being damaged.

The super high molecular weight high-density polyethylene resin of outer layer 1,2 used in the present invention, preferably following superelevation High molecular weight high density polyethylene resin: as described above, density (measuring method: being based on JIS K7112) is preferably 940~962Kg/ M3, further preferably 944~946Kg/m3, weight average molecular weight (measuring method: being preferably as described later) 22~260,000, into One step is preferably 24~260,000, and (measuring method: being preferably as described later) 12 hereinafter, further to molecular weight distribution (Mw/Mn) Preferably 11 hereinafter, melting tension (measuring method: Japanese polyethylene process, use TOYO SEIKI KOGYO CO.LTD. manufacture Capillary rheometer, with 210 DEG C, hole L:8mm, D:2.095mm, piston falling speed 10mm/min, winding speed 3.9mm/ Min is measured) it is preferably 18~30g, further preferably 22~26g, super high molecular weight high-density polyethylene resin lead to It crosses and the super high molecular weight high-density polyethylene resin is used to outer layer 1,2, improve mouldability and mechanical strength etc., drawdown is not present The problems such as, yield etc. is also improved.

Since the molecular weight distribution (Mw/Mn) for the super high molecular weight high-density polyethylene resin for forming outer layer 1,2 is relatively narrow 12 hereinafter, melt-processed and be quickly cooled down this kind of common processing and forming under the conditions of multi-layer forming made of blow molding layer The outer layer 1,2 of folded container is made of fine and close little crystallization aggregate, therefore the transparency and mechanical strength are improved.

(Mw/Mn) for forming the super high molecular weight high-density polyethylene resin of outer layer 1,2 is preferably 12 hereinafter, further excellent Be selected as 11 hereinafter, if (Mw/Mn) more than 12, melt-processed and be quickly cooled down this kind of common processing and forming under the conditions of multilayer The crystallization of the outer layer for the blow molding stacked containers being molded with becomes larger, and becomes loose, cannot be by fine and close little crystallization aggregate It constitutes, there is a possibility that transparency and insufficient mechanical strength.

When forming the weight average molecular weight of the super high molecular weight high-density polyethylene resin of outer layer 1,2 less than 220,000, there are machines A possibility that tool intensity is insufficient, when weight average molecular weight is more than 260,000, since the melt viscosity of resin is high, there is also mouldabilities A possibility that being deteriorated, leading to molecule cutting etc. because of shear stress.

When the density and melting tension for forming the super high molecular weight high-density polyethylene resin of outer layer 1,2 are less than lower limit value, In the presence of a possibility that drawdown is to be difficult to control wall thickness occurs, on the other hand, if being more than upper limit value, exists and occur in bottle surface A possibility that the problem of melt fracture (rough surface).

Super high molecular weight high-density polyethylene resin used in outer layer 1,2 be containing selected from ethylene, propylene, 1- butylene, The homopolymer or copolymer of at least one of 4-methyl-1-pentene, 1- hexene, 1- octene can be used and have the characteristic Commercially available product.Wherein, it is preferable to use Alathon, ethylene and propylene, 1- butylene, 4-methyl-1-pentene, 1- hexene, 1- octene The copolymer of equal alpha-olefins.The content of alpha-olefin in copolymer is preferably 15 mass % or less.If obtaining having density is 940 The polymer or copolymer of characteristic described in~962Kg/m3 etc., then the molecular structure of copolymer can be random, isotactic or syndiotactic Or any one in their mixture, it is not particularly limited, polymerization for example can be by low-pressure process or middle-pressure process It is any.

In outer layer 1,2 used in the present invention, preferably so that the transmissivity of the visible light of 500~800nm of wavelength is 35% Above (passing through measuring method described hereinafter), 200~400nm of wavelength ultraviolet transmittance (pass through institute hereinafter for 1% or less The measuring method stated) mode, with specified amount blend the light-proofness pigment selected from organic light-proofness pigment and/or inorganic in At least one light-proofness pigment.

As organic light-proofness pigment and the light-proofness pigment of inorganic, as long as by being mixed with specified amount outer layer It closes, 35% or more the transmissivity of the visible light of 500~800nm of wavelength, the ultraviolet transmittance of 200~400nm of wavelength can be made For 1% hereinafter, and do not damage other characteristics of outer layer, be not particularly limited.

However, light-proofness pigment or carbon black selected from the organics such as quinacridine ketone, phthalocyanines, Anthraquinones, monoazo class, The screening of at least one of the light-proofness pigment of the inorganics such as iron oxide, zinc oxide, ultramarine, chromium oxide, titanium oxide, silica Photosensitiveness pigment can reach purpose with less amount of blending, therefore preferably use in the present invention.

As quinacridine ketone light-proofness pigment, specifically, can for example enumerate TET48183 and TET78310 (TOYOCOLOR CO., LTD. manufacture).

As phthalocyanines light-proofness pigment, specifically, can for example enumerate 7F2852 (Dainichiseika Color& Chemicals Mfg.Co., Ltd. manufacture), TET58335 (TOYOCOLOR CO., LTD. manufacture) and EPH-525328 (POLYCOL CO., LTD. manufacture).

As monoazo class light-proofness pigment, specifically, can for example enumerate TET38013 (TOYOCOLOR CO., LTD. manufacture) and ECE-6293 (POLYCOL CO., LTD. manufacture).

As carbon black class light-proofness pigment, specifically, can for example enumerate TET01337 (TOYOCOLOR CO., LTD. Manufacture) and EPH-K-51680 (POLYCOL CO., LTD. manufacture).

As iron oxides light-proofness pigment, specifically, can for example enumerate EPH-C-1045 (POLYCOL CO., LTD. manufacture) and TET68473 (TOYOCOLOR CO., LTD. manufacture.

As ultramarine class light-proofness pigment, specifically, can for example enumerate EPH-B-46662 (POLYCOL CO., LTD. manufacture) and TET26146 (TOYOCOLOR CO., LTD. manufacture).

As titanium oxide light-proofness pigment, specifically, can for example enumerate EB-1427 (DIC manufacture), EPH-H- 2481 (POLYCOL CO., LTD. manufactures) and TET28318 (TOYOCOLOR CO., LTD. manufacture).

The blended amount of light-proofness pigment is as described above, it is often preferred that the range of 0.01~0.04 mass %, more preferably The range of 0.025~0.035 mass %, the particularly preferably range of 0.029~0.031 mass %.

When less than 0.01 mass %, a possibility that being become inadequate there are ultraviolet-shielding type, if more than 0.04 mass %, Then there is a possibility that transparency is impaired.The masterbatch for being blended with light-proofness pigment can also be used.For example, in embodiment 1, 1 matter is blended in super high molecular weight high-density polyethylene resin (Japan polyethylene Corporation manufactures HB111R) (TOYOCOLOR CO., LTD. manufacture TET- to the masterbatch for being blended with 3 mass % monoazo class light-proofness pigment of amount % 38013).Therefore, in this example embodiment, monoazo class light-proofness pigment mixing relative to super high molecular weight high-density polyethylene resin Resultant is 0.030 mass %.

When using these light-proofness pigment, preferably avoids the pigment of bad dispersibility or promote the face of the oxidative degradation of container Material.

In the present invention, it is determining to form the super high molecular weight high-density polyethylene resin and light-proofness face of outer layer 1,2 It after type of material etc., is preferably tested in advance, so that the transmissivity of the visible light of 500~800nm of wavelength is 35% or more, wave The ultraviolet transmittance of long 200~400nm is the blended amount that 1% mode below determines light-proofness pigment.

If the purple that the transmissivity that can reach the visible light of 500~800nm of wavelength is 35% or more, 200~400nm of wavelength Outside line transmissivity is by 1% hereinafter, the visibility of the object then accommodated is excellent, and can assign can prevent the storage liquid of storage rotten Ultraviolet-shielding type, can be used, for example, as photoresist liquid etc. and go bad because of ultraviolet light and cured chemicals or fragrance etc. Ultra-high purity chemicals container.

In outer layer 1,2 used in the present invention, preferably with specified amount blend (0.05~0.30 mass %) be selected from by phenols, The antioxidant of at least one of Phosphorus, sulphur class antioxidant composition group, can prevent the scaling loss of resin, prevent because of scaling loss tree The deterioration etc. of appearance caused by rouge.

As phenol antioxidant, phosphorus antioxidants, sulphur class antioxidant, as long as antioxidation is high, it is outer not damage Other characteristics of layer 1,2, are not particularly limited.

As phenol antioxidant, specifically, can for example enumerate the ADK STAB of ADEKA CORPORATION manufacture AO60。

As phosphorus antioxidants, specifically, can for example enumerate the ADK STAB of ADEKA CORPORATION manufacture 2112。

As sulphur class antioxidant, specifically, can for example enumerate Mitsubishi Chemical Corporation The DSTP of manufacture.

Relative to the super high molecular weight high-density polyethylene resin for forming outer layer 1,2, it preferably is blended with 0.05~0.30 matter The above-mentioned antioxidant measured %, more preferably blend 0.10~0.25 mass %.If there are antioxygenic properties less than 0.05 mass A possibility that variation, if more than 0.30 mass %, a possibility that exudation there are additive from vessel surface.

In outer layer 1,2 used in the present invention, although being blended with light-proofness pigment, the antioxidant that can be used as contaminant particles Deng, but since outer layer 1,2 is far from as the internal layer 1,2 for connecing liquid level, stop simultaneous bonding resin layer 2, adhesiveness layer 3,5, resistance Barrier 4 etc. prevents the contaminant particles from these light-proofness pigment, antioxidants etc. from oozing out into storage liquid, therefore not into container It is oozed out in chemicals of keeping storage etc..

In the present invention, in outer layer 1,2, benzene can also be suitably used as needed while using light-proofness pigment And the resistance to light stabilizer such as triazole type resistance to light stabilizer or triazines resistance to light stabilizer.

If using benzotriazole resistance to light stabilizer or triazines resistance to light stabilizer, can shield respectively UV-B (200~ 320nm) with UV-A (320~400nm), by being carried out simultaneously using can not damage other characteristics, significantly improve with specific quantity Ultraviolet-shielding type.

As resistance to light stabilizer, 2- (5- methyl -2- hydroxy phenyl) benzotriazole, 2- (3- tert-butyl -5- first can be enumerated Base -2- hydroxy phenyl) -5- chlorobenzotriazole, 2- (2- hydroxy-5-methyl base phenyl benzotriazole), 2- (the chloro- 2- benzo three of 5- Azoles) -6- tert-butyl-cresols, 2- (bis- tertiary amino -2- hydroxy phenyl of 3,5-) benzotriazole, 2- (2H- benzotriazole -2- base) be right The benzotriazoles such as cresols resistance to light stabilizer, 2- [4,6- bis- (2,4 xylyl) -1,3,5- triazine -2- base] -5,2,4,6- tri- (2- hydroxyl -4- hexyl oxygroup -3- aminomethyl phenyl) -1,3,5- triazine, 2- (4,6- diphenyl -1,3,5- triazine -2- base) -5- The triazines resistance to light stabilizer, bis- (2,2,6,6- tetramethyl -4- piperidines) last of the ten Heavenly stems such as [2- (2- ethyl hexanoyl oxygroup) ethyoxyl] phenol Two acid esters, poly- ({ 6- (1,1,3,3- tetramethyl butyl) amino -1,3,5- triazine -2,4- diyl } { (2,2,6,6- tetramethyl -4- Piperidyl) imino group hexa-methylene (2,2,6,6- tetramethyl -4- piperidyl) imino group) hindered amines resistance to light stabilizer.

The content of the additive contained in resin is following values: using tetrahydrofuran (THF), extracts 8 with Soxhlet extractor Hour, value obtained from being separated as liquid chromatography to extracting solution, being quantitative.The determination condition are as follows: device is GULLIVER (JASCO Corporation manufacture), chromatographic column are (the JASCO Corporation system of Finepak GEL 101 Make), solvent THF, detector is UV-970 (JASCO Corporation manufacture) and 830-RI (JASCO Corporation Manufacture).

In the measuring method of the molecular weight of the resin of container, the resin combination for cutting from container is dissolved in solvent (neighbour two Chlorobenzene), and as sample solution, molecular weight and molecular weight distribution are measured by GPC.Divided equally again by the calculating of following formula Son amount and number-average molecular weight.

Weight average molecular weight Mw=Σ (M × w)/Σ w (2)

Number-average molecular weight Mn=Σ w/ Σ (w/M) (3)

Molecular weight distribution=weight-average molecular weight/number-average molecular weight (Mw/Mn)

Wherein, M is molecular weight, and w is weight fraction.

In addition, the determination condition of GPC are as follows: device is 150CV (manufacture of Waters company), and chromatographic column is TSK gel GMH- HT (TOSOH CORPORATION manufacture), solvent are o-dichlorohenzene, and temperature is 138 DEG C, and detector is differential refractometer.In order to The molecular weight distribution of container is controlled as the range, material resin must also have a certain range of molecular weight distribution.

For forming method, as long as the chemical-resistant resistance that can make the transparency of the invention excellent by blow molding method Property blow molding stacked containers molding, be not particularly limited, can be selected from the molding machine of commercially available blow molding stacked containers Select use.

In addition, the explanation of above embodiment is for illustrating the present invention, do not limit invention documented by claims, Or it reduces the scope.In addition, each section composition of the invention is not limited to above embodiment, it can be in skill documented by claims Various modifications are carried out within the scope of art.

Embodiment

Hereinafter, by embodiment, the present invention is described in detail, but as long as not departing from purport of the invention, then not by this The restriction of a little embodiments.

(embodiment 1)

It the use of MFR is 25g/10min, the nothing that specific gravity 1.86, fusing point are 223 DEG C, loss on heating is 0.16 mass % adds Add the fluororesin (EP-610 of DAIKIN INDUSTRIES, LTD. manufacture) of agent to be used as internal layer 1, using MFR be 25g/10min, Additive-free fluororesin (the DAIKIN that specific gravity is 1.74, fusing point is 195 DEG C, loss on heating is 0.35 mass % INDUSTRIES, LTD. manufacture RP-5000) be used as internal layer 2, using have with the adhesive function of the fluororesin of internal layer 2, no Additive-free polyamide (Daicel-Evonik containing the additive comprising the additive or lubricant that intentionally add Ltd. the Z4887 manufactured, relative viscosity 1.87) as simultaneous bonding resin layer is stopped, use maleic anhydride modified polyolefin tree Rouge (FT71A of Japan polyethylene Corporation) bonds the polyamide and barrier layer as having The adhesiveness layer of function, and use barrier resin (ethylene-vinyl alcohol copolymer resin F171B:KURARAY CO., LTD manufacture, Saponification rate is 99.99%) as barrier layer, in addition, as outer layer 1, using to super high molecular weight high-density polyethylene resin (HB111R of Japan polyethylene Corporation manufacture) (HL-MFR (measuring method: JIS K7112) is 6g/ 10min, density 946Kg/m3, weight average molecular weight are 250,000, and melting tension is 25g), blend the maleic anhydride of 30 mass % Modified polyolefin resin (Japan polyethylene Corporation FT71A), 1 mass % are (as monoazo class shading Property pigment when, blended amount is 0.030 mass %) for improving the light-proofness pigment of visibility and ultraviolet-shielding type (TET-38013 of TOYOCOLOR CO., LTD. manufacture, is blended with the masterbatching of the monoazo class light-proofness pigment of 3 mass % Glue), the antioxidant of 0.2 mass % (phenol antioxidant, the ADK STAB AO60 of ADEKA CORPORATION manufacture) Super high molecular weight high-density polyethylene resin, under following conditions of molding, the problems such as making there is no drawdown, formed by 6 layers The excellent chemical resistance blow molding stacked containers of the transparency of the invention (gross mass 400g, internal layer 1 are 50 μm, Internal layer 2 is 100 μm, stops and bonding resin layer is 50 μm, adhesiveness layer is 50 μm, and barrier layer is 50 μm, and outer layer 1 is 1500 μ M, average total wall thickness are 1.8mm, capacity 3750ML) molding.

(condition of molding)

(6 kinds of extruders are used, with 1 die head using blow molding machine (6 kinds 6 layers of BLENS CORPORATION manufacture) (die head) is laminated for 6 layers of type).

The fluororesin of internal layer 1: screw diameter 40mm Φ set temperature: 260 DEG C

The fluororesin of internal layer 2: screw diameter 20mm Φ set temperature: 240 DEG C

Polyamide resin layer: screw diameter 20mm Φ set temperature: 200 DEG C

Maleic anhydride modified polyolefin resin layer: screw diameter 20mm Φ set temperature: 220 DEG C

Ethylene-vinyl alcohol copolymer resin layer: screw diameter 40mm Φ set temperature: 230 DEG C

The super high molecular weight high-density polyethylene resin of outer layer 1: screw diameter 50mm Φ set temperature: 220 DEG C

Die head temperature: set temperature: 235 DEG C

In addition, having used using drying machine about with the hygroscopic polyamide and barrier resin at 80 DEG C Under be dried to eliminate the polyamide and barrier resin of moisture.

Then, by following test methods, using sample bottle, measurement is just completed after extracting at 23 DEG C and is stored 30 days Contaminant particles the amount of dissolution (number/ml) after extracting again and just completed at 40 DEG C after extracting and storage extract again within 30 days after it is miscellaneous Matter particle the amount of dissolution (number/ml) is evaluated permeability and visibility by following test methods, is cut from bottle metastomium wall 4cm × 4cm × 1.8mm sample evaluates ultraviolet transmittance, visible transmission by following test methods using the sample Then rate fills pure water in a reservoir, evaluate metal dissolving by following test methods, evaluated by following test methods Falling strength and fragrance adaptability, evaluate internal layer 1,2 by the test method and as the loss on heating for the layer for connecing liquid level, For economy, when the material without using high price is also capable of providing economic container, merchantability is high, is evaluated as zero, and due to Using the material of high price, although depending on the application and have merchantability, Economic Evaluation be ×, then in summary evaluation carry out Comprehensive judgement.Show the result in 1~table of table 2.Loss on heating documented by table 1 is internal layer 1 or the heating as the layer for connecing liquid level Loss.

The excellent chemical resistance blow molding stacking appearance of the transparency of the invention is obtained using forming in embodiment 1 The fluororesin (EP-610 of DAIKIN INDUSTRIES, LTD. manufacture) of the internal layer 1 of device and the fluororesin (DAIKIN of internal layer 2 The RP-5000 of INDUSTRIES, LTD. manufacture), infrared spectroscopic analysis is carried out by following determination conditions.

(infrared spectroscopic analysis determination condition)

Measurement device: the IR Affinity-1 of Shimadzu Corporation manufacture

It measures sample: using extruder at 240 DEG C, the diaphragm that 50 μ m-thicks of internal layer 1,2 are made is gone forward side by side to exercise and be used.

Measure wavelength: 600~4000cm-1

Fig. 3 indicate internal layer 1 infrared spectroscopic analysis as a result, the longitudinal axis be absorbance (%), horizontal axis be wavelength (cm-1).

Fig. 4 indicate internal layer 2 infrared spectroscopic analysis as a result, the longitudinal axis be absorbance (%), horizontal axis be wavelength (cm-1).

If Fig. 3 is overlapped with Fig. 4 it is found that the two is several other than the sharp absorption at the wavelength 1800 (cm-1) of Fig. 4 Identical waveform.

Biggish sharp absorption (being depicted with arrows) is the absorption peak of carbonate group at the wavelength 1800 (cm-1) of Fig. 4, is sentenced The fluororesin for determining internal layer 2 has adhesiveness functionality group (carbonate group).

The fluororesin of internal layer 2 is copolymerized by the monomer (α) with adhesiveness functional group as described above and is prepared, Neng Goutong The amount of the adhesiveness functional group of the fluororesin of the copolymerization amount control internal layer 2 of monomer (α) is crossed, thereby, it is possible to control the fluorine tree of internal layer 2 Adhesiveness and fusing point of rouge etc., internal layer 2 have good adhesiveness to the fluororesin of internal layer 1 and blocking and bonding resin layer, and Fusing point etc. can be controlled in the range.

The biggish sharp absorption peak is not found at the wavelength 1800 (cm-1) of Fig. 3, indicates that the fluororesin of internal layer 1 does not have Adhesive functionality group (carbonate group).Internal layer 1 has good adhesiveness to the fluororesin of internal layer 2 but does not have to other layers It is adhesive.

Fig. 3,4 wavelength 3000 (cm-1) biggish sharp absorption peak be the ethylene from copolymerization absorption peak.

(test method)

(measuring methods of contaminant particles (particle))

Following measurements carries out in (grade 100) in dust free room.

2. a measurement specimen: filling ultrapure water in molding container, just completed at 23 DEG C after extracting and store 30 days again It is just completed after being extracted again within 30 days after extracting with storage after extraction or at 40 DEG C, 20 minutes is stood with upright state, from container In take measurement sample, as measurement a specimen.

3. after cleaning particle collector with ultrapure water before the assay, cleaning 2 measurement devices using 25ml ultrapure water.

4. 10ml ultrapure water after cleaning, is injected particle collector, granule number is measured.Carry out 2 operations, confirmation 0.2 μm or more of granule number is zero (A).

5. the measurement specimen using 25ml cleans 2 measurement devices.

6. after cleaning, taking out the ultrapure water of a measurement specimen of 10ml from the container (bottle) for filling water, particle meter is injected In number device, granule number is measured.2 operations are carried out, the average value (B) of 0.2 μm or more of granule number is found out.

7. calculating the grain value in 1ml by measured value by following formula.

10ml=/ml of (B (a)) ÷

OTR oxygen transmission rate [cm3/ (pkg.24h.atm)]:

Using the container (wall thickness of bottle central portion: 1.8mm) of 3.75L, on the basis of JIS K7126-2, (OX- is used TRAN 2/21) (MOCON Inc. manufacture) measurement device, it measures the oxygen from outside of containers to inside and penetrates.Temperature and humidity: outside 1 atmospheric pressure, 23 DEG C, 50%RH oxygen.The atmospheric pressure of inside 1,23 DEG C, drying nitrogen.

(ultraviolet transmittance)

Using the V-670 of Japan's light splitting (company), the transmissivity of the ultraviolet range of 200~400nm is found out.

(transmission of visible light)

Using the V-670 of Japan's light splitting (company), the transmissivity of the visible ray regions of 400~800nm is found out.

(visibility)

In the interior of 750 Luxs, tap water is added into container, asks the 3 people with the naked eye tap water from outside of containers. Then the evaluation of following four grades is carried out.

Evaluation:

◎: tap water can obviously be confirmed.

Zero: confirming tap water.

△: tap water is confirmed when examining.

×: tap water can not be confirmed.

(Falling strength)

It is filled out into container and is filled with water to the 80% of capacity, container bottom is downward, under making it from 1.2m eminence to concrete surface It falls 5 times, container side is downward, so that it is fallen 1 time, determines rupture and leakage by visual observation.

(fragrance adaptability)

As the example of representative fragrance, using limonene (product name: orange oil, purity 96.4%, T.HASEGAWA CO., LTD. manufacture), citrus (product name: Lemon essence, T.HASEGAWA CO., LTD. system Make), crab oil (15% dimethyl sulfide, propylene glycol solution, T.HASEGAWA CO., LTD. manufacture), rice salad (rice Salad) (product name: big rice bran oil, T.HASEGAWA CO., LTD. manufacture), ethyl butyric acid ester (product name: esters, purity 100%, T.HASEGAWA CO., LTD. manufacture), trans- -2- hexenoic aldehyde (product name: aldehydes, purity 99.7%, T.HASEGAWA CO., LTD. manufacture), each fragrance of 1kg is filled respectively, and be sealed, place 1 month under room temperature, normal pressure And 3 months.Wherein, only crab oily (15% dimethyl sulfide, propylene glycol solution) is stored refrigerated 1 month and 3 under room temperature, normal pressure A month.

After placing 3 months, for each Specimen Determination container mass, checks whether the object accommodated dissipates, ask 10 group members Sensory test is carried out, checks whether rotten, specific gravity and refractive index is measured, checks whether it has variation, for analyzable sample, Ingredient is checked by gas chromatography, is evaluated with following evaluation criteria.

Evaluation criteria:

Zero: not dissipating, go bad, change, storage-stable is high, has merchantability.

△: it is slightly worse compared with zero, but almost without dissipation, rotten, variation etc., storage-stable is high, has merchantability.

×: there is dissipation, rotten, variation etc., storage-stable is low, does not have merchantability.

(metal dissolving)

Fill pure water into sample container, placed 30 days at 23 DEG C and 40 DEG C with the state of heating, using the pure water as A specimen is measured using ICP-MASS (the 8800 of Agilent Technologies manufacture) to ppb grades.If 10ng/L or less It is then qualification.(grade 1000) is measured in dust free room.Measure 23 elements, i.e. Li, Na, Mg, Al, K, Ca, Ti, V, Cr、Mn、Fe、Co、Ni、Cu、Zn、As、Ag、Cd、Sn、Ba、W、Au、Pb。

(comprehensive judgement)

Grain value after being stored 30 days at 23 DEG C be 5/ml hereinafter, and the grain value after being stored 30 days at 40 DEG C be 10 hereinafter,

OTR oxygen transmission rate be 0.003 [cm3/ (pkg.24h.atm)] hereinafter,

Ultraviolet transmittance be 1% hereinafter,

Transmission of visible light is 35% or more,

Visibility is zero,

Falling strength: it is not damaged,

Fragrance adaptability is zero~△,

Metal dissolving be 10 (ng/L) hereinafter,

Economy is zero.

At this point, comprehensive judgement is zero.By any one of its it is poorer than the situation be evaluated as ×.

(comparative example 1)

In addition to using the identical polyamide that joined antioxidant (hindered phenol anti-oxidants, 2000ppm) (opposite By 1.87) replacing additive-free polyamide used in embodiment 1, (Daicel-Evonik Ltd. is manufactured viscosity Z4887 it other than) (stopping simultaneous binder resin, relative viscosity 1.87), in the same manner as example 1, makes for comparing Blow molding stacked containers, and evaluated.Show the result in 1~table of table 2.

(comparative example 2)

It is that 956Kg/m3, HL-MFR (measuring method: JIS K7112, load 21.6Kg) is in addition to having used density 8g/10min, Mw/Mn=11, molecular weight are the high density polyethylene (HDPE) (TOSOH that 1000 ingredients below are 0.2 mass % The 9D01A of CORPORATION manufacture) connect liquid layer instead of other than internal layer 1,2 used in embodiment 1, with same as Example 1 Mode, make blow molding stacked containers for comparing, and evaluated.Show the result in 1~table of table 2.

(comparative example 3)

In addition to being 0.35 matter without using internal layer 1 used in embodiment 1 and by loss on heating used in embodiment 1 The internal layer 2 of amount %, which is used as, to be connect other than liquid layer, in the same manner as example 1, is made the blow molding for comparing and is laminated and hold Device, and evaluated.Show the result in 1~table of table 2.

(comparative example 4)

In addition to being heated 120 minutes with 260 DEG C ± 1 DEG C of furnace temperature to the fluororesin for connecing liquid layer used in comparative example 3, And use other than the fluororesin for reducing loss on heating (loss on heating is 0.31 mass %), in a manner of identical with comparative example 3, The blow molding stacked containers for comparing are made, and are evaluated.Show the result in 1~table of table 2.

(comparative example 5)

In addition to using vial (FUJIFILM Electronic Materials Co., the Ltd. (capacity for comparing Other than 2500ML)), evaluated in the same manner as example 1.Show the result in 1~table of table 2.

(comparative example 7)

In addition to use the commercially available plastics for comparing to manufacture air-tight bottle (commercially available perfume container, Hokusan Co., Ltd. manufacture, 1L) other than, it is evaluated in the same manner as example 1.Show the result in 1~table of table 2.

Determined by 1~table of table 2, the grain value of the chemical resistance blow molding stacked containers of embodiment 1, oxygen penetrate Rate, ultraviolet transmittance, transmission of visible light, visibility, Falling strength, fragrance adaptability, metal dissolving and economy are whole All excellent, comprehensive judgement zero, in contrast, any one characteristic of the container for comparing of comparative example 1~6 are poor.

Industrial applicibility

In chemical resistance blow molding stacked containers of the invention, by using do not have adhesiveness functional group, it is right The fluororesin of internal layer 2 has adhesiveness but does not have adhesiveness to other layers, and additive-free loss on heating is 0.20 mass % Specific fluororesin below is as the internal layer 1, and using with adhesiveness functional group, the fluororesin and blocking to internal layer 1 are simultaneous Bonding resin layer has adhesiveness, and additive-free loss on heating is described in 0.40 mass % specific fluororesin below is used as Internal layer 2 uses the polyamide without containing the additive comprising the additive or lubricant that intentionally add as blocking And bonding resin layer, this makes it possible to obtain be equivalent to vial, store 30 days at 23 DEG C after be 5 or less and to be store at 40 DEG C Hiding was 10 cleanliness below after 30 days, plays and can be improved chemical resistance, and can strongly reduce the change of odour component The remarkable result of matter improves oxygen by the way that the excellent barrier layer being made of ethylene-vinyl alcohol copolymer resin of oxygen barrier is arranged Gas block, by using big melting tension, ultraviolet-shielding type and the excellent superelevation such as the transparency and mechanical strength to outer layer High molecular weight high density polyethylene resin improves mouldability and ultraviolet-shielding type, therefore plays remarkable result below: Neng Gouti For a kind of high price that can be used as fragrance or photoresist liquid etc. and the high chemical substance of risk also more ultra-high purity chemical drugs The container of product, the transparency is excellent and contaminant particles the amount of dissolution is few chemical resistance blow molding stacked containers, so Industrial utility value is high.

Description of symbols

1A: internal layer 1；1B: internal layer 2；2: stopping simultaneous bonding resin layer；3: adhesiveness layer；4: barrier layer；5: adhesiveness layer； 6A: outer layer 2；6B: outer layer 1；7: ultra-high purity chemicals；8A, 8B: chemical resistance blow molding stacked containers.

Claims

The chemical resistance blow molding stacked containers that 1. a kind of transparency is excellent and contaminant particles the amount of dissolution is few, by from Container inside to outside stacks gradually following internal layers 1, internal layer 2, stops simultaneous bonding resin layer, adhesiveness layer, barrier layer and outer layer 1 It forms, each layer has the transparency, which is characterized in that

Contaminant particles the amount of dissolution (number/ml) after storing 30 days at 23 DEG C is 5 hereinafter, and after storing 30 days at 40 DEG C Contaminant particles the amount of dissolution (number/ml) be 10 hereinafter,

Internal layer 1: to there is adhesiveness to the fluororesin of internal layer 2 but do not have bonding to other layers without adhesiveness functional group Property additive-free fluororesin, loss on heating be 0.20 mass % hereinafter,

Internal layer 2: for adhesiveness functional group, fluororesin and blocking and bonding resin layer to internal layer 1 have the nothing of adhesiveness The fluororesin of additive, loss on heating be 0.40 mass % hereinafter,

Stop and bonding resin layer: for it is without containing the additive comprising the additive or lubricant that intentionally add, selected from by leading to The polyamide of at least one of group of the composition of polyamide obtained from the open loop polycondensation of caprolactam is crossed,

Adhesiveness layer: for maleic anhydride modified polyolefin resin,

Barrier layer: for ethylene-vinyl alcohol copolymer resin,

Outer layer 1: for super high molecular weight high-density polyethylene resin, containing maleic anhydride modified polyolefin resin, and with it is described The adhesiveness on barrier layer is excellent, and the ultraviolet transmittance of 200~400nm of wavelength is 1% or less.
The chemical resistance blow molding stacked containers that 2. a kind of transparency is excellent and contaminant particles the amount of dissolution is few, by from Container inside to outside stacks gradually following internal layers 1, internal layer 2, stops simultaneous bonding resin layer, adhesiveness layer, barrier layer, adhesiveness Layer and outer layer 2 form, and each layer has the transparency, which is characterized in that

Contaminant particles the amount of dissolution (number/ml) after storing 30 days at 23 DEG C is 5 hereinafter, and after storing 30 days at 40 DEG C Contaminant particles the amount of dissolution (number/ml) be 10 hereinafter,

Internal layer 1: to there is adhesiveness to the fluororesin of internal layer 2 but do not have bonding to other layers without adhesiveness functional group Property additive-free fluororesin, loss on heating be 0.20 mass % hereinafter,

Internal layer 2: for adhesiveness functional group, fluororesin and blocking and bonding resin layer to internal layer 1 have the nothing of adhesiveness The fluororesin of additive, loss on heating be 0.40 mass % hereinafter,

Stop and bonding resin layer: for it is without containing the additive comprising the additive or lubricant that intentionally add, selected from by leading to The polyamide of at least one of group of the composition of polyamide obtained from the open loop polycondensation of caprolactam is crossed,

Adhesiveness layer: for maleic anhydride modified polyolefin resin,

Barrier layer: for ethylene-vinyl alcohol copolymer resin,

Adhesiveness layer: for maleic anhydride modified polyolefin resin,

Outer layer 2: the ultraviolet transmittance for 200~400nm of wavelength is 1% super high molecular weight high density polyethylene (HDPE) tree below Rouge.
3. chemical resistance blow molding stacked containers according to claim 1 or 2, which is characterized in that the internal layer 2 Used in fluororesin be selected from by tetrafluoroethylene/hexafluoropropylene/monomer (α) copolymer, tetrafluoroethylene/perfluoro (alkyl vinyl Base ether)/monomer (α) copolymer, ethylene/tetrafluoroethylene/monomer (α) copolymer, ethylene/tetrafluoroethylene/hexafluoropropene/monomer (α) copolymer, chlorotrifluoroethylene/monomer (α) copolymer, chlorotrifluoroethylene/tetrafluoroethene/monomer (α) copolymer and ethylene/chlorine At least one of the group of trifluoro-ethylene/monomer (α) copolymer composition, the monomer (α) indicate there is adhesiveness functional group Monomer, and the fluororesin has following characteristics,

(characteristic)

MFR (265 DEG C, 5Kg load g/10min): 10~40,

Specific gravity: 1.7~1.9,

Fusing point (DEG C): 150~220.
4. chemical resistance blow molding stacked containers described in any one of claim 1 to 3, which is characterized in that Fluororesin used in the internal layer 1 does not have the adhesiveness functional group, and has following characteristics,

(characteristic)

MFR (297 DEG C, 5Kg load g/10min): 9~35,

Specific gravity: 1.7~2.0,

Fusing point (DEG C): 200~240.
5. chemical resistance blow molding stacked containers according to any one of claims 1 to 4, which is characterized in that The polyamide has following characteristics,

(characteristic)

Fusing point (DEG C): 170~250,

Density (Kg/m³): 1.0~1.2.
6. chemical resistance blow molding stacked containers according to any one of claims 1 to 5, which is characterized in that The barrier layer is the excellent ethylene-vinyl alcohol copolymer resin of the oxygen barrier with following characteristics,

(characteristic)

MFR (210 DEG C, 2.16Kg load g/10min): 2~5,

Density (Kg/m³): 1.1~1.3,

Fusing point (DEG C): 170~200.
7. chemical resistance blow molding stacked containers according to claim 1, which is characterized in that the outer layer 1 by The super high molecular weight high-density polyethylene resin being made of polyethylene or ethene-alpha-olefin copolymer and group with following characteristics It closes object 1 to constitute, the composition 1 is containing 0.01~0.04 mass % for assigning ultraviolet-shielding type and the transparency, choosing Freely it is selected from the organics light-proofness pigment such as quinacridine ketone, phthalocyanines, Anthraquinones, monoazo class or carbon black, iron oxide, oxidation At least one of the inorganics light-proofness pigment such as zinc, ultramarine, chromium oxide, titanium oxide, silica light-proofness pigment composition Group at least one of light-proofness pigment, the antioxidant of 0.05~0.30 mass %, 25~65 mass % maleic anhydride change Property polyolefin resin, the transmission of visible light of 500~800nm of wavelength is 35% or more, the ultraviolet light of 200~400nm of wavelength Transmissivity be 1% hereinafter,

(characteristic)

Density: 940~962Kg/m³,

Weight average molecular weight: 220,000~260,000,

Molecular weight distribution (Mw/Mn): 12 hereinafter,

Melt tension: 18~30g.
8. chemical resistance blow molding stacked containers according to claim 2, which is characterized in that the outer layer 2 by The super high molecular weight high-density polyethylene resin being made of polyethylene or ethene-alpha-olefin copolymer and group with following characteristics It closes object 2 to constitute, the composition 2 is containing 0.01~0.04 mass % for assigning ultraviolet-shielding type and the transparency, choosing Freely it is selected from the organics light-proofness pigment such as quinacridine ketone, phthalocyanines, Anthraquinones, monoazo class or carbon black, iron oxide, oxidation At least one of the inorganics light-proofness pigment such as zinc, ultramarine, chromium oxide, titanium oxide, silica light-proofness pigment composition The antioxidant of at least one of group light-proofness pigment, 0.05~0.30 mass %, the visible light of 500~800nm of wavelength Transmissivity is 35% or more, the ultraviolet transmittance of 200~400nm of wavelength be 1% hereinafter,

(characteristic)

Density: 940~962Kg/m³,

Weight average molecular weight: 220,000~260,000,

Molecular weight distribution (Mw/Mn): 12 hereinafter,

Melt tension: 18~30g.