WO2017216827A1 - Chemical-resistant blow-molded laminate container leaching few impurity particles - Google Patents
Chemical-resistant blow-molded laminate container leaching few impurity particles Download PDFInfo
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- WO2017216827A1 WO2017216827A1 PCT/JP2016/002928 JP2016002928W WO2017216827A1 WO 2017216827 A1 WO2017216827 A1 WO 2017216827A1 JP 2016002928 W JP2016002928 W JP 2016002928W WO 2017216827 A1 WO2017216827 A1 WO 2017216827A1
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- Prior art keywords
- less
- layer
- resin
- container
- adhesive
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- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- MBDOYVRWFFCFHM-UHFFFAOYSA-N trans-2-hexenal Natural products CCCC=CC=O MBDOYVRWFFCFHM-UHFFFAOYSA-N 0.000 description 1
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- 239000003643 water by type Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/00—Layered products comprising a layer of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/402—Coloured
- B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7244—Oxygen barrier
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
Definitions
- the present invention relates to a chemical-resistant blow-molded laminated container with a small amount of impure particulate elution, and more specifically, excellent in chemical resistance and mechanical strength.
- the present invention relates to a chemical-resistant blow-molded laminated container with a small amount of impure fine particles that can be used as an ultra-high-purity chemical container with no visibility.
- plastic containers such as glass containers and sealer bottles (commercially available fragrance containers) and containers coated with the inner surface of metal containers are used as containers for storing chemicals and fragrances.
- a glass container is inconvenient to handle because it is heavy, and may be broken by dropping.
- a molded container made of polyethylene resin has the advantage that it is difficult to break during handling and is lightweight.
- high-purity chemicals used for etching and cleaning in semiconductor manufacturing such as sulfuric acid, nitric acid, hydrogen peroxide water, and high-purity solvent-based resists and dilution solvents used for semiconductor processes and liquid crystal displays,
- high-purity chemicals used for etching and cleaning in semiconductor manufacturing such as sulfuric acid, nitric acid, hydrogen peroxide water, and high-purity solvent-based resists and dilution solvents used for semiconductor processes and liquid crystal displays
- methyl alcohol, ethyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, acetone, ethyl acetate, toluene, dimethylformamide, ethylene glycol acetate, methoxypropyl acetate, butyl cellosolve, etc. and used for pharmaceuticals such as sterilization, disinfection, and drug substance
- High purity solvents such
- the impure fine particles are leached from the resin composition forming the container into the chemical that is the content, and the degree to which the impure fine particles impair the content is indicated.
- the degree of cleanness is that after molding a test container and storing ultrapure water in the test container for a certain period (30 days at 23 ° C.), the particle size is 0.2 ⁇ m or more in 1 ml of water stored in the resin container. Calculate how many fine particles there are.
- Measuring apparatus A particle counter “KL-26” RION KL-26 manufactured by Rion Co., Ltd. is used.
- Sample to be measured An ultrapure water filled in a molded container, stored at 23 ° C. for 30 days, and collected from a container left standing for 20 minutes in an upright state is used as a sample to be measured.
- the particle counter Prior to measurement, the particle counter is purged with ultrapure water, and then the measuring device is washed twice with 25 ml of ultrapure water. 4). After washing, ultrapure water is injected into a 10 ml particle counter and the number of particles is measured.
- This operation is performed twice to confirm that the number of particles of 0.2 ⁇ m or more is zero (A). 5.
- the measuring device is washed twice with a 25 ml measuring sample. 6). After washing, 10 ml is injected into a particle counter from a container (bottle) filled with ultrapure water as a measurement sample, and the number of particles is measured. This operation is performed twice to obtain an average value (B) of the number of particles of 0.2 ⁇ m or more. 7).
- the particle value in 1 ml is calculated from the measured value by the following formula.
- Elution amount of impure fine particles of 2 ⁇ m or more is 5 or less, and elution amount of impure fine particles having a particle size of 0.2 ⁇ m or more in 1 ml of ultrapure water after 30 days storage at 40 ° C. ml) is required to be 10 or less.
- Cans and sealer bottles with fluorine coating on the inner surface of metal cans are used on the market as containers used in the perfume field, but in the case of metal cans, there are problems of dents and rust. The problem of quality deterioration as a fragrance frequently occurs.
- the weight average molecular weight of the raw material resin made of polyethylene or ethylene- ⁇ -olefin copolymer is in a certain range
- the content of the light-shielding pigment and the dispersant in the resin composition is in a certain range
- the resin composition A container molded from a resin composition composed of polyethylene or ethylene- ⁇ -olefin copolymer with a low molecular weight polymer and additive content less than a certain weight in the product is excellent in mechanical strength and easy to handle. It has been proposed as a light-shielding container for high-purity chemicals having a light-shielding property (see Patent Document 1), which is easy and has very little leaching of impure fine particles into stored and stored chemicals.
- this container satisfies the cleanliness of less than 500 / ml according to the conventional measurement method, but does not become less than 5 / ml, and has an oxygen barrier property to prevent alteration of the contained liquid. There was a problem such as not having.
- At least the inner surface of the resin is made of a resin of polyethylene or ethylene- ⁇ -olefin copolymer having a density of 940 to 970 Kg / m 3, and the neutralizing agent, antioxidant and light-resistant stabilizer in the resin are quantified by liquid chromatography.
- the content is 0.01% by weight or less with respect to the total weight of the resin, and the resin has a weight average molecular weight of 120,000 to 260,000 as measured by gel permeation chromatography. Minute High purity solvent containers amount 1,000 of the polymer is less than 2.5% by weight relative to the total weight of the resin (see Patent Document 2) are proposed.
- the high purity solvent container of Patent Document 2 satisfies the cleanliness of less than 500 / ml by the conventional measurement method, but the cleanliness does not become less than 5 / ml and prevents the contained liquid content from being altered. There is a problem that it is inferior in ultraviolet blocking ability.
- a polyethylene or ethylene- ⁇ -olefin copolymer resin having a density of 940 to 970 kg / m 3, at least 0.01 wt% to 5 wt% of a light-shielding pigment such as titanium oxide or carbon black, and a liquid or gas barrier resin
- a high-purity chemical container comprising a resin composition to which 4 to 25% by weight of the resin is added, wherein the resin has a weight average molecular weight of 120,000 to 260,000 as measured by gel permeation chromatography, A polymer having a weight average molecular weight of 1,000 or less is less than 5% by weight of the resin, and the ⁇ -olefin is selected from propylene, butene-1,4-methyl-pentene-1, hexene-1 and octene-1. At least one kind of high-purity chemical container (see Patent Document 3) has been proposed.
- Patent Document 3 still satisfies the cleanliness of less than 500 / ml by the conventional measurement method, and has a problem that the cleanliness does not fall below 5 / ml.
- Solvents containing poly (ethylene-co-vinyl alcohol) and an inner layer made of a high-purity resin containing various types of neutralizing agents, antioxidants, and light stabilizers at a maximum content of 0.01% by weight A container in which an intermediate layer of a barrier resin and an outer layer made of a resin composition containing a light-shielding substance are blow-molded, and the minimum absorbance at a wavelength of 400 nm or less of all layers of the container measured by a spectrophotometer is 2.
- the absorption coefficient at a wavelength of 400 nm obtained by dividing the absorbance of all layers of the container by the thickness of the entire layer is not less than 1.5 mm ⁇ 1 and also at a wavelength of 600 nm.
- High purity chemicals liquid container see Patent Document 4 it has been proposed, wherein the extinction coefficient is 1.5 mm-1 or less.
- the high-purity chemical solution container of Patent Document 4 satisfies the cleanliness of less than 100 / ml by the conventional measurement method, and has a problem that the cleanliness does not become 5 / ml or less.
- the applicant of the present invention firstly sprays an ultra-high-purity chemical obtained by laminating at least an inner layer having the following characteristics, an oxygen barrier layer containing polyvinyl alcohol resin, and an outer layer containing a light-shielding pigment in order from the inside to the outside of the container.
- a molded laminated container having a visible light transmittance of 1% or less at a wavelength of 500 to 800 nm and an ultraviolet transmittance of a wavelength of 200 to 400 nm of 1% or less, and entering the stored chemical from the container side.
- Inner layer high density having the following characteristics comprising a homopolymer or copolymer containing at least one selected from ethylene, propylene, butene-1,4-methyl-pentene-1, hexene-1 and octene-1 Polyolefin resin.
- Patent Literature 1 Japanese Patent No. 2805723
- Patent Literature 2 Japanese Patent No. 2749513
- Patent Literature 3 Japanese Patent No. 2805188
- Patent Literature 4 Japanese Patent No. 4167745
- Patent Literature 5 Japanese Patent Application No. 2015-234798
- a test container is molded, and the test container is filled with ultrapure water and filled in 1 ml of ultrapure water after being stored at 23 ° C. for 30 days.
- the chemical-resistant blow-molded laminated container (see Patent Document 5) is excellent in chemical resistance and mechanical strength.
- the object of the present invention is excellent in chemical resistance, mechanical strength, etc., and the cleanliness as an index indicating the number of impure fine particles leached from the container side into ultra-high purity chemicals stored and stored is 23 ° C. 5 or less after storage for 30 days and 10 or less after storage at 40 ° C. for 30 days, and has excellent oxygen barrier properties, and has a transmittance of 1% for visible light having a wavelength of 500 to 800 nm. Visibility of contents that can be used as ultra-high-purity chemical containers such as fragrances and photoresist liquids. It is an object of the present invention to provide a chemical-resistant blow-molded laminated container having a small amount of impure fine particles that are not dissolved.
- the present inventors have intensively studied, for example, in order from the inner side to the outer side of the container, the inner layer 1, the inner layer 2, the barrier / adhesive resin layer, the adhesive layer, the barrier layer, and the outer layer.
- the inner layer 1 does not have an adhesive functional group, has an adhesive property to the fluororesin of the inner layer 2, but has an adhesive property to other layers.
- Additive-free heat loss without additives is 0.20% by mass or less, and the inner layer 2 has an adhesive functional group, the inner layer 1 fluororesin and the barrier / adhesive resin layer Additives containing additives and lubricants that are intentionally added as a barrier / adhesive resin layer using a specific fluororesin having an adhesive-free heat loss of 0.40% by mass or less. Do not use polyamide resin
- the impure fine particle elution amount (number / ml) after storage at 23 ° C. for 30 days is 5 or less
- the impure fine particle elution amount (number / ml) after storage at 40 ° C. for 30 days is 10 or less.
- an ethylene vinyl alcohol copolymer resin By using an ethylene vinyl alcohol copolymer resin, it is possible to improve gas barrier properties, excellent in UV blocking properties and visible light blocking properties, and by using an ultra high molecular weight high density polyethylene resin having a high melt tension, drawdown, etc. Since the moldability and mechanical strength are improved, the visibility of contents that can be used as containers for ultra-high-purity chemicals that contain a lot of expensive and dangerous chemicals such as fragrances and photoresist solutions The present inventors have found that a chemical-resistant blow-molded laminated container with a small amount of impure fine particles eluted can be obtained, and the present invention has been achieved.
- the invention of claim 1 of the present invention for solving the above-mentioned problem is to laminate the following inner layer 1, inner layer 2, barrier / adhesive resin layer, adhesive layer, barrier layer and outer layer 1 in order from the inside to the outside of the container.
- a chemical-resistant blow-molded laminated container having a visible light transmittance of 500 to 800 nm of 1% or less and an ultraviolet transmittance of 200 to 400 nm of 1% or less at 23 ° C.
- Impure particulate elution amount (number / ml) after storage for 30 days is 5 or less
- impure particulate elution amount (number / ml) after storage for 30 days at 40 ° C. is 10 or less.
- This is a chemical-resistant blow-molded laminated container with a low content.
- Inner layer 1 is an additive-free fluororesin that has no adhesive functional group, has adhesiveness to the fluororesin of the inner layer 2 but has no adhesiveness to other layers, and has 0 weight loss on heating. 20% by mass or less.
- Inner layer 2 An additive-free fluororesin having an adhesive functional group and adhesiveness to the fluororesin and barrier / adhesive resin layer of the inner layer 1, and having a loss on heating of 0.40% by mass or less.
- Barrier / adhesive resin layer At least one polyamide selected from the group consisting of polyamides obtained by ring-opening polycondensation of caprolactam, which does not contain additives that are intentionally added or lubricants.
- Adhesive layer a maleic anhydride-modified polyolefin resin.
- Barrier layer an ethylene vinyl alcohol copolymer resin.
- Outer layer 1 an ultra high molecular weight high density polyethylene resin that includes a light shielding pigment and a maleic anhydride-modified polyolefin resin and is excellent in adhesion to the barrier layer.
- the invention of claim 2 of the present invention is formed by laminating the following inner layer 1, inner layer 2, barrier / adhesive resin layer, adhesive layer, barrier layer, adhesive layer and outer layer 2 in order from the inside to the outside of the container.
- a chemical-resistant blow-molded layered container that has a visible light transmittance of 1% or less at a wavelength of 500 to 800 nm, an ultraviolet transmittance of a wavelength of 200 to 400 nm of 1% or less, and is stored at 23 ° C. for 30 days.
- the impure fine particle elution amount (number / ml) is 5 or less
- the impure fine particle elution amount (number / ml) after storage at 40 ° C. for 30 days is 10 or less. It is a chemical blow molded laminated container.
- Inner layer 1 is an additive-free fluororesin that has no adhesive functional group, has adhesiveness to the fluororesin of the inner layer 2 but has no adhesiveness to other layers, and has 0 weight loss on heating. 20% by mass or less.
- Inner layer 2 An additive-free fluororesin having an adhesive functional group and adhesiveness to the fluororesin and barrier / adhesive resin layer of the inner layer 1, and having a loss on heating of 0.40% by mass or less.
- Barrier / adhesive resin layer At least one polyamide selected from the group consisting of polyamides obtained by ring-opening polycondensation of caprolactam, which does not contain additives that are intentionally added or lubricants.
- Adhesive layer a maleic anhydride-modified polyolefin resin.
- Barrier layer an ethylene vinyl alcohol copolymer resin.
- Adhesive layer a maleic anhydride-modified polyolefin resin.
- Outer layer 2 Ultra high molecular weight high density polyethylene resin containing light blocking pigment
- the invention according to claim 3 of the present invention is the chemical resistant blow-molded laminated container according to claim 1 or 2, wherein the fluororesin used for the inner layer 2 is tetrafluoroethylene / hexafluoropropylene / monomer.
- ( ⁇ ) copolymer tetrafluoroethylene / perfluoro (alkyl vinyl ether) / monomer ( ⁇ ) copolymer, ethylene / tetrafluoroethylene / monomer ( ⁇ ) copolymer, ethylene / tetrafluoroethylene / Hexafluoropropylene / monomer ( ⁇ ) copolymer, chlorotrifluoroethylene / monomer ( ⁇ ) copolymer, chlorotrifluoroethylene / tetrafluoroethylene / monomer ( ⁇ ) copolymer, and ethylene / Chlorotrifluoroethylene / monomer ( ⁇ ) copolymer is at least one selected from the group consisting of copolymers, and the monomer ( ⁇ ) is a monomer having an adhesive functional group. And a fluororesin having the following characteristics.
- the invention according to claim 4 of the present invention is the chemical resistant blow molded laminated container according to any one of claims 1 to 3, wherein the fluororesin used for the inner layer 1 is the adhesive functional group. It is characterized by being a fluororesin having the following characteristics.
- the invention of claim 5 of the present invention is characterized in that, in the chemical-resistant blow-molded laminated container of any one of claims 1 to 4, the polyamide resin has the following characteristics.
- the invention according to claim 6 of the present invention is the chemical resistant blow-molded laminated container according to any one of claims 1 to 5, wherein the barrier layer is ethylene having excellent oxygen barrier properties having the following characteristics: It is a vinyl alcohol copolymer resin.
- the invention according to claim 7 of the present invention is the chemical resistant blow molded laminated container according to claim 1, wherein the outer layer 1 is made of polyethylene or ethylene- ⁇ -olefin copolymer having the following characteristics.
- High density polyethylene resin organic light-shielding pigments such as quinacridone, phthalocyanine, anthraquinone, monoazo, etc., carbon black, iron oxide, zinc oxide, ultramarine blue
- the invention according to claim 8 of the present invention is the chemical resistant blow molded laminated container according to claim 2, wherein the outer layer 2 is made of polyethylene or ethylene- ⁇ -olefin copolymer having the following characteristics.
- High density polyethylene resin organic light-shielding pigments such as quinacridone, phthalocyanine, anthraquinone, monoazo, etc., carbon black, iron oxide, zinc oxide, ultramarine blue
- 0.05 to 0.30 mass% visible light transmittance at a wavelength of 500 to 800 nm is 1% or less, and a wavelength of 200 to 400 nm Wherein the external line transmission is composed of the composition 2 is 1% or less.
- the invention of claim 1 of the present invention is a chemical-resistant spray comprising a laminate of the inner layer 1, inner layer 2, barrier / adhesive resin layer, adhesive layer, barrier layer and outer layer 1 in this order from the inside to the outside of the container.
- Impregnated fine particle container having a visible light transmittance of 500 to 800 nm of 1% or less, an ultraviolet transmittance of 200 to 400 nm of wavelength of 1% or less, and stored at 23 ° C. for 30 days
- the inner layer 1 does not have an adhesive functional group, and the fluororesin of the inner layer 2 has adhesiveness but does not have adhesiveness to other layers.
- a specific fluororesin is used, and the inner layer 2 has an adhesive functional group, and has an adhesive-free functional heating loss of 0.40% by mass.
- the cleanliness is 30 ° C. at 30 ° C. It is 5 or less after day storage and 10 or less after storage at 40 ° C. for 30 days, a cleanness equivalent to a glass bottle can be obtained, chemical resistance can be improved, and alteration of odor components can be reduced as much as possible. Prominent effect That.
- the oxygen barrier properties are improved, while the fluororesin, polyamide resin, and adhesive resin are melted and the melt tension is lowered at a stretch.
- problems such as draw-down occur in blow molding.
- the outer layer 1 has melt tension.
- Use of ultra-high molecular weight high-density polyethylene resin with excellent UV blocking properties, visible light blocking properties, and mechanical strength improves moldability and UV blocking properties, so it is expensive and dangerous for fragrances and photoresist solutions.
- the chemical-resistant blow-molded laminated container of the present invention includes a maleic anhydride-modified polyolefin resin as the outer layer 1 and uses an outer layer excellent in adhesiveness with the barrier layer, the outer layer 1 and the barrier layer There is no need to provide an adhesive layer (maleic anhydride-modified polyolefin resin) between them, and there is a remarkable effect that workability and economy are further improved.
- the chemical-resistant blow-molded laminated container of the present invention is heavy, easily damaged, and unlike a glass bottle that lacks safety, is not easily damaged, has excellent mechanical strength, and has a barrier layer. Oxygen barrier property is improved by the above, so it can be used as a perfume bottle, etc., and it can be used safely and safely as a versatile plastic container that can be used for various other contents. There is a remarkable effect of being able to. Since the chemical-resistant blow molded laminated container of the present invention has the above-mentioned characteristics, it is easy for the environment and health, contributes to environmental problems and health problems, and is economical because it also reduces costs. There is a remarkable effect of being.
- the invention of claim 2 of the present invention is formed by laminating the inner layer 1, the inner layer 2, the barrier / adhesive resin layer, the adhesive layer, the barrier layer, the adhesive layer and the outer layer 2 in this order from the inside to the outside of the container.
- a chemical-resistant blow-molded layered container that has a visible light transmittance of 1% or less at a wavelength of 500 to 800 nm, an ultraviolet transmittance of a wavelength of 200 to 400 nm of 1% or less, and is stored at 23 ° C. for 30 days.
- the impure fine particle elution amount (number / ml) is 5 or less
- the impure fine particle elution amount (number / ml) after storage at 40 ° C. for 30 days is 10 or less.
- a chemical blow-molded laminated container The chemical-resistant blow-molded laminated container according to claim 2 of the present invention is economically acceptable because an adhesive layer (maleic anhydride-modified polyolefin resin) is provided between the outer layer 2 and the barrier layer.
- an adhesive layer maleic anhydride-modified polyolefin resin
- the adhesiveness between the two is ensured, it is used depending on the purpose and purpose. Except for this point, it has the same configuration as the chemical-resistant blow-molded laminated container of claim 1 of the present invention.
- the effect and effect are the same as those of the chemical-resistant blow-molded laminated container of claim 1 of the present invention.
- the invention according to claim 3 of the present invention is the chemical resistant blow-molded laminated container according to claim 1 or 2, wherein the fluororesin used for the inner layer 2 is tetrafluoroethylene / hexafluoropropylene / monomer.
- ( ⁇ ) copolymer tetrafluoroethylene / perfluoro (alkyl vinyl ether) / monomer ( ⁇ ) copolymer, ethylene / tetrafluoroethylene / monomer ( ⁇ ) copolymer, ethylene / tetrafluoroethylene / Hexafluoropropylene / monomer ( ⁇ ) copolymer, chlorotrifluoroethylene / monomer ( ⁇ ) copolymer, chlorotrifluoroethylene / tetrafluoroethylene / monomer ( ⁇ ) copolymer, and ethylene / Chlorotrifluoroethylene / monomer ( ⁇ ) copolymer is at least one selected from the group consisting of copolymers, and the monomer ( ⁇ ) is a monomer having an adhesive functional group.
- the invention of claim 4 of the present invention is the chemical resistant blow molded laminated container according to any one of claims 1 to 3, wherein the fluororesin used for the inner layer 1 has the adhesive functional group.
- it is characterized by being a fluororesin having the above-mentioned characteristics, and it has excellent adhesiveness to the fluororesin of the inner layer 2 and can be coextruded at a molding temperature comparable to polyolefin. Has a remarkable effect.
- the invention of claim 5 of the present invention is the chemical-resistant blow-molded laminated container according to any one of claims 1 to 4, wherein the polyamide resin has the above characteristics. And By improving the adhesion of the inner layer 2 with the fluororesin and making it free of additives and lubricants, the amount of impure particles eluted due to the additives can be greatly reduced, and a cleanliness equivalent to a glass bottle can be obtained. There is a further remarkable effect.
- the invention according to claim 6 of the present invention is the chemical-resistant blow-molded laminated container according to any one of claims 1 to 5, wherein the barrier layer is excellent in oxygen barrier properties having the above characteristics. It is characterized by being an ethylene vinyl alcohol copolymer resin, There is a further remarkable effect that the oxygen barrier property is surely further improved.
- the invention according to claim 7 of the present invention is the chemical resistant blow-molded laminated container according to claim 1, wherein the outer layer 1 is made of polyethylene or ethylene- ⁇ -olefin copolymer having the above characteristics.
- High density polyethylene resin organic light-shielding pigments such as quinacridone, phthalocyanine, anthraquinone, monoazo, etc., carbon black, iron oxide, zinc oxide, ultramarine blue
- Transmittance of light is less than 1%, which is characterized in that ultraviolet transmittance at a wavelength 200 ⁇ 400 nm is composed of the composition 1 is 1% or less, Fluorine resin, polyamide resin, and adhesive resin are melted and the melt tension drops at a stretch, causing problems such as draw-down in blow molding. For example, a uniform-thick container cannot be molded or defective products are generated.
- the use of an ultra-high molecular weight high density polyethylene resin having a large weight average molecular weight and high melt tension for the outer layer 1 eliminates problems such as drawdown and improves moldability and mechanical strength. Improved, By using an appropriate amount of the light-shielding pigment, the visible light blocking property and the ultraviolet blocking property are surely improved, the visible light transmittance at a wavelength of 500 to 800 nm is surely 1% or less, and the ultraviolet transmittance at a wavelength of 200 to 400 nm is ensured.
- 1% or less can be achieved, and it is a chemical-resistant blow-molded laminated container with a small amount of impure fine particles that can be used as a container for ultra-high-purity chemicals that contain a lot of expensive and dangerous chemicals such as fragrances and photoresist solutions.
- the antioxidant in the above range the resin can be prevented from being burnt, and the physical properties and the appearance can be prevented from being deteriorated due to the burnt resin.
- the chemical-resistant blow-molded laminated container of the present invention includes a maleic anhydride-modified polyolefin resin as the outer layer 1 and uses an outer layer excellent in adhesiveness with the barrier layer, so that the outer layer 1 and the barrier layer There is no need to provide an adhesive layer (maleic anhydride-modified polyolefin resin) between them, and there is a further remarkable effect that workability and economy are further improved.
- the chemical-resistant blow-molded laminated container of the present invention is heavy, easily damaged, and unlike a glass bottle that lacks safety, is not easily damaged, has excellent mechanical strength, and has a barrier layer. Oxygen barrier properties are improved by this, so it can be used as a perfume bottle and can be used safely and safely as a versatile plastic container that can be used for various other contents. , Has a further remarkable effect.
- the invention according to claim 8 of the present invention is the chemical resistant blow molded laminated container according to claim 2, wherein the outer layer 2 is made of polyethylene or ethylene- ⁇ -olefin copolymer having the following characteristics.
- High density polyethylene resin organic light-shielding pigments such as quinacridone, phthalocyanine, anthraquinone, monoazo, etc., carbon black, iron oxide, zinc oxide, ultramarine blue
- Visible light having a wavelength of 500 to 800 nm containing 0.05 to 0.30% by mass is 1% or less and purple having a wavelength of 200 to 400 nm
- the linear transmittance is constituted from a composition 2 is 1% or less
- the visible light blocking property and the ultraviolet blocking property are surely improved, the visible light transmittance at a wavelength of 500 to 800 nm is surely 1% or less, and the ultraviolet light transmission at a wavelength of 200 to 400 nm is performed.
- the chemical-resistant blow-molded laminated container of the present invention is heavy, easy to break, hard to break, has excellent mechanical strength, and has a barrier layer compared to a glass bottle lacking safety. Oxygen barrier properties are improved by this, so it can be used as a perfume bottle and can be used safely and safely as a versatile plastic container that can be used for various other contents. This has a further remarkable effect.
- FIG. 1 is an explanatory view illustrating a cross section of an example of a chemical-resistant blow-molded laminated container of the present invention.
- 1A of the chemical resistant blow-molded laminated container 8A of the present invention consists of the fluororesin having no adhesive functional group, and the inner layers 1 and 1B made of the fluororesin having adhesive functional group.
- Inner layers 2 and 2 are barrier / adhesive resin layers made of the polyamide resin
- 3 is an adhesive layer made of maleic anhydride-modified polyolefin resin
- 4 is a barrier layer made of ethylene vinyl alcohol copolymer resin
- 5 is Adhesive layer 6A comprising maleic anhydride-modified polyolefin resin, ultra high molecular weight high density polyethylene having a visible light transmittance of 1% or less at a wavelength of 500-800 nm and an ultraviolet transmittance of 200% to 400 nm of 1% or less
- Each of the outer layers 2 made of resin is shown.
- 7 shows the ultra-high purity chemical as the contents.
- FIG. 2 is an explanatory view illustrating a cross section of another example of the chemical-resistant blow-molded laminated container of the present invention.
- 1A of the chemical resistant blow molded laminated container 8B of the present invention is composed of the fluororesin having no adhesive functional group, and the inner layer 1 and 1B made of the fluororesin having adhesive functional group.
- Inner layers 2 and 2 are barrier / adhesive resin layers made of the polyamide resin
- 3 is an adhesive layer made of maleic anhydride-modified polyolefin resin
- 4 is a barrier layer made of ethylene vinyl alcohol copolymer resin
- 6B is Ultra-high molecular weight comprising maleic anhydride-modified polyolefin resin having excellent adhesiveness to the barrier layer 4 and having visible light transmittance of 1% or less at a wavelength of 500 to 800 nm and ultraviolet transmittance of wavelength of 200 to 400 nm of 1% or less
- the outer layers 1 made of high-density polyethylene resin are shown respectively.
- 7 shows the ultra-high purity chemical as the contents.
- the outer layer 1 contains 25 to 65% by mass of a maleic anhydride-modified polyolefin resin, the outer layer 1 has excellent adhesion between the outer layer 1 and the barrier layer 4, and has no problems such as drawdown, moldability and mechanical properties. Excellent strength.
- the maleic anhydride-modified polyolefin resin is less than 25% by mass, the adhesion between the outer layer 1 and the barrier layer 4 may be insufficient, and if the maleic anhydride-modified polyolefin resin exceeds 65% by mass, the drawdown may occur. Such problems may occur.
- the fluororesin used for the inner layer 2 is not particularly limited, but specifically, for example, tetrafluoroethylene / hexafluoropropylene / monomer ( ⁇ ) copolymer, tetrafluoroethylene / perfluoro (Alkyl vinyl ether) / monomer ( ⁇ ) copolymer, ethylene / tetrafluoroethylene / monomer ( ⁇ ) copolymer, ethylene / tetrafluoroethylene / hexafluoropropylene / monomer ( ⁇ ) copolymer , Chlorotrifluoroethylene / monomer ( ⁇ ) copolymer, chlorotrifluoroethylene / tetrafluoroethylene / monomer ( ⁇ ) copolymer, and ethylene / chlorotrifluoroethylene / monomer ( ⁇ ) copolymer When it is a fluororesin that is at least one selected from the group consisting of polymers and copolymerized with the mono
- the fluororesin used for the inner layer 1 in the present invention is a fluororesin that does not copolymerize the monomer ( ⁇ ) having an adhesive functional group and does not have the adhesive functional group, and is free of additives. It is preferable to use an additive grade fluororesin.
- the fluororesin used for the inner layer 1 has a heat loss measured by the following heat loss measurement method of 0.20% by mass or less, preferably 0.15 or less, and the fluororesin used for the inner layer 2 is the same measurement. It is necessary that the loss on heating measured by the method is 0.40% by mass or less, preferably 0.30 or less. If it is within this range, it is possible to achieve 5 or less after storage at 23 ° C. for 30 days and 10 or less after storage at 40 ° C. for 30 days. is there.
- MFR (265 ° C., 5 kg load g / 10 min) (measuring method: 265 ° C., ASTM D1238) is preferably 10 to 40, more preferably 20 to 30. If it is less than 10, the melt viscosity is high, and the blow melt moldability is high. There is a possibility that the drive energy will be worsened, and if it exceeds 40, the melt tension is low and problems such as draw-down may occur during blow molding.
- the specific gravity may be a commercially available specific gravity of 1.7 to 1.9, more preferably 1.72 to 1.76. If the specific gravity is less than 1.7, there is a concern that the adhesiveness may be lowered, and if it exceeds 1.9, the strength of the container may be insufficient.
- the melting point (° C.) (measurement method: ASTM D792) varies depending on the amount and type of the monomer ( ⁇ ) to be copolymerized, but may be a melting point of 150 to 200 ° C. of a commercially available product. The temperature is preferably 190 to 200 ° C. If the melting point is less than 150 ° C., a difference in melting point from other resins may occur, which may cause problems of adhesive strength and moldability. If the melting point exceeds 200 ° C., it may be difficult to laminate with other resins. .
- the monomer ( ⁇ ) to be copolymerized is not particularly limited as long as it has an adhesive functional group and can be copolymerized, but the amount and type are controlled in consideration of melt molding. It is preferable that the fluororesin of the inner layer 2 is in the melting point (° C.) range and has excellent adhesion with the fluororesin of the inner layer 1 and the barrier / adhesive resin layer (polyamide resin).
- the adhesive functional group include an epoxy group, a hydroxyl group, a carboxylic anhydride residue, a carboxylic acid group, an acrylate group, a carbonate group, and an amino group.
- this copolymer include the ethylene-tetrafluoroethylene-hexafluoropropylene-ethylene carbonate copolymer EFEP used in Example 1 (for example, RP5000 manufactured by Daikin Industries, Ltd.).
- MFR (297 ° C., 5 kg load g / 10 min) (measuring method: 265 ° C., ASTM D1238) is preferably 9 to 35, more preferably 15 to 25. If it is less than 9, the melt viscosity is high and the blow melt moldability is high. There is a possibility that the drive energy will be worsened, and if it exceeds 35, the melt tension is low, and there is a risk that problems such as draw-down may occur during blow molding.
- the specific gravity (measurement method: ASTM D-792) may be a commercially available specific gravity of 1.7 to 1.9, more preferably 1.83 to 1.89. If the specific gravity is less than 1.7, there is a concern that the adhesiveness may be lowered, and if it exceeds 1.9, the strength of the container may be insufficient.
- the melting point (° C.) (measurement method: ASTM D792) may be a commercially available melting point of 200 to 240 ° C., more preferably 208 to 228 ° C. If the melting point is less than 200 ° C., a difference in melting point from other resins may occur, which may cause problems of adhesive strength and moldability. If the melting point exceeds 240 ° C., it may be difficult to laminate with other resins. .
- the above-mentioned polyamide resin of the barrier and adhesive resin layer used in the present invention is an additive-free grade polyamide resin to which additives including additives and lubricants that are usually added intentionally are not added / blended.
- additives including additives and lubricants that are usually added intentionally are not added / blended.
- Z4887 manufactured by Daicel Evonik Co., Ltd. can be given.
- the polyamide obtained by ring-opening polycondensation of caprolactam is at least one polyamide selected from nylon 6, nylon 11, nylon 12, nylon 66 and the like, and a polyamide that does not contain additives and additives including a lubricant is It can be preferably used.
- the maleic anhydride-modified polyolefin resin of the adhesive layer used in the present invention has excellent adhesion to the barrier / adhesive resin layer (polyamide resin) and the barrier layer (ethylene vinyl alcohol copolymer resin). Furthermore, the maleic anhydride-modified polyolefin resin of the adhesive layer has excellent adhesion to the barrier layer (ethylene vinyl alcohol copolymer resin) and the outer layer (ultra high molecular weight high density polyethylene resin), The adhesive layer is formed by adhering the two, and any commercially available product can be used as long as it can be melt-molded.
- the inner layers 1 and 2 fluororesin
- Combined recovered material including barrier / adhesive resin layer (polyamide resin), adhesive layer (maleic anhydride modified polyolefin resin), barrier layer (ethylene vinyl alcohol copolymer resin) and outer layer (ultra high molecular weight high density polyethylene resin) can do. This is because the maleic anhydride-modified polyolefin resin in which the recovered material of the adhesive layer is blended is separated from the fluororesin of the inner layer 1 serving as the liquid contact surface, so that there is practically no risk of impairing cleanliness. .
- the maleic anhydride-modified polyolefin resin having excellent adhesion to the outer layer may be the same or different, and is preferably determined by testing in advance.
- the barrier layer ethylene vinyl alcohol copolymer resin (ethylene 24-44 mol% copolymer) used in the present invention is a resin obtained by hydrolyzing ethylene vinyl alcohol copolymer and almost completely saponified, and has an aroma retaining property. It has excellent gas barrier properties and is widely used in containers and packaging materials for chemicals, cosmetics, etc., and has high resistance to oils and organic solvents. By using a polymerized resin, oxygen barrier properties can be secured, and since MFR, melting point, etc. are close to ultrahigh molecular weight high-density polyethylene resin and excellent in stable moldability, they can be preferably used.
- ethylene vinyl alcohol copolymer resin for the barrier layer examples include, for example, F171B (ethylene 32 mol% copolymerization, melting point 183 ° C., saponification rate 99.99%) manufactured by Kuraray Co., Ltd. be able to.
- MFR (Characteristic) MFR (210 ° C., 2.16 kg load g / 10 min): 2 to 5 Density (Kg / m3): (ISO 1183 compliant) 1.1 to 1.3 Melting point (° C): (ISO 1346 compliant): 170-200
- the MFR is preferably 2 to 5, more preferably 3 to 5, the density is preferably 1.1 to 1.3, more preferably 1.2 to 1.3, and the melting point (° C.). Is preferably 170 to 200, more preferably 190 to 200.
- gas barrier properties, strength, stable moldability and the like are all excellent, but at least one of these characteristics may be impaired outside the above ranges.
- the ultrahigh molecular weight high-density polyethylene resin of the outer layers 1 and 2 used in the present invention preferably has a density (measurement method: JIS K7112 compliant), preferably 940 to 962 Kg / m3, more preferably 944 to 946 Kg / m3.
- the weight average molecular weight is preferably 2260 to 260,000, more preferably 240 to 260,000, and the molecular weight distribution (Mw / Mn) (measurement method: described later) is preferably 12 or less, more preferably 11 or less, melt tension (measurement method: Japanese polyethylene method, 210 ° C.
- Ren resin is preferable, the ultra high molecular weight high density polyethylene resin such as moldability and mechanical strength by using the outer layer 1 is improved, there is no problems such as drawdown is also improved such as yield.
- (Mw / Mn) of the ultra-high molecular weight high-density polyethylene resin forming the outer layers 1 and 2 is preferably 12 or less, more preferably 11 or less. When (Mw / Mn) exceeds 12, melt processing and rapid cooling are performed. However, the outer layer of the blow-molded laminated container that has been formed into a multilayer structure under the normal molding process conditions is not composed of a dense small crystal aggregate due to an increase or variation in the outer layer, and the mechanical strength may be insufficient.
- the weight average molecular weight of the ultrahigh molecular weight high density polyethylene resin is less than 220,000, the mechanical strength may be insufficient, and the weight average molecular weight exceeds 260,000. Further, since the melt viscosity of the resin is high, the moldability is deteriorated, and there is a possibility that molecular cutting by shear stress may occur.
- the density and melt tension of the ultra-high molecular weight high-density polyethylene resin forming the outer layers 1 and 2 are less than the lower limit values, it may be difficult to draw down and control the wall thickness. In addition, there is a possibility that a problem of melt fracture (rough skin) may occur.
- ethylene homopolymers and copolymers of ethylene and ⁇ -olefins such as propylene, butene-1,4-methyl-pentene-1, hexene-1 and octene-1 are preferably used.
- the content of ⁇ -olefin in the copolymer is preferably 15% by mass or less.
- the molecular structure of the copolymer is atactic, isotactic, syndiotactic or a mixture thereof.
- the low pressure method or the intermediate pressure method may be used.
- At least one light-shielding pigment selected from organic light-shielding pigments and / or inorganic light-shielding pigments has a visible light transmittance of 1 to 500 nm. It is preferable to add a predetermined amount so that the ultraviolet transmittance at a wavelength of 200 to 400 nm is 1% or less (according to the measurement method described later).
- the organic light-shielding pigment and the inorganic light-shielding pigment have a visible light transmittance of 1% or less at a wavelength of 500 to 800 nm and an ultraviolet transmittance of a wavelength of 200 to 400 nm when blended in a predetermined amount in the outer layer. It can be 1% or less, and is not particularly limited as long as other characteristics of the outer layer are not impaired.
- organic light-shielding pigments such as quinacridone, phthalocyanine, anthraquinone, and monoazo
- inorganic light-shielding properties such as carbon black, iron oxide, zinc oxide, ultramarine, chromium oxide, titanium oxide, and silicon dioxide
- At least one light-shielding pigment selected from pigments can be used preferably in the present invention because the object can be achieved by a relatively small amount of the pigment.
- quinacridone-based light-shielding pigment examples include TET48183 and TET78310 (manufactured by Toyocolor Co., Ltd.).
- phthalocyanine-based light-shielding pigment examples include 7F2854 (manufactured by Dainichi Seika Kogyo Co., Ltd.), TET58335 (manufactured by Toyocolor Co., Ltd.), and EPH-525328 (manufactured by Polycol Kogyo Co., Ltd.). Can do.
- monoazo light-shielding pigment examples include TET38013 (manufactured by Toyocolor Co., Ltd.) and ECE-6293 (manufactured by Polycol Kogyo Co., Ltd.).
- carbon black light-shielding pigment examples include TET01337 (manufactured by Toyocolor Co., Ltd.) and EPH-K-51680 (manufactured by Polycol Kogyo Co., Ltd.).
- iron oxide-based light-shielding pigment examples include EPH-C-1045 (manufactured by Polycol Kogyo Co., Ltd.) and TET68473 (manufactured by Toyocolor Co., Ltd.).
- ultramarine light-shielding pigment examples include EPH-B-46662 (manufactured by Polycol Kogyo Co., Ltd.) and TET26146 (manufactured by Toyocolor Co., Ltd.).
- titanium oxide-based light-shielding pigment examples include EB-1427 (manufactured by DIC Corporation), EPH-H-2481 (manufactured by Polycol Kogyo Co., Ltd.), and TET28318 (manufactured by Toyocolor Co., Ltd.). Can be mentioned.
- the blending amount of the light-shielding pigment is tested in advance, and a visible wavelength of 500 to 800 nm It is preferable to determine such that the light transmittance is 1% or less and the ultraviolet transmittance at a wavelength of 200 to 400 nm is 1% or less.
- the transmittance of visible light with a wavelength of 500 to 800 nm is 1% or less and the transmittance of ultraviolet light with a wavelength of 200 to 400 nm is 1% or less, the contents are not visible and the contained liquid content can be prevented from being altered.
- It can be used as an ultra-high-purity chemical container such as a chemical or a fragrance that can be imparted with ultraviolet blocking properties, such as a photoresist solution, which is denatured and cured by ultraviolet rays.
- the light-shielding pigment and the blending amount As a specific example of the light-shielding pigment and the blending amount, an example in which 2% by mass of a phthalocyanine-based light-shielding pigment (trade name: 7F2854: manufactured by Dainichi Seika Kogyo Co., Ltd.) is blended in the outer layer in Example 1 to be described later. be able to. Since 7F2854 is a master batch containing 6% by mass of phthalocyanine, in the above example, 0.012% by mass of phthalocyanine was blended in the outer layer, and the ultraviolet transmittance was 1% or less and the visible light transmittance was 1% or less. The result is obtained.
- 7F2854 is a master batch containing 6% by mass of phthalocyanine
- 0.012% by mass of phthalocyanine was blended in the outer layer, and the ultraviolet transmittance was 1% or less and the visible light transmittance was 1% or less. The result is obtained.
- the outer layers 1 and 2 used in the present invention contain a predetermined amount (0.05 to 0.30% by mass) of at least one antioxidant selected from the group consisting of phenolic, phosphorus and sulfur antioxidants. It is preferable to prevent the resin from being burnt and to prevent the appearance from being deteriorated due to the burnt resin.
- the phenolic antioxidant, phosphorus antioxidant, and sulfur antioxidant are not particularly limited as long as they have a high antioxidant action and do not impair the other characteristics of the outer layers 1 and 2.
- phenolic antioxidants include ADEKA STAB AO60 manufactured by ADEKA Corporation.
- phosphorus-based antioxidant include ADK STAB 2112 manufactured by ADEKA Corporation.
- sulfur-based antioxidant include DSTP manufactured by Yoshitomi Mitsubishi Chemical Corporation.
- antioxidants are preferably added in an amount of 0.05 to 0.30% by mass, and 0.10 to 0.25% by mass, based on the ultrahigh molecular weight high density polyethylene resin forming the outer layers 1 and 2. More preferably. If it is less than 0.05% by mass, the antioxidant performance may be inferior, and if it exceeds 0.30% by mass, the additive may bleed out on the surface of the container.
- the outer layers 1 and 2 used in the present invention are blended with light-shielding pigments and antioxidants that can become impure fine particles, but the outer layers 1 and 2 are separated from the inner layers 1 and 2 that are in contact with the liquid. Since the barrier / adhesive resin layer 2, the adhesive layers 3, 5, and the barrier layer 4 prevent the impure fine particles due to the light-shielding pigment, antioxidant, etc. from leaching into the content liquid, they are stored in a container. Do not leach into chemicals.
- a light-resistant stabilizer such as a benzotriazole-based light-resistant stabilizer and a triazine-based light-resistant stabilizer can be appropriately used for the outer layers 1 and 2 as necessary, together with the light-shielding pigment.
- a benzotriazole light stabilizer or a triazine light stabilizer can block UV-B (200 to 320 nm) and UV-A (320 to 400 nm), respectively.
- the ultraviolet blocking property can be remarkably improved without deteriorating.
- Examples of the light-resistant stabilizer include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2 -Hydroxy-5-methylphenylbenzotriazole), 2- (5-chloro-2-benzotriazole) -6-t-butyl-cresol, 2- (3,5-di-t-amino-2-hydroxyphenyl) Benzotriazole light stabilizers such as bendtriazole and 2- (2H-benzotriazol-2-yl) -p-cresol, 2- [4,6-di (2,4xylyl) -1,3,5-triazine -2-yl] -5,2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine, 2- (4,6-diphe 1,3,5-triazin-2-yl) -5- [2-
- the content of the additive contained in the resin is a value obtained by separating and quantifying the extracted solution extracted with a Soxhlet extractor using tetrahydrofuran (THF) for 8 hours by liquid chromatography.
- the measurement conditions are as follows: GULIVER (manufactured by JASCO Corporation), column is Finepak® GEL-101 (manufactured by JASCO Corporation), solvent is THF, detector is UV-970 (manufactured by JASCO Corporation) and 830-RI. (Manufactured by JASCO Corporation).
- the resin composition cut out from the container is dissolved in a solvent (orthodichlorobenzene) to form a sample solution, and the molecular weight and molecular weight distribution are measured by GPC.
- the weight average molecular weight and the number average molecular weight are calculated by the following equations.
- Weight average molecular weight Mw ⁇ (M ⁇ w) / ⁇ w (2)
- Number average molecular weight Mn ⁇ w / ⁇ (w / M) (3)
- Molecular weight distribution weight average molecular weight / number average molecular weight (Mw / Mn)
- M is molecular weight and w is a weight fraction.
- GPC measurement conditions were 150 CV (manufactured by Waters) for the apparatus, TSKgel GMH-HT (manufactured by Tosoh Corporation) for the column, orthodichlorobenzene for the solvent, temperature of 138 ° C., and a detector for the differential refractometer. .
- the raw material resin In order to control the molecular weight distribution of the container within the above range, the raw material resin must also have a certain range of molecular weight distribution.
- the molding method is not particularly limited as long as it can form the chemical-resistant blow molded laminate container excellent in transparency of the present invention by the blow molding method. It can also be used by selecting from a molding machine.
- Example 1 The inner layer 1 is MFR 25 g / 10 min, the specific gravity is 1.86, the melting point is 223 ° C., and the additive-free fluororesin (EP-610 manufactured by Daikin Industries, Ltd.) having a loss on heating of 0.16% by mass is used.
- the inner layer 2 is MFR 25 g.
- additive-free fluororesin (RP-5000 manufactured by Daikin Industries, Ltd.) having a loss on heating of 0.35% by mass is used as a barrier and adhesive resin layer
- Additive-free polyamide resin (Z4887, manufactured by Daicel Evonik Co., Ltd.) having a function of adhering to the fluororesin of the inner layer 2 and containing no additive that is intentionally added or a lubricant. 87), and maleic anhydride-modified polyolefin resin (Nippon Polyethylene Co., Ltd.) as an adhesive layer having an adhesive function between the polyamide resin and the barrier layer.
- T71A and a barrier resin (ethylene-vinyl alcohol copolymer resin F171B: manufactured by Kuraray Co., Ltd., saponification rate 99.99%) as the barrier layer, and ultrahigh molecular weight high-density polyethylene as the outer layer 1
- Maleic anhydride-modified polyolefin resin for resin (HB111R manufactured by Nippon Polyethylene Co., Ltd.) (HL-MFR (measurement method: JIS K7112) 6 g / 10 min, density 946 Kg / m3, weight average molecular weight 250,000, melt tension 25 g) (Nippon Polyethylene Co., Ltd.
- FT71A 30% by mass
- phthalocyanine-based light-shielding pigment (trade name: 7F2854: manufactured by Dainichi Seika Kogyo Co., Ltd., containing 6% by mass of phthalocyanine) Masterbatch) 2% by mass
- phenolic antioxidant as antioxidant (trade name: ADK STAB O60: ADEKA Co., Ltd.)
- phosphorus antioxidant (trade name: ADK STAB 2112: ADEKA Co., Ltd.) in a total of 0.2% by mass were used, and the following high molecular weight high density polyethylene resin was used.
- the chemical-resistant blow molded laminated container of the present invention consisting of 6 layers (total mass 400 g, inner layer 1 50 ⁇ m, inner layer 2 100 ⁇ m, barrier and adhesive resin layer 50 ⁇ m, adhesiveness) Layer 50 ⁇ m, barrier layer 50 ⁇ m, outer layer 1 1500 ⁇ m, average total wall thickness 1.8 mm, capacity 3750 ML).
- IR Affinity-1 manufactured by Shimadzu Corporation
- Measurement sample A 50 ⁇ m-thick film sheet of inner layers 1 and 2 was prepared using a 240 ° C. press.
- Measurement wavelength 600 to 4000 cm-1
- FIG. 3 shows the result of infrared spectroscopic analysis of the inner layer 1, wherein the vertical axis represents absorbance (%) and the horizontal axis represents wavelength (cm-1).
- FIG. 4 shows the result of infrared spectroscopic analysis of the inner layer 2, wherein the vertical axis represents absorbance (%) and the horizontal axis represents wavelength (cm-1).
- a large sharp absorption (indicated by an arrow) at a wavelength of 1800 (cm-1) in FIG. 4 is an absorption peak of a carbonate group, and it can be seen that the fluororesin of the inner layer 2 has an adhesive functional group (carbonate group).
- the fluororesin of the inner layer 2 is produced by copolymerizing the monomer ( ⁇ ) having an adhesive functional group as described above, and the fluororesin of the inner layer 2 depends on the copolymerization amount of the monomer ( ⁇ ).
- the amount of the adhesive functional group can be controlled, thereby controlling the adhesiveness of the fluororesin of the inner layer 2 so that the inner layer 2 has good adhesion to the fluororesin of the inner layer 1 and the barrier / adhesive resin layer.
- the melting point and the like can be controlled to be within the predetermined range.
- the large sharp absorption peak is not observed at a wavelength of 1800 (cm-1) in FIG. 3, indicating that the fluororesin of the inner layer 1 does not have an adhesive functional group (carbonate group).
- the inner layer 1 has good adhesion to the fluororesin of the inner layer 2 but does not have adhesion to other layers.
- the large and sharp absorption peak of wavelength 3000 (cm-1) in FIGS. 3 and 4 is an absorption peak derived from copolymerized ethylene.
- Test method Measurement method of impure particles
- the following measurements are performed in a clean room (Class 100).
- Measuring apparatus A particle counter “KL-26” RION KL-26 manufactured by Rion Co., Ltd. is used.
- Sample to be measured filled with ultrapure water in a molded container and stored at 23 ° C. immediately after extraction and for 30 days and extracted or stored at 40 ° C. immediately after extraction and for 30 days and extracted, then 20 in an upright state A sample obtained by collecting a measurement sample from a container that has been allowed to stand for minutes is taken as a measurement sample.
- the particle counter Prior to measurement, the particle counter is purged with ultrapure water, and then the measuring device is washed twice with 25 ml of ultrapure water.
- Oxygen permeability [cm3 / (pg.24h.atm)]: Using a 3.75L container (wall thickness at the center of the bottle: 1.8 mm), using the measuring device (OX-TRAN2 / 21) (manufactured by MOCON) in accordance with JIS K7126-2, from the outside of the container The oxygen transmission to the inside was measured. Temperature and humidity: 1 atm outside, 23 ° C., 50% RH oxygen. Inside 1 atm, 23 ° C., dry nitrogen.
- UV transmittance Using JASCO Corporation V-670, the transmittance in the ultraviolet region of 200 to 400 nm is obtained.
- fragrances include limonene (trade name: orange oil, purity 96.4%, manufactured by Hasegawa Fragrance Co., Ltd.), citrus fruits (trade name: lemon essence, manufactured by Hasegawa Fragrance Co., Ltd.), crab oil (15%) Dimethyl sulfide, propylene glycol solution, manufactured by Hasegawa Fragrance Co., Ltd.), rice salad (trade name: rice oil, manufactured by Hasegawa Fragrance Co., Ltd.), ethyl butyrate (trade name: esters, purity 100%, Hasegawa Fragrance Co., Ltd.) ), Trans-2-hexenal (trade name: aldehydes, purity 99.7%, manufactured by Hasegawa Fragrance Co., Ltd.), filled with 1 kg of each fragrance, sealed, sealed at room temperature and pressure for 1 month and Left for 3 months.
- crab oil (15% dimethyl sulfide, propylene glycol solution) was refrigerated at room temperature and pressure for 1 month and 3 months. After standing for 3 months, measure the container mass for each sample and check if the contents are dissipated, conduct a sensory test with 10 panel members to check whether it has been altered, and determine the specific gravity and refractive index. It was measured to check whether it was fluctuating, and for a sample that could be analyzed, the components were checked by a gas chromatograph and evaluated according to the following evaluation criteria.
- Evaluation criteria There is no dissipation, alteration, fluctuation, etc., storage stability is high, and there is marketability.
- ⁇ Slightly inferior to ⁇ , but practically free from dissipation, alteration, fluctuation, etc., and has high storage stability and marketability.
- X There are dissipation, alteration, fluctuation, etc., storage stability is low, and there is no marketability.
- the particle value after 23 days at 30 ° C. is 5 particles / ml or less, and the particle value after 30 days at 40 ° C. is 10 particles / ml or less, Oxygen permeability is 0.003 [cm3 / (pg.24 h.atm)] or less, UV transmittance is 1% or less, Visible light transmittance is 1% or less, Visibility is ⁇ (the internal tap water cannot be confirmed), Drop strength: no destruction, Perfume is appropriate ⁇ ⁇ ⁇ , Metal elution is 10 (ng / L) or less. If all pass, pass the overall judgment. If any of these is inferior to the above, the overall judgment is judged as x.
- Example 1 Comparative Example 1
- an antioxidant hindered phenol-based antioxidant, A blow-molded laminated container for comparison was made and evaluated in the same manner as in Example 1 except that the same polyamide resin containing 2000 ppm) (relative viscosity 1.87) was used. The results are shown in Tables 1 and 2.
- a blow molded laminated container for comparison was made and evaluated in the same manner as in Example 1 except that a wetted layer using 0.2% by mass of high density polyethylene (9D01A manufactured by Tosoh Corporation) was used. . The results are shown in Tables 1 and 2.
- Example 3 (Comparative Example 3) In the same manner as in Example 1, except that the inner layer 1 used in Example 1 was not used and the inner layer 2 having a heat loss of 0.35% by mass used in Example 1 was used as the wetted layer, A blow molded laminated container was made and evaluated. The results are shown in Tables 1 and 2.
- Comparative Example 4 The fluororesin of the wetted layer used in Comparative Example 3 was heated at an electric furnace temperature of 260 ° C. ⁇ 1 ° C. for 120 minutes to reduce the loss on heating (heating loss of 0.31% by mass). In the same manner as in Comparative Example 3, a blow molded laminated container for comparison was made and evaluated. The results are shown in Tables 1 and 2.
- the chemical-resistant blow-molded laminated container of Example 1 has a particle value, oxygen transmittance, ultraviolet transmittance, visible light transmittance, visibility, drop strength, perfume suitability, metal elution It can be seen that the container for comparison of Comparative Examples 1 to 6 is inferior in any one of the above, while the overall judgment is excellent.
- the chemical-resistant blow-molded laminated container of the present invention does not have an adhesive functional group as the inner layer 1 and has adhesiveness to the fluororesin of the inner layer 2 but not to other layers.
- the inner layer 2 has an adhesive functional group, and has adhesiveness to the fluororesin of the inner layer 1 and the barrier / adhesive resin layer.
- the said polyamide which does not contain the additive which contains the additive and lubricant which are intentionally added to a barrier and adhesive resin layer using the specific fluororesin whose loss on heating is 0.40 mass% or less which has an additive free
- the cleanliness is 5 or less after storage at 23 ° C.
- the oxygen barrier properties are improved, and the outer layer has a high UV-blocking property with a high melt tension.
- Use of ultra-high molecular weight, high-density polyethylene resin that excels in visible light resistance and mechanical strength improves moldability and UV blocking properties, so expensive and highly dangerous chemicals such as fragrances and photoresist solutions
- As a container for ultra-high-purity chemicals there is no visibility of the contents, and there is a remarkable effect of providing a chemical-resistant blow-molded laminated container with a small amount of impure particulate elution. Is expensive.
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Abstract
Description
クリーン度はいったん検査容器を成形し、その検査容器に一定期間超純水を貯蔵(23℃で30日)した後、樹脂製の容器が貯蔵していた水1ml中に粒径0.2μm以上の微粒子がいくつ存在するかを算定して求める。 While the chemical is stored in the container for a long period of time, the impure fine particles are leached from the resin composition forming the container into the chemical that is the content, and the degree to which the impure fine particles impair the content is indicated. There is an index of cleanliness.
The degree of cleanness is that after molding a test container and storing ultrapure water in the test container for a certain period (30 days at 23 ° C.), the particle size is 0.2 μm or more in 1 ml of water stored in the resin container. Calculate how many fine particles there are.
1. 測定装置:(株)リオン製パーティクルカウンター「KL-26」RION KL-26を使用する。
2. 測定検体:成形された容器に超純水を満水に充填して23℃で30日貯蔵後、直立の状態で20分間静置した容器から測定試料を採取したものを測定検体とする。
3. 測定前に超純水でパーティクルカウンターをパージ後、超純水25mlで2回、測定装置を洗浄する。
4. 洗浄後、超純水を10mlパーティクルカウンターに注入して、パーティクル数を測定する。この操作を2回して、0.2μm以上のパーティクル数がゼロ(A)であることを確認する。
5. 25mlの測定検体で2回、測定装置を洗浄する。
6. 洗浄後、測定検体の超純水を満水にした容器(ボトル)から10mlをパーティクルカウンターに注入して、パーティクル数を測定する。この操作を2回して、0.2μm以上のパーティクル数の平均値(B)を求める。
7. 測定値から1ml中のパーティクル値を次式で計算して求める。
(B(個))÷10ml=個/ml
従来は、クリーン度が500個/ml未満であると、半導体、液晶の品質および歩留りを向上することができるとされていた。現在はさらに厳しくなり、従来の測定法で5個/ml以下が要求される場合が多くなっている。
しかし、最近は、クリーン度の要求が更に高くなり、検査容器を成形し、その検査容器に超純水を満水に充填して23℃で30日貯蔵後の超純水1ml中に粒径0.2μm以上の不純微粒子の溶出量(個数/ml)が5以下であり、かつ40℃で30日貯蔵後の超純水1ml中に粒径0.2μm以上の不純微粒子の溶出量(個数/ml)が10以下であることが求められるようになった。 (Conventional measurement method for impure particles)
1. Measuring apparatus: A particle counter “KL-26” RION KL-26 manufactured by Rion Co., Ltd. is used.
2. Sample to be measured: An ultrapure water filled in a molded container, stored at 23 ° C. for 30 days, and collected from a container left standing for 20 minutes in an upright state is used as a sample to be measured.
3. Prior to measurement, the particle counter is purged with ultrapure water, and then the measuring device is washed twice with 25 ml of ultrapure water.
4). After washing, ultrapure water is injected into a 10 ml particle counter and the number of particles is measured. This operation is performed twice to confirm that the number of particles of 0.2 μm or more is zero (A).
5. The measuring device is washed twice with a 25 ml measuring sample.
6). After washing, 10 ml is injected into a particle counter from a container (bottle) filled with ultrapure water as a measurement sample, and the number of particles is measured. This operation is performed twice to obtain an average value (B) of the number of particles of 0.2 μm or more.
7). The particle value in 1 ml is calculated from the measured value by the following formula.
(B (pieces)) ÷ 10 ml = pieces / ml
Conventionally, when the cleanness is less than 500 / ml, it has been said that the quality and yield of semiconductors and liquid crystals can be improved. At present, it becomes more severe, and there are many cases where the conventional measurement method requires 5 pieces / ml or less.
Recently, however, the requirement for cleanliness is further increased, and a test container is molded, and the test container is filled with ultrapure water and stored at 23 ° C. for 30 days. .Elution amount of impure fine particles of 2 μm or more (number / ml) is 5 or less, and elution amount of impure fine particles having a particle size of 0.2 μm or more in 1 ml of ultrapure water after 30 days storage at 40 ° C. ml) is required to be 10 or less.
内層:エチレン、プロピレン、ブテン-1、4-メチル-ペンテン-1、ヘキセン-1、オクテン-1から選択される少なくとも1種類を含む単独重合体あるいは共重合体から成る下記の特性を有する高密度ポリオレフィン樹脂。
(特性)
中和剤、酸化防止剤、および耐光安定剤を意図的には添加せず、最大含有量0.005質量%以下、
クリーン度:5個/ml以下、
密度:950~962Kg/m3
重量平均分子量:18~25万
分子量1,000以下の成分:0.4質量%以下
分子量分布(Mw/Mn):12以下
HL-MFR(190℃、21.6Kg荷重 g/10min):6.5~9.5 The applicant of the present invention firstly sprays an ultra-high-purity chemical obtained by laminating at least an inner layer having the following characteristics, an oxygen barrier layer containing polyvinyl alcohol resin, and an outer layer containing a light-shielding pigment in order from the inside to the outside of the container. A molded laminated container having a visible light transmittance of 1% or less at a wavelength of 500 to 800 nm and an ultraviolet transmittance of a wavelength of 200 to 400 nm of 1% or less, and entering the stored chemical from the container side. A blow molded laminated container for ultra-high-purity chemicals having no visibility of the content with a cleanness of 5 / ml or less as an index indicating the number of impure fine particles to be leached was proposed (see Patent Document 5).
Inner layer: high density having the following characteristics comprising a homopolymer or copolymer containing at least one selected from ethylene, propylene, butene-1,4-methyl-pentene-1, hexene-1 and octene-1 Polyolefin resin.
(Characteristic)
Neutralizing agent, antioxidant, and light stabilizer are not added intentionally, maximum content 0.005 mass% or less,
Cleanliness: 5 / ml or less,
Density: 950 to 962 kg / m3
Weight average molecular weight: 18 to 250,000 Molecular weight 1,000 or less: 0.4 mass% or less Molecular weight distribution (Mw / Mn): 12 or less HL-MFR (190 ° C., 21.6 kg load g / 10 min): 6. 5 to 9.5
特許文献2:特許第2749513号公報
特許文献3:特許第2805188号公報
特許文献4:特許第4167745号公報
特許文献5:特願2015-234798号明細書 Patent Literature 1: Japanese Patent No. 2805723 Patent Literature 2: Japanese Patent No. 2749513 Patent Literature 3: Japanese Patent No. 2805188 Patent Literature 4: Japanese Patent No. 4167745 Patent Literature 5: Japanese Patent Application No. 2015-234798
内層2:接着性官能基を有し、内層1のフッ素樹脂およびバリアー兼接着樹脂層に接着性を有する、添加剤フリーのフッ素樹脂であって、加熱減量が0.40質量%以下である。
バリアー兼接着樹脂層:意図的に添加される添加剤や潤滑剤を含む添加物を含有しない、カプロラクタムの開環重縮合により得られるポリアミドからなる群より選択される少なくとも1種のポリアミドである。
接着性層:無水マレイン酸変性ポリオレフィン樹脂である。
バリアー層:エチレンビニルアルコール共重合樹脂である。
外層1:遮光性顔料および無水マレイン酸変性ポリオレフィン樹脂を含み、前記バリアー層との接着性に優れる超高分子量高密度ポリエチレン樹脂である。
Inner layer 2: An additive-free fluororesin having an adhesive functional group and adhesiveness to the fluororesin and barrier / adhesive resin layer of the
Barrier / adhesive resin layer: At least one polyamide selected from the group consisting of polyamides obtained by ring-opening polycondensation of caprolactam, which does not contain additives that are intentionally added or lubricants.
Adhesive layer: a maleic anhydride-modified polyolefin resin.
Barrier layer: an ethylene vinyl alcohol copolymer resin.
Outer layer 1: an ultra high molecular weight high density polyethylene resin that includes a light shielding pigment and a maleic anhydride-modified polyolefin resin and is excellent in adhesion to the barrier layer.
内層2:接着性官能基を有し、内層1のフッ素樹脂およびバリアー兼接着樹脂層に接着性を有する、添加剤フリーのフッ素樹脂であって、加熱減量が0.40質量%以下である。
バリアー兼接着樹脂層:意図的に添加される添加剤や潤滑剤を含む添加物を含有しない、カプロラクタムの開環重縮合により得られるポリアミドからなる群より選択される少なくとも1種のポリアミドである。
接着性層:無水マレイン酸変性ポリオレフィン樹脂である。
バリアー層:エチレンビニルアルコール共重合樹脂である。
接着性層:無水マレイン酸変性ポリオレフィン樹脂である。
外層2:遮光性顔料を含む超高分子量高密度ポリエチレン樹脂である。
Inner layer 2: An additive-free fluororesin having an adhesive functional group and adhesiveness to the fluororesin and barrier / adhesive resin layer of the
Barrier / adhesive resin layer: At least one polyamide selected from the group consisting of polyamides obtained by ring-opening polycondensation of caprolactam, which does not contain additives that are intentionally added or lubricants.
Adhesive layer: a maleic anhydride-modified polyolefin resin.
Barrier layer: an ethylene vinyl alcohol copolymer resin.
Adhesive layer: a maleic anhydride-modified polyolefin resin.
Outer layer 2: Ultra high molecular weight high density polyethylene resin containing light blocking pigment.
MFR(265℃、5Kg荷重 g/10min):10~40
比重:1.7~1.9
融点(℃):150~200 (Characteristic)
MFR (265 ° C., 5 kg load g / 10 min): 10 to 40
Specific gravity: 1.7 to 1.9
Melting point (° C): 150-200
MFR(297℃、5Kg荷重 g/10min):9~35
比重:1.7~1.9
融点(℃):200~240 (Characteristic)
MFR (297 ° C., 5 kg load g / 10 min): 9 to 35
Specific gravity: 1.7 to 1.9
Melting point (° C): 200-240
融点(℃):170~250
密度(Kg/m3):1.0~1.2 (Characteristic)
Melting point (° C): 170-250
Density (Kg / m3): 1.0 to 1.2
MFR(210℃、2.16Kg荷重 g/10min):2~5
密度(Kg/m3):1.1~1.3
融点(℃):170~200 (Characteristic)
MFR (210 ° C., 2.16 kg load g / 10 min): 2 to 5
Density (Kg / m3): 1.1 to 1.3
Melting point (° C): 170-200
密度:940~962Kg/m3
重量平均分子量:220,000~260,000
分子量分布(Mw/Mn):12以下
溶融張力:18~30g (Characteristic)
Density: 940 to 962 kg / m3
Weight average molecular weight: 220,000-260,000
Molecular weight distribution (Mw / Mn): 12 or less Melt tension: 18-30 g
密度:940~962Kg/m3
重量平均分子量:220,000~260,000
分子量分布(Mw/Mn):12以下
溶融張力:18~30g (Characteristic)
Density: 940 to 962 kg / m3
Weight average molecular weight: 220,000-260,000
Molecular weight distribution (Mw / Mn): 12 or less Melt tension: 18-30 g
前記内層1として、接着性官能基を有さず、内層2のフッ素樹脂には接着性を有するが他の層には接着性を有さない添加剤フリーの加熱減量が0.20質量%以下である特定のフッ素樹脂を用い、前記内層2として、接着性官能基を有し、内層1のフッ素樹脂およびバリアー兼接着樹脂層に接着性を有する添加剤フリーの加熱減量が0.40質量%以下である特定のフッ素樹脂を用い、バリアー兼接着樹脂層に意図的に添加される添加剤や潤滑剤を含む添加物を含有しないポリアミド樹脂を使用することにより、クリーン度が、23℃で30日貯蔵後で5以下であり、かつ40℃で30日貯蔵後で10以下という、硝子瓶相当のクリーン度が得られ、耐薬品性を向上できるとともに、匂い成分の変質を極力低減できる、という顕著な効果を奏する。 The invention of
The
本発明の耐薬品性吹込み成形積層容器は、前記のような特性を有するので、環境や健康に易しく、環境問題や健康問題に貢献するものであり、また経費削減にもなるので経済的である、という顕著な効果を奏する。 In addition, the chemical-resistant blow-molded laminated container of the present invention is heavy, easily damaged, and unlike a glass bottle that lacks safety, is not easily damaged, has excellent mechanical strength, and has a barrier layer. Oxygen barrier property is improved by the above, so it can be used as a perfume bottle, etc., and it can be used safely and safely as a versatile plastic container that can be used for various other contents. There is a remarkable effect of being able to.
Since the chemical-resistant blow molded laminated container of the present invention has the above-mentioned characteristics, it is easy for the environment and health, contributes to environmental problems and health problems, and is economical because it also reduces costs. There is a remarkable effect of being.
本発明の請求項2の耐薬品性吹込み成形積層容器は、外層2と前記バリア層との間に接着性層(無水マレイン酸変性ポリオレフィン樹脂)を設けたことにより、経済性は許容範囲内でやや低下するが両者の接着性が確実になるので、用途や目的によって使用されるものであり、この点以外は本発明の請求項1の耐薬品性吹込み成形積層容器と同じ構成を有しており、作用・効果も本発明の請求項1の耐薬品性吹込み成形積層容器と同じである、という顕著な効果を奏する。 The invention of
The chemical-resistant blow-molded laminated container according to
接着性官能基を有する単量体(α)を共重合したフッ素樹脂を前記内層2に使用することにより、内層1のフッ素樹脂およびバリアー兼接着樹脂層(ポリアミド樹脂)に優れた接着性を有するとともに、ポリオレフィン並みの成形温度で共押し出し成形が可能になる、というさらなる顕著な効果を奏する。 The invention according to
By using a fluororesin copolymerized with a monomer (α) having an adhesive functional group for the
内層2のフッ素樹脂との接着性が向上し、そして添加剤や潤滑剤フリーとしたことにより、前記添加物に起因する不純パーティクル溶出量を大きく低減でき、硝子瓶相当のクリーン度が得られる、というさらなる顕著な効果を奏する。 The invention of claim 5 of the present invention is the chemical-resistant blow-molded laminated container according to any one of
By improving the adhesion of the
酸素バリアー性が確実にさらに改善される、というさらなる顕著な効果を奏する。 The invention according to claim 6 of the present invention is the chemical-resistant blow-molded laminated container according to any one of
There is a further remarkable effect that the oxygen barrier property is surely further improved.
フッ素樹脂やポリアミド樹脂や接着性樹脂は溶融後、溶融張力が一気に低下するので、吹込み成形においてドローダウンなどの問題が発生し、例えば均一肉厚の容器を成形できないとか、不良品が発生し歩留が悪化するなどという問題があったが、外層1に重量平均分子量および溶融張力が大きい超高分子量高密度ポリエチレン樹脂を用いることによってドローダウンなどの問題がなくなり成形性や機械的強度などが改善され、
遮光性顔料を適量用いることにより可視光遮断性および紫外線遮断性が確実に改善され、確実に波長500~800nmの可視光の透過率が1%以下であり、波長200~400nmの紫外線透過率が1%以下を達成できるので、香料やフォトレジスト液などの高価で危険性の高い化学物質も多い超高純度薬品の容器としても対応可能な不純微粒子溶出量の少ない耐薬品性吹込み成形積層容器をより確実に提供でき、酸化防止剤を前記範囲で用いることにより樹脂の焼けを防止し、焼け樹脂に起因する物性低下や外観の悪化などを防止できる、というさらなる顕著な効果を奏する。 The invention according to
Fluorine resin, polyamide resin, and adhesive resin are melted and the melt tension drops at a stretch, causing problems such as draw-down in blow molding. For example, a uniform-thick container cannot be molded or defective products are generated. Although there was a problem that the yield deteriorated, the use of an ultra-high molecular weight high density polyethylene resin having a large weight average molecular weight and high melt tension for the
By using an appropriate amount of the light-shielding pigment, the visible light blocking property and the ultraviolet blocking property are surely improved, the visible light transmittance at a wavelength of 500 to 800 nm is surely 1% or less, and the ultraviolet transmittance at a wavelength of 200 to 400 nm is ensured. 1% or less can be achieved, and it is a chemical-resistant blow-molded laminated container with a small amount of impure fine particles that can be used as a container for ultra-high-purity chemicals that contain a lot of expensive and dangerous chemicals such as fragrances and photoresist solutions. Can be provided more reliably, and by using the antioxidant in the above range, the resin can be prevented from being burnt, and the physical properties and the appearance can be prevented from being deteriorated due to the burnt resin.
フッ素樹脂やポリアミド樹脂や接着樹脂は溶融後、溶融張力が一気に低下するので、吹込み成形においてドローダウンなどの問題が発生し、例えば均一肉厚の容器を成形できないとか、不良品が発生し歩留が悪化するなどという問題があったが、外層2に重量平均分子量および溶融張力が大きい超高分子量高密度ポリエチレン樹脂を用いることによってドローダウンなどの問題がなくなり成形性や機械的強度などが改善され、遮光性顔料を適量用いることにより可視光遮断性および紫外線遮断性が確実に改善され、確実に波長500~800nmの可視光の透過率が1%以下であり、波長200~400nmの紫外線透過率が1%以下を達成できるので、香料やフォトレジスト液などの高価で危険性の高い化学物質も多い超高純度薬品の容器としても対応可能な不純微粒子溶出量の少ない耐薬品性吹込み成形積層容器をより確実に提供でき、酸化防止剤を前記範囲で用いることにより樹脂の焼けを防止し、焼け樹脂に起因する物性低下や外観の悪化などを防止できる、というさらなる顕著な効果を奏する。 The invention according to claim 8 of the present invention is the chemical resistant blow molded laminated container according to
Since the melt tension of fluororesin, polyamide resin, and adhesive resin decreases at once after melting, problems such as draw-down occur in blow molding, for example, it is impossible to form a uniform-thickness container, or defective products are generated. However, the use of ultra-high molecular weight high-density polyethylene resin with a large weight average molecular weight and high melt tension eliminates problems such as drawdown and improves moldability and mechanical strength. By using an appropriate amount of the light-shielding pigment, the visible light blocking property and the ultraviolet blocking property are surely improved, the visible light transmittance at a wavelength of 500 to 800 nm is surely 1% or less, and the ultraviolet light transmission at a wavelength of 200 to 400 nm is performed. Since the rate can reach 1% or less, containers of ultra-high purity chemicals with many expensive and dangerous chemicals such as perfumes and photoresist solutions However, it is possible to more reliably provide a chemical-resistant blow-molded laminated container with a small amount of impure fine particles that can be handled, and by using an antioxidant within the above range, the resin can be prevented from being burned, and the physical properties resulting from the burned resin There is a further remarkable effect that the deterioration and the deterioration of the appearance can be prevented.
すなわち、本発明の耐薬品性吹込み成形積層容器は、重く、破損し易く、安全性に欠ける硝子瓶と対比して、破損し難く、優れた機械的強度を有し、バリアー層を設けることによって酸素バリアー性が改善されるので、香料ボトルなどとしても使用できる性能を有し、その他種々の内容物に対しても使用できる万能なプラスチック容器として、味覚や臭覚などに関して安全・安心に使用できるという、さらなる顕著な効果を奏する。 By providing an adhesive layer (maleic anhydride-modified polyolefin resin) between the
That is, the chemical-resistant blow-molded laminated container of the present invention is heavy, easy to break, hard to break, has excellent mechanical strength, and has a barrier layer compared to a glass bottle lacking safety. Oxygen barrier properties are improved by this, so it can be used as a perfume bottle and can be used safely and safely as a versatile plastic container that can be used for various other contents. This has a further remarkable effect.
図1は、本発明の耐薬品性吹込み成形積層容器の1例の断面を説明する説明図である。
図1において、本発明の耐薬品性吹込み成形積層容器8Aの1Aは、接着性官能基を有さない前記フッ素樹脂からなる内層1、1Bは、接着性官能基を有する前記フッ素樹脂からなる内層2、そして2は、前記ポリアミド樹脂からなるバリアー兼接着樹脂層、3は、無水マレイン酸変性ポリオレフィン樹脂からなる接着性層、4は、エチレンビニルアルコール共重合樹脂からなるバリアー層、5は、無水マレイン酸変性ポリオレフィン樹脂からなる接着性層、6Aは、波長500~800nmの可視光の透過率が1%以下、波長200~400nmの紫外線透過率が1%以下である超高分子量高密度ポリエチレン樹脂からなる外層2をそれぞれ示す。7は、内容物である超高純度薬品を示す。 Hereinafter, the present invention will be described in detail with reference to the drawings.
FIG. 1 is an explanatory view illustrating a cross section of an example of a chemical-resistant blow-molded laminated container of the present invention.
In FIG. 1, 1A of the chemical resistant blow-molded
図2において、本発明の耐薬品性吹込み成形積層容器8Bの1Aは、接着性官能基を有さない前記フッ素樹脂からなる内層1、1Bは、接着性官能基を有する前記フッ素樹脂からなる内層2、そして2は、前記ポリアミド樹脂からなるバリアー兼接着樹脂層、3は、無水マレイン酸変性ポリオレフィン樹脂からなる接着性層、4は、エチレンビニルアルコール共重合樹脂からなるバリアー層、6Bは、前記バリアー層4との接着性に優れる波長500~800nmの可視光の透過率が1%以下、波長200~400nmの紫外線透過率が1%以下である無水マレイン酸変性ポリオレフィン樹脂を含む超高分子量高密度ポリエチレン樹脂からなる外層1をそれぞれ示す。7は、内容物である超高純度薬品を示す。
前記外層1は、無水マレイン酸変性ポリオレフィン樹脂が25~65質量%含まれているので、前記外層1とバリアー層4との接着性に優れるとともに、ドローダウンなどの問題がなく、成形性や機械的強度などに優れる。しかし、無水マレイン酸変性ポリオレフィン樹脂が25質量%未満では、前記外層1とバリアー層4との接着性が不十分となる恐れがあり、無水マレイン酸変性ポリオレフィン樹脂が65質量%を超えるとドローダウンなどの問題が発生する恐れがある。 FIG. 2 is an explanatory view illustrating a cross section of another example of the chemical-resistant blow-molded laminated container of the present invention.
In FIG. 2, 1A of the chemical resistant blow molded
Since the
本発明で内層2に使用するフッ素樹脂は、添加剤フリーの無添加グレードのフッ素樹脂を用いることが好ましい。 The fluororesin used for the
The fluororesin used for the
アルミカップを天秤で質量を0.1mgまで精秤する(WO)。
試料5.00±0.01gをアルミカップに入れ、合計の質量を0.1mgまで精秤する(W)。
電気炉の温度を260℃±1℃に調整後、試料を240分加熱する。
加熱後、試料を取り出しデシケーター内で冷却し、試料を0.1mgまで精秤する(W1)。
そして、次式により加熱減量を算出する。
加熱減量(質量%)=[(W-W1)/(W-W0)]×100 (Health loss measurement method)
The aluminum cup is precisely weighed to a weight of 0.1 mg with a balance (WO).
Sample 5.00 ± 0.01 g is put in an aluminum cup, and the total mass is precisely weighed to 0.1 mg (W).
After adjusting the temperature of the electric furnace to 260 ° C. ± 1 ° C., the sample is heated for 240 minutes.
After heating, the sample is taken out and cooled in a desiccator, and the sample is precisely weighed to 0.1 mg (W1).
Then, the heating loss is calculated by the following equation.
Loss on heating (% by mass) = [(W−W1) / (W−W0)] × 100
MFR(265℃、5Kg荷重 g/10min)(測定法:265℃、ASTM D1238)は好ましくは10~40、さらに好ましくは20~30であり、10未満では溶融粘性が高く、吹き込み溶融成形性が悪化し駆動エネルギーも増大する恐れがあり、40を超えると溶融張力が低く吹き込み成形時にドローダウンなどの問題が生じる恐れがある。 (Preferred characteristics of inner layer 2)
MFR (265 ° C., 5 kg load g / 10 min) (measuring method: 265 ° C., ASTM D1238) is preferably 10 to 40, more preferably 20 to 30. If it is less than 10, the melt viscosity is high, and the blow melt moldability is high. There is a possibility that the drive energy will be worsened, and if it exceeds 40, the melt tension is low and problems such as draw-down may occur during blow molding.
融点(℃)(測定法:ASTM D792)は、共重合する単量体(α)の量や種類によって変化するが、通常市販されている市販品の融点150~200℃であってよく、さらに好ましくは190~200℃である。融点が150℃未満では他の樹脂との融点差が生じ、接着強度や成形性の問題が生じる恐れがあり、融点が200℃を超えると他の樹脂と積層するのが困難となる恐れがある。 The specific gravity (measurement method: ASTM D-792) may be a commercially available specific gravity of 1.7 to 1.9, more preferably 1.72 to 1.76. If the specific gravity is less than 1.7, there is a concern that the adhesiveness may be lowered, and if it exceeds 1.9, the strength of the container may be insufficient.
The melting point (° C.) (measurement method: ASTM D792) varies depending on the amount and type of the monomer (α) to be copolymerized, but may be a melting point of 150 to 200 ° C. of a commercially available product. The temperature is preferably 190 to 200 ° C. If the melting point is less than 150 ° C., a difference in melting point from other resins may occur, which may cause problems of adhesive strength and moldability. If the melting point exceeds 200 ° C., it may be difficult to laminate with other resins. .
接着性官能基の具体例としては、例えば、エポキシ基、水酸基、カルボン酸無水物残基、カルボン酸基、アクリレート基、カーボネート基、アミノ基などを挙げることができる。この共重合体の具体例としては、実施例1に用いたエチレン-テトラフルオロエチレン-ヘキサフルオロプロピレン-エチレンカーボネート共重合体EFEP(例えば、ダイキン工業(株)製RP5000)を挙げることができる。 The monomer (α) to be copolymerized is not particularly limited as long as it has an adhesive functional group and can be copolymerized, but the amount and type are controlled in consideration of melt molding. It is preferable that the fluororesin of the
Specific examples of the adhesive functional group include an epoxy group, a hydroxyl group, a carboxylic anhydride residue, a carboxylic acid group, an acrylate group, a carbonate group, and an amino group. Specific examples of this copolymer include the ethylene-tetrafluoroethylene-hexafluoropropylene-ethylene carbonate copolymer EFEP used in Example 1 (for example, RP5000 manufactured by Daikin Industries, Ltd.).
MFR(297℃、5Kg荷重 g/10min)(測定法:265℃、ASTM D1238)は好ましくは9~35、さらに好ましくは15~25であり、9未満では溶融粘性が高く、吹き込み溶融成形性が悪化し駆動エネルギーも増大する恐れがあり、35を超えると溶融張力が低く吹き込み成形時にドローダウンなどの問題が生じる恐れがある。 (Preferred characteristics of inner layer 1)
MFR (297 ° C., 5 kg load g / 10 min) (measuring method: 265 ° C., ASTM D1238) is preferably 9 to 35, more preferably 15 to 25. If it is less than 9, the melt viscosity is high and the blow melt moldability is high. There is a possibility that the drive energy will be worsened, and if it exceeds 35, the melt tension is low, and there is a risk that problems such as draw-down may occur during blow molding.
融点(℃)(測定法:ASTM D792)は、通常市販されている市販品の融点200~240℃であってよく、さらに好ましくは208~228℃である。融点が200℃未満では他の樹脂との融点差が生じ、接着強度や成形性の問題が生じる恐れがあり、融点が240℃を超えると他の樹脂と積層するのが困難となる恐れがある。 The specific gravity (measurement method: ASTM D-792) may be a commercially available specific gravity of 1.7 to 1.9, more preferably 1.83 to 1.89. If the specific gravity is less than 1.7, there is a concern that the adhesiveness may be lowered, and if it exceeds 1.9, the strength of the container may be insufficient.
The melting point (° C.) (measurement method: ASTM D792) may be a commercially available melting point of 200 to 240 ° C., more preferably 208 to 228 ° C. If the melting point is less than 200 ° C., a difference in melting point from other resins may occur, which may cause problems of adhesive strength and moldability. If the melting point exceeds 240 ° C., it may be difficult to laminate with other resins. .
中でも、カプロラクタムの開環重縮合により得られる、ナイロン6、ナイロン11、ナイロン12、ナイロン66などから選択される少なくとも1種のポリアミドであり、添加剤や潤滑剤を含む添加物を含有しないポリアミドは好ましく使用できる。 The above-mentioned polyamide resin of the barrier and adhesive resin layer used in the present invention is an additive-free grade polyamide resin to which additives including additives and lubricants that are usually added intentionally are not added / blended. For example, Z4887 manufactured by Daicel Evonik Co., Ltd. can be given.
Among them, the polyamide obtained by ring-opening polycondensation of caprolactam is at least one polyamide selected from nylon 6, nylon 11, nylon 12, nylon 66 and the like, and a polyamide that does not contain additives and additives including a lubricant is It can be preferably used.
融点(℃)(ISO11357準拠):170~250
密度(Kg/m3)(ASTM D1250-80準拠):1.0~1.2
融点(℃)は好ましくは170~250、さらに好ましくは175~190、密度(Kg/m3)は好ましくは1.0~1.2、さらに好ましくは1.00~1.03である。
融点が下限値未満では、接着性が不足する恐れがあり、上限値を超えると成形性が悪化する恐れがある。
密度が下限値未満では、接着性が不足する恐れがあり、上限値を超えると成形性が悪化する恐れがある。 (Characteristic)
Melting point (° C) (according to ISO11357): 170 to 250
Density (Kg / m3) (according to ASTM D1250-80): 1.0 to 1.2
The melting point (° C.) is preferably 170 to 250, more preferably 175 to 190, and the density (Kg / m 3) is preferably 1.0 to 1.2, and more preferably 1.00 to 1.03.
If the melting point is less than the lower limit, the adhesion may be insufficient, and if it exceeds the upper limit, the moldability may deteriorate.
If the density is less than the lower limit, the adhesion may be insufficient, and if it exceeds the upper limit, the moldability may be deteriorated.
前記接着性層の前記回収物を配合した無水マレイン酸変性ポリオレフィン樹脂は、接液面となる内層1のフッ素樹脂から離れているので、実用的にはクリーン度が損なわれる恐れがないからである。 In the maleic anhydride-modified polyolefin resin of the adhesive layer that bonds the barrier layer and the outer layer (ultra high molecular weight high density polyethylene resin), the
This is because the maleic anhydride-modified polyolefin resin in which the recovered material of the adhesive layer is blended is separated from the fluororesin of the
MFR(210℃、2.16Kg荷重 g/10min):2~5
密度(Kg/m3):(ISO1183準拠)1.1~1.3
融点(℃):(ISO1346準拠):170~200
MFRは好ましくは2~5であり、さらに好ましくは3~5であり、密度は好ましくは1.1~1.3であり、さらに好ましくは1.2~1.3であり、融点(℃)は好ましくは170~200であり、さらに好ましくは190~200である。MFR、密度、融点が前記範囲内にあるとガスバリアー性、強度、安定成形性などいずれも優れるが、前記範囲外ではこれらの特性の少なくとも1つが損なわれる恐れがある。 (Characteristic)
MFR (210 ° C., 2.16 kg load g / 10 min): 2 to 5
Density (Kg / m3): (ISO 1183 compliant) 1.1 to 1.3
Melting point (° C): (ISO 1346 compliant): 170-200
The MFR is preferably 2 to 5, more preferably 3 to 5, the density is preferably 1.1 to 1.3, more preferably 1.2 to 1.3, and the melting point (° C.). Is preferably 170 to 200, more preferably 190 to 200. When the MFR, density, and melting point are within the above ranges, gas barrier properties, strength, stable moldability and the like are all excellent, but at least one of these characteristics may be impaired outside the above ranges.
有機系遮光性顔料および無機系の遮光性顔料としては、外層に所定量配合することにより、波長500~800nmの可視光の透過率が1%以下であり、波長200~400nmの紫外線透過率が1%以下とすることができ、外層の他の特性を損なわないものであれば特に限定されるものではない。 In the
The organic light-shielding pigment and the inorganic light-shielding pigment have a visible light transmittance of 1% or less at a wavelength of 500 to 800 nm and an ultraviolet transmittance of a wavelength of 200 to 400 nm when blended in a predetermined amount in the outer layer. It can be 1% or less, and is not particularly limited as long as other characteristics of the outer layer are not impaired.
本発明においては、外層1、2を形成する超高分子量高密度ポリエチレン樹脂および遮光性顔料の種類などを決めた後、遮光性顔料の配合量は、予め試験して、波長500~800nmの可視光の透過率が1%以下であり、波長200~400nmの紫外線透過率が1%以下となるように決めることが好ましい。
波長500~800nmの可視光の透過率が1%以下、波長200~400nmの紫外線透過率が1%以下を達成できると、内容物の視認性がなく、かつ収容した内容液の変質を防止できる紫外線遮断性を付与でき、例えばフォトレジスト液などのように紫外線によって変質して硬化するような薬品や香料などの超高純度薬品容器としても使用可能となる。 In using these light-shielding pigments, it is preferable to avoid pigments with poor dispersibility and pigments that promote oxidative deterioration of containers.
In the present invention, after determining the types of the ultrahigh molecular weight high-density polyethylene resin and the light-shielding pigment that form the
When the transmittance of visible light with a wavelength of 500 to 800 nm is 1% or less and the transmittance of ultraviolet light with a wavelength of 200 to 400 nm is 1% or less, the contents are not visible and the contained liquid content can be prevented from being altered. It can be used as an ultra-high-purity chemical container such as a chemical or a fragrance that can be imparted with ultraviolet blocking properties, such as a photoresist solution, which is denatured and cured by ultraviolet rays.
フェノール系酸化防止剤、リン系酸化防止剤、サルファー系酸化防止剤としては、酸化防止作用が高く、外層1、2の他の特性を損なわないものであれば特に限定されるものではない。 The
The phenolic antioxidant, phosphorus antioxidant, and sulfur antioxidant are not particularly limited as long as they have a high antioxidant action and do not impair the other characteristics of the
リン系酸化防止剤としては、具体的には、例えば、ADEKA(株)製アデカスタブ2112を挙げることができる。
サルファー系酸化防止剤としては、具体的には、例えば、ヨシトミ三菱化学(株)製DSTPを挙げることができる。 Specific examples of phenolic antioxidants include ADEKA STAB AO60 manufactured by ADEKA Corporation.
Specific examples of the phosphorus-based antioxidant include ADK STAB 2112 manufactured by ADEKA Corporation.
Specific examples of the sulfur-based antioxidant include DSTP manufactured by Yoshitomi Mitsubishi Chemical Corporation.
ベンゾトリアゾール系耐光安定剤やトリアジン系耐光安定剤を使用すると、UV-B(200~320nm)とUV-A(320~400nm)をそれぞれ遮断でき、両者を特定量併用することにより他の特性を損なわずに紫外線遮断性を著しく改善することができる。 In the present invention, a light-resistant stabilizer such as a benzotriazole-based light-resistant stabilizer and a triazine-based light-resistant stabilizer can be appropriately used for the
Using a benzotriazole light stabilizer or a triazine light stabilizer can block UV-B (200 to 320 nm) and UV-A (320 to 400 nm), respectively. The ultraviolet blocking property can be remarkably improved without deteriorating.
重量平均分子量Mw=Σ(M×w)/Σw ・・・(2)
数平均分子量Mn=Σw/Σ(w/M) ・・・(3)
分子量分布=重量平均分子量/数平均分子量(Mw/Mn)
ただし、Mは分子量、wは重量分率である。 In the method for measuring the molecular weight of the resin in the container, the resin composition cut out from the container is dissolved in a solvent (orthodichlorobenzene) to form a sample solution, and the molecular weight and molecular weight distribution are measured by GPC. The weight average molecular weight and the number average molecular weight are calculated by the following equations.
Weight average molecular weight Mw = Σ (M × w) / Σw (2)
Number average molecular weight Mn = Σw / Σ (w / M) (3)
Molecular weight distribution = weight average molecular weight / number average molecular weight (Mw / Mn)
However, M is molecular weight and w is a weight fraction.
内層1としてMFR25g/10min、比重1.86、融点223℃、加熱減量が0.16質量%の添加剤フリーのフッ素樹脂(ダイキン工業(株)製EP-610)を使用し、内層2としてMFR25g/10min、比重1.74、融点195℃、加熱減量が0.35質量%の添加剤フリーのフッ素樹脂(ダイキン工業(株)製RP-5000)を使用し、そして、バリアー兼接着樹脂層として内層2のフッ素樹脂との接着機能を有した、意図的に添加される添加剤や潤滑剤を含む添加物を含有しない、添加剤フリーのポリアミド樹脂(ダイセルエボニック(株)製Z4887、相対粘度1.87)を用い、前記ポリアミド樹脂とバリアー層との接着機能を有する接着性層として無水マレイン酸変性ポリオレフィン樹脂(日本ポリエチレン(株)FT71A)を用い、そしてバリアー層としてバリアー樹脂(エチレン-ビニルアルコール共重合体樹脂F171B:(株)クラレ製、ケン化率99.99%)を用い、そして外層1として、超高分子量高密度ポリエチレン樹脂(日本ポリエチレン(株)製HB111R)(HL-MFR(測定法:JIS K7112)6g/10min、密度946Kg/m3、重量平均分子量25万、溶融張力25g)に対して、無水マレイン酸変性ポリオレフィン樹脂(日本ポリエチレン(株)FT71A)を30質量%、可視光遮断性と紫外線遮断性向上のためにフタロシアニン系遮光性顔料(商品名:7F2854:大日精化工業(株)製、フタロシアニン6質量%含有マスターバッチ)2質量%、酸化防止剤としてフェノール系酸化防止剤(商品名:アデカスタブAO60:ADEKA(株)製)とリン系酸化防止剤(商品名:アデカスタブ2112:ADEKA(株)製)を合計0.2質量%を配合した超高分子量高密度ポリエチレン樹脂を用いて、下記の成形条件でドローダウンなどの問題がなく、6層からなる本発明の耐薬品性吹込み成形積層容器(全質量400g、内層1が50μm、内層2が100μm、バリアー兼接着樹脂層50μm、接着性層50μm、バリアー層50μm、外層1が1500μm、平均全肉厚1.8mm、容量3750ML)を成形した。 Example 1
The
ブロー成形機((株)ブレンズ製6種6層)(6種の押出機を用い1個のダイヘッドで6層に積層するタイプ)を使用した。
内層1のフッ素樹脂:スクリュウ径40mmΦ 設定温度:260℃
内層2のフッ素樹脂:スクリュウ径20mmΦ 設定温度:240℃
ポリアミド樹脂層:スクリュウ径20mmΦ 設定温度:200℃
無水マレイン酸変性ポリオレフィン樹脂層:スクリュウ径20mmΦ 設定温度:220℃
エチレン-ビニルアルコール共重合体樹脂層:スクリュウ径40mmΦ 設定温度:230℃
外層1の超高分子量高密度ポリエチレン樹脂:スクリュウ径50mmΦ 設定温度:220℃
ダイヘッド温度:設定温度:235℃
なお、吸湿性のある前記ポリアミド樹脂とバリアー樹脂は乾燥機を用いて80℃で乾燥して水分除去したものを使用した。 (Molding condition)
A blow molding machine (6 types, 6 layers, manufactured by Brenzu Co., Ltd.) (a type in which 6 types of extruders are used to laminate 6 layers with one die head) was used.
Fluororesin of inner layer 1: Screw diameter 40mmΦ Set temperature: 260 ℃
Fluorine resin of inner layer 2: Screw diameter 20 mmΦ Set temperature: 240 ° C
Polyamide resin layer: Screw diameter 20mmΦ Setting temperature: 200 ℃
Maleic anhydride-modified polyolefin resin layer: Screw diameter 20 mmΦ Setting temperature: 220 ° C
Ethylene-vinyl alcohol copolymer resin layer: Screw diameter 40mmΦ Setting temperature: 230 ℃
Ultrahigh molecular weight high-density polyethylene resin of outer layer 1: Screw diameter 50 mmΦ Setting temperature: 220 ° C
Die head temperature: Set temperature: 235 ° C
The hygroscopic polyamide resin and barrier resin were dried at 80 ° C. using a drier to remove moisture.
表1に記載の加熱減量は、内層1あるいは接液面となる層の加熱減量である。 Then, the amount of impure fine particles eluted (number / ml) immediately after extraction at 23 ° C. and 30 days and extracted, and the amount of impure fine particles eluted (number / ml) after extraction after storage at 40 ° C. for 30 days. Measured using a sample bottle by the following test method, evaluated for oxygen permeability and visibility by the following test method, cut out a sample of 4 cm × 4 cm × 1.8 mm from the bottle body wall, and used it to Evaluation of UV transmittance and visible light transmittance by the test method of, and filling the container with pure water, evaluating metal elution by the following test method, evaluating the drop strength and perfume suitability by the following test method, The above test method evaluates the heat loss of the
The heat loss described in Table 1 is the heat loss of the
測定装置:島津製作所(株)製 IR Affinity-1
測定試料:240℃プレス機を用いて内層1、2の50μm厚のフィルムシートを作成して使用した。
測定波長:600~4000cm-1 (Infrared spectroscopic analysis measurement conditions)
Measuring device: IR Affinity-1 manufactured by Shimadzu Corporation
Measurement sample: A 50 μm-thick film sheet of
Measurement wavelength: 600 to 4000 cm-1
図4は、内層2の赤外分光分析の結果を示すものであり、縦軸が吸光度(%)、横軸が波長(cm-1)を示す。
図3と図4を重ね合わせると、図4の波長1800(cm-1)におけるシャープな吸収を除くと、両者はほぼ同じ波形であることが判る。 FIG. 3 shows the result of infrared spectroscopic analysis of the
FIG. 4 shows the result of infrared spectroscopic analysis of the
When FIG. 3 and FIG. 4 are overlapped, it can be seen that both have substantially the same waveform except for sharp absorption at a wavelength of 1800 (cm-1) in FIG.
内層2のフッ素樹脂は、前記のように接着性官能基を有する単量体(α)を共重合して製造されており、単量体(α)の共重合量によって内層2のフッ素樹脂の接着性官能基の量を制御することができ、それによって、内層2のフッ素樹脂の接着性などを制御して、内層2が内層1のフッ素樹脂およびバリアー兼接着樹脂層に良好な接着性を有するとともに融点などが前記所定の範囲内となるように制御することができる。
図3の波長1800(cm-1)には前記大きいシャープな吸収ピークは見られず、内層1のフッ素樹脂は接着性官能性基(カーボネート基)を有さないことを示している。内層1は、内層2のフッ素樹脂には良好な接着性を有するが他の層には接着性を有さない。
図3、4の波長3000(cm-1)の大きいシャープな吸収ピークは、共重合したエチレン由来の吸収ピークである。 A large sharp absorption (indicated by an arrow) at a wavelength of 1800 (cm-1) in FIG. 4 is an absorption peak of a carbonate group, and it can be seen that the fluororesin of the
The fluororesin of the
The large sharp absorption peak is not observed at a wavelength of 1800 (cm-1) in FIG. 3, indicating that the fluororesin of the
The large and sharp absorption peak of wavelength 3000 (cm-1) in FIGS. 3 and 4 is an absorption peak derived from copolymerized ethylene.
(不純微粒子(パーティクル)の測定法)
下記の測定はクリーンルーム内(クラス100)で行う。
1. 測定装置:(株)リオン製パーティクルカウンター「KL-26」RION KL-26を使用する。
2. 測定検体:成形された容器に超純水を満水に充填して23℃で抽出直後と30日貯蔵して抽出後あるいは40℃で抽出直後と30日貯蔵して抽出後、直立の状態で20分間静置した容器から測定試料を採取したものを測定検体とする。
3. 測定前に超純水でパーティクルカウンターをパージ後、超純水25mlで2回、測定装置を洗浄する。
4. 洗浄後、超純水を10mlパーティクルカウンターに注入して、パーティクル数を測定する。この操作を2回して、0.2以上μmのパーティクル数がゼロ(A)であることを確認する。
5. 25mlの測定検体で2回、測定装置を洗浄する。
6. 洗浄後、測定検体の超純水を満水にした容器(ボトル)から10mlをパーティクルカウンターに注入して、パーティクル数を測定する。この操作を2回して、0.2μm以上のパーティクル数の平均値(B)を求める。
7. 測定値から1ml中のパーティクル値を次式で計算して求める。
(B(個))÷10ml=個/ml (Test method)
(Measurement method of impure particles)
The following measurements are performed in a clean room (Class 100).
1. Measuring apparatus: A particle counter “KL-26” RION KL-26 manufactured by Rion Co., Ltd. is used.
2. Sample to be measured: filled with ultrapure water in a molded container and stored at 23 ° C. immediately after extraction and for 30 days and extracted or stored at 40 ° C. immediately after extraction and for 30 days and extracted, then 20 in an upright state A sample obtained by collecting a measurement sample from a container that has been allowed to stand for minutes is taken as a measurement sample.
3. Prior to measurement, the particle counter is purged with ultrapure water, and then the measuring device is washed twice with 25 ml of ultrapure water.
4). After washing, ultrapure water is injected into a 10 ml particle counter and the number of particles is measured. This operation is performed twice to confirm that the number of particles of 0.2 μm or more is zero (A).
5. The measuring device is washed twice with a 25 ml measuring sample.
6). After washing, 10 ml is injected into a particle counter from a container (bottle) filled with ultrapure water as a measurement sample, and the number of particles is measured. This operation is performed twice to obtain an average value (B) of the number of particles of 0.2 μm or more.
7). The particle value in 1 ml is calculated from the measured value by the following formula.
(B (pieces)) ÷ 10 ml = pieces / ml
3.75Lの容器(ボトル中央部の肉厚:1.8mm)を使用し、JIS K7126-2に準拠し、(OX-TRAN2/21)(MOCON社製)測定装置を用いて、容器外側から内側への酸素透過を測定した。温湿度:外側1気圧、23℃、50%RH酸素。内側1気圧、23℃、ドライ窒素。 Oxygen permeability [cm3 / (pg.24h.atm)]:
Using a 3.75L container (wall thickness at the center of the bottle: 1.8 mm), using the measuring device (OX-TRAN2 / 21) (manufactured by MOCON) in accordance with JIS K7126-2, from the outside of the container The oxygen transmission to the inside was measured. Temperature and humidity: 1 atm outside, 23 ° C., 50% RH oxygen. Inside 1 atm, 23 ° C., dry nitrogen.
日本分光(株)V-670を使用し、200~400nmの紫外線領域の透過率を求める。 (UV transmittance)
Using JASCO Corporation V-670, the transmittance in the ultraviolet region of 200 to 400 nm is obtained.
日本分光(株)V-670を使用し、500~800nmの可視光線領域の透過率を求める。 (Visible light transmittance)
Using JASCO Corporation V-670, the transmittance in the visible light region of 500 to 800 nm is obtained.
750ルックスの室内で、容器に水道水を入れて、3人で容器外側から肉眼で水道水を観察する。そして下記の4段階の評価を行う。
評価:
×:水道水を確認できる。
△:水道水をよく見ると確認できる。
○:水道水を確認できない。 (Visibility)
In a room of 750 lux, tap water is put into a container, and three people observe the tap water with the naked eye from the outside of the container. Then, the following four stages of evaluation are performed.
Rating:
X: Tap water can be confirmed.
Δ: Can be confirmed by looking closely at tap water.
○: Tap water cannot be confirmed.
容器に水を容量の80%充填し、高さ1.2mからコンクリート面に容器底部を下にして5回落下させ、容器側部を下にして1回落下させ、割れや漏れを目視で判定する。 (Drop strength)
Fill the container with 80% of its capacity, drop it 5 times from a height of 1.2m onto the concrete surface with the bottom of the container down, and drop once with the side of the container down, and visually check for cracks and leaks. To do.
代表的な香料の例として、リモネン(商品名:オレンジオイル、純度96.4%、長谷川香料(株)製)、柑橘類(商品名:レモンエッセンス、長谷川香料(株)製)、カニオイル(15%ジメチルサルファイド、プロピレングリコール溶液、長谷川香料(株)製)、コメサラダ(商品名:コメ油、長谷川香料(株)製)、エチルブチレート(商品名:エステル類、純度100%、長谷川香料(株)製)、トランス-2-ヘキセナール(商品名:アルデヒド類、純度99.7%、長谷川香料(株)製)を使用し、各香料1kgをそれぞれ充填、密封し、常温、常圧で1ケ月および3ケ月放置した。ただし、カニオイル(15%ジメチルサルファイド、プロピレングリコール溶液)だけは、常温、常圧で1ケ月および3ケ月、冷蔵保存した。
3ケ月放置後、各試料について、容器質量を測定し内容物が散逸していないかをチェックし、パネルメンバー10人で官能試験を行って変質していないかをチェックし、比重・屈折率を測定して変動していないかをチェックし、分析可能な試料についてはガスクロマトグラフにより成分をチェックして下記の評価基準により評価した。 (Perfume is appropriate)
Examples of typical fragrances include limonene (trade name: orange oil, purity 96.4%, manufactured by Hasegawa Fragrance Co., Ltd.), citrus fruits (trade name: lemon essence, manufactured by Hasegawa Fragrance Co., Ltd.), crab oil (15%) Dimethyl sulfide, propylene glycol solution, manufactured by Hasegawa Fragrance Co., Ltd.), rice salad (trade name: rice oil, manufactured by Hasegawa Fragrance Co., Ltd.), ethyl butyrate (trade name: esters, purity 100%, Hasegawa Fragrance Co., Ltd.) ), Trans-2-hexenal (trade name: aldehydes, purity 99.7%, manufactured by Hasegawa Fragrance Co., Ltd.), filled with 1 kg of each fragrance, sealed, sealed at room temperature and pressure for 1 month and Left for 3 months. However, only crab oil (15% dimethyl sulfide, propylene glycol solution) was refrigerated at room temperature and pressure for 1 month and 3 months.
After standing for 3 months, measure the container mass for each sample and check if the contents are dissipated, conduct a sensory test with 10 panel members to check whether it has been altered, and determine the specific gravity and refractive index. It was measured to check whether it was fluctuating, and for a sample that could be analyzed, the components were checked by a gas chromatograph and evaluated according to the following evaluation criteria.
○:散逸、変質、変動などがなく貯蔵安定性が高く市場性がある。
△:○よりやや劣るが、散逸、変質、変動などが実質的になく実用的に貯蔵安定性が高く市場性がある。
×:散逸、変質、変動などがあり貯蔵安定性が低く市場性がない。 Evaluation criteria:
○: There is no dissipation, alteration, fluctuation, etc., storage stability is high, and there is marketability.
Δ: Slightly inferior to ○, but practically free from dissipation, alteration, fluctuation, etc., and has high storage stability and marketability.
X: There are dissipation, alteration, fluctuation, etc., storage stability is low, and there is no marketability.
試料容器に純水を満水に充填し、23℃および40℃で加温した状態で30日間放置し、この純水を検体としてICP-MASS(アジレントテクノロジー(株)製8800を使用しppbレベルまで測定する。測定はクリーンルーム内(クラス1000)で行う。測定した元素Li、Na、Mg、Al、K、Ca、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、As、Ag、Cd、Sn、Ba、W、Au、Pbの23元素を測定する。10ng/L以下であれば合格。 (Metal elution)
Fill the sample container with pure water and leave it at 23 ° C. and 40 ° C. for 30 days. Using this pure water as a specimen, use ICP-MASS (8800 manufactured by Agilent Technologies) to the ppb level. Measure in the clean room (class 1000) Measured elements Li, Na, Mg, Al, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Ag , Cd, Sn, Ba, W, Au, Pb 23 elements are measured, and pass if it is 10 ng / L or less.
23℃・30日後のパーティクル値が5個/ml以下、かつ40℃・30日後のパーティクル値が10個/ml以下、
酸素透過率が0.003[cm3/(pkg.24h.atm)]以下、
紫外線透過率が1%以下、
可視光透過率が1%以下、
視認性が○(内部の水道水を確認できず)、
落下強度:破壊なし、
香料適正が○~△、
金属溶出が10(ng/L)以下。
全てが合格の場合に総合判定を○とする。これらのいずれかが前記より劣る場合は総合判定を×と判定する。 (Comprehensive judgment)
The particle value after 23 days at 30 ° C. is 5 particles / ml or less, and the particle value after 30 days at 40 ° C. is 10 particles / ml or less,
Oxygen permeability is 0.003 [cm3 / (pg.24 h.atm)] or less,
UV transmittance is 1% or less,
Visible light transmittance is 1% or less,
Visibility is ○ (the internal tap water cannot be confirmed),
Drop strength: no destruction,
Perfume is appropriate ○ ~ △,
Metal elution is 10 (ng / L) or less.
If all pass, pass the overall judgment. If any of these is inferior to the above, the overall judgment is judged as x.
実施例1において使用した添加剤フリーの前記ポリアミド樹脂(ダイセルエボニック(株)製Z4887)(バリアー兼接着樹脂、相対粘度1.87)の替わりに、酸化防止剤(ヒンダードフェノール系酸化防止剤、2000ppm)入り同ポリアミド樹脂(相対粘度1.87)を用いた以外は、実施例1と同様にして比較のための吹込み成形積層容器を作り評価した。結果を表1~表2に示す。 (Comparative Example 1)
Instead of the additive-free polyamide resin used in Example 1 (Z4887 manufactured by Daicel Evonik) (barrier and adhesive resin, relative viscosity 1.87), an antioxidant (hindered phenol-based antioxidant, A blow-molded laminated container for comparison was made and evaluated in the same manner as in Example 1 except that the same polyamide resin containing 2000 ppm) (relative viscosity 1.87) was used. The results are shown in Tables 1 and 2.
実施例1において使用した内層1、2の替りに、密度956Kg/m3、HL-MFR(測定法:JIS K7112、荷重21.6Kg)8g/10min、Mw/Mn=11、分子量1000以下の成分が0.2質量%の高密度ポリエチレン(東ソー(株)製9D01A)を使用した接液層を用いた以外は、実施例1と同様にして、比較のための吹込み成形積層容器を作り評価した。結果を表1~表2に示す。 (Comparative Example 2)
Instead of the
実施例1において使用した内層1を使用せず、実施例1において使用した加熱減量が0.35質量%の内層2を接液層として使用した以外は、実施例1と同様にして、比較のための吹込み成形積層容器を作り評価した。結果を表1~表2に示す。 (Comparative Example 3)
In the same manner as in Example 1, except that the
比較例3において使用した接液層のフッ素樹脂を、電気炉の温度260℃±1℃で120分加熱して、加熱減量を低減(加熱減量0.31質量%)したフッ素樹脂を使用した以外は、比較例3と同様にして、比較のための吹込み成形積層容器を作り評価した。結果を表1~表2に示す。 (Comparative Example 4)
The fluororesin of the wetted layer used in Comparative Example 3 was heated at an electric furnace temperature of 260 ° C. ± 1 ° C. for 120 minutes to reduce the loss on heating (heating loss of 0.31% by mass). In the same manner as in Comparative Example 3, a blow molded laminated container for comparison was made and evaluated. The results are shown in Tables 1 and 2.
比較のために、硝子瓶(富士フィルムエレクトロニクスマテリアルズ、容量2500ML)を使用した以外は、実施例1と同様にして、評価した。結果を表1~表2に示す。 (Comparative Example 5)
For comparison, evaluation was performed in the same manner as in Example 1 except that a glass bottle (Fuji Film Electronics Materials, capacity 2500 ML) was used. The results are shown in Tables 1 and 2.
比較のために、市販のプラスチック製のシーラーボトル(市販の香料容器、北酸(株)製、1L)を使用した以外は、実施例1と同様にして、評価した。結果を表1~表2に示す。 (Comparative Example 6)
For comparison, evaluation was performed in the same manner as in Example 1 except that a commercially available plastic sealer bottle (commercially available fragrance container, manufactured by North Acid Co., Ltd., 1 L) was used. The results are shown in Tables 1 and 2.
1B 内層2
2 バリアー兼接着樹脂層
3 接着性層
4 バリアー層
5 接着性層
6A 外層2
6B 外層1
7 超高純度薬品
8A、8B 耐薬品性吹込み成形積層容器
2 Barrier and
6B
7 Ultra
Claims (8)
- 容器の内側から外側に順に、下記の内層1、内層2、バリアー兼接着樹脂層、接着性層、バリアー層および外層1を積層してなる耐薬品性吹込み成形積層容器であって、波長500~800nmの可視光の透過率が1%以下であり、波長200~400nmの紫外線透過率が1%以下であり、23℃で30日貯蔵後の不純微粒子溶出量(個数/ml)が5以下、かつ40℃で30日貯蔵後の不純微粒子溶出量(個数/ml)が10以下であることを特徴とする不純微粒子溶出量の少ない耐薬品性吹込み成形積層容器。
内層1:接着性官能基を有さず、内層2のフッ素樹脂には接着性を有するが他の層には接着性を有さない、添加剤フリーのフッ素樹脂であって、加熱減量が0.20質量%以下である。
内層2:接着性官能基を有し、内層1のフッ素樹脂およびバリアー兼接着樹脂層に接着性を有する、添加剤フリーのフッ素樹脂であって、加熱減量が0.40質量%以下である。
バリアー兼接着樹脂層:意図的に添加される添加剤や潤滑剤を含む添加物を含有しない、カプロラクタムの開環重縮合により得られるポリアミドからなる群より選択される少なくとも1種のポリアミドである。
接着性層:無水マレイン酸変性ポリオレフィン樹脂である。
バリアー層:エチレンビニルアルコール共重合樹脂である。
外層1:遮光性顔料および無水マレイン酸変性ポリオレフィン樹脂を含み、前記バリアー層との接着性に優れる超高分子量高密度ポリエチレン樹脂である。 A chemical-resistant blow-molded laminated container in which the following inner layer 1, inner layer 2, barrier / adhesive resin layer, adhesive layer, barrier layer and outer layer 1 are laminated in order from the inside to the outside of the container, and has a wavelength of 500 The transmittance of visible light at ˜800 nm is 1% or less, the transmittance of ultraviolet rays at a wavelength of 200 to 400 nm is 1% or less, and the elution amount of impure fine particles (number / ml) after storage at 23 ° C. for 30 days is 5 or less. A chemical-resistant blow-molded laminated container with a small amount of impure fine particles eluted after storage for 30 days at 40 ° C. (number / ml) is 10 or less.
Inner layer 1 is an additive-free fluororesin that has no adhesive functional group, has adhesiveness to the fluororesin of the inner layer 2 but has no adhesiveness to other layers, and has 0 weight loss on heating. 20% by mass or less.
Inner layer 2: An additive-free fluororesin having an adhesive functional group and adhesiveness to the fluororesin and barrier / adhesive resin layer of the inner layer 1, and having a loss on heating of 0.40% by mass or less.
Barrier / adhesive resin layer: At least one polyamide selected from the group consisting of polyamides obtained by ring-opening polycondensation of caprolactam, which does not contain additives that are intentionally added or lubricants.
Adhesive layer: a maleic anhydride-modified polyolefin resin.
Barrier layer: an ethylene vinyl alcohol copolymer resin.
Outer layer 1: an ultra high molecular weight high density polyethylene resin that includes a light shielding pigment and a maleic anhydride-modified polyolefin resin and is excellent in adhesion to the barrier layer. - 容器の内側から外側に順に、下記の内層1、内層2、バリアー兼接着樹脂層、接着性層、バリアー層、接着性層および外層2を積層してなる耐薬品性吹込み成形積層容器であって、波長500~800nmの可視光の透過率が1%以下であり、波長200~400nmの紫外線透過率が1%以下であり、23℃で30日貯蔵後の不純微粒子溶出量(個数/ml)が5以下、かつ40℃で30日貯蔵後の不純微粒子溶出量(個数/ml)が10以下であることを特徴とする不純微粒子溶出量の少ない耐薬品性吹込み成形積層容器。
内層1:接着性官能基を有さず、内層2のフッ素樹脂には接着性を有するが他の層には接着性を有さない、添加剤フリーのフッ素樹脂であって、加熱減量が0.20質量%以下である。
内層2:接着性官能基を有し、内層1のフッ素樹脂およびバリアー兼接着樹脂層に接着性を有する、添加剤フリーのフッ素樹脂であって、加熱減量が0.40質量%以下である。
バリアー兼接着樹脂層:意図的に添加される添加剤や潤滑剤を含む添加物を含有しない、カプロラクタムの開環重縮合により得られるポリアミドからなる群より選択される少なくとも1種のポリアミドである。
接着性層:無水マレイン酸変性ポリオレフィン樹脂である。
バリアー層:エチレンビニルアルコール共重合樹脂である。
接着性層:無水マレイン酸変性ポリオレフィン樹脂である。
外層2:遮光性顔料を含む超高分子量高密度ポリエチレン樹脂である。 A chemical-resistant blow-molded laminated container in which the following inner layer 1, inner layer 2, barrier / adhesive resin layer, adhesive layer, barrier layer, adhesive layer and outer layer 2 are laminated in order from the inside to the outside of the container. The transmittance of visible light having a wavelength of 500 to 800 nm is 1% or less, the transmittance of ultraviolet light having a wavelength of 200 to 400 nm is 1% or less, and the amount of impure fine particles eluted after storage at 23 ° C. for 30 days (number / ml ) Is 5 or less, and the amount of impure fine particles eluted (number / ml) after storage at 40 ° C. for 30 days is 10 or less.
Inner layer 1 is an additive-free fluororesin that has no adhesive functional group, has adhesiveness to the fluororesin of the inner layer 2 but has no adhesiveness to other layers, and has 0 weight loss on heating. 20% by mass or less.
Inner layer 2: An additive-free fluororesin having an adhesive functional group and adhesiveness to the fluororesin and barrier / adhesive resin layer of the inner layer 1, and having a loss on heating of 0.40% by mass or less.
Barrier / adhesive resin layer: At least one polyamide selected from the group consisting of polyamides obtained by ring-opening polycondensation of caprolactam, which does not contain additives that are intentionally added or lubricants.
Adhesive layer: a maleic anhydride-modified polyolefin resin.
Barrier layer: an ethylene vinyl alcohol copolymer resin.
Adhesive layer: a maleic anhydride-modified polyolefin resin.
Outer layer 2: Ultra high molecular weight high density polyethylene resin containing light blocking pigment. - 前記内層2に使用するフッ素樹脂が、テトラフルオロエチレン/ヘキサフルオロプロピレン/単量体(α)共重合体、テトラフルオロエチレン/パーフルオロ(アルキルビニルエーテル)/単量体(α)共重合体、エチレン/テトラフルオロエチレン/単量体(α)共重合体、エチレン/テトラフルオロエチレン/ヘキサフルオロプロピレン/単量体(α)共重合体、クロロトリフルオロエチレン/単量体(α)共重合体、クロロトリフルオロエチレン/テトラフルオロエチレン/単量体(α)共重合体、及びエチレン/クロロトリフルオロエチレン/単量体(α)共重合体からなる群より選択された少なくとも1種であり、前記単量体(α)は接着性官能基を有する単量体であることを示し、そして下記特性を有するフッ素樹脂であることを特徴とする請求項1あるいは請求項2記載の耐薬品性吹込み成形積層容器。
(特性)
MFR(265℃、5Kg荷重 g/10min):10~40
比重:1.7~1.9
融点(℃):150~200 The fluororesin used for the inner layer 2 is tetrafluoroethylene / hexafluoropropylene / monomer (α) copolymer, tetrafluoroethylene / perfluoro (alkyl vinyl ether) / monomer (α) copolymer, ethylene / Tetrafluoroethylene / monomer (α) copolymer, ethylene / tetrafluoroethylene / hexafluoropropylene / monomer (α) copolymer, chlorotrifluoroethylene / monomer (α) copolymer, It is at least one selected from the group consisting of chlorotrifluoroethylene / tetrafluoroethylene / monomer (α) copolymer and ethylene / chlorotrifluoroethylene / monomer (α) copolymer, 3. The chemical resistance according to claim 1, wherein the monomer (α) is a monomer having an adhesive functional group and is a fluororesin having the following characteristics: Blow molded laminated container.
(Characteristic)
MFR (265 ° C., 5 kg load g / 10 min): 10 to 40
Specific gravity: 1.7 to 1.9
Melting point (° C): 150-200 - 前記内層1に使用するフッ素樹脂は、前記接着性官能基を有さず、下記特性を有するフッ素樹脂であることを特徴とする請求項1から3のいずれか1項に記載の耐薬品性吹込み成形積層容器。
(特性)
MFR(297℃、5Kg荷重 g/10min):9~35
比重:1.7~1.9
融点(℃):200~240 4. The chemical-resistant blower according to claim 1, wherein the fluororesin used for the inner layer 1 is a fluororesin that does not have the adhesive functional group and has the following characteristics. Molded laminated container.
(Characteristic)
MFR (297 ° C., 5 kg load g / 10 min): 9 to 35
Specific gravity: 1.7 to 1.9
Melting point (° C): 200-240 - 前記ポリアミド樹脂が、下記特性を有することを特徴とする請求項1から請求項4のいずれか1項に記載の耐薬品性吹込み成形積層容器。
(特性)
融点(℃):170~250
密度(Kg/m3):1.0~1.2 The chemical-resistant blow-molded laminated container according to any one of claims 1 to 4, wherein the polyamide resin has the following characteristics.
(Characteristic)
Melting point (° C): 170-250
Density (Kg / m3): 1.0 to 1.2 - 前記バリアー層は、下記の特性を有する酸素バリアー性に優れたエチレンビニルアルコール共重合樹脂であることを特徴とする請求項1から請求項5のいずれか1項に記載の耐薬品性吹込み成形積層容器。
(特性)
MFR(210℃、2.16Kg荷重 g/10min):2~5
密度(Kg/m3):1.1~1.3
融点(℃):170~200 The chemical barrier blow molding according to any one of claims 1 to 5, wherein the barrier layer is an ethylene vinyl alcohol copolymer resin having the following characteristics and excellent oxygen barrier properties. Laminated container.
(Characteristic)
MFR (210 ° C., 2.16 kg load g / 10 min): 2 to 5
Density (Kg / m3): 1.1 to 1.3
Melting point (° C): 170-200 - 前記外層1が、下記特性を有するポリエチレンあるいはエチレン-α-オレフィン共重合体からなる超高分子量高密度ポリエチレン樹脂と、紫外線遮断性および可視光遮断性を付与するためのキナクリドン系、フタロシアニン系、アンスラキノン系、モノアゾ系などの有機系の遮光性顔料や、カーボンブラック、酸化鉄、酸化亜鉛、群青、酸化クロム、酸化チタン、二酸化珪素などの無機系の遮光性顔料から選択される少なくとも1種の遮光性顔料からなる群から選択される少なくとも1種の遮光性顔料を含むと共に、酸化防止剤を0.05~0.30質量%、無水マレイン酸変性ポリオレフィン樹脂を25~65質量%含み、波長500~800nmの可視光の透過率が1%以下であり、波長200~400nmの紫外線透過率が1%以下である組成物1から構成されることを特徴とする請求項1記載の耐薬品性吹込み成形積層容器。
(特性)
密度:940~962Kg/m3
重量平均分子量:220,000~260,000
分子量分布(Mw/Mn):12以下
溶融張力:18~30g The outer layer 1 comprises an ultra-high molecular weight high-density polyethylene resin comprising polyethylene or an ethylene-α-olefin copolymer having the following characteristics, and a quinacridone, phthalocyanine, anthracite for imparting UV blocking properties and visible light blocking properties. At least one selected from organic light-shielding pigments such as quinone and monoazo, and inorganic light-shielding pigments such as carbon black, iron oxide, zinc oxide, ultramarine, chromium oxide, titanium oxide, and silicon dioxide. It contains at least one light-shielding pigment selected from the group consisting of light-shielding pigments, contains 0.05 to 0.30% by weight of antioxidant, 25 to 65% by weight of maleic anhydride-modified polyolefin resin, and has a wavelength The transmittance of visible light at 500 to 800 nm is 1% or less, and the transmittance of ultraviolet light at a wavelength of 200 to 400 nm is 1% or less. Chemical resistance blow molding laminated container according to claim 1, characterized in that they are composed of a certain composition 1.
(Characteristic)
Density: 940 to 962 kg / m3
Weight average molecular weight: 220,000-260,000
Molecular weight distribution (Mw / Mn): 12 or less Melt tension: 18-30 g - 前記外層2が、下記特性を有するポリエチレンあるいはエチレン-α-オレフィン共重合体からなる超高分子量高密度ポリエチレン樹脂と、紫外線遮断性および可視光遮断性を付与するためのキナクリドン系、フタロシアニン系、アンスラキノン系、モノアゾ系などの有機系の遮光性顔料や、カーボンブラック、酸化鉄、酸化亜鉛、群青、酸化クロム、酸化チタン、二酸化珪素などの無機系の遮光性顔料から選択される少なくとも1種の遮光性顔料からなる群から選択される少なくとも1種の遮光性顔料を含むと共に、酸化防止剤を0.05~0.30質量%含み、波長500~800nmの可視光の透過率が1%以下であり、波長200~400nmの紫外線透過率が1%以下である組成物2から構成されることを特徴とする請求項2記載の耐薬品性吹込み成形積層容器。
(特性)
密度:940~962Kg/m3
重量平均分子量:220,000~260,000
分子量分布(Mw/Mn):12以下
溶融張力:18~30g The outer layer 2 comprises an ultra-high molecular weight high-density polyethylene resin made of polyethylene or an ethylene-α-olefin copolymer having the following characteristics, and quinacridone, phthalocyanine, anthra for imparting UV blocking properties and visible light blocking properties. At least one selected from organic light-shielding pigments such as quinone and monoazo, and inorganic light-shielding pigments such as carbon black, iron oxide, zinc oxide, ultramarine, chromium oxide, titanium oxide, and silicon dioxide. It contains at least one light-shielding pigment selected from the group consisting of light-shielding pigments, contains 0.05 to 0.30% by weight of an antioxidant, and has a visible light transmittance of 1% or less at a wavelength of 500 to 800 nm. 3. A composition 2 having an ultraviolet transmittance of 1% or less at a wavelength of 200 to 400 nm. Chemical resistance blow molding laminated container.
(Characteristic)
Density: 940 to 962 kg / m3
Weight average molecular weight: 220,000-260,000
Molecular weight distribution (Mw / Mn): 12 or less Melt tension: 18-30 g
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CN201680086864.7A CN109311553B (en) | 2016-06-17 | 2016-06-17 | Chemical-resistant blow-molded laminated container with reduced amount of elution of foreign particles |
PCT/JP2016/002928 WO2017216827A1 (en) | 2016-06-17 | 2016-06-17 | Chemical-resistant blow-molded laminate container leaching few impurity particles |
KR1020197001662A KR102192237B1 (en) | 2016-06-17 | 2016-06-17 | Chemical-resistant blow molded laminated container with low impurity particulate elution |
JP2018522901A JP6518840B2 (en) | 2016-06-17 | 2016-06-17 | Chemical-resistant blow-molded laminated containers with low impurity particle elution |
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WO2019245889A1 (en) * | 2018-06-18 | 2019-12-26 | Baker Hughes, A Ge Company, Llc | Methods of manufacturing polyolefin drag reducing agents |
US11199296B2 (en) | 2019-06-14 | 2021-12-14 | Baker Hughes Oilfield Operations Llc | Drag reducing agents |
CN118243648A (en) * | 2024-05-30 | 2024-06-25 | 新恒汇电子股份有限公司 | Photosensitive dry film quality detection method |
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EP3722086A1 (en) * | 2019-04-12 | 2020-10-14 | Nitto Denko Corporation | Multilayer films for airbag applications |
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