JP6839489B2 - Injection-molded laminated container for ultra-high purity chemicals with no visibility of contents - Google Patents

Description

The present invention relates to a blow-molded laminated container for ultra-high-purity chemicals having no visibility of the contents, and more specifically, an ultra-high-purity chemical having excellent chemical resistance and mechanical strength and stored. It is a blow-molded (blow-molded) laminated container with a very low cleanliness of 5 pieces / ml or less as an index indicating the number of impure fine particles leached from the container side into the container, and the contained content liquid is taken from the outside. It cannot be visually confirmed and has excellent UV blocking properties and oxygen barrier properties that can prevent deterioration of the contained content liquid. It is inexpensive and economical, and it is a blower for ultra-high purity chemicals that does not have visibility of the contents. It relates to a build-in laminated laminated container.

Generally, glass containers and plastic containers have been used as containers for storing chemicals, but especially in the field of semiconductors, it is necessary to store ultra-high-purity chemicals stored in ultra-high purity.
That is, due to the rapid progress of electronic devices, if fine impure fine particles are leached from the container side into ultra-high purity chemicals such as resist liquid used for microfabrication of integrated circuits, the integrated circuit may be broken. There is a problem that a big trouble is caused or the photosensitive component is deteriorated due to the mixing of impure fine particle metal or the like.

Single-layer or multi-layer laminated containers with a polyethylene-based resin as the inner layer have the advantages of being hard to break during handling and being lightweight, but high-purity chemicals used for etching and cleaning in semiconductor manufacturing, such as sulfuric acid, nitrate, and hydrogen peroxide. High-purity solvent-based resists and diluting solvents used for water, semiconductor processes, liquid crystal displays, etc., such as methyl alcohol, ethyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, acetone, ethyl acetate, toluene, dimethyl. During storage, high-purity solvents such as formamide, ethylene glycol acetate, methoxypropyl acetate, butyl cellosolve, and pharmaceuticals used for sterilization, disinfection, and pharmaceutical ingredients, such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, are stored. In addition, there is a problem that these are leached as impure fine particles into the chemicals stored from the resin composition or the additive forming the container, and the purity of the chemicals is impaired.

For this reason, it is necessary to solve the problems that have a significant adverse effect on the quality of the semiconductor itself, the liquid crystal, and the yield. In addition, in order to solve the problem that the chemicals deteriorate and the storage period is shortened, UV blocking property and oxygen There is a demand for a container having barrier properties and the like.
It is necessary to minimize the leaching of fine impure fine particles in ultra-high purity chemical liquids such as resist liquids used for microfabrication of integrated circuits and the like, and most of the containers currently used are glass bottles.
However, since the glass container itself is heavy, it is inconvenient to handle, and there is a problem that it breaks when dropped. It is inferior in safety, and if it breaks and chemicals leak, environmental pollution and health problems occur.

While the chemical is stored in the container for a long period of time, the impure fine particles are leached from the container side into the chemical as the content, and the degree of cleanliness is an index indicating the degree to which the impure fine particles impure the content.
The degree of cleanliness is the number of fine particles with a particle size of 0.2 μm or more in 1 ml of water stored in the container after molding the test container and storing ultrapure water in the test container for a certain period of time. It shows. Next, a method for measuring impure fine particles (particles) is shown.

(Measurement method of impure fine particles (particles))
1. 1. Measuring device: A particle counter "KL-26" manufactured by Rion Co., Ltd. is used.
2. 2. Measurement sample: Fill the container with ultrapure water at a nominal capacity of 80%, lay it on its side, roll it forward one turn with a mill, roll it backward one turn, and then return it to its original position for 30 cycles. The measurement sample is taken from the container after being stationary for a minute.
3. 3. 10 ml of ultrapure water as a measurement sample is collected from a container and injected into a particle counter to measure the number of particles of 0.2 μm or more. This operation is repeated twice to obtain the average value (B) of the number of particles of 0.2 μm or more.
4. The particle value in 1 ml is calculated from the measured value by the following formula to calculate the cleanliness (impure fine particles (particles) / ml).
(B (pieces)) ÷ 10 ml = pieces / ml
Conventionally, it has been said that the quality and yield of semiconductors and liquid crystals can be improved when the cleanliness measured by the above-mentioned measuring method is less than 500 pieces / ml.
However, it is becoming more severe now, and there are many cases where 5 pieces / ml or less is required.

The weight average molecular weight of the raw material resin composed of polyethylene or ethylene-α-olefin copolymer is in a certain range, and the contents of the light-shielding pigment and the dispersant in the resin composition are in a certain range. A container molded from a resin composition made of a low molecular weight polymer and a polyethylene or ethylene-α-olefin copolymer having an additive content of less than a certain weight has excellent mechanical strength and is easy to handle. , A light-shielding container for high-purity chemicals (see Patent Document 1) having a light-shielding property, in which impure fine particles are extremely little leached into the stored chemicals, has been proposed.

However, although this container satisfies the cleanliness of less than 500 pieces / ml, the cleanliness does not become 5 pieces / ml or less, and it does not have an oxygen barrier property for preventing deterioration of the contained content liquid. There was a problem.

A container for containing a high-purity solvent of methyl alcohol, ethyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, acetone, ethyl acetate, toluene, dimethylformamide, ethylene glycol acetate, methoxypropyl acetate or butyl cellosolve. At least the inner surface of the resin is a resin of polyethylene or ethylene-α-olefin copolymer having a density of 940 to 970 kg / m ³ , and a neutralizing agent, an antioxidant and a light-resistant stabilizer in the resin quantified by liquid chromatography. The content of the resin is 0.01% by weight or less with respect to the total weight of the resin, and the weight average molecular weight of the resin measured by gel permeation chromatography is 120,000 to 260,000. A container for a high-purity solvent (see Patent Document 2) in which a polymer having a molecular weight of 1,000 or less in a resin is less than 2.5% by weight based on the total weight of the resin has been proposed.

However, the container for high-purity solvent of Patent Document 2 satisfies the cleanliness of less than 500 pieces / ml, but the cleanliness is not less than 5 pieces / ml, and the contained content liquid has an ultraviolet blocking property that can prevent deterioration of the contained liquid. There is also the problem of being inferior.

Further, a resin of polyethylene or ethylene-α-olefin copolymer having a density of 940 to 970 kg / m ³ is mixed with at least 0.01% by weight to 5% by weight of a light-shielding pigment such as titanium oxide or carbon black, and a liquid or gas barrier property. A container for high-purity chemicals composed of a resin composition to which 4% to 25% by weight of a resin is added, and the weight average molecular weight of the resin measured by gel permeation chromatography is 120,000 to 260,000. , A polymer having a weight average molecular weight of 1,000 or less is less than 5% by weight of the resin, and the α-olefin is among propylene, butene-1, 4-methyl-pentene-1, hexene-1, and octene-1. At least one type of container for high-purity chemicals (see Patent Document 3) has been proposed.

However, the container for high-purity chemicals of Patent Document 3 still satisfies the cleanliness of less than 500 pieces / ml, and has a problem that the cleanliness is not less than 5 pieces / ml.

Further, at least one selected from a polymer of an olefin of ethylene, propylene, butene-1, 4-methyl-pentene-1, hexene-1, or octene-1, and a copolymer of ethylene and other olefins. An inner layer made of a high-purity resin containing a maximum of 0.01% by weight of each of a neutralizing agent, an antioxidant and a light-resistant stabilizer, and a solvent containing poly (ethylene-co-vinyl alcohol). 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 of all layers of the container measured by a spectrophotometer at a wavelength of 400 nm or less is 2. The absorbance at a wavelength of 400 nm, which is 0 or more and the absorbance of all layers of the container divided by the thickness of the entire layer, is 1.5 mm ^-1 or more, and the absorbance at a wavelength of 600 nm is 1.5 mm ^-1 or less. A characteristic container for a high-purity chemical solution (see Patent Document 4) has been proposed.

However, the container for a high-purity chemical solution of Patent Document 4 satisfies a cleanliness of less than 100 pieces / ml, and has a problem that the cleanliness is not 5 pieces / ml or less.

The applicant is a chemical-resistant blow-molded laminated container in which the following inner layer, barrier / adhesive resin layer, adhesive layer, barrier layer, adhesive layer and outer layer are laminated in this order from the inside to the outside of the container. Therefore, we have proposed a chemical-resistant blow-molded laminated container in which each of the layers is transparent and has excellent transparency (see Patent Document 5).
Inner layer: Fluorine resin barrier and adhesive resin layer: Special polyamide resin Adhesive layer: Maleic anhydride-modified polyolefin resin Barrier layer: Ethylene vinyl alcohol copolymer resin Adhesive layer: Maleic anhydride-modified polyolefin resin Outer layer: Ultra-high molecular weight high-density polyethylene resin

The highly transparent chemical-resistant blow-molded laminated container proposed by the applicant has excellent chemical resistance and mechanical strength, and impure particles in stored chemicals and fragrances. It has less leaching, a cleanliness of 5 pieces / ml or less, and the contained content can be visually confirmed from the outside, which is comparable to a transparent glass bottle, and also has excellent UV blocking and oxygen barrier properties. However, the inner layer is a fluororesin such as tetrafluoroethylene / hexafluoropropylene / monomer (α) copolymer, and the barrier / adhesive resin layer is a special polyamide that does not contain additives such as additives and lubricants. In addition to using an expensive resin such as a resin, the outer layer of the ultra-high molecular weight high-density polyethylene resin has a visible light transmittance of 35% or more at a wavelength of 500 to 800 nm and an ultraviolet transmittance of 1% or less at a wavelength of 200 to 400 nm. It was necessary to add an expensive nucleating agent or light-resistant stabilizer to impart the properties.

In addition, the applicant has not used an expensive resin such as the fluorine resin as the inner layer and a special polyamide resin which does not contain additives such as additives and lubricants as the barrier / adhesive resin layer, and the inside of the container. From to the outside, the inner layer made of the following high-density polyethylene, the oxygen barrier layer containing polyvinyl alcohol, and the outer layer containing at least a nucleating agent and a light-resistant stabilizer are laminated at least. A built-in laminated container having a visible light transmittance of 35% or more at a wavelength of 500 to 800 nm, an ultraviolet transmittance of 1% or less at a wavelength of 200 to 400 nm, and a container side into a stored chemical. We have proposed a blow-molded laminated container for ultra-high-purity chemicals, which has an index of cleanliness of 5 pieces / ml or less, which indicates the number of impure fine particles leached from the container, and has excellent visibility (see Patent Document 6).

Inner layer: High density having the following properties, consisting of a homopolymer or copolymer containing at least one selected from ethylene, propylene, butene-1, 4-methyl-pentene-1, hexene-1, and octene-1. polyethylene.
(Characteristic)
No neutralizers, antioxidants, and light-resistant stabilizers were intentionally added, with a maximum content of 0.005% by weight or less, cleanliness: 5 pieces / ml or less, density: 950-962 kg / m ³ , weight. Average molecular weight: 180,000 to 250,000, component with molecular weight of 1,000 or less: 0.4% by mass or less, molecular weight distribution (Mw / Mn): 12 or less, HL-MFR (190 ° C., 21.6 kg load g / 10 min) : 6.5-9.5

However, in the blow-molded laminated container for ultra-high-purity chemicals, which has been proposed earlier by the applicant and has excellent visibility, the fluororesin is added as an inner layer and additives and lubricants are added as a barrier / adhesive resin layer. No expensive resin such as special polyamide resin containing substances is used, but the transmittance of visible light at a wavelength of 500 to 800 nm is set to 35% or more in order to impart transparency to the outer layer of ultra-high molecular weight high-density polyethylene resin. It is still economical because it is necessary to add an expensive nucleating agent for the purpose, and it is necessary to add an expensive light-resistant stabilizer in order to reduce the ultraviolet transmittance at a wavelength of 200 to 400 nm to 1% or less. While the problem remains, it has the required characteristics such as cleanliness and fragrance retention, but there is a problem that it cannot meet the demand that the contents contained in the container should not be seen from the outside.

Japanese Patent No. 2805723 Japanese Patent No. 2749513 Japanese Patent No. 2805188 Japanese Patent No. 4167745 Japanese Patent No. 5706512 Japanese Patent Application No. 2015-129894

An object of the present invention is to have excellent chemical resistance, mechanical strength, etc., and to have a cleanliness of 5 as an index indicating the number of impure fine particles leached from the container side into ultra-high purity chemicals stored and stored. It is a blow-molded (blow-molded) laminated container with a very small amount of ml or less, and the contained content liquid cannot be visually confirmed from the outside. It is an object of the present invention to provide a blow-molded laminated container for ultra-high purity chemicals, which is excellent, has a lower cost than the conventional product, and has excellent economic efficiency, and has no visibility of the contents.

As a result of diligent research, the present inventors intended a neutralizing agent, an antioxidant, and a light-resistant stabilizer as inner layers to be wetted surfaces in order from the inside to the outside of the container in order to solve the conventional problems. Maximum content 0.005% by mass or less, cleanliness: 5 pieces / ml or less, density: 950 to 962 kg / m ³ , weight average molecular weight: 180 to 250,000, molecular weight 1,000 or less Ingredients: 0.4% by 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 high-density polyolefin resin An ultra-high-purity chemical blower that contains at least an inner layer, an oxygen barrier layer containing a polyvinyl alcohol resin, and an outer layer that contains a predetermined amount of light-shielding pigment but does not require the addition of an expensive light-resistant stabilizer or nucleating agent. The built-in laminated container has excellent chemical resistance, mechanical strength, etc., has a very small visible light transmission rate of 1% or less at a wavelength of 500 to 800 nm, and an ultraviolet wave transmission rate of 1% or less at a wavelength of 200 to 400 nm. In addition, the cleanliness as an index indicating the number of impure fine particles leached into the stored chemicals from the container side is 5 pieces / ml or less, and the contained content liquid cannot be visually confirmed from the outside, and the stored content liquid cannot be visually confirmed. The present invention has been found to be able to provide a blow-molded laminated container for ultra-high-purity chemicals, which is excellent in ultraviolet blocking property, oxygen barrier property, etc. that can prevent deterioration of the above-mentioned products, and is more economical than the conventional product at a lower cost. Has come to be achieved.

The object of the present onset bright for solving, in order from the inside of the container to the outside, an inner layer below the oxygen barrier layer and an outer layer containing a light-shielding pigment comprising polyvinyl alcohol resin formed by at least laminating ultra-high purity chemicals A blow-molded laminated container having a visible light transmittance of 1% or less at a wavelength of 500 to 800 nm, an ultraviolet transmittance of 1% or less at a wavelength of 200 to 400 nm, and a container in a stored chemical. It is a blow-molded laminated container for ultra-high purity chemicals having no visibility of the contents, characterized in that the cleanliness as an index indicating the number of impure fine particles leached from the side is 5 pieces / ml or less.

Inner layer: High density having the following properties, consisting of 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)
Neutralizers, antioxidants, and light-resistant stabilizers were not intentionally added, and the maximum content was 0.005% by mass or less.
Cleanliness: 5 pieces / ml or less Density: 950-962 kg / m ³
Weight average molecular weight: 180 to 250,000 molecular weight 1,000 or less component: 0.4% by mass or less Molecular weight distribution (Mw / Mn): 12 or less HL-MFR (190 ° C., 21.6 kg load g / 10 min): 6. 5-9.5

This onset Ming, in the blow molding the laminated container, and is characterized in that formed by laminating the adhesive layer composed of the inner layer and the oxygen barrier layer and the oxygen barrier layer and the outer layer of the maleic acid-modified polyolefin resin ..

This onset Ming, in the blow molding the laminated container, said barrier layer is characterized in that comprising an oxygen barrier property superior ethylene vinyl alcohol copolymer resin having the following characteristics.

(Characteristic)
MFR (210 ° C, 2.16 kg load g / 10 min): 2-5
Density (Kg / m ³ ): 1.1 to 1.3
Melting point (° C): 170-200

Select the onset Ming, in the blow molding the laminated container, wherein the outer layer comprises a high density polyethylene resin having the following characteristics, in addition to phenol of the light-shielding pigment, a phosphorus, from the group consisting of Sulfur-based antioxidants It is characterized by comprising a resin composition containing at least 0.05 to 0.30% by mass of the above-mentioned antioxidant. Further, the outer layer in the present invention further contains a high-density polyethylene resin having the following characteristics and at least one antioxidant selected from the group consisting of phosphorus-based and sulfer-based antioxidants, and the said antioxidant. , It is more preferable to contain 0.05 to 0.30% by mass with respect to the high-density polyethylene resin.

(Characteristic)
Density: 940-962Kg / m ³
Weight average molecular weight: 220,000 to 260,000 molecular weight distribution (Mw / Mn): 12 or less Melt tension: 20 to 30 g
HL-MFR (190 ° C, 21.6 kg load g / 10 min): 5-7
Visible light transmittance with a wavelength of 500 to 800 nm is 1% or less. Ultraviolet transmittance with a wavelength of 200 to 400 nm is 1% or less.

This onset Ming, in order from the inside of the container to the outside, the inner layer, there oxygen barrier layer and an outer layer comprising a light-shielding pigment formed by at least laminating ultra-high purity chemicals for blow molding the laminated container comprising polyvinyl alcohol resin Therefore, the transmittance of visible light having a wavelength of 500 to 800 nm is 1% or less, the transmittance of ultraviolet rays having a wavelength of 200 to 400 nm is 1% or less, and the impure fine particles leached into the stored chemicals from the container side. It is a blow-molded laminated container for ultra-high-purity chemicals with no visibility of the contents, which is characterized in that the cleanliness as an index indicating the number is 5 pieces / ml or less.
No additives such as neutralizing agent, antioxidant, and light-resistant stabilizer are intentionally added as the inner layer to be the wetted surface, the maximum content is 0.005% by quality or less, and the cleanliness is 5. / Ml or less, density 950 to 962 kg / m ³ , weight average molecular weight: 180,000 to 250,000, molecular weight 1,000 or less components are 0.4% by mass or less, (Mw / Mn): 12 or less, HL -By using a specific high-density polyolefin resin with an MFR (190 ° C, 21.6 kg load g / 10 min) of 6.5 to 9.5, it is excellent in chemical resistance and mechanical strength, and has a molecular weight of 1. Since the components of 000 or less are 0.4% by mass or less and the molecular weight distribution (Mw / Mn) is as narrow as 12 or less, the cleanliness of the inner layer itself is surely 5 pieces / ml or less, for example, adjacent to each other. Even if there are impure fine particles that migrate from the layer, the inner layer can prevent them from seeping into the content liquid, so the cleanliness of the container can be reliably maintained at 5 pieces / ml or less, and ethylene vinyl alcohol copolymerization with excellent oxygen barrier properties. Oxygen barrier properties can be improved by providing a barrier layer made of resin, and for example, organic light-shielding pigments such as quinacridone, phthalocyanine, anthracinone, and monoazo, carbon black, iron oxide, zinc oxide, and ultramarine. By providing an outer layer containing a predetermined amount of at least one light-shielding pigment selected from inorganic light-shielding pigments such as chromium oxide, titanium oxide, and silicon dioxide, the transmission rate of visible light having a density of 500 to 800 nm is 1%. The following is a specific function, such as the ability to achieve an ultraviolet transmittance of 1% or less at a wavelength of 200 to 400 nm, which eliminates the visibility of the contents and imparts an ultraviolet blocking property capable of preventing deterioration of the contained content liquid. Due to the structure in which each layer having the above is laminated, the leaching of impure particles from the container side into the ultra-high purity chemicals and various fragrances stored and stored is very small, and the degree of cleanliness is 5 pieces. It can achieve / ml or less, has excellent chemical resistance and mechanical strength, and has excellent ultraviolet blocking property, oxygen barrier property, and antioxidant property that can prevent deterioration of the contained content liquid, and is suitable for various fragrance storage stability. It has a remarkable effect that it can be used as a container for ultra-high-purity chemicals and various fragrances, which are excellent, have many expensive and highly dangerous chemical substances.

The blow-molded laminated container of the present invention contains a fluororesin such as the tetrafluoroethylene / hexafluoropropylene / monomer (α) copolymer as an inner layer and an additive or a lubricant as a barrier / adhesive resin layer. In order to eliminate the use of expensive resins such as special polyamide resins that do not contain additives and to impart transparency to the ultra-high molecular weight high-density polyethylene resin in the outer layer, the transmittance of visible light with a wavelength of 500 to 800 nm is 35% or more. Since it is not necessary to add an expensive nucleating agent for the above-mentioned, and it is not necessary to add an expensive light-resistant stabilizer in order to reduce the ultraviolet transmittance at a wavelength of 200 to 400 nm to 1% or less. It has the remarkable effect of being much cheaper and more economical.

In addition, the blow-formed laminated container of the present invention is heavy, easily broken, and has excellent mechanical strength, which is hard to break, as compared with a glass bottle which lacks safety, and has a cleanliness of 5 pieces / ml. As it is as follows, it has excellent ultraviolet blocking property and oxygen barrier property, so it can be used safely and securely as a plastic container that can be used for various other contents, it is easy for the environment, and it is suitable for environmental problems and health problems. It contributes, improves yield and reduces costs, so it has a remarkable effect of being economical.
Since the oxygen barrier layer containing the polyvinyl alcohol resin is provided, the oxygen barrier property is surely improved, and deterioration of the contained content liquid can be prevented.

This onset Ming, in the blow molding laminated containers, which are characterized by being laminated by an adhesive layer composed of the inner layer and the oxygen barrier layer and the oxygen barrier layer and the outer layer of the maleic acid-modified polyolefin resin ,
Since it is laminated by an adhesive layer made of the same or different maleic anhydride-modified polyolefin resin, each layer can be surely laminated well, it is hard to be damaged, and excellent mechanical strength can be imparted, which is a further remarkable effect. Play.

This onset Ming, in the blow molding the laminated container, wherein the barrier layer is, which is characterized by comprising an oxygen barrier property superior ethylene vinyl alcohol copolymer resin having the properties,
The oxygen barrier property is surely improved, and it has a further remarkable effect of preventing deterioration of the contained content liquid.

Select the onset Ming, in the blow molding the laminated container, wherein the outer layer comprises a high density polyethylene resin having a characteristic, in addition to phenol of the light-shielding pigment, a phosphorus, from the group consisting of Sulfur-based antioxidants It is characterized by comprising a resin composition containing at least 0.05 to 0.30% by mass of at least one of the antioxidants, and more preferably a group consisting of phosphorus-based and sulfer-based antioxidants. It contains at least one antioxidant selected from the above, and is characterized by containing 0.05 to 0.30% by mass of the antioxidant with respect to the high-density polyethylene resin.
By using the outer layer, it is excellent in processing characteristics such as no drawdown, chemical resistance and mechanical strength, and for example, organic light-shielding pigments such as quinacridone-based, phthalocyanine-based, anthracinone-based, and monoazo-based pigments. Cleanliness by providing an outer layer containing a predetermined amount of at least one light-shielding pigment selected from inorganic light-shielding pigments such as carbon black, iron oxide, zinc oxide, ultramarine, chromium oxide, titanium oxide, and silicon dioxide. Since the transmittance of visible light having a wavelength of 500 to 800 nm is 1% or less and the transmittance of ultraviolet rays having a wavelength of 200 to 400 nm is 1% or less without impairing the content, the contents are not visible and are accommodated. In addition to being able to impart ultraviolet blocking properties that can prevent deterioration of the content liquid, because the molecular weight distribution (Mw / Mn) is as narrow as 12 or less, blow molding is multi-layered under the normal molding conditions of melt processing and rapid cooling. Since the outer layer of the laminated container is composed of dense small crystal aggregates, the mechanical strength is further improved, and since a predetermined amount of antioxidant is blended, the antioxidant performance is improved, the resin is prevented from burning, and the burnt resin is burnt. It has a further remarkable effect of preventing deterioration of the appearance caused by the above.

FIG. 1 is an explanatory view schematically illustrating a wall cross section of a blow-molded laminated container for ultra-high purity chemicals in which the contents of the present invention are not visible. FIG. 2 is an explanatory view schematically illustrating a wall cross section of another blow-molded laminated container for ultra-high purity chemicals in which the contents of the present invention are not visible.

Hereinafter, the present invention will be described in detail with reference to the drawings.
FIG. 1 is an explanatory view illustrating a wall cross section of a blow-molded laminated container for ultra-high purity chemicals in which the contents of the present invention are not visible.
Reference numeral 1 denotes a high polymer having the following characteristics, which comprises a homopolymer or a copolymer containing at least one selected from ethylene, propylene, butene-1, 4-methyl-pentene-1, hexene-1, and octene-1. An inner layer made of a density polyolefin resin, 2 is an adhesive layer made of a maleic anhydride-modified polyolefin resin, 3 is a barrier layer made of an oxygen barrier resin containing an ethylene vinyl alcohol copolymer resin, and 4 is a maleic anhydride-modified polyolefin resin. The adhesive layer 5 indicates an outer layer containing a light-shielding pigment, respectively. Reference numeral 6 denotes a blow-molded laminated container for ultra-high purity chemicals having no visibility of the contents of the present invention, and 7 indicates an ultra-high purity chemical.

FIG. 2 is an explanatory view schematically illustrating a wall cross section of another blow-molded laminated container for ultra-high purity chemicals in which the contents of the present invention are not visible.
As shown in FIG. 2, other ultra-high purity chemicals for blow molding the laminated container 6 ^'of the present invention, in order outward from the inside, the inner layer 1, the adhesive layer 2, barrier resin 3, the adhesive layer 4, It has a structure in which a recovery layer 8 and an outer layer 5 are laminated. The recovery layer 8 is formed of a mixture of, for example, equal amounts of recovered products from the inner layer 1, the barrier resin 3, the adhesive layers 2, 4 and the outer layer 5, which are melt-mixed. 7 indicates an ultra-high purity chemical.

The resin used for the inner layer in the present invention is a high-density polyolefin resin having the following characteristics.
(Characteristic)
Neutralizers, antioxidants, and light-resistant stabilizers were not intentionally added, and the maximum content was 0.005% by mass or less.
Cleanliness: 5 pieces / ml or less Density: 950-962 kg / m ³
Weight average molecular weight: 180 to 250,000 molecular weight 1,000 or less component: 0.4% by mass or less Molecular weight distribution (Mw / Mn): 12 or less HL-MFR (190 ° C., 21.6 kg load g / 10 min): 6. 5-9.5

The high-density polyolefin resin used for the inner layer in the present invention has a maximum content of 0.005% or less without intentionally adding additives such as a neutralizing agent, an antioxidant, and a light-resistant stabilizer. A homopolymer or copolymer containing at least one selected from ethylene, propylene, butene-1, 4-methyl-pentene-1, hexene-1, and octene-1, which have a cleanliness of 5 pieces / ml or less. Commercially available products that are coalesced and have the above characteristics can be used. Of these, ethylene homopolymers and copolymers of ethylene with α-olefins such as propylene, butene-1, 4-methyl-pentene-1, hexene-1, and octene-1 are preferably used. The content of α-olefin in the copolymer is preferably 15% by mass or less. The polymerization method is not particularly limited as long as a polymer or copolymer having the above characteristics such as a density of 950 to 962 kg / m ³ can be obtained, and for example, either a low pressure method or a medium pressure method may be used. ..

Neutralizers, antioxidants, and light-resistant stabilizers are not intentionally added, and the maximum content is 0.005% by mass or less (according to the method for measuring the content of additives described later), preferably 0.003% by mass. % Or less, and if it exceeds 0.005% by mass, the cleanliness of the inner layer (according to the measurement method described later) may not be reduced to 5 pieces / ml or less.
The density of the inner layer (measurement method: conforming to JIS K7112) is 950 to 962 Kg / m ³ , preferably 955 to 960 Kg / m ³ , and if the density is ^{less than 950 Kg / m 3,} there is a risk of insufficient strength and the density is high. If it exceeds 962 kg / m ³ , there is a risk of insufficient adhesiveness.

The weight average molecular weight of the inner layer (according to the measurement method described later) is 180 to 250,000, preferably 190 to 220,000, and when the weight average molecular weight is less than 180,000, the component having a molecular weight of 1,000 or less is 0.4% by mass. There is a possibility that the following will not be obtained, and if it exceeds 250,000, the moldability may be inferior.

The component having a molecular weight of 1,000 or less in the inner layer is 0.4% by mass or less (according to the measurement method described later), preferably 0.3% by mass or less, and when it exceeds 0.4% by mass, the cleanliness is 5 It may not be possible to reduce the number to less than 1 ml.

The (Mw / Mn) of the inner layer is 12 or less (according to the measurement method described later), preferably 11 or less, and if it exceeds 12, the component having a molecular weight of 1,000 or less may not be 0.4% by mass or less. At the same time, the crystals in the inner layer of the blow-molded laminated container, which are multi-layer molded under the normal molding conditions of melt processing and rapid cooling, become large or scattered and are not composed of dense small crystal aggregates. The target strength may be inferior.

The HL-MFR of the inner layer is measured in accordance with JIS K7210 at a measurement temperature of 190 ° C. and a load of 21.6 kg, and the measurement result is expressed in (g / 10 min). The HL-MFR of the polyolefin resin is 6.5 to 9.5, preferably 7.5 to 9.0, and if it is less than 6.5, the processing characteristics deteriorate and the inner surface of the bottle has melt fracture (rough skin). If it exceeds 9.5, the cleanliness may not be reduced to 5 pieces / ml or less.

The maleic anhydride-modified polyolefin resin of the adhesive layer used in the present invention has excellent adhesiveness to the inner layer and the barrier layer (ethylene vinyl alcohol copolymer resin), and further, the maleic anhydride-modified polyolefin resin of the adhesive layer is modified. The polyolefin resin has excellent adhesiveness to the barrier layer (ethylene vinyl alcohol copolymer resin) and the outer layer, and the two are bonded to form an adhesive layer. If melt molding is possible, the polyolefin resin is formed. Well, a commercially available product that is usually commercially available can be used.

The maleic anhydride-modified polyolefin resin of the adhesive layer has an inner layer, an adhesive layer (maleic anhydride-modified polyolefin resin), a barrier layer (ethylene vinyl alcohol copolymer resin), and adhesion as long as the properties such as adhesiveness are not impaired. A recovered product containing a layer (maleic anhydride-modified polyolefin resin) and an outer layer can be blended.
The maleic anhydride-modified polyolefin resin containing the recovered product of the adhesive layer is separated from the high-density polyolefin resin of the inner layer to be the wetted surface, and even if there are impure fine particles in the adhesive layer, they are impure. This is because the inner layer can prevent the fine particles from leaching into the content liquid, so that the cleanliness is not impaired.
In the present invention, as shown in FIG. 2, since the recovered material layer composed of only the recovered material has excellent adhesiveness to the adhesive layer and the outer layer, the recovered material layer is between the adhesive layer and the outer layer. It is also possible to provide a configuration.

Malean anhydride-modified polyolefin resin having excellent adhesion to the inner layer and the barrier layer (ethylene vinyl alcohol copolymer resin), and excellent adhesion to the barrier layer (ethylene vinyl alcohol copolymer resin) and the outer layer. It may be the same as or different from the maleic anhydride-modified polyolefin resin having the above, and it is preferable to determine by pre-testing.

The ethylene vinyl alcohol copolymer resin (ethylene 24-44 mol% copolymer) of the barrier layer used in the present invention is a resin obtained by hydrolyzing the ethylene vinyl alcohol copolymer and almost completely saponifying it, and has a fragrance-retaining property. It is widely used as a container and packaging material for chemicals, cosmetics, etc. because it has excellent gas barrier properties such as oxygen barrier properties, and has high resistance to oils, organic solvents, etc., and has the following characteristics in particular. By using the ethylene vinyl alcohol copolymer resin, the oxygen barrier property can be ensured, and the MFR, melting point, etc. are close to those of the high-density polyethylene resin preferably used for the outer layer, and the stable moldability is excellent, so that the resin can be preferably used.
Specific examples of the ethylene vinyl alcohol copolymer resin of the barrier layer include F171B (32 mol% ethylene copolymer, melting point 183 ° C., saponification rate 99.99%) manufactured by Kuraray Co., Ltd. be able to.

(Characteristic)
MFR (210 ° C, 2.16 kg load g / 10 min): 2-5
Density (Kg / m ³ ): 1.1 to 1.3
Melting point (° C): 170-200
The MFR is measured in accordance with JIS K7210 at a measurement temperature of 210 ° C. and a load of 2.16 kg, and the measurement result is expressed in (g / 10 min).
Density is measured according to ASTM D1250-80.
The melting point is measured according to ISO 11357.

The MFR is preferably 2-5, more preferably 3-5, the density is preferably 1.1-1.3, even more preferably 1.2-1.3, and the melting point (° C.). Is preferably 170 to 200, and more preferably 180 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 outside the above ranges, at least one of these characteristics may be impaired.

As the thermoplastic resin used for the outer layer in the present invention, it is used with good processability for molding a blow-molded laminated container for ultra-high-purity chemicals, which has no visibility of the contents of the present invention as shown in FIGS. 1 and 2. It is particularly limited as long as it is a thermoplastic resin that can be made, has excellent properties such as physical, chemical, and mechanical strength that should be possessed as an outer layer, and can obtain an excellent blow-molded laminated container of the present invention. It's not a thing.
Specifically, for example, a homopolymer or copolymer containing at least one selected from ethylene, propylene, butene-1, 4-methyl-pentene-1, hexene-1, and octene-1 can be preferably used. ..
In the present invention, it is more preferable to use a high-density polyethylene resin having the above-mentioned characteristics as the polyethylene or ethylene-α-olefin copolymer forming the outer layer.
Hereinafter, an example in which a high-density polyethylene resin is used as the resin used for the outer layer will be described.

The outer layer used in the present invention contains at least one light-shielding pigment selected from organic light-shielding pigments and / or inorganic light-shielding pigments, and has a visible light transmittance of 1% or less at a wavelength of 500 to 800 nm (1% or less). 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).
As the organic light-shielding pigment and the inorganic light-shielding pigment, by blending a predetermined amount in the outer layer, the transmittance of visible light having a wavelength of 500 to 800 nm is 1% or less, and the transmittance of ultraviolet rays having a wavelength of 200 to 400 nm is increased. It is not particularly limited as long as it can be 1% or less and does not impair other characteristics of the outer layer.

However, organic light-shielding pigments such as quinacridone, phthalocyanine, anthracinone, and monoazo, and inorganic light-shielding pigments such as carbon black, iron oxide, zinc oxide, ultramarine, chromium oxide, titanium oxide, and silicon dioxide. At least one light-shielding pigment selected from the pigments can be preferably used in the present invention because the object can be achieved by blending in a relatively small amount.

Specific examples of the quinacridone-based light-shielding pigment include TET48183 and TET78310 (manufactured by Toyo Color Co., Ltd.).

Specific examples of the phthalocyanine-based light-shielding pigment include 7F2852 (manufactured by Dainichiseika Kogyo Co., Ltd.), TET58335 (manufactured by Toyo Color Co., Ltd.) and EPH-525328 (manufactured by Polycol Kogyo Co., Ltd.). Can be done.

Specific examples of the monoazo-based light-shielding pigment include TET38013 (manufactured by Toyo Color Co., Ltd.) and ECE-6293 (manufactured by Polycol Kogyo Co., Ltd.).

Specific examples of the carbon black light-shielding pigment include TET01337 (manufactured by Toyo Color Co., Ltd.) and EPH-K-15680 (manufactured by Polycol Kogyo Co., Ltd.).

Specific examples of the iron oxide-based light-shielding pigment include EPH-C-1045 (manufactured by Polycol Kogyo Co., Ltd.) and TET68473 (manufactured by Toyo Color Co., Ltd.).

Specific examples of the ultramarine light-shielding pigment include EPH-B-466662 (manufactured by Polycol Kogyo Co., Ltd.) and TET26146 (manufactured by Toyo Color Co., Ltd.).

Specific examples of the titanium oxide-based light-shielding pigment include EB-1427 (manufactured by DIC Corporation), EPH-H-2481 (manufactured by Polycol Kogyo Co., Ltd.) and TET28318 (manufactured by Toyo Color Co., Ltd.). Can be mentioned.

Specific examples of the light-shielding pigment and the blending amount include an example in which the light-shielding pigment is added in the range of 2 to 5% by mass.
When using these light-shielding pigments, it is preferable to avoid pigments having poor dispersibility and pigments that promote oxidative deterioration of the container.

In the present invention, after determining the types of the high-density polyethylene resin forming the outer layer and the light-shielding pigment, the blending amount of the light-shielding pigment is tested in advance, and the transmittance of visible light having a wavelength of 500 to 800 nm is 1. % Or less, and it is preferable to determine so that the ultraviolet transmittance at a wavelength of 200 to 400 nm is 1% or less.

It is preferable that the outer layer used in the present invention contains a predetermined amount of at least one antioxidant selected from the group consisting of phenol-based, phosphorus-based, and sulfer-based antioxidants.
The phenol-based antioxidant, the phosphorus-based antioxidant, and the sulfer-based antioxidant are not particularly limited as long as they have a high antioxidant effect and do not impair other properties of the outer layer.

Specific examples of the phenol-based antioxidant include ADEKA STAB AO60 manufactured by ADEKA Corporation.
Specific examples of the phosphorus-based antioxidant include ADEKA STAB 2112 manufactured by ADEKA Corporation.
Specific examples of the sulfa-based antioxidant include DSTP manufactured by Yoshitomi Mitsubishi Chemical Corporation.

These antioxidants are preferably blended in an amount of 0.05 to 0.30% by mass, more preferably 0.10 to 0.25% by mass, based on the high-density polyethylene resin forming the outer layer. .. 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 be bleeded out on the surface of the container.

The outer layer used in the present invention contains a light-shielding pigment, an antioxidant, etc. that can be impure fine particles. However, since the outer layer is separated from the inner layer, which is the liquid contact surface, these light-shielding pigments, antioxidants, etc. Since the inner layer and the like prevent the impure fine particles caused by the above from leaching into the content liquid, they do not leached into the chemicals stored in the container.

As the high-density polyethylene resin used in the present invention, as described above, the density (measurement method: JIS K7112) is preferably 940 to 962 kg / m ³ , more preferably 944 to 946 kg / m ³ , and the weight average molecular weight (measurement method). : Described later) is preferably 220,000 to 260,000, more preferably 240,000 to 260,000, molecular weight distribution (Mw / Mn) (measurement method: described later) is preferably 12 or less, further preferably 11 or less, and melt tension (measurement). Method: Measured at 210 ° C. using a capillograph manufactured by Nippon Polyethylene Method, Toyo Seiki Seisakusho, orifice L: 8 mm, D: 2.095 mm, piston descent speed 10 mm / min, winding speed 3.9 mm / min) is preferably 20. ~ 30 g, more preferably 22 to 26 g, HL-MFR conforms to JIS K7210, measured at 190 ° C. and 21.6 kg load, and the result is expressed in (g / 10 min), preferably 5 to 7. More preferably, a high-density polyethylene resin having a value of 5.5 to 6.5 is preferable, and by using this high-density polyethylene resin for the outer layer, moldability, mechanical strength, etc. are improved, and problems such as drawdown are eliminated. Yield is also improved.

Since the molecular weight distribution (Mw / Mn) of the high-density polyethylene resin forming the outer layer is as narrow as 12 or less, the outer layer of the blow-molded laminated container that has been multi-layered under the normal molding conditions of melt processing and rapid cooling is dense. Since it is composed of small crystal aggregates, the mechanical strength is improved.

The (Mw / Mn) of the high-density polyethylene resin forming the outer layer is preferably 12 or less, more preferably 11 or less, and when (Mw / Mn) exceeds 12, it is melt-processed and rapidly cooled, which is a normal molding processing condition. The crystals in the outer layer of the blow-molded laminated container molded in multiple layers may become large or scattered and may not be composed of dense small crystal aggregates, resulting in insufficient mechanical strength.

If the weight average molecular weight of the high-density polyethylene resin forming the outer layer is less than 220,000, the mechanical strength may be insufficient, and if the weight average molecular weight exceeds 260,000, the melt viscosity of the resin is high and the moldability deteriorates. However, molecular breakage due to shear stress may occur.

If the density and melt tension of the high-density polyethylene resin that forms the outer layer are less than the lower limit, drawdown may occur and it may be difficult to control the wall thickness. On the other hand, if the upper limit is exceeded, melt fracture (rough skin) may occur on the bottle surface. May cause problems.
If the HL-MFR (190 ° C., 21.6 kg load g / 10 min) of the high-density polyethylene resin forming the outer layer is less than 5, the processing characteristics may deteriorate and the problem of melt fracture (rough skin) may occur on the outer surface of the bottle. Yes, if it exceeds 7, there is a risk that drawdown cannot be prevented.

The high-density polyethylene resin used for the outer layer is a homopolymer or copolymer containing at least one selected from ethylene, propylene, butene-1, 4-methyl-pentene-1, hexene-1, and octene-1. Yes, a commercially available product having the above characteristics can be used. Of these, ethylene homopolymers and copolymers of ethylene with α-olefins such as propylene, butene-1, 4-methyl-pentene-1, hexene-1, and octene-1 are preferably used. The content of α-olefin in the copolymer is preferably 15% by mass or less. The polymerization method is not particularly limited as long as a polymer or copolymer having the above characteristics such as a density of 940 to 962 kg / m ³ can be obtained, and for example, either a low pressure method or a medium pressure method may be used. ..

By containing the high-density polyethylene resin having the above-mentioned characteristics and a predetermined amount of light-shielding pigment in the outer layer, the transmittance of visible light having a wavelength of 500 to 800 nm is 1% or less without impairing the cleanliness, and the wavelength is Since the ultraviolet transmittance of 200 to 400 nm can be achieved at 1% or less, the visibility of the contents is lost, and the contained liquid can be provided with an ultraviolet blocking property that can prevent deterioration of the contained liquid. For example, ultraviolet rays such as a photoresist liquid can be provided. It can also be used as a container for ultra-high-purity chemicals such as chemicals and fragrances that change in quality and harden, and at least one antioxidant selected from the group consisting of phenol-based, phosphorus-based, and sulfer-based antioxidants 0 By containing at least .05 to 0.30% by mass, it is possible to prevent the resin from being burnt and to prevent deterioration of the appearance due to the burnt resin.

In the present invention, a light-resistant stabilizer such as a benzotriazole-based light-resistant stabilizer or a triazine-based light-resistant stabilizer can be appropriately used together with the light-shielding pigment, if necessary.
By using a benzotriazole-based light-resistant stabilizer or a triazine-based light-resistant stabilizer, UV-B (200 to 320 nm) and UV-A (320 to 400 nm) can be blocked, respectively, and by using both in a specific amount, other characteristics can be obtained. The UV blocking property can be remarkably improved without impairing.

Examples of the light-resistant stabilizer include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, and 2- (2). -Hydroxy-5-methylphenylbenzotriazole), 2- (5-chloro-2-benzotriazole) -6-t-butyl-cresol, 2- (3,5-di-t-amino-2-hydroxyphenyl) Bendotriazole-based light-resistant stabilizers such as bendtriazole, 2- (2H-benzotriazole-2-yl) -p-cresol, 2- [4,6-di (2,4 xsilyl) -1,3,5-triazine -2-yl] -5,2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine, 2- (4,6-diphenyl-1,3) , 5-Triazine-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] Triazine-based light-resistant stabilizers such as phenol, bis (2,2,6,6-tetramethyl-4-piperidine) ) Sevacate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-) 4-Piperidyl) imino} hexamethylene (2,2,6,6-tetramethyl-4-piperidyl) imino}] hindered amine-based light-resistant stabilizers can be mentioned.

The content of the additive contained in the resin is a value obtained by separating and quantifying the extract extracted by a Soxhlet extractor for 8 hours using tetrahydrofuran (THF) by liquid chromatography. The measurement conditions are as follows: the device is GULLIVER (manufactured by JASCO Corporation), the column is Finepak GEL 101 (manufactured by JASCO Corporation), the solvent is THF, and the detectors are UV-970 (manufactured by JASCO Corporation) and 830-RI. (Manufactured by JASCO Corporation).

The method for measuring the molecular weight of the resin in the container is to dissolve the resin composition cut out from the container in a solvent (orthodichlorobenzene) to prepare a sample solution, and measure the molecular weight and the molecular weight distribution with GPC. The weight average molecular weight and the number average molecular weight are calculated by the following formulas.
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 the molecular weight and w is the weight fraction.

The measurement conditions for GPC are: the device is 150 CV (manufactured by Waters), the column is TSKgel GMH-HT (manufactured by Tosoh Corporation), the solvent is orthodichlorobenzene, the temperature is 138 ° C, and the detector is a differential refractometer. .. In order to control the molecular weight distribution of the container within the above range, the raw material resin must also have a molecular weight distribution within a certain range.

The molding method is not particularly limited as long as it can mold the highly transparent chemical-resistant blow-molded laminated container of the present invention by the blow-molding method. It can also be used by selecting from a molding machine.

It should be noted that the description of the above-described embodiment is for explaining the present invention, and does not limit or reduce the scope of the invention described in the claims. Further, the configuration of each part of the present invention is not limited to the above embodiment, and various modifications can be made within the technical scope described in the claims.

Next, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples as long as it does not deviate from the gist of the present invention.

(Example 1)
As an inner layer, high-density polyethylene resin (HL-MFR 8 g / 10 min, density 956 kg / m ³ , weight average molecular weight 190,000, (Mw / Mn) 11, component 0.2 mass% with molecular weight 1,000 or less, neutralizer, oxidation No inhibitor or light-resistant stabilizer was intentionally added, 0.005% by mass or less, cleanliness of 5 pieces / ml or less measured by the measurement method described later, 09D01A manufactured by Toso Co., Ltd.) was used. (Ethethylene-vinyl alcohol copolymer resin F171B: manufactured by Kuraray Co., Ltd.) is used as the barrier resin, and maleic anhydride-modified polyolefin resin (Nippon Polyethylene Co., Ltd.) is used as the adhesive layer having an adhesive function between the inner layer and the barrier resin. FT71A) is used, and a mixture obtained by mixing equal amounts of the inner layer, the barrier resin, the adhesive layer, and the recovered material from the outermost layer below is used as the recovery layer, and the barrier layer made of the barrier resin and the recovery layer are adhered to each other. The maleic anhydride-modified polyolefin resin (FT71A, Nippon Polyethylene Co., Ltd.) is used as the adhesive layer having a function, and the high-density polyethylene resin (Nippon Polyethylene (Nippon Polyethylene)) is used as the outermost layer having an adhesive function with the recovery layer above the recovery layer. HB111R, HL-MFR 6g / 10min, density 946Kg / m ³ , weight average molecular weight 250,000, (Mw / Mn) 11, melt tension 25g) and phthalocyanine-based light-shielding pigment (trade name: 7F2854: Dainichi Seika Kogyo Co., Ltd.) 2% by mass (manufactured by ADEKA Co., Ltd.), phenolic antioxidant (trade name: Adecastab AO60: manufactured by ADEKA Co., Ltd.) and phosphorus-based antioxidant (trade name: Adecaster 2112: manufactured by ADEKA Co., Ltd.) A high-density polyethylene resin to which a total of 0.2% by mass was added was used.

There is no problem such as drawdown under the following molding conditions, and the injection-molded laminated container of the present invention consisting of 6 layers (mass 330 g, inner layer 300 μm, adhesive layer 50 μm, barrier resin layer 50 μm, adhesive layer 50 μm, recovery layer 550 μm, outer layer 1,000 μm, total wall thickness 2,000 μm, capacity 3,750 ml) were molded.

(Molding condition)
A blow molding machine (6 types, 6 layers manufactured by Blends Co., Ltd.) (a type in which 6 types of extruders are used and one die head is used to stack 6 types) was used.
High-density polyethylene resin for the inner layer: Screw diameter 40 mmΦ Set temperature: 200 ° C
Maleic anhydride-modified polyolefin resin layer of adhesive layer: Screw diameter 20 mmΦ Set temperature: 210 ° C
Ethylene-vinyl alcohol copolymer resin layer: screw diameter 20 mmΦ Set temperature: 230 ° C
Maleic anhydride-modified polyolefin resin layer of adhesive layer: Screw diameter 20 mmΦ Set temperature: 210 ° C
Recovery layer: Screw diameter 40 mmΦ Set temperature: 210 ° C
High-density polyethylene resin for outer layer: Screw diameter 50 mmΦ Set temperature: 210 ° C
Die head temperature: Set temperature: 220 ° C
The hygroscopic barrier resin used was dried at 80 ° C. using a dryer to remove water.

(Comparative Example 1)
An additive-free fluororesin (RP-5000 manufactured by Daikin Industries, Ltd.) with an MFR of 25 g / 10 min, a specific gravity of 1.74, and a melting point of 195 ° C. is used as the inner layer, and the additive free has an adhesive function with the fluororesin. A special polyamide resin (Dyamide Z4887 Natural manufactured by Daicel Ebony Co., Ltd., barrier-cum-adhesive resin, relative viscosity 1.87) is used, and a barrier-resin (ethylene-vinyl alcohol copolymer resin F171B: Clare Co., Ltd.) is used. Made of maleic anhydride-modified polyolefin resin (FT71A, Nippon Polyethylene Co., Ltd.) having a function of adhering to a special polyamide resin and a saponification rate of 99.99%), and the barrier resin and the fluororesin and the above. The outermost layer used to compensate for the decrease in melt tension of the polyamide resin, dissazoiero-0.025% by mass and azoiero-0.007% by mass as pigments, and sodium bis (4-thibutylphenyl) phosphee as a nucleating agent. -To (trade name: Adecasterve NA11) is 1.5% by mass, benzotriazol-based (UVA) is 0.1% by mass of LA32 manufactured by ADEKA Co., Ltd. as a light-resistant stabilizer, and ADEKA is triazine-based (UVB). High-density polyethylene resin containing 0.1% by mass of LA-F70 manufactured by Nippon Polyethylene Co., Ltd. (HB111R manufactured by Nippon Polyethylene Co., Ltd.) (HL-MFR (measurement method: JIS K7112) 6 g / 10 min, density 946 Kg / m ³ , weight Using maleic anhydride-modified polyolefin resin (FT71A, Nippon Polyethylene Co., Ltd.), which has an adhesive function with an average molecular weight of 250,000 and a melt tension of 25 g), there are no problems such as drawdown under the following molding conditions, and it consists of 6 layers. Chemical resistant blow-molded laminated container with excellent transparency for comparison (total mass 400 g, inner layer 100 μm, barrier-cum-adhesive resin layer 40 μm, adhesive layer 40 μm, barrier layer 40 μm, adhesive layer 40 μm, outer layer 1540 μm, average The total wall thickness was 1.8 mm and the capacity was 3,750 CC).

(Molding condition)
A blow molding machine (6 types, 6 layers manufactured by Blends Co., Ltd.) (a type in which 6 types of extruders are used and one die head is used to stack 6 types) was used.
Fluororesin in the inner layer: Screw diameter 40 mmΦ Set temperature: 240 ° C
Special polyamide resin layer: screw diameter 20 mmΦ Set temperature: 260 ° C
Maleic anhydride-modified polyolefin resin layer: Screw diameter 20 mmΦ Set temperature: 240 ° C
Ethylene-vinyl alcohol copolymer resin layer: screw diameter 20 mmΦ Set temperature: 230 ° C
Maleic anhydride-modified polyolefin resin layer: Screw diameter 40 mmΦ Set temperature: 220 ° C
Ultra-high molecular weight high-density polyethylene resin in the outer layer: Screw diameter 50 mmΦ Set temperature: 210 ° C
Die head temperature: Set temperature: 220 ° C
As the hygroscopic special polyamide resin and the barrier resin, those dried at 80 ° using a dryer to remove water were used.

For each of the 10 blow-formed laminated containers of Example 1 and Comparative Example 1 of the present invention thus obtained, cleanliness, ultraviolet transmittance, visible light transmittance, oxygen transmittance, and drop strength were obtained by the following test methods. And various fragrance storage stability was measured, and a comprehensive judgment was made by comprehensively comparing the results of cleanliness, ultraviolet transmittance, visible light transmittance, oxygen transmittance, average drop intensity and various fragrance storage stability.

A blow-molded container having the same thickness as the outer layer made of only the same high-density polyethylene resin as the outer layer was prepared, and the visible light transmittance and the oxygen transmittance were measured by the following test method.
For the cleanliness of the high-density polyethylene resin used for the inner layer, a blow-molded container having the same thickness as that of Example 1 was molded using only the high-density polyethylene resin used for the inner layer, and cleaned by the test method described later. The degree (number / ml) was measured.

(Test method)
Cleanliness (number / ml):
1. 1. Measuring device: A particle counter "KL-26" manufactured by Rion Co., Ltd. is used.
2. 2. Measurement sample: Fill the container with ultrapure water at a nominal capacity of 80%, lay it on its side, roll it forward one turn with a mill, roll it backward one turn, and then return it to its original position for 30 cycles. The measurement sample is taken from the container after being stationary for a minute.
3. 3. 10 ml of ultrapure water as a measurement sample is injected into a particle counter from a container, and the number of particles of 0.2 μm or more is measured. This operation is repeated twice to obtain the average value (B) of the number of particles of 0.2 μm or more.
4. The particle value in 1 ml is calculated from the measured value by the following formula.
(B (pieces)) ÷ 10 ml = pieces / ml
Conventionally, it has been considered that the quality and yield of semiconductors and liquid crystals can be improved when the cleanliness is less than 500 pieces / ml. However, it is becoming more severe now, and there are many cases where 5 pieces / ml or less is required.

Oxygen permeability (ml / 1 container)
The container was measured according to JIS K7126-2, and oxygen permeation from the outside to the inside of the container was measured using an OX-TRAN2 / 21) (manufactured by MOCON) measuring device. Temperature and humidity: outside: 1 atm, 23 ° C, 50% RH air, inside 23 ° C, dry nitrogen.

UV transmittance:
Cut the smooth part of the container into 4 cm squares and apply ultraviolet rays to the outer layer side for measurement. The measuring instrument used was JASCO Corporation V-670, and the measurement was performed in the range of 200 to 400 nm at a scanning speed of 400 nm / min.

Visible Light Transmittance,
Cut the smooth part of the container into 4 cm squares and apply visible light to the outer layer side for measurement. The measuring instrument used was JASCO Corporation V-670, and the measurement was performed in the range of 400 to 800 nm at a scanning speed of 400 nm / min.

Drop strength (1.2m height):
Fill the container with 80% of its capacity, drop it from a height of 1.2 m onto the concrete surface 5 times with the bottom of the container down, and drop it once with the side of the container down, and visually judge cracks and leaks. To do.

Various fragrance storage stability:
Examples of typical fragrances are 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%). Dimethylsulfide, propylene glycol solution, manufactured by Hasegawa Fragrance Co., Ltd.), acid (butyric acid: trade name: acids, purity 96.4%, manufactured by Hasegawa Fragrance Co., Ltd.), rice salad (trade name: rice oil, manufactured by Hasegawa Fragrance Co., Ltd.) ), Ethylbutyrate (trade name: esters, 100% purity, manufactured by Hasegawa Fragrance Co., Ltd.), Trans-2-hexenal (trade name: aldehydes, purity 99.7%, manufactured by Hasegawa Fragrance Co., Ltd.) ), 1 kg of each fragrance was filled and sealed, and left at room temperature and normal pressure for 1 month and 3 months. However, only crab oil (15% dimethyl sulfide, propylene glycol solution) was refrigerated for 1 month and 3 months at normal temperature and pressure.
After leaving for 3 months, for each sample, measure the container mass to check if the contents are dissipated, perform a sensory test with 10 panel members to check if it has deteriorated, and determine the specific gravity and refractive index. It was measured and checked for fluctuations, and for analyzable samples, the components were checked by 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.
Δ: Slightly inferior to ○, but practically highly stable in storage and marketable with virtually no dissipation, alteration, or fluctuation.
×: Storage stability is low due to dissipation, alteration, fluctuation, etc., and there is no marketability.

(Comparative Example 2)
For comparison, a transparent glass bottle (manufactured by Fuji Film Electronics Materials Co., Ltd., capacity 2,500 ml) was used, and the cleanliness, ultraviolet transmittance, and visible light transmittance were measured by the above test method in the same manner as in Example 1. , Oxygen permeability, drop strength and storage stability of various fragrances were measured, and these results were combined to make a comprehensive judgment.
Table 1 shows the test results of various fragrance storage stability together with the test results of Example 1 and Comparative Example 1.

(Comparative Example 3)
For comparison, a sealer bottle (trade name: manufactured by Hokuo Acid Co., Ltd., capacity 1000 ml, plastic container), which is currently widely used as a fragrance container, is used and cleaned by the above test method in the same manner as in Example 1. The degree, ultraviolet transmittance, visible light transmittance, oxygen transmittance, drop intensity and storage stability of various fragrances were measured, and a comprehensive judgment was made by integrating these results.
The test results of various fragrance storage stability are shown in Table 1 together with the test results of Example 1 and Comparative Examples 1 and 2.

The blow-molded laminated container of Comparative Example 1 uses an expensive resin such as a fluororesin and a special polyamide resin that does not contain additives such as additives and lubricants as a barrier / adhesive resin layer, and also uses a high-density polyethylene resin as an outer layer. A predetermined amount of an expensive nucleating agent is added to impart transparency to the resin, that is, to increase the transmittance of visible light having a wavelength of 500 to 800 nm to 35% or more, and to transmit ultraviolet rays having a wavelength of 200 to 400 nm. Since a predetermined amount of an expensive light-resistant stabilizer is added to reduce the rate to 1% or less, the cost increases and the economic efficiency is inferior.

On the other hand, the blow-molded laminated container of Example 1 of the present invention does not use an expensive fluororesin and a special polyamide resin that does not contain additives such as additives and lubricants as a barrier / adhesive resin layer. Moreover, since no expensive nucleating agent or light-resistant stabilizer is added, the cost is about half that of the blow-molded laminated container of Comparative Example 1, which is economical. Very good.
From Table 1, the blow-molded laminated container of Example 1 of the present invention is slightly inferior in aroma retention to the blow-molded laminated container of Comparative Example 1 and the glass bottle of Comparative Example 2, but in practical use. It can be used without any problems, and compared to the plastic container (sealer bottle) of Comparative Example 3, which is currently widely used as a fragrance container, the fragrance retention property is greatly improved and the marketability is very high. It turns out that it is expensive.

Comprehensive judgment criteria:
The cleanliness, ultraviolet transmittance, visible light transmittance, oxygen transmittance, drop intensity, and storage stability of various fragrances are comprehensively judged.
◯: Highly marketable as a blow-molded laminated container for ultra-high purity chemicals in which the contained content liquid cannot be visually confirmed from the outside.
Δ: Slightly inferior to ○, but it is marketable as a blow-molded laminated container for ultra-high purity chemicals in which the contained content liquid cannot be visually confirmed from the outside.
X: There is no marketability as a blow-molded laminated container for ultra-high purity chemicals in which the contained content liquid cannot be visually confirmed from the outside.

(Measurement result and comprehensive judgment) of (Example 1)
Cleanliness: 1.9 pieces / ml
Ultraviolet transmittance: 0.1% or less Visible light transmittance: 0.1% or less Oxygen transmittance: 0.01 (ml / 1 container) or less Drop strength: No cracks Various fragrance storage stability: ○
Comprehensive judgment: ○
Ultraviolet transmittance of the outer layer: 0.1% or less Visible light transmittance of the outer layer: 0.1% or less Further, the blow-formed laminated container of Example 1 is filled with ultrapure water and kept at room temperature for one month. After leaving it in a pressure clean room, the degree of cleanliness was measured in the same manner. The measurement result was cleanliness: 1.5 pieces / ml.

(Comparative Example 1) (Measurement result and comprehensive judgment)
Cleanliness: 0.5 pieces / ml
Ultraviolet transmittance: 0.1% or less Visible light transmittance: 45%
Oxygen permeability: 0.01 (ml / 1 container) or less Drop strength: No cracks Storage stability of various fragrances: ○
Comprehensive judgment: ×
Ultraviolet transmittance of outer layer: 0.1% or less Visible light transmittance of outer layer: 45%

(Comparative Example 2) (Measurement result and comprehensive judgment)
Cleanliness: 4.5 pieces / ml
UV transmittance: 3%
Visible light transmittance: 50%
Oxygen permeability: 0.01 (ml / 1 container) or less Drop strength: Various cracked fragrances Storage stability: ○
Comprehensive judgment: ×

(Comparative Example 3) (Measurement Results and Comprehensive Judgment)
Cleanliness: 58 pieces / ml
UV transmittance: 1%
Visible light transmittance: 15%
Oxygen permeability: 0.180 (ml / 1 container)
Drop strength: No cracks Storage stability of various fragrances: ×
Comprehensive judgment: ×

As a result of the above, the containers of Comparative Examples 1 to 3 are inferior in any respects including economic efficiency, and are not marketable as containers for ultra-high purity chemicals in which the contained content liquid cannot be visually confirmed from the outside. On the other hand, it was found that the blow-molded laminated container of Example 1 was excellent in all respects as a blow-molded laminated container for ultra-high purity chemicals having no visibility of the contents and was highly marketable.

(Example 2)
High density polyethylene resin (HL-MFR 8g / 10min, density 957Kg / m ³ , weight average molecular weight 190,000, (Mw / Mn) 12, component 0.4% by mass with molecular weight 1,000 or less, neutralizer, oxidation as inner layer The same as in Example 1 except that the inhibitor and the light-resistant stabilizer were not intentionally added, 0.005% by mass or less, the cleanliness was 5 pieces / ml or less, and Toso Co., Ltd. 09D01C) was used. The blow-molded laminated container of the present invention consisting of 6 layers (mass 330 g, inner layer 300 μm, adhesive layer 50 μm, barrier resin layer 50 μm, adhesive layer 50 μm, recovery layer 550 μm, outer layer 1,000 μm) without problems such as drawdown. , Total wall thickness 2,000 μm, capacity 3,750 ml), and in the same manner as in Example 1, cleanliness, ultraviolet transmission rate, visible light transmission rate, oxygen transmission rate, drop strength, and storage stability of various fragrances were obtained. It was measured.
The measurement results and comprehensive judgment are shown below.

(Measurement result and comprehensive judgment) of (Example 2)
Cleanliness: 4.9 pieces / ml
Ultraviolet transmittance: 0.1% or less Visible light transmittance: 0.1% or less Oxygen transmittance: 0.01 (ml / 1 container) or less Drop strength: No cracks Various fragrance storage stability: ○
Comprehensive judgment: ○
Ultraviolet transmittance of outer layer: 0.1% or less Visible light transmittance of outer layer: 0.1% or less

(Example 3)
High density polyethylene resin (HL-MFR 8g / 10min, density 958Kg / m ³ , weight average molecular weight 200,000, (Mw / Mn) 12, 0.2% by mass of components with molecular weight of 1,000 or less, neutralizer, oxidation as inner layer The same as in Example 1 except that an inhibitor and a light-resistant stabilizer were not intentionally added, 0.005% by mass or less, a cleanliness of 5 pieces / ml or less, and 13D01A manufactured by Toso Co., Ltd. was used. The blow-molded laminated container of the present invention consisting of 6 layers (mass 330 g, inner layer 300 μm, adhesive layer 50 μm, barrier resin layer 50 μm, adhesive layer 50 μm, recovery layer 550 μm, outer layer 1,000 μm) without problems such as drawdown. , Total wall thickness 2,000 μm, capacity 3,750 ml), and in the same manner as in Example 1, cleanliness, ultraviolet transmission rate, visible light transmission rate, oxygen transmission rate, drop strength, and storage stability of various fragrances were obtained. It was measured.
The measurement results and comprehensive judgment are shown below.

(Measurement result and comprehensive judgment) of (Example 3)
Cleanliness: 1.0 pieces / ml
Ultraviolet transmittance: 0.1% or less Visible light transmittance: 0.1% or less Oxygen transmittance: 0.01 (ml / 1 container) or less Drop strength: No cracks Various fragrance storage stability: ○
Comprehensive judgment: ○
Ultraviolet transmittance of outer layer: 0.1% or less Visible light transmittance of outer layer: 0.1% or less

(Comparative Example 4)
High density polyethylene resin (HL-MFR 7g / 10min, density 957Kg / m ³ , weight average molecular weight 190,000, (Mw / Mn) 12, component 0.9% by mass with molecular weight 1,000 or less, neutralizer, oxidation as inner layer The same as in Example 1 except that an inhibitor and a light-resistant stabilizer were not intentionally added, 0.005% by mass or less, a cleanliness of 10 pieces / ml, and 8D01A manufactured by Toso Co., Ltd. was used. , Drawdown and other problems, 6-layer blow-molded laminated container (mass 330 g, inner layer 300 μm, adhesive layer 50 μm, barrier resin layer 50 μm, adhesive layer 50 μm, recovery layer 550 μm, outer layer 1,000 μm , Total wall thickness 2,000 μm, capacity 3,750 ml), and in the same manner as in Example 1, cleanliness, ultraviolet transmission rate, visible light transmission rate, oxygen transmission rate, drop strength, and storage stability of various fragrances were obtained. It was measured.
The measurement results and comprehensive judgment are shown below.

(Comparative Example 4) (Measurement result and comprehensive judgment)
Cleanliness: 11 pieces / ml
Ultraviolet transmittance: 0.1% or less Visible light transmittance: 0.1% or less Oxygen transmittance: 0.01 (ml / 1 container) or less Drop strength: No cracks Various fragrance storage stability: ○
Comprehensive judgment: ×
Ultraviolet transmittance of outer layer: 0.1% or less Visible light transmittance of outer layer: 0.1% or less

(Comparative Example 5)
High-density polyethylene resin as the inner layer (according to JIS K7210, measured at a measurement temperature of 190 ° C. and a load of 2.16 kg, MFR expressed in (g / 10 min) is 0.35 g / 10 min, density 958 kg / m ³ , Weight average molecular weight 150,000, (Mw / Mn) 11, 1.5% by mass of components having a molecular weight of 1,000 or less, neutralizing agent, antioxidant, light-resistant stabilizer were not intentionally added, and 0. Similar to Example 1 except that 005% by mass or less, cleanliness of 20 pieces / ml, and 8022) manufactured by Toso Co., Ltd. were used, there was no problem such as drawdown, and a blowing for comparison consisting of 6 layers. A built-in laminated container (mass 330 g, inner layer 300 μm, adhesive layer 50 μm, barrier resin layer 50 μm, adhesive layer 50 μm, recovery layer 550 μm, outer layer 1,000 μm, total wall thickness 2,000 μm, capacity 3,750 ml) is molded and carried out. In the same manner as in Example 1, the cleanliness, ultraviolet ray transmission rate, visible light transmission rate, oxygen transmission rate, drop intensity and storage stability of various fragrances were measured.
The measurement results and comprehensive judgment are shown below.

(Comparative Example 5) (Measurement result and comprehensive judgment)
Cleanliness: 25 pieces / ml
Ultraviolet transmittance: 0.1% or less Visible light transmittance: 0.1% or less Oxygen transmittance: 0.01 (ml / 1 container) or less Drop strength: No cracks Various fragrance storage stability: ○
Comprehensive judgment: ×
Ultraviolet transmittance of outer layer: 0.1% or less Visible light transmittance of outer layer: 0.1% or less

(Comparative Example 6)
High-density polyethylene resin as the inner layer (according to JIS K7210, measured at a measurement temperature of 190 ° C. and a load of 2.16 kg, MFR expressed in (g / 10 min) is 0.30 g / 10 min, density 957 kg / m ³ , Weight average molecular weight 150,000, (Mw / Mn) 16, 2.0% by mass of components having a molecular weight of 1,000 or less, neutralizing agent, antioxidant, and light-resistant stabilizer were not intentionally added, and 0. Similar to Example 1 except that 005% by mass or less, cleanliness of 30 pieces / ml, and HB534N manufactured by Nippon Polyethylene Co., Ltd. were used, there was no problem such as drawdown, and the comparison consisted of 6 layers. A blow-molded laminated container (mass 330 g, inner layer 300 μm, adhesive layer 50 μm, barrier resin layer 50 μm, adhesive layer 50 μm, recovery layer 550 μm, outer layer 1,000 μm, total wall thickness 2,000 μm, capacity 3,750 ml) was molded. In the same manner as in Example 1, the cleanliness, ultraviolet transmittance, visible light transmittance, oxygen transmission, drop intensity and storage stability of various fragrances were measured.
The measurement results and comprehensive judgment are shown below.

(Comparative Example 6) (Measurement result and comprehensive judgment)
Cleanliness: 31 pieces / ml
Ultraviolet transmittance: 0.1% or less Visible light transmittance: 0.1% or less Oxygen transmittance: 0.01 (ml / 1 container) or less Drop strength: No cracks Various fragrance storage stability: ○
Comprehensive judgment: ×
Ultraviolet transmittance of outer layer: 0.1% or less Visible light transmittance of outer layer: 0.1% or less

Table 2 summarizes the measurement results of the inner and outer layers, the measurement results of the containers, and the comprehensive judgment results, such as the layer structure of the containers of Examples 1 to 3 and Comparative Examples 1 to 6, and the characteristics of each layer and the container. ..
○ in Table 2 indicates that the characteristics or layer structure are within the range of the present invention, and the measurement results and the comprehensive judgment results are excellent. It indicates that it deviates, and that the measurement result and the comprehensive judgment result are inferior, and-indicates that it does not have the above-mentioned layer structure.
In Table 2, MW represents a weight average molecular weight, Mw / Mn represents a molecular weight distribution, HL-MFR represents a HiLoad-Melt Flow Rate, and UV represents an ultraviolet ray.

As described above, the containers of Comparative Examples 1 to 3 are inferior in any respects including economic efficiency, and are not marketable as containers for ultra-high purity chemicals in which the contained content liquid cannot be visually confirmed from the outside. Since the cleanliness of the blow-molded laminated containers of Comparative Examples 4 to 6 greatly exceeds 5 pieces / ml, it may not be marketable as a blow-molded laminated container for ultra-high purity chemicals. understood.

On the other hand, the blow-formed laminated containers for ultra-high-purity chemicals having no visibility of the contents of the present invention of Examples 1 to 3 have a low cleanliness of 5 pieces / ml or less, and are therefore stored and stored. Very little leaching of impure particles from the container side into ultra-high-purity chemicals and various fragrances, excellent drop strength, excellent chemical resistance and mechanical strength, etc. As a container for ultra-high-purity chemicals that can prevent UV rays, has excellent oxygen barrier properties and antioxidant properties, has excellent storage stability for various fragrances, and contains many expensive and dangerous chemical substances. It can be seen that it is highly marketable because it can be sufficiently handled, and it is low in cost and excellent in economic efficiency.

The blow-formed laminated container for ultra-high purity chemicals, which has no visibility of the contents of the present invention, is excellent in chemical resistance, mechanical strength, etc. by using a specific high-density polyolefin resin for the inner layer, and has a molecular weight of 1. Since the components of 000 or less are 0.4% by mass or less and the molecular weight distribution (Mw / Mn) is as narrow as 12 or less, the cleanliness of the inner layer itself is surely 5 pieces / ml or less, for example, adjacent to each other. Even if there are impure fine particles that migrate from the layer, the inner layer can prevent them from seeping into the content liquid, so the cleanliness of the container can be maintained at 5 pieces / ml or less, and the ethylene vinyl alcohol copolymer resin with excellent oxygen barrier properties. The oxygen barrier property can be improved by providing a barrier layer made of the above, and by providing an outer layer containing a predetermined amount of a light-shielding pigment, the transmittance of visible light having a wavelength of 500 to 800 nm is 1% or less, and the wavelength is 200 to 400 nm. Since the ultraviolet transmittance can be achieved at 1% or less, the visibility of the contents is lost and the contained liquid can be provided with an ultraviolet blocking property that can prevent deterioration of the contained liquid. As a result, the leaching of impure particles from the container side into the ultra-high-purity chemicals and various fragrances that are stored and stored is extremely small, a cleanliness of 5 particles / ml or less can be achieved, and resistance is achieved. It has excellent chemical properties and mechanical strength, is excellent in UV blocking property, oxygen barrier property and antioxidant property that can prevent deterioration of the contained content liquid, is excellent in storage stability of various fragrances, and is expensive and dangerous. It can be used as a container for ultra-high-purity chemicals and various fragrances with many high chemical substances, can be used safely and securely, is easy on the environment, contributes to environmental and health problems, and is inexpensive and economical. Because it has a remarkable effect, it has a very high industrial utility value.

1 inner second adhesive layer 3 barrier layer 4 adhesive layer 5 outer layer 6,6 ^'ultra-high purity chemicals for blow molding the laminated container 7 ultra high purity chemicals 8 collection layer is not visibility of product content

Claims (3)

An ultra-high-purity chemical blow-molded laminated container in which the following inner layer, an oxygen barrier layer containing a polyvinyl alcohol resin, and an outer layer containing a light-shielding pigment are laminated in this order from the inside to the outside of the container, and has a wavelength of 500 to. As an index showing the number of impure fine particles leached from the container side into the stored chemicals, the transmittance of visible light at 800 nm is 1% or less, the transmittance of ultraviolet rays at wavelengths of 200 to 400 nm is 1% or less. cleanness der 5 cells / ml or less of is,
The outer layer further contains a high-density polyethylene resin having the following characteristics and at least one antioxidant selected from the group consisting of phosphorus-based and sulfer-based antioxidants, and the antioxidant is used in the high density. A blow-molded laminated container for ultra-high purity chemicals, which is characterized by containing 0.05 to 0.30% by mass with respect to polyethylene resin and has no visibility of the contents.
Inner layer: High density having the following properties, consisting of 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.
(Characteristics of inner layer)
Neutralizers, antioxidants, and light-resistant stabilizers were not intentionally added, and the maximum content was 0.005% by mass or less.
Cleanliness: 5 pieces / ml or less Density: 950 to 962 kg / m ³
Weight average molecular weight: 180 to 250,000 molecular weight 1,000 or less component: 0.4% by mass or less Molecular weight distribution (Mw / Mn): 12 or less HL-MFR (190 ° C., 21.6 kg load g / 10 min): 6. 5-9.5
(Characteristics of high-density polyethylene resin contained in the outer layer)
Density: 940-962Kg / m ³
Weight average molecular weight: 220,000-260,000
Molecular weight distribution (Mw / Mn): 12 or less
Melt tension: 20 to 30 g
HL-MFR (190 ° C, 21.6 kg load g / 10 min): 5-7
Visible light transmittance with a wavelength of 500 to 800 nm is 1% or less
UV transmittance at wavelengths of 200 to 400 nm is 1% or less The blow-molded laminated container according to claim 1, wherein the inner layer and the oxygen barrier layer, and the oxygen barrier layer and the outer layer are laminated by an adhesive layer made of a maleic anhydride-modified polyolefin resin. The blow-molded laminated container according to claim 1 or 2, wherein the barrier layer is made of an ethylene vinyl alcohol copolymer resin having the following characteristics and excellent oxygen barrier properties.
(Characteristic)
MFR (210 ° C, 2.16 kg load g / 10 min): 2-5
Density (Kg / m ³ ): 1.1 to 1.3
Melting point (° C): 170-200