KR102192237B1 - Chemical-resistant blow molded laminated container with low impurity particulate elution - Google Patents

Abstract

In the present invention, the inner layer 1 (with no adhesive functional group, additive-free, heat loss 0.20 mass% or less fluororesin), inner layer 2 (having an adhesive functional group, additive-free and heating) in order from the inside of the container to the outside. Loss of 0.40% by mass or less fluororesin), barrier and adhesive resin layer (polyamide containing no additives), adhesive layer (maleic anhydride modified polyolefin resin), barrier layer (ethylene vinyl alcohol copolymer resin) and outer layer 1 (tea An ultra-high molecular weight high-density polyethylene resin containing a photosensitive pigment and a maleic anhydride-modified polyolefin resin) is laminated, and the amount of impurity fine particles eluted after storage at 23°C and 40°C for 30 days, with a visible light transmittance of 1% or less, an ultraviolet transmittance of 1% or less, and storage at 23°C and 40°C for 30 days. /Ml) is a chemical-resistant blow molded laminated container of 5 or less and 10 or less, respectively, has excellent UV protection, oxygen barrier properties, etc., less elution of impurity particles, and no visibility of the contents.

Description

Chemical-resistant blow molded laminated container with low impurity particulate elution

The present invention relates to a chemical-resistant blow molded laminated container with a small amount of elution of impure fine particles, and more particularly, excellent in chemical resistance and mechanical strength, for example, in medicines or perfumes stored at 40°C for 30 days. The elution amount (number/ml) of impurity particles is very small (10 or less), that is, it is a blow-molded (blow-molded) laminated container with good cleanliness. It has excellent UV protection and oxygen barrier properties, and can be used as an ultra-high purity chemical container. It relates to a chemical-resistant blow-molded laminated container with little elution of impurity fine particles without visibility.

In general, plastic containers such as glass containers or sealer bottles (commercially available fragrance containers), or containers in which the inner surface of a metal container is coated is used as a container for storing medicines or fragrances.

In the semiconductor field, it is necessary to be able to preserve stored high-purity chemicals while maintaining high purity. Since the container itself is heavy, the glass container is inconvenient to handle, and may be broken by dropping or the like.

On the other hand, a molded container made of a polyethylene resin is not easily cracked during handling, and has the advantage of being lightweight. However, high-purity chemicals used for etching or cleaning in semiconductor manufacturing, such as sulfuric acid, nitric acid, hydrogen peroxide, etc., and high-purity solvent-based resists or diluted solvents used for semiconductor processes and liquid crystal displays, such as methyl Alcohol, ethyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, acetone, ethyl acetate, toluene, dimethylformamide, ethylene glycol acetate, methoxypropyl acetate, butyl cellosolve, etc., and sterilization, disinfection, preparation raw materials, etc. During storage and storage of high-purity solvents, such as methyl alcohol, ethyl alcohol, isopropyl alcohol, etc., that are used for medicine, impurity particulates leach from the resin composition or additives forming the container into the stored drug ( As a result, there is a problem in that the product is taken out and the purity of the drug is impaired. For this reason, there is a problem that the quality and yield of semiconductors and liquid crystals are remarkably adversely affected, or the storage period of the drug is shortened.

While the drug is stored for a long period of time in the container, impurity fine particles are leached from the resin composition forming the container into the drug as the contents, and there is a cleanness index as an index indicating the degree to which the impurity fine particles impurity the contents.

For cleanliness, once the test container is molded, ultrapure water is stored in the test container for a certain period of time (30 days at 23°C), and there are several fine particles with a particle diameter of 0.2µm or more in 1 ml of water stored in the resin container. Calculate whether or not.

(Conventional method of measuring impurity fine particles (particles))

1. Measurement device: RION KL-26 particle counter "KL-26" manufactured by Leon Corporation is used.

2. Measurement sample: After filling the molded container with full water with ultrapure water and storing it at 23°C for 30 days, a measurement sample obtained from a container left standing in an upright state for 20 minutes is used as a measurement sample.

3. Purge the particle counter with ultrapure water before measurement, and then wash the measuring device twice with 25 ml of ultrapure water.

4. After washing, ultrapure water is poured into a particle counter of 10 ml, and the number of particles is measured. This operation is performed twice, and it is confirmed that the number of particles of 0.2 µm or more is zero (A).

5. Wash the measuring device twice with a measuring sample of 25 ml.

6. After washing, 10 ml of a container (bottle) filled with ultrapure water of the measurement specimen is poured into the particle counter, and the number of particles is measured. This operation is performed twice, and the average value (B) of the number of particles of 0.2 µm or more is obtained.

7. Calculate the particle value in 1 ml from the measured value by the following equation.

(B(pcs))÷10ml=pcs/ml

Conventionally, it has been said that if the degree of cleanliness is less than 500 pieces/ml, the quality and yield of semiconductors and liquid crystals can be improved. Nowadays, it is more stringent, and there are many cases where 5 pieces/ml or less is required by the conventional measurement method.

However, in recent years, the demand for the degree of cleanliness has increased further, and the amount of impurity fine particles having a particle diameter of 0.2 µm or more in 1 ml of ultrapure water after molding a test container and filling the test container with ultrapure water with full water and storing at 23°C for 30 days /Ml) is 5 or less, and the elution amount (number/ml) of impurity fine particles having a particle size of 0.2 µm or more in 1 ml of ultrapure water after storage at 40°C for 30 days is required to be 10 or less.

As a container used in the perfume field, fluorine-coated cans or sealer bottles on the inner surface of metal cans are used in the market, but metal cans have problems of dents or rust, and sealer bottles have problems of dents and rust, and the sealer bottle deteriorates the quality as a perfume. The problem is occurring frequently.

Therefore, the weight average molecular weight of the raw material resin made of polyethylene or ethylene-α-olefin copolymer is within a certain range, the content of the light-shielding pigment and dispersant in the resin composition is within a certain range, and the low molecular weight polymer and additive in the resin composition A container molded from a resin composition made of polyethylene or ethylene-α-olefin copolymer with a content of less than a certain weight has excellent mechanical strength, is easy to handle, and prevents leaching of impurity particles into stored chemicals. It is proposed as a light-shielding container for high-purity chemicals (refer to Patent Document 1) having very few light-shielding properties.

However, this container satisfies a clean level of less than 500 pieces/ml by the conventional measurement method, but the clean level is not less than 5 pieces/ml, and does not have oxygen barrier properties to prevent deterioration of the contained solution. There was a problem such as not.

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

However, the container for high-purity solvents of Patent Document 2 satisfies the cleanliness of less than 500 pieces/ml by the conventional measurement method, but the cleanliness does not become 5 pieces/ml or less, and it is possible to prevent deterioration of the contained solution. There is a problem in that it is also inferior in UV protection.

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

However, the container for high purity chemicals of Patent Literature 3 also satisfies the cleanliness of less than 500 pieces/ml by the conventional measuring method, and there is a problem that the cleanliness levels do not become 5 pieces/ml or less.

In addition, at least one selected from olefin polymers of ethylene, propylene, butene-1,4-methyl-pentene-1, hexene-1, or octene-1, and copolymers of ethylene and other olefins are included, , An inner layer made of a high-purity resin in which each content of a neutralizing agent, an antioxidant, and a light-resistant stabilizer is up to 0.01% by weight, an intermediate layer of a solvent barrier resin containing poly(ethylene-co-vinyl alcohol), and a light-shielding material. The outer layer of the containing resin composition is a blow-molded container, and the minimum absorbance at a wavelength of 400 nm or less of the entire layer of the container measured by a spectrophotometer is 2.0 or more, and the absorbance of the entire layer of the container is the thickness of the entire layer. A container for a high purity chemical solution (refer to Patent Document 4), characterized in that the absorption coefficient at a divided wavelength of 400 nm is 1.5 mm ^-1 or more and the absorption coefficient at a wavelength of 600 nm equal to or less than 1.5 mm ^-1 is proposed. .

However, the container for a high-purity chemical liquid of Patent Document 4 satisfies a cleanliness of less than 100 pieces/ml by a conventional measurement method, and there is a problem that the cleanliness levels do not become 5 pieces/ml or less.

First, the applicant of the present invention first, in order from the inside of the container to the outside, at least an inner layer having the following characteristics, an oxygen barrier layer containing a polyvinyl alcohol resin, and an outer layer containing a light-shielding pigment is laminated for ultra-high purity chemical blow molding As a laminated container, the transmittance of visible light at a wavelength of 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, and indicates the number of impurity fine particles leached from the container side into the stored chemical. A blow molded laminated container for ultra-high purity chemicals having no visibility of the contents having a cleanness of 5 pieces/ml or less as an index was proposed (see Patent Document 5).

Inner layer: A high-density polyolefin resin having the following properties consisting of a homopolymer or a copolymer containing at least one type selected from ethylene, propylene, butene-1,4-methyl-pentene-1, hexene-1, and octene-1.

(characteristic)

A neutralizing agent, an antioxidant, and a light-resistant stabilizer are not intentionally added, and the maximum content is 0.005% by mass or less,

Cleanliness: 5 pieces/ml or less,

Density:950∼962Kg/㎥

Weight average molecular weight: 18-250,000

A component having a molecular weight of 1,000 or less: 0.4% by mass or less

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

HL-MFR (190℃, 21.6Kg load g/10min): 6.5 to 9.5

Japanese Patent No. 28 05723 Japanese Patent No. 2749513 Japanese Patent No. 2805188 Japanese Patent No. 4167745 Japanese Patent Application No. 2015-234798 Specification

As described above, in recent years, the demand for cleanliness has become even higher, and the amount of impurity fine particles having a particle diameter of 0.2 µm or more in 1 ml of ultrapure water after molding a test container and filling the test container with full water and storing for 30 days at 23°C. It is required that the (number/ml) is 5 or less, and the elution amount (number/ml) of impure fine particles having a particle diameter of 0.2 µm or more in 1 ml of ultrapure water after storage at 40°C for 30 days is 10 or less.

The blow molded laminated container for ultra-high purity chemicals without visibility of the contents proposed by the present applicant (refer to Patent Document 5) has excellent chemical resistance and mechanical strength, and contains impurity particles in storage and storage of chemicals or perfumes. Less leaching, and the elution amount of impurity fine particles with a particle diameter of 0.2 μm or more in 1 ml of ultrapure water after storage at 23°C for 30 days (hereinafter sometimes referred to as cleanliness) (number/ml) is 5 or less, and visible light with a wavelength of 500 to 800 nm Transmittance of 1% or less, excellent visible light blocking, UV transmittance at a wavelength of 200 to 400 nm is 1% or less, excellent UV protection, and excellent oxygen barrier properties, but 1 ml of ultrapure water after storage at 40°C for 30 days There was a problem in that the elution amount (number/ml) of impurity fine particles having a particle diameter of 0.2 µm or more exceeded 10.

An object of the present invention is excellent in chemical resistance and mechanical strength, and the degree of cleanliness as an index indicating the number of impurity fine particles leached from the container side into the middle of storage and storage of ultra-high purity drugs is stored at 23°C for 30 days. It is 5 or less afterwards, and 10 or less after storage at 40°C for 30 days, has excellent oxygen barrier properties, and has a transmittance of 1% or less of visible light at a wavelength of 500 to 800 nm, and has excellent visible light blocking properties, and has a wavelength of 200 to Provides a chemical-resistant blown molded laminated container with less than 1% UV transmittance of 400 nm, excellent UV protection, and a low amount of elution of impurity fine particles without visibility of the contents, which can be used as an ultra-high purity chemical container such as fragrance or photoresist. will be.

As a result of intensive research to solve the conventional problem, for example, the inner layer 1, the inner layer 2, the barrier and adhesive resin layer, the adhesive layer, the barrier layer and the outer layer are laminated in order from the inside of the container to the outside. A chemical-resistant blow molded laminated container comprising, as the inner layer 1, having no adhesive functional group, and having adhesiveness to the fluororesin of the inner layer 2, but having no adhesiveness to the other layers, wherein an additive-free heating loss is 0.20% by mass or less. A fluororesin is used, and as the inner layer 2, a specific fluororesin having an adhesive functional group and an additive-free additive-free having adhesiveness to the fluororesin of the inner layer 1 and the barrier and adhesive resin layer is 0.40% by mass or less, By using a polyamide resin that does not contain additives that are intentionally added as a barrier and adhesive resin layer or an additive containing a lubricant, the elution amount (number/ml) of impurity fine particles after storage at 23°C for 30 days is 5 or less and 40°C. The elution amount (number/ml) of impurity fine particles after storage for 30 days at 10 or less can be achieved, and gas barrier properties can be improved by using an ethylene vinyl alcohol copolymer resin as a barrier layer, and UV blocking properties and visible light blocking properties This excellent, high-molecular-weight high-density polyethylene resin with high melt tension does not cause drawdown and improves moldability and mechanical strength.Therefore, there are many expensive and high-risk chemicals such as fragrances and photoresist solutions. It was found that a chemical-resistant blow-molded laminated container with a small amount of elution of impurity fine particles without visibility of the contents, which could cope with a container for ultra-high purity drugs, was obtained, and reached the point of achieving the present invention.

The invention of claim 1 of the present invention for solving the above problems is obtained by laminating the following inner layer 1, inner layer 2, barrier and adhesive resin layer, adhesive layer, barrier layer and outer layer 1 in order from inside to outside of the container. As a chemical-resistant blow molded laminated container, the transmittance of visible light at a wavelength of 500 to 800 nm is 1% or less, an ultraviolet transmittance at a wavelength of 200 to 400 nm is 1% or less, and the elution amount of impurity fine particles after storage at 23°C for 30 days (number/ Ml) is 5 or less, and the dissolution amount (number/ml) of impurity fine particles after storage at 40°C for 30 days is 10 or less.

Inner layer 1: It is an additive-free fluororesin, which does not have an adhesive functional group, has adhesiveness to the fluororesin of the inner layer 2 but does not have adhesiveness to other layers, and has a heating loss of 0.20% by mass or less.

Inner layer 2: It is an additive-free fluororesin, which has an adhesive functional group and has adhesiveness to the fluororesin of the inner layer 1 and the barrier and adhesive resin layer, and the heating loss is 0.40% by mass or less.

Barrier and adhesive resin layer: At least one type of polyamide selected from the group consisting of polyamides obtained by ring-opening polycondensation of caprolactam, which does not contain any additives intentionally added or additives including lubricants.

Adhesive layer: Maleic anhydride-modified polyolefin resin.

Barrier layer: It is an ethylene vinyl alcohol copolymer resin.

Outer layer 1: It contains a light-shielding pigment and a maleic anhydride-modified polyolefin resin, and is an ultra-high molecular weight high-density polyethylene resin having excellent adhesion to the barrier layer.

The invention of claim 2 of the present invention is chemical-resistant blown 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 of the container to the outside. As a molded laminated container, the transmittance of visible light at a wavelength of 500 to 800 nm is 1% or less, the transmittance of ultraviolet light at a wavelength of 200 to 400 nm is 1% or less, and the elution amount (number/ml) of impure fine particles after storage at 23° C. for 30 days is It is a chemical-resistant blow molded laminated container with a small amount of impurity fine particles eluted, characterized in that the amount of impurity fine particles eluted (number/ml) is 10 or less after storage at 40°C for 30 days or less.

Inner layer 1: It is an additive-free fluororesin, which does not have an adhesive functional group, has adhesiveness to the fluororesin of the inner layer 2 but does not have adhesiveness to other layers, and has a heating loss of 0.20% by mass or less.

Inner layer 2: It is an additive-free fluororesin, which has an adhesive functional group and has adhesiveness to the fluororesin of the inner layer 1 and the barrier and adhesive resin layer, and the heating loss is 0.40% by mass or less.

Barrier and adhesive resin layer: At least one type of polyamide selected from the group consisting of polyamides obtained by ring-opening polycondensation of caprolactam, which does not contain any additives intentionally added or additives including lubricants.

Adhesive layer: Maleic anhydride-modified polyolefin resin.

Barrier layer: It is an ethylene vinyl alcohol copolymer resin.

Adhesive layer: Maleic anhydride-modified polyolefin resin.

Outer layer 2: It is an ultra-high molecular weight high-density polyethylene resin containing a light-shielding pigment.

In the invention of claim 3 of the present invention, in the chemical-resistant blow molded laminated container according to claim 1 or 2, 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, chlorotrifluoroethylene/tetrafluoroethylene/monomer (α) copolymer, and ethylene/chlorotrifluoroethylene/monomer (α) It is at least one type selected from the group consisting of copolymers, and the monomer (α) is a monomer having an adhesive functional group, and is characterized in that it is a fluororesin having the following characteristics.

(characteristic)

MFR (265℃, 5Kg load g/10min): 10 to 40

Specific gravity: 1.7-1.9

Melting point (℃): 150-200

In the invention according to claim 4 of the present invention, in the chemical-resistant blow molded laminated container according to any one of claims 1 to 3, the fluororesin used for the inner layer 1 does not have the adhesive functional group, and has the following characteristics: It is characterized by having a fluorine resin.

(characteristic)

MFR (297℃, 5Kg load g/10min): 9 to 35

Specific gravity: 1.7-1.9

Melting point (℃): 200-240

In the invention of claim 5 of the present invention, in the chemical-resistant blow molded laminated container according to any one of claims 1 to 4, the polyamide resin has the following characteristics.

(characteristic)

Melting point (℃): 170-250

Density (Kg/㎥): 1.0∼1.2

In the sixth invention of the present invention, in the chemical-resistant blow molded laminated container according to any one of claims 1 to 5, the barrier layer is an ethylene vinyl alcohol copolymer resin having excellent oxygen barrier properties having the following characteristics: It is characterized.

(characteristic)

MFR (210℃, 2.16Kg load g/10min): 2 to 5

Density (Kg/㎥):1.1∼1.3

Melting point (℃): 170-200

In the invention of claim 7 of the present invention, in the chemical-resistant blow molded laminated container according to claim 1, the outer layer 1 is an ultra-high molecular weight high-density polyethylene resin comprising polyethylene or an ethylene-α-olefin copolymer having the following characteristics, and an ultraviolet ray. Light-shielding pigments of organic systems such as quinacridone-based, phthalocyanine-based, anthraquinone-based, and monoazo-based to impart blocking properties and visible light blocking properties, carbon black, iron oxide, zinc oxide, ultramarine, chromium oxide, titanium oxide, and dioxide In addition to containing at least one light-shielding pigment selected from inorganic light-shielding pigments such as silicon, 0.05 to 0.30 mass% of an antioxidant, 25 to 65 mass% of maleic anhydride-modified polyolefin resin, wavelength 500 It is characterized in that it is composed of Composition 1, wherein the transmittance of visible light of -800 nm is 1% or less, and the ultraviolet transmittance of 200-400 nm is 1% or less.

(characteristic)

Density:940∼962Kg/㎥

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

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

Melt tension: 18-30 g

In the invention of claim 8 of the present invention, in the chemical-resistant blow molded laminated container according to claim 2, the outer layer 2 is an ultra-high molecular weight high-density polyethylene resin made of polyethylene or an ethylene-α-olefin copolymer having the following characteristics, and an ultraviolet ray. Light-shielding pigments of organic systems such as quinacridone-based, phthalocyanine-based, anthraquinone-based, and monoazo-based to impart blocking properties and visible light blocking properties, carbon black, iron oxide, zinc oxide, ultramarine, chromium oxide, titanium oxide, and dioxide It contains at least one light-shielding pigment selected from inorganic light-shielding pigments such as silicon, contains 0.05 to 0.30 mass% of an antioxidant, and has a transmittance of visible light having a wavelength of 500 to 800 nm of 1% or less, It is characterized by consisting of Composition 2 having a UV transmittance of 1% or less with a wavelength of 200 to 400 nm.

(characteristic)

Density:940∼962Kg/㎥

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

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

Melt tension: 18-30 g

The invention of claim 1 of the present invention is a chemical-resistant blow molded laminated container obtained by laminating the inner layer 1, the inner layer 2, the barrier/adhesive resin layer, the adhesive layer, the barrier layer and the outer layer 1 in order from the inside of the container to the outside. As, the transmittance of visible light at a wavelength of 500 to 800 nm is 1% or less, an ultraviolet transmittance at a wavelength of 200 to 400 nm is 1% or less, and the elution amount (number/ml) of impure fine particles after storage at 23° C. for 30 days is 5 or less, In addition, it is a chemical-resistant blow molded laminated container with a small amount of impurity fine particles eluted, characterized in that the elution amount (number/ml) of impurity fine particles after storage at 40° C. for 30 days is 10 or less,

As the inner layer 1, a specific fluororesin having an additive-free heating loss of 0.20% by mass or less, which does not have an adhesive functional group and has adhesiveness to the fluororesin of the inner layer 2 but does not have adhesiveness to other layers, is used, and the inner layer 2 As, a specific fluororesin having an adhesive functional group and having an adhesive property-free additive-free heat loss of 0.40% by mass or less to the fluororesin of the inner layer 1 and the barrier and adhesive resin layer is intentionally added to the barrier and adhesive resin layer. By using a polyamide resin containing no additives or lubricants, the cleanliness level is 5 or less after 30 days storage at 23°C, and 10 or less after 30 days storage at 40°C, equivalent to a glass bottle. While cleanliness can be obtained, chemical resistance can be improved, and deterioration of odor components can be reduced as much as possible.

In addition, by forming a barrier layer made of an ethylene vinyl alcohol copolymer resin having excellent oxygen barrier properties, oxygen barrier properties are improved.On the other hand, fluorine resins, polyamide resins, and adhesive resins are blown because the melt tension decreases at once after melting. Problems such as drawdown occurred in molding, for example, it was not possible to mold a container with a uniform thickness, or defective products were generated and the yield was deteriorated. However, the outer layer 1 had a large melt tension. The use of ultra-high molecular weight high-density polyethylene resin with excellent visible light blocking properties and mechanical strength improves moldability and UV protection, so it can be used as a container for ultra-high purity chemicals with many expensive and dangerous chemicals such as fragrances and photoresist solutions. It has a remarkable effect that it is possible to provide a chemical-resistant blow-molded laminated container having a small amount of elution of impurity fine particles without visibility of the contents.

In addition, since the chemical-resistant blow molded laminated container of the present invention contains maleic anhydride-modified polyolefin resin as the outer layer 1 and an outer layer having excellent adhesion to the barrier layer is used, an adhesive layer between the outer layer 1 and the barrier layer The need to form (maleic anhydride-modified polyolefin resin) is eliminated, and the remarkable effect of improving workability and economic efficiency is exhibited.

In addition, the chemical-resistant blow molded laminated container of the present invention is not easily damaged, has excellent mechanical strength, and improves oxygen barrier properties by forming a barrier layer, compared to a glass bottle that is heavy, fragile, and lacks safety. As a universal plastic container that can be used as a perfume bottle or the like, and can be used for various other contents, it has a remarkable effect that it can be safely and safely used for taste and smell.

Since the chemical-resistant blow molded laminated container of the present invention has the above characteristics, it is suitable for the environment and health, contributes to environmental and health problems, and also reduces costs, thereby exhibiting a remarkable effect of economical.

The invention of claim 2 of the present invention is chemical-resistant blown by laminating the above inner layer 1, inner layer 2, barrier/adhesive resin layer, adhesive layer, barrier layer, adhesive layer and outer layer 2 in order from inside to outside of the container. As a molded laminated container, the transmittance of visible light at a wavelength of 500 to 800 nm is 1% or less, the transmittance of ultraviolet light at a wavelength of 200 to 400 nm is 1% or less, and the elution amount (number/ml) of impure fine particles after storage at 23° C. for 30 days is It is a chemical-resistant blow molded laminated container with a small amount of impurity fine particles eluted, characterized in that the elution amount (number/ml) of impure fine particles after storage at 40° C. for 30 days is not more than 5,

In the chemical-resistant blow molded laminated container of claim 2 of the present invention, by forming an adhesive layer (maleic anhydride-modified polyolefin resin) between the outer layer 2 and the barrier layer, the economical efficiency is slightly lowered within the allowable range, but the adhesiveness of both Since it becomes clear, it is used according to the purpose or purpose, and except for this point, it has the same configuration as the chemical-resistant blow-molded laminated container of claim 1 of the present invention, and the functions and effects are also chemical-resistant blow-molded laminated container of claim 1 of the present invention. The remarkable effect of being the same as

In the invention of claim 3 of the present invention, in the chemical-resistant blow molded laminated container according to claim 1 or 2, 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, chlorotrifluoroethylene/tetrafluoroethylene/monomer (α) copolymer, and ethylene/chlorotrifluoroethylene/monomer (α) It is at least one selected from the group consisting of copolymers, and the monomer (α) represents a monomer having an adhesive functional group, and is characterized in that it is a fluororesin having the above properties, and a monomer having an adhesive functional group (α ) Is used for the inner layer 2, so that the fluorine resin of the inner layer 1 and the barrier/adhesive resin layer (polyamide resin) have excellent adhesion, and coextrusion molding is possible at the same molding temperature as polyolefin. It exerts an additional remarkable effect.

In the invention of claim 4 of the present invention, in the chemical-resistant blow molded laminated container according to any one of claims 1 to 3, the fluororesin used for the inner layer 1 does not have the adhesive functional group and has the above properties. It is characterized by being a fluororesin, and exhibits an additional remarkable effect that the fluororesin of the inner layer 2 has excellent adhesiveness and can be coextruded at the same molding temperature as polyolefin.

In the fifth invention of the present invention, in the chemical-resistant blow molded laminated container according to any one of claims 1 to 4, the polyamide resin has the above characteristics,

The adhesion of the inner layer 2 to the fluororesin is improved, and by making it free of additives or lubricants, the elution amount of impurity particles resulting from the additives can be greatly reduced, resulting in an additional remarkable effect of obtaining a cleanness equivalent to a glass bottle. do.

In the sixth invention of the present invention, in the chemical-resistant blow molded laminated container according to any one of claims 1 to 5, the barrier layer is an ethylene vinyl alcohol copolymer resin having excellent oxygen barrier properties having the above characteristics. It is characterized by that,

It exerts an additional remarkable effect that the oxygen barrier property is reliably further improved.

In the invention of claim 7 of the present invention, in the chemical-resistant blow molded laminated container according to claim 1, the outer layer 1 is an ultra-high molecular weight high-density polyethylene resin made of polyethylene or ethylene-α-olefin copolymer having the above properties, and an ultraviolet ray. Light-shielding pigments of organic systems such as quinacridone-based, phthalocyanine-based, anthraquinone-based, and monoazo-based to impart blocking properties and visible light blocking properties, carbon black, iron oxide, zinc oxide, ultramarine, chromium oxide, titanium oxide, and dioxide In addition to containing at least one light-shielding pigment selected from inorganic light-shielding pigments such as silicon, 0.05 to 0.30 mass% of an antioxidant, 25 to 65 mass% of maleic anhydride-modified polyolefin resin, wavelength 500 It is characterized in that it is composed of Composition 1 having a transmittance of 1% or less of visible light at -800 nm and 1% or less of ultraviolet transmittance at a wavelength of 200 to 400 nm,

Since the melt tension of the fluororesin, polyamide resin or adhesive resin decreases at once after melting, a drawdown or the like occurs in blow molding, and for example, a container having a uniform thickness cannot be molded or defective products are There was a problem such as deterioration of yield due to occurrence, but by using an ultra-high molecular weight high-density polyethylene resin having a large weight average molecular weight and melt tension in the outer layer 1, drawdown and other problems were eliminated, thereby improving moldability and mechanical strength.

By using an appropriate amount of a light-shielding pigment, visible light blocking properties and ultraviolet blocking properties are reliably improved, and the transmittance of visible light at a wavelength of 500 to 800 nm is 1% or less, and the ultraviolet transmittance at a wavelength of 200 to 400 nm is 1% or less. Because it can be achieved, it is possible to more reliably provide a chemical-resistant blow-molded laminated container with a small amount of elution of impurity particles that can be handled as a container for ultra-high purity chemicals with many expensive and high-risk chemical substances such as fragrances and photoresist liquids. By using the inhibitor in the above range, it is possible to prevent burning of the resin, and to prevent deterioration of physical properties or appearance caused by the burning resin.

In addition, since the chemical-resistant blow molded laminated container of the present invention contains maleic anhydride-modified polyolefin resin as the outer layer 1 and an outer layer having excellent adhesion to the barrier layer is used, an adhesive layer between the outer layer 1 and the barrier layer The need to form (maleic anhydride-modified polyolefin resin) is eliminated, resulting in an additional remarkable effect of further improving workability and economy.

In addition, the chemical-resistant blow molded laminated container of the present invention is not easily damaged, has excellent mechanical strength, and improves oxygen barrier properties by forming a barrier layer, compared to a glass bottle that is heavy, fragile, and lacks safety. As a universal plastic container that can be used as a perfume bottle, etc., and can be used for various other contents, it has an additional remarkable effect that it can be safely and safely used for taste and smell.

In the invention of claim 8 of the present invention, in the chemical-resistant blow molded laminated container according to claim 2, the outer layer 2 is an ultra-high molecular weight high-density polyethylene resin made of polyethylene or an ethylene-α-olefin copolymer having the following characteristics, and an ultraviolet ray. Light-shielding pigments of organic systems such as quinacridone-based, phthalocyanine-based, anthraquinone-based, and monoazo-based to impart blocking properties and visible light blocking properties, carbon black, iron oxide, zinc oxide, ultramarine, chromium oxide, titanium oxide, and dioxide The transmittance of visible light at a wavelength of 500 to 800 nm is 1% or less, which contains at least one light-shielding pigment selected from inorganic light-shielding pigments such as silicon, and contains 0.05 to 0.30 mass% of an antioxidant, It is characterized in that it is composed of composition 2 having a UV transmittance of 1% or less with a wavelength of 200 to 400 nm,

Since the melt tension of the fluororesin, polyamide resin, or adhesive resin decreases at once after melting, problems such as drawdown occur in blow molding, for example, a container with a uniform thickness cannot be molded, or defective products occur. As a result, there was a problem such as deterioration of the yield, but by using an ultra-high molecular weight high-density polyethylene resin having a large weight average molecular weight and melt tension for the outer layer 2, drawdown and other problems were eliminated, thereby improving moldability and mechanical strength, and light-shielding pigments. By using an appropriate amount, visible light blocking properties and UV blocking properties are reliably improved, and the transmittance of visible light at a wavelength of 500 to 800 nm is 1% or less, and an ultraviolet transmittance at a wavelength of 200 to 400 nm is 1% or less. Therefore, it is possible to more reliably provide a chemical-resistant blown molded laminated container with a small amount of elution of impurity particles that can be handled as a container for ultra-high purity chemicals with many expensive and high-risk chemical substances such as fragrances and photoresist liquids. By using it within the range, it exhibits an additional remarkable effect of preventing burning of the resin and preventing deterioration of physical properties or appearance caused by the burning resin.

By forming an adhesive layer (maleic anhydride-modified polyolefin resin) between the outer layer 2 and the barrier layer, the economical efficiency is slightly lowered within the allowable range, but the adhesiveness of both becomes certain, so it is used depending on the purpose or purpose. Other than that, it has the same configuration as the outer layer 1, and exhibits an additional remarkable effect that the function and effect are also the same as the chemical-resistant blow molded laminated container of the present invention using the outer layer 1.

That is, the chemical-resistant blow-molded laminated container of the present invention is not easily damaged, has excellent mechanical strength, and improves oxygen barrier property by forming a barrier layer, compared to a glass bottle that is heavy, fragile, and lacks safety, As a universal plastic container that can be used as a perfume bottle or the like, and can be used for various other contents, it exhibits an additional remarkable effect that it can be safely and safely used for taste and smell.

1 is an explanatory diagram schematically illustrating a wall cross-section of an example of a chemical-resistant blow molded laminated container of the present invention.
2 is an explanatory diagram schematically illustrating a wall cross-section of another example of the chemical-resistant blow molded laminated container of the present invention.
3 is a graph showing the results of infrared spectral analysis of the inner layer 1 of the chemical-resistant blow molded laminated container of the present invention.
Fig. 4 is a graph showing the results of infrared spectral analysis of the inner layer 2 of the chemical-resistant blow molded laminated container of the present invention.

Hereinafter, the present invention will be described in detail with reference to the drawings.

1 is an explanatory diagram 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 laminated container 8A of the present invention is an inner layer 1 made of the fluororesin having no adhesive functional group, and 1B is an inner layer 2 made of the fluororesin having an adhesive functional group. , And 2 is a barrier and adhesive resin layer made of the polyamide resin, 3 is an adhesive layer made of a maleic anhydride-modified polyolefin resin, 4 is a barrier layer made of ethylene vinyl alcohol copolymer resin, and 5 is maleic anhydride The adhesive layer 6A made of a modified polyolefin resin represents an outer layer 2 made of an ultra-high molecular weight high-density polyethylene resin in which the transmittance of visible light at a wavelength of 500 to 800 nm is 1% or less and an ultraviolet transmittance at a wavelength of 200 to 400 nm is 1% or less. 7 shows an ultra-high purity drug as the contents.

2 is an explanatory diagram 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 laminated container 8B of the present invention is an inner layer 1 made of the fluororesin having no adhesive functional group, and 1B is an inner layer 2 made of the fluororesin having an adhesive functional group. , And 2 is a barrier and adhesive resin layer made of the polyamide resin, 3 is an adhesive layer made of a maleic anhydride-modified polyolefin resin, 4 is a barrier layer made of an ethylene vinyl alcohol copolymer resin, and 6B is the barrier layer. (4) Ultra-high molecular weight high-density polyethylene resin containing maleic anhydride-modified polyolefin resin having a transmittance of 1% or less for visible light at a wavelength of 500 to 800 nm and 1% or less at a wavelength of 200 to 400 nm with excellent adhesion to Each of the formed outer layers 1 is shown. 7 shows an ultra-high purity drug as the contents.

Since the outer layer 1 contains 25 to 65% by mass of maleic anhydride-modified polyolefin resin, the outer layer 1 and the barrier layer 4 have excellent adhesiveness, and there are no drawdown or other problems. It has excellent strength and the like. However, if the maleic anhydride-modified polyolefin resin is less than 25% by mass, there is a risk that 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, drawdown, etc. There is a fear that a problem may occur.

The fluororesin used for the inner layer 2 is not particularly limited, but specifically, for example, 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/ It is at least one selected from the group consisting of monomer (α) copolymer, chlorotrifluoroethylene/tetrafluoroethylene/monomer (α) copolymer, and ethylene/chlorotrifluoroethylene/monomer (α) copolymer, As long as it is a fluororesin copolymerized with a monomer (α) having an adhesive functional group having the above characteristics, the inner layer 2 has excellent adhesiveness as the fluorine resin of the inner layer 1 and a barrier and adhesive resin layer (polyamide resin), such as polyolefin. Since co-extrusion molding is possible at the molding temperature, it can be preferably used.

As for the fluororesin used for the inner layer 2 in the present invention, it is preferable to use an additive-free, additive-free grade fluororesin.

In the present invention, the fluororesin used for the inner layer 1 is a fluororesin that does not copolymerize the monomer (α) having an adhesive functional group and does not have the adhesive functional group, and uses an additive-free additive-free grade fluorine resin. desirable.

In addition, the fluorine resin used for the inner layer 1 in the present invention has a heating loss of 0.20 mass% or less, preferably 0.15 or less, as measured by the following heating loss measurement method, and the fluorine resin used for the inner layer 2 is a heating loss measured by the same measurement method. It is required that it is 0.40 mass% or less, preferably 0.30 or less. If each falls within these ranges, the cleanliness can be 5 or less after storage at 23°C for 30 days, and 10 or less after storage at 40°C for 30 days, but outside the above ranges, there is a fear that this cleanliness cannot be achieved.

(Measurement of loss on heating)

The aluminum cup is precisely weighed to 0.1 mg with a balance (WO).

Put 5.00±0.01 g of a sample into an aluminum cup, and precisely weigh the total mass to 0.1 mg (W).

After adjusting the temperature of the electric furnace to 260℃±1℃, the sample is heated for 240 minutes.

After heating, the sample is taken out, 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.

Heating loss (mass%) = [(W-W1)/(W-W0)]×100

(About desirable properties of inner layer 2)

MFR (265°C, 5Kg load g/10min) (Measurement method: 265°C, ASTM D1238) is preferably 10 to 40, more preferably 20 to 30, and if less than 10, the melt viscosity is high and blown melt moldability There is a fear that the driving energy may increase due to deterioration, and if it exceeds 40, the melt tension is low and there is a fear that problems such as drawdown may occur during blow molding.

The specific gravity (measurement method: ASTM D-792) should just be 1.7 to 1.9, and more preferably 1.72 to 1.76 of a commercially available product. If the specific gravity is less than 1.7, there is a concern that adhesiveness may be deteriorated, and if it exceeds 1.9, there is a concern that the strength of the container may be insufficient.

The melting point (°C) (Measurement method: ASTM D792) varies depending on the amount or type of the monomer (α) to be copolymerized, but the melting point of a commercially available product may be 150 to 200°C, more preferably 190 to 200°C. . If the melting point is less than 150 DEG C, a difference in melting point with other resins may occur, and there is a concern that problems in adhesive strength and moldability may occur, and when the melting point exceeds 200 DEG C, there is a concern that lamination with another resin may become difficult.

The monomer (α) to be copolymerized is not particularly limited as long as it is a monomer that can be copolymerized with an adhesive functional group, but the amount or type is controlled in consideration of melt molding so that the fluororesin of the inner layer 2 is within the above melting point (°C). In addition, it is preferable that the fluororesin of the inner layer 1 and the barrier and adhesive resin layer (polyamide resin) have more excellent adhesiveness.

As a specific example of an adhesive functional group, an epoxy group, a hydroxyl group, a carboxylic anhydride residue, a carboxylic acid group, an acrylate group, a carbonate group, an amino group, etc. are mentioned, for example. As a specific example of this copolymer, the ethylene-tetrafluoroethylene-hexafluoropropylene-ethylene carbonate copolymer EFEP (for example, RP5000 manufactured by Daikin Industries, Ltd.) used in Example 1 is mentioned.

(About desirable properties of inner layer 1)

MFR (297°C, 5Kg load g/10min) (Measurement method: 265°C, ASTM D1238) is preferably 9 to 35, more preferably 15 to 25, and if less than 9, the melt viscosity is high and blown melt moldability It may deteriorate and drive energy may also increase, and if it exceeds 35, the melt tension is low and there is a concern that problems such as drawdown may occur during blow molding.

The specific gravity (measurement method: ASTM D-792) should just be 1.7 to 1.9, more preferably 1.83 to 1.89 of a commercially available product. If the specific gravity is less than 1.7, there is a concern that adhesiveness may be deteriorated, and if it exceeds 1.9, there is a concern that the strength of the container may be insufficient.

The melting point (°C) (Measurement Method: ASTM D792) may be 200 to 240°C, more preferably 208 to 228°C, of a commercially available product. If the melting point is less than 200°C, there is a concern that a difference in melting point with other resins may occur, and problems in adhesive strength and moldability may arise. If the melting point exceeds 240°C, there is a concern that lamination with other resins may become difficult.

The polyamide resin of the barrier and adhesive resin layer used in the present invention is an additive-free grade polyamide resin in which additives or additives usually intentionally added or additives including a lubricant are not added or blended, and has the following characteristics, specifically As an example, Daicel Evonik Co., Ltd. Z4887 is mentioned.

Among them, polyamide is at least one polyamide selected from nylon 6, nylon 11, nylon 12, nylon 66, etc., obtained by ring-opening polycondensation of caprolactam, and does not contain additives including additives or lubricants. Can be used.

(characteristic)

Melting point (℃) (according to ISO11357): 170 to 250

Density (Kg/㎥) (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, more preferably 1.00 to 1.03.

When the melting point is less than the lower limit, there is a fear that the adhesiveness may be insufficient, and when the melting point exceeds the upper limit, the moldability may be deteriorated.

When the density is less than the lower limit, there is a fear that the adhesiveness may be insufficient, and when the density exceeds the upper limit, the moldability may be deteriorated.

The maleic anhydride-modified polyolefin resin of the adhesive layer used in the present invention has excellent adhesion to the barrier and adhesive resin layer (the polyamide resin) and the barrier layer (ethylene vinyl alcohol copolymer resin), and Maleic anhydride-modified polyolefin resin has excellent adhesion to the barrier layer (ethylene vinyl alcohol copolymer resin) and the outer layer (ultra high molecular weight high density polyethylene resin), and bonds both to form an adhesive layer, and melt molding is possible. What is necessary is just to do it, and a commercially available product can be used.

To 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 inner layers 1 and 2 (fluorine resin), both as a barrier and bonding as long as the adhesion is not impaired. A recovered product comprising a resin layer (the polyamide resin), an adhesive layer (maleic anhydride-modified polyolefin resin), a barrier layer (ethylene vinyl alcohol copolymer resin), and an outer layer (ultra high molecular weight high density polyethylene resin) can be blended.

This is because the maleic anhydride-modified polyolefin resin in which the recovered product of the adhesive layer is blended is far from the fluororesin of the inner layer 1 serving as the wetted surface, and thus there is no fear of impairing the degree of cleanliness practically.

A maleic anhydride-modified polyolefin resin having excellent adhesion to the barrier and adhesive resin layer (the polyamide resin) and the barrier layer (ethylene vinyl alcohol copolymer resin), the barrier layer (ethylene vinyl alcohol copolymer resin) and the outer layer (ultra high molecular weight) The maleic anhydride-modified polyolefin resin having excellent adhesion to the high-density polyethylene resin) may be the same or different, and it is preferable to determine it by testing in advance.

The ethylene vinyl alcohol copolymer resin (ethylene 24-44 mol% copolymerization) of the barrier layer used in the present invention is a resin obtained by hydrolyzing ethylene vinyl alcohol copolymerization and almost completely saponified, and has excellent gas barrier properties such as excellent retention properties. Therefore, it is widely used in container packaging materials such as pharmaceuticals and cosmetics, and has high resistance to oils and organic solvents. In particular, it is possible to secure oxygen barrier properties by using an ethylene vinyl alcohol copolymer resin having the following characteristics. In addition, MFR, melting point, and the like are close to those of ultra-high molecular weight high-density polyethylene resins, so they can be preferably used because they have excellent stable moldability. Specifically as an example of the ethylene vinyl alcohol copolymer resin of a barrier layer, F171B (ethylene 32 mol% copolymerization, melting|fusing point 183 degreeC, 99.99% of saponification rate) manufactured by Kuraray Co., Ltd. is mentioned, for example.

(characteristic)

MFR (210℃, 2.16Kg load g/10min): 2 to 5

Density (Kg/㎥): (According to ISO1183) 1.1 to 1.3

Melting point (℃): (according to ISO1346): 170 to 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, and stable moldability are all excellent, but outside the above ranges, at least one of these properties may be impaired.

The ultra-high molecular weight high-density polyethylene resin of the outer layers 1 and 2 used in the present invention has a density (measurement method: JIS K7112 compliant) as described above, preferably 940 to 962 Kg/m 3, more preferably 944 to 946 Kg/m 3, and weight. The average molecular weight (measurement method: described later) is preferably 220,000 to 260,000, more preferably 24 to 260,000, and molecular weight distribution (Mw/Mn) (measurement method: to be described later) is preferably 12 or less, more preferably 11 or less, melt tension (Measurement method: Nippon Polyethylene method, Toyo Seiki Manufacturing Co., Ltd. using a capigraph at 210°C, orifice is L:8mm, D:2.095mm, piston descent speed 10mm/min, winding speed 3.9mm /min) is preferably 18 to 30 g, more preferably 22 to 26 g, and an ultra-high molecular weight high-density polyethylene resin is preferred, and by using this ultra-high molecular weight high-density polyethylene resin for the outer layers 1 and 2, moldability, mechanical strength, etc. This improves, and problems such as drawdown are eliminated, and the yield and the like are also improved.

Since the molecular weight distribution (Mw/Mn) of the ultra-high molecular weight high-density polyethylene resin forming the outer layers 1 and 2 is narrow to 12 or less, the outer layer 1 of the blow molded laminated container is multi-layered under normal molding processing conditions such as melt processing and rapid cooling. Since 2 is composed of a dense small crystal aggregate, mechanical strength is improved.

The (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, and when (Mw/Mn) exceeds 12, melt processing and rapid cooling are common. The crystals of the outer layer of the multilayered blow-molded laminated container formed under phosphorus molding processing conditions become large or non-uniform, so that the crystals are not formed into a dense microcrystalline aggregate, and there is a fear that mechanical strength may be insufficient.

The high-density polyethylene resin forming the outer layers 1 and 2 may lack mechanical strength when the weight average molecular weight of the ultra-high molecular weight high-density polyethylene resin is less than 220,000, and when the weight average molecular weight exceeds 260,000, the melt viscosity of the resin is Because it is high, the moldability deteriorates, and there is a fear that molecular breakage due to shear stress may occur.

When 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, drawdown may cause difficulty in controlling the thickness. On the other hand, when the upper limit is exceeded, melt fractures on the bottle surface (rough skin ), there is a risk of occurrence.

The ultra-high molecular weight polyethylene resin used for outer layers 1 and 2 is a homopolymer or copolymer containing at least one type selected from ethylene, propylene, butene-1,4-methyl-pentene-1, hexene-1, and octene-1 And, a commercial item having the above characteristics can be used. Among them, an ethylene homopolymer, a copolymer of ethylene and an ?-olefin such as propylene, butene-1,4-methyl-pentene-1, hexene-1, and octene-1 is preferably used. The content of the α-olefin in the copolymer is preferably 15% by mass or less. In the polymerization method, if a polymer or copolymer having the above properties such as a density of 940 to 962 Kg/m 3 is obtained, the molecular structure of the copolymer may be atactic, isotactic, syndiotactic, or a mixture thereof. However, it is not particularly limited, and for example, any one of a low pressure method or a medium pressure method may be used.

In the outer layers 1 and 2 used in the present invention, at least one light-shielding pigment selected from organic light-shielding pigments and/or inorganic light-shielding pigments has a transmittance of 1% or less of visible light having a wavelength of 500 to 800 nm (to be described later). It is preferable to blend in a predetermined amount so that the ultraviolet transmittance at a wavelength of 200 to 400 nm is 1% or less (by a measurement method described later).

As organic light-shielding pigments and inorganic light-shielding pigments, the transmittance of visible light at a wavelength of 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 by blending in a predetermined amount in the outer layer. It is not particularly limited as long as it does not impair other properties of the outer layer.

However, light-shielding pigments of organic systems such as quinacridone-based, phthalocyanine-based, anthraquinone-based, and monoazo-based, and inorganic-based 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 can be used preferably in the present invention, since 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.).

Specifically, as a phthalocyanine-based light-shielding pigment, for example, 7F2854 (manufactured by Dainichi Seika Co., Ltd.), TET58335 (manufactured by Toyo Color Co., Ltd.) and EPH-525328 (manufactured by Polycol Heung-up Co., Ltd.) Can be lifted.

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

Specific examples of the carbon black-based light-shielding pigment include TET01337 (manufactured by Toyo Color Co., Ltd.) and EPH-K-51680 (manufactured by Polycol Heung-up Co., Ltd.).

As an iron oxide-based light-shielding pigment, specifically, EPH-C-1045 (manufactured by Polycol Heung-up Co., Ltd.) and TET68473 (manufactured by Toyo Color Co., Ltd.) are mentioned, for example.

As the ultramarine-based light-shielding pigment, specifically, EPH-B-46662 (manufactured by Polycol Heung-up Co., Ltd.) and TET26146 (manufactured by Toyo Color Co., Ltd.) are mentioned, for example.

As a titanium oxide-based light-shielding pigment, specifically, for example, EB-1427 (manufactured by DIC Corporation), EPH-H-2481 (manufactured by Polycol Heung-up Co., Ltd.) and TET28318 (manufactured by Toyo Color Co., Ltd.) ).

In the use of these light-shielding pigments, it is preferable to avoid pigments with poor dispersibility and pigments that promote oxidation deterioration of containers.

In the present invention, after determining the kind of the ultra-high molecular weight high density polyethylene resin and the light-shielding pigment forming the outer layers 1 and 2, 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.

If the transmittance of visible light with a wavelength of 500 to 800 nm is 1% or less and the transmittance of ultraviolet rays with a wavelength of 200 to 400 nm is 1% or less, there is no visibility of the contents, and deterioration of the contained solution can be prevented. It can impart UV-blocking properties, and can be used as an ultra-high-purity chemical container such as a chemical or fragrance that is denatured and cured by ultraviolet rays such as a photoresist solution.

As a specific example of the light-shielding pigment and the blending amount, the example in which a phthalocyanine-based light-shielding pigment (trade name: 7F2854: manufactured by Dainichi Seika Co., Ltd.) in Example 1 described later is blended in an outer layer of 2% by mass can be given. Since 7F2854 is a master batch containing 6% by mass of phthalocyanine, in the above example, 0.012% by mass of phthalocyanine is blended into the outer layer, resulting in a UV transmittance of 1% or less and a visible light transmittance of 1% or less.

In the outer layers 1 and 2 used in the present invention, a predetermined amount (0.05 to 0.30 mass%) of at least one antioxidant selected from the group consisting of phenolic, phosphorus, and sulfur antioxidants is preferably blended. By preventing, it is possible to prevent deterioration of appearance and the like caused by the burning resin.

The phenolic antioxidant, phosphorus antioxidant, and sulfur antioxidant are not particularly limited as long as they have high antioxidant properties and do not impair other properties of the outer layers 1 and 2.

As a phenolic antioxidant, specifically, ADEKA Co., Ltd. Adecastab AO60 is mentioned, for example.

As a phosphorus antioxidant, specifically, ADEKA Co., Ltd. Adecastab 2112 is mentioned, for example.

As a sulfur-type antioxidant, specifically, Yoshitomi Mitsubishi Chemical Co., Ltd. DSTP is mentioned, for example.

With respect to the ultra-high molecular weight high-density polyethylene resin forming the outer layers 1 and 2, these antioxidants are preferably blended in an amount of 0.05 to 0.30% by mass, and more preferably 0.10 to 0.25% by mass. If it is less than 0.05% by mass, the antioxidant performance may be deteriorated, and if it exceeds 0.30% by mass, the additive may bleed out to the container surface.

The outer layers 1 and 2 used in the present invention are blended with light-shielding pigments and antioxidants that may become impure fine particles, but the outer layers 1 and 2 are separated from the inner layers 1 and 2 serving as the wetted surface, so these light-shielding pigments, The barrier and adhesive resin layer (2), adhesive layer (3, 5), barrier layer (4), etc. prevent impurity particulates from leaching into the solution. Does not leach into the middle.

In the present invention, in the outer layers 1 and 2, light-resistant stabilizers such as benzotriazole-based light-resistant stabilizers and triazine-based light-resistant stabilizers can also be suitably used as necessary in addition to the light-shielding pigment.

When a benzotriazole-based light-resistant stabilizer or a triazine-based light-resistant stabilizer is used, UV-B (200 to 320 nm) and UV-A (320 to 400 nm) can be respectively blocked, and other properties are not impaired by using both together in a specific amount. UV protection can be remarkably improved without.

Examples of the light stabilizer include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-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- Benzotriazole-based light stabilizers such as 2-hydroxyphenyl)benzotriazole and 2-(2H-benzotriazol-2-yl)-p-cresol, 2-[4,6-di(2,4 xylyl) -1,3,5-triazine-2-yl]-5,2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine, Triazine-based light stabilizers such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, bis( 2,2,6,6-tetramethyl-4-piperidine) sebacate, 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 light-resistant stabilizers.

The content of the additive contained in the resin is a value obtained by separating and quantifying the extract obtained by using tetrahydrofuran (THF) for 8 hours with a Soxhlet extractor by liquid chromatography. The measurement conditions were GULLIVER (manufactured by Nippon Spectroscopy Co., Ltd.), the column was Finepak GEL 101 (manufactured by Nippon Spectroscopy Co., Ltd.), the solvent was THF, and the detector was UV-970 (manufactured by Nippon Spectroscopy Co., Ltd.) and 830-RI (Nippon Spectroscopy Co., Ltd.). Manufacturing).

In the method of 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 obtain 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 formula.

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 a molecular weight, and w is a weight fraction.

In addition, the measurement conditions of GPC are 150 CV (manufactured by Waters) as an apparatus, TSKgel GMH-HT (manufactured by Tosoh Corporation) as a column, orthodichlorobenzene as a solvent, a temperature of 138°C, and a differential refractometer as a detector. 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 is capable of molding the chemical-resistant blow molded laminated container excellent in transparency of the present invention by the blow molding method, and may be used by selecting from a molding machine for a commercially available blow molded laminated container.

In addition, the description of the above embodiments is for explaining the present invention, and does not limit the invention described in the claims or to reduce the scope. In addition, each sub-configuration of the present invention is not limited to the above embodiments, and various modifications are possible within the technical range described in the claims.

[Example]

Next, the present invention will be described in detail by examples, but it is not limited to these examples unless departing from the gist of the present invention.

(Example 1)

As inner layer 1, an additive-free fluororesin (EP-610 manufactured by Daikin Industries Co., Ltd.) with MFR 25 g/10 min, specific gravity 1.86, melting point 223° C., and 0.16 mass% heating loss was used, and MFR 25 g/10 min as inner layer 2 , A specific gravity of 1.74, a melting point of 195°C, and an additive-free fluororesin having a heating loss of 0.35% by mass (RP-5000 manufactured by Daikin Industries, Ltd.) was used, and the fluororesin of the inner layer 2 was used as a barrier and adhesive resin layer. Using an additive-free polyamide resin (Z4887 manufactured by Daicel Evonik Co., Ltd., a relative viscosity of 1.87), which does not contain additives that have an adhesive function and contains intentionally added additives or lubricants, and the polyamide resin Maleic anhydride-modified polyolefin resin (Nippon Polyethylene Co., Ltd. FT71A) is used as the adhesive layer having an adhesion function of the barrier layer and the barrier layer, and a barrier resin (ethylene-vinyl alcohol copolymer resin F171B: Kuraray Co., Ltd.) Manufacturing, saponification rate 99.99%), and as outer layer 1, ultra-high molecular weight high-density polyethylene resin (HB111R manufactured by Nippon Polyethylene Corporation) (HL-MFR (Measurement Method: JIS K7112) 6g/10min, density 946Kg/m3, weight For an average molecular weight of 250,000 and a melt tension of 25 g), 30% by mass of maleic anhydride-modified polyolefin resin (Nippon Polyethylene Co., Ltd. FT71A) was used, and a phthalocyanine-based light-shielding pigment (trade name: 7F2854: Dainichi Seika Co., Ltd.manufactured, master batch containing phthalocyanine 6% by mass) 2% by mass, phenolic antioxidant (brand name: Adecastab AO60: manufactured by ADEKA Co., Ltd.) and phosphorus antioxidant (brand name: Ade Castab 2112 (manufactured by ADEKA Co., Ltd.) using an ultra-high molecular weight high-density polyethylene resin blended with a total of 0.2% by mass, there is no problem such as drawdown under the following molding conditions, and the chemical resistance of the present invention consisting of six layers Molded lamination container (total mass 400 g, inner layer 1 is 50 μm, inner layer 2 is 100 μm, barry An adhesive resin layer 50 µm, an adhesive layer 50 µm, a barrier layer 50 µm, an outer layer 1 of 1500 µm, an average total thickness of 1.8 mm, and a capacity of 3750 ML) were molded.

(Molding conditions)

A blow molding machine (6 layers, 6 layers manufactured by Brense Co., Ltd.) (a type in which 6 layers are stacked with one die head using 6 types of extruders) was used.

Fluoro resin of inner layer 1: Screw diameter 40㎜Φ Set temperature: 260℃

Fluorine resin of inner layer 2: Screw diameter 20mmΦ Set temperature: 240℃

Polyamide resin layer: Screw diameter 20mmΦ Set temperature: 200℃

Maleic anhydride-modified polyolefin resin layer: Screw diameter 20 mmΦ Set temperature: 220°C

Ethylene-vinyl alcohol copolymer resin layer: screw diameter 40㎜Φ Set temperature: 230℃

Ultra-high molecular weight high-density polyethylene resin for outer layer 1: screw diameter 50㎜Φ Set temperature: 220℃

Die head temperature: Set temperature: 235℃

In addition, the hygroscopic polyamide resin and the barrier resin were dried at 80° C. using a dryer to remove moisture.

Then, the samples were stored immediately after extraction and 30 days at 23°C, and the elution amount of impure fine particles after extraction (number/ml) and the elution amount of impure particles after extraction and after extraction at 40°C (number/ml) were sampled by the following test method. It was measured using a bottle, and the oxygen permeability and visibility were evaluated by the following test method, and a sample of 4 cm x 4 cm x 1.8 mm was cut out from the wall of the bottle body, and the ultraviolet transmittance, The visible light transmittance was evaluated, and pure water was filled into the container, and the metal elution was evaluated by the following test method, and the drop strength and flavor was evaluated by the following test method, and the inner layers 1 and 2 and the wetted surface by the above test method Evaluating the heating loss of the layer, and for economical efficiency, if expensive materials are not used and the container can be provided economically, the marketability is high. ○ Or, since expensive materials are used, marketability depending on the application There is, however, an evaluation of economic feasibility as x, and comprehensive judgment was made by putting them together. The results are shown in Tables 1 to 2.

The heating loss described in Table 1 is the heating loss of the inner layer 1 or the layer serving as the liquid contact surface.

The fluororesin of the inner layer 1 (EP-610 manufactured by Daikin Industries, Ltd.) and the fluororesin of the inner layer 2 (from Daikin Industries, Ltd. RP-) of the chemical-resistant blow molded laminated container of the present invention obtained by molding in Example 1 5000) was used, and infrared spectroscopic analysis was performed under the following measurement conditions.

(Infrared spectral analysis measurement conditions)

Measuring device: IR Affinity-1 manufactured by Shimadzu Corporation

Measurement sample: A film sheet having a thickness of 50 µm of the inner layers 1 and 2 was prepared and used using a 240°C press machine.

Measurement wavelength: 600∼4000cm ^-1

3 shows the results of infrared spectroscopic analysis of the inner layer 1, the vertical axis indicating absorbance (%), and the horizontal axis indicating wavelength (cm ^-1 ).

4 shows the results of infrared spectroscopy analysis of the inner layer 2, the vertical axis indicates absorbance (%), and the horizontal axis indicates wavelength (cm ^-1 ).

When FIG. 3 and FIG. 4 are superimposed, it can be seen that, except for the sharp absorption at a wavelength of 1800 (cm ⁻¹ ) in FIG. 4, both have substantially the same waveform.

The 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 is understood that the fluororesin of the inner layer 2 has an adhesive functional group (carbonate group).

The fluororesin of the inner layer 2 is prepared by copolymerizing a monomer (α) having an adhesive functional group as described above, and the amount of the adhesive functional group of the fluororesin of the inner layer 2 can be controlled by the copolymerization amount of the monomer (α). Accordingly, the adhesion of the fluororesin of the inner layer 2 is controlled so that the inner layer 2 has good adhesion to the fluororesin of the inner layer 1 and the barrier and adhesive resin layer, and the melting point, etc. is within the predetermined range. can do.

At a wavelength of 1800 (cm ⁻¹ ) in FIG. 3, the large sharp absorption peak was not observed, and the fluorine resin of the inner layer 1 showed no 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 the other layers.

The large sharp absorption peak at a wavelength of 3000 (cm ^-1 ) in Figs. 3 and 4 is an absorption peak derived from copolymerized ethylene.

(Test method)

(Measurement method of impurity fine particles (particles))

The following measurements are carried out in a clean room (class 100).

1. Measurement device: RION KL-26 particle counter "KL-26" manufactured by Leon Corporation is used.

2. Measurement specimen: Fill the molded container with full water and store it immediately after extraction and 30 days at 23°C. After extraction or immediately after extraction and 30 days at 40°C. After extraction, from the container left standing upright for 20 minutes. Take a measurement sample and use it as a measurement sample.

3. Purge the particle counter with ultrapure water before measurement, and then wash the measuring device twice with 25 ml of ultrapure water.

4. After washing, ultrapure water is poured into a particle counter of 10 ml, and the number of particles is measured. This operation is performed twice, and it is confirmed that the number of particles of 0.2 µm or more is zero (A).

5. Wash the measuring device twice with a measuring sample of 25 ml.

6. After washing, 10 ml of a container (bottle) filled with ultrapure water of the measurement specimen is poured into the particle counter, and the number of particles is measured. This operation is performed twice, and the average value (B) of the number of particles of 0.2 µm or more is obtained.

7. Calculate the particle value in 1 ml from the measured value by the following equation.

(B(pcs))÷10ml=pcs/ml

Oxygen permeability [cm 3 /(pkg.24h.atm)]:

Using a 3.75 L container (thickness at the center of the bottle: 1.8 mm) and using a measuring device (OX-TRAN2/21) (manufactured by MOCON) according to JIS K7126-2, oxygen from the outside to the inside of the container Permeation was measured. Temperature and humidity: 1 atmosphere outside, 23°C, 50% RH oxygen. 1 atmosphere inside, 23°C, dry nitrogen.

(Ultraviolet ray transmittance)

Using Nippon Spectroscopy V-670, the transmittance in the ultraviolet region of 200 to 400 nm is determined.

(Visible light transmittance)

Using Nippon Spectroscopy V-670, the transmittance of the visible light region of 500 to 800 nm is determined.

(Visibility)

In a 750 lux room, tap water was put into a container, and three people observed tap water visually from the outside of the container. And the following three-stage evaluation is performed.

evaluation:

×: Tap water can be confirmed.

△: You can check it by looking at the tap water.

○: Tap water cannot be confirmed.

(Fall strength)

The container is filled with water 80% of its capacity, and the container is dropped 5 times with the bottom of the container down on a concrete surface from a height of 1.2 m, and dropped once with the side of the container down, and cracks or leakage are visually judged.

(Perfume appropriate)

Examples of typical fragrances include limonene (brand name: orange oil, 96.4% purity, manufactured by Hasegawa Fragrance Co., Ltd.), citrus fruits (brand name: Lemon Essence, manufactured by Hasegawa Fragrance Co., Ltd.), and crab oil (15% dimethyl sulfide, Propylene glycol solution, Hasegawa Fragrance Co., Ltd.), rice salad (trade name: rice oil, Hasegawa Fragrance Co., Ltd.), ethyl butyrate (trade name: esters, purity 100%, Hasegawa Fragrance Co., Ltd.), trans- Using 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 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 room temperature and pressure.

After standing for 3 months, for each sample, the container mass was measured and the contents were checked to see if the contents were scattered, and a sensory test was conducted with 10 panel members to check whether it was deteriorated, and the specific gravity and refractive index were checked. It was checked whether there was any fluctuation by measurement, and the components were checked by a gas chromatograph about the sample which can be analyzed, and evaluated by the following evaluation criteria.

Evaluation standard:

○: There is no acid, deterioration, fluctuation, etc., and storage stability is high, and it is marketable.

Although it is slightly inferior to △:○, there is practically no acid, deterioration, fluctuation, etc., and practically has high storage stability, so it is marketable.

X: There are acid, alteration, fluctuation, etc., and storage stability is low, and there is no marketability.

(Metal elution)

Fill the sample container with pure water, and let it stand for 30 days while warming at 23℃ and 40℃, and measure it to the ppb level using ICP-MASS (8800 manufactured by Agilent Technologies) using this pure water as a sample. do. Measurements are made in a 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 Measure the element. Pass if it is 10ng/ℓ or less.

(Total judgment)

The particle value after 23°C and 30 days is 5 particles/ml or less, and the particle value after 40°C and 30 days is 10 particles/ml or less,

Oxygen transmittance of 0.003 [cm 3 /(pkg.24h.atm)] or less,

UV transmittance is 1% or less,

Visible light transmittance is 1% or less,

Visibility ○ (cannot check the tap water inside),

Drop strength: no destruction,

Flavoring titration is ○-△,

Metal elution is less than 10 (ng/ℓ).

If all are passed, the overall judgment is made ○. When any of these is inferior to the above, the overall judgment is judged as x.

(Comparative Example 1)

In place 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 phenolic antioxidant, 2000 ppm) was contained. Except having used the polyamide resin (relative viscosity of 1.87), it carried out similarly to Example 1, and made and evaluated the blow molding laminated container for comparison. The results are shown in Tables 1 to 2.

(Comparative Example 2)

In place of the inner layers 1 and 2 used in Example 1, a density of 956 Kg/m 3, HL-MFR (Measurement method: JIS K7112, load 21.6 Kg) 8 g/10 min, Mw/Mn = 11, a component having a molecular weight of 1000 or less is 0.2% by mass Except having used the liquid-contacting layer using phosphorus high-density polyethylene (Tosoh Co., Ltd. 9D01A), it carried out similarly to Example 1, and the blow molded laminated container for comparison was made and evaluated. The results are shown in Tables 1 to 2.

(Comparative Example 3)

Blow molding lamination for comparison was carried out 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 heating loss of 0.35 mass% used in Example 1 was used as the liquid contact layer. I made courage and evaluated it. The results are shown in Tables 1 to 2.

(Comparative Example 4)

The fluororesin of the liquid-contacting layer used in Comparative Example 3 was heated for 120 minutes at a temperature of 260°C±1°C in an electric furnace to reduce the heating loss (heat loss 0.31% by mass), except that the fluororesin was used. In the same way, a blow molded laminated container for comparison was prepared and evaluated. The results are shown in Tables 1 to 2.

(Comparative Example 5)

For comparison, evaluation was carried out in the same manner as in Example 1, except that a glass bottle (Fujifilm Electronics Materials, capacity 2500ML) was used. The results are shown in Tables 1 to 2.

(Comparative Example 6)

For comparison, evaluation was carried out in the same manner as in Example 1, except that a commercially available plastic sealer bottle (commercially available fragrance container, manufactured by Hokusan Corporation, 1 L) was used. The results are shown in Tables 1 to 2.

[Table 1]

[Table 2]

From Tables 1 to 2, the chemical-resistant blow molded laminated container of Example 1 was excellent in all of particle value, oxygen transmittance, ultraviolet transmittance, visible light transmittance, visibility, drop strength, flavor appropriateness, and metal elution, and the overall judgment was ○. In contrast, it can be seen that any one of these containers for comparison in Comparative Examples 1 to 6 is separated.

[Industrial availability]

The chemical-resistant blow molded laminated container of the present invention, as the inner layer 1, does not have an adhesive functional group, and has an adhesive property to the fluororesin of the inner layer 2, but the additive-free heating loss is 0.20% by mass. The following specific fluororesin was used, and as the inner layer 2, a specific fluororesin having an adhesive functional group and an additive-free additive having adhesiveness to the fluororesin of the inner layer 1 and the barrier and adhesive resin layer, having a heating loss of 0.40% by mass or less By using the above polyamide resin, which does not contain additives or additives containing lubricants or additives intentionally added to the barrier and adhesive resin layer, the degree of cleanliness is 5 or less after 30 days storage at 23°C, and 40°C. After storage for 30 days at 10 or less, a clean degree equivalent to a glass bottle is obtained, chemical resistance can be improved, and deterioration of odor components can be reduced as much as possible, exhibiting a remarkable effect, and excellent oxygen barrier properties. By forming a barrier layer made of ethylene vinyl alcohol copolymer resin, oxygen barrier properties are improved, and the outer layer is formed with high-molecular-weight high-density polyethylene resin with excellent melt tension and excellent UV protection and visible light protection and mechanical strength. Because of its improved properties, it is possible to provide a chemical-resistant blown molded laminated container with a small amount of elution of impurity fine particles without visibility of the contents that can be coped with even as a container for ultra-high purity chemicals containing many expensive and high-risk chemical substances such as fragrances and photoresist. Since it exhibits a remarkable effect, it has high industrial use value.

1A inner layer 1
1B inner floor 2
2 barrier and adhesive resin layer
3 adhesive layer
4 barrier layer
5 adhesive layer
6A outer layer 2
6B outer layer 1
7 Ultra high purity chemicals
8A, 8B chemical resistant blow molded laminated container

Claims (8)

A chemical-resistant blow molded laminated container formed by laminating 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 of the container to the outside, with visible light having a wavelength of 500 to 800 nm. Transmittance of 1% or less, UV transmittance of 200 to 400 nm, 1% or less, and impurity after storage at 23°C for 30 days (number/ml) of impurity particles elution (number/ml) of 5 or less, and impurities after storage at 40°C for 30 days A chemical-resistant blow-molded laminated container having a small amount of dissolution of impurity fine particles of 10 or less.
Inner layer 1: It is an additive-free fluororesin, which does not have an adhesive functional group, has adhesiveness to the fluororesin of the inner layer 2 but does not have adhesiveness to other layers, and has a heating loss of 0.20% by mass or less.
Inner layer 2: It is an additive-free fluororesin, which has an adhesive functional group and has adhesiveness to the fluororesin of the inner layer 1 and the barrier and adhesive resin layer, and the heating loss is 0.40% by mass or less.
Barrier and adhesive resin layer: At least one type of polyamide selected from the group consisting of polyamides obtained by ring-opening polycondensation of caprolactam, which does not contain any additives intentionally added or additives including lubricants.
Adhesive layer: Maleic anhydride-modified polyolefin resin.
Barrier layer: It is an ethylene vinyl alcohol copolymer resin.
Outer layer 1: It contains a light-shielding pigment and a maleic anhydride-modified polyolefin resin, and is an ultra-high molecular weight high-density polyethylene resin having excellent adhesion to the barrier layer. A chemical-resistant blow molded laminated container obtained by laminating the following inner layer 1, inner layer 2, barrier and adhesive resin layer, adhesive layer, barrier layer, adhesive layer and outer layer 2 in order from inside to outside of the container, with wavelengths of 500 to 800 The transmittance of visible light at nm is 1% or less, the UV transmittance at wavelengths 200 to 400 nm is 1% or less, and the elution amount (number/ml) of impure fine particles after storage at 23°C for 30 days is 5 or less, and at 40°C for 30 days A chemical-resistant blow-molded laminated container having a small amount of impurity fine particles eluted after storage (number/ml) of 10 or less.
Inner layer 1: It is an additive-free fluororesin, which does not have an adhesive functional group, has adhesiveness to the fluororesin of the inner layer 2 but does not have adhesiveness to other layers, and has a heating loss of 0.20% by mass or less.
Inner layer 2: It is an additive-free fluororesin, which has an adhesive functional group and has adhesiveness to the fluororesin of the inner layer 1 and the barrier and adhesive resin layer, and the heating loss is 0.40% by mass or less.
Barrier and adhesive resin layer: At least one type of polyamide selected from the group consisting of polyamides obtained by ring-opening polycondensation of caprolactam, which does not contain any additives intentionally added or additives including lubricants.
Adhesive layer: Maleic anhydride-modified polyolefin resin.
Barrier layer: It is an ethylene vinyl alcohol copolymer resin.
Adhesive layer: Maleic anhydride-modified polyolefin resin.
Outer layer 2: It is an ultra-high molecular weight high-density polyethylene resin containing a light-shielding pigment. The method according to claim 1 or 2,
The fluorine resin 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, chlorotrifluoroethylene/ Tetrafluoroethylene/monomer (α) copolymer, and at least one selected from the group consisting of ethylene/chlorotrifluoroethylene/monomer (α) copolymer, and the monomer (α) is a monomer having an adhesive functional group A chemical-resistant blow-molded laminated container, which is a fluororesin having the following properties.
(characteristic)
MFR (265℃, 5Kg load g/10min): 10 to 40
Specific gravity: 1.7-1.9
Melting point (℃): 150-200 The method according to claim 1 or 2,
The fluororesin used for the inner layer 1 is a fluororesin having the following characteristics without having the adhesive functional group.
(characteristic)
MFR (297℃, 5Kg load g/10min): 9 to 35
Specific gravity: 1.7-1.9
Melting point (℃): 200-240 The method according to claim 1 or 2,
A chemical-resistant blow molded laminated container, wherein the polyamide resin has the following characteristics.
(characteristic)
Melting point (℃): 170-250
Density (Kg/㎥): 1.0∼1.2 The method according to claim 1 or 2,
The barrier layer is a chemical-resistant blow molded laminated container, characterized in that it is an ethylene vinyl alcohol copolymer resin having excellent oxygen barrier properties having the following characteristics.
(characteristic)
MFR (210℃, 2.16Kg load g/10min): 2 to 5
Density (Kg/㎥):1.1∼1.3
Melting point (℃): 170-200 The method according to claim 1,
The outer layer 1 is an ultra-high molecular weight high-density polyethylene resin made of polyethylene or ethylene-α-olefin copolymer having the following characteristics, and quinacridone-based, phthalocyanine-based, anthraquinone-based, mono for imparting UV-blocking properties and visible light-blocking properties. Including at least one light-shielding pigment selected from inorganic light-shielding pigments such as azo-based organic light-shielding pigment, carbon black, iron oxide, zinc oxide, ultramarine, chromium oxide, titanium oxide, and silicon dioxide, It contains 0.05 to 0.30 mass% of an antioxidant and 25 to 65 mass% of a maleic anhydride-modified polyolefin resin, the transmittance of visible light at a wavelength of 500 to 800 nm is 1% or less, and the ultraviolet transmittance at a wavelength of 200 to 400 nm is 1% Chemical-resistant blow molded laminated container, characterized in that consisting of the following composition 1.
(characteristic)
Density:940∼962Kg/㎥
Weight average molecular weight: 220,000 to 260,000
Molecular weight distribution (Mw/Mn): 12 or less
Melt tension: 18-30 g The method according to claim 2,
The outer layer divalent, an ultra-high molecular weight high-density polyethylene resin made of polyethylene or ethylene-α-olefin copolymer having the following characteristics, and quinacridone-based, phthalocyanine-based, anthraquinone-based, mono for imparting UV-blocking properties and visible light-blocking properties. Including at least one light-shielding pigment selected from inorganic light-shielding pigments such as azo-based organic light-shielding pigment, carbon black, iron oxide, zinc oxide, ultramarine, chromium oxide, titanium oxide, and silicon dioxide, Chemical-resistant blowing, characterized in that it is composed of composition 2 containing an antioxidant in an amount of 0.05 to 0.30 mass%, a transmittance of visible light at a wavelength of 500 to 800 nm of 1% or less, and an ultraviolet transmittance of 1% or less at a wavelength of 200 to 400 nm Molded laminated container.
(characteristic)
Density:940∼962Kg/㎥
Weight average molecular weight: 220,000 to 260,000
Molecular weight distribution (Mw/Mn): 12 or less
Melt tension: 18-30 g

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