JP6518840B2 - Chemical-resistant blow-molded laminated containers with low impurity particle elution - Google Patents

Description

  The present invention relates to a chemical-resistant blow-molded laminated container in which the amount of leaching of impure fine particles is small, and more specifically, it is excellent in chemical resistance, mechanical strength and the like, for example, chemicals and stored for 30 days at 40 ° C. It is a blow-molded (blow-molded) laminate container with a very small amount of elution (number / ml) of impure particles in perfume etc., ie 10 or less, that is, ultraviolet shielding property, oxygen barrier property The present invention also relates to a chemical-resistant blow-molded laminated container having a low amount of impure fine particle elution without visibility of contents which can be used as an ultrahigh-purity chemical container.

  Generally, a container made of plastic such as a glass container or a sealer bottle (commercially available fragrance container) or a container obtained by coating the inner surface of a metal container is used as a container for storing medicines, perfumes and the like.

  In the semiconductor field, it is necessary to be able to store stored high purity chemicals with high purity. The glass container is inconvenient to handle because the container itself is heavy, and may be broken by dropping or the like.

  On the other hand, a molded container made of a polyethylene-based resin is resistant to cracking during handling and has the advantage of being lightweight. However, high purity chemicals used for etching and cleaning in semiconductor manufacturing, such as sulfuric acid, nitric acid, hydrogen peroxide water, etc., and high purity solvent-based resists and dilution solvents used for semiconductor processes, liquid crystal displays, etc. For example, methyl alcohol, ethyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, acetone, ethyl acetate, toluene, dimethylformamide, ethylene glycol acetate, methoxypropyl acetate, butyl cellosolve, etc., and use for medicines such as sterilization, disinfection, drug substance High purity solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol etc., during storage storage, from the resin composition forming the container and from the There leach, there is a problem that the purity of the chemicals is impaired, the semiconductor for this, or have a significant adverse effect on the liquid crystal quality and yield, a problem of shortening the storage period of drugs.

While the drug is stored for a long time in the container, the impure fine particles leach out from the resin composition forming the container into the drug which is the content, and the impure fine particles show the degree to which the content is impure. There is a degree of cleanliness as an index.
The cleanliness degree once molded the test container and stored ultrapure water in the test container for a certain period (30 days at 23 ° C), then the particle size was 0.2 μm or more in 1 ml of water stored in the resin container. Calculate and calculate how many fine particles are present.

(Conventional method for measuring impure fine particles (particles))
1. Measuring device: Particle counter "KL-26" made by Rion Co., Ltd. RION KL-26 is used.
2. Measurement specimen: A container filled with ultrapure water in a molded container filled with water and stored at 23 ° C. for 30 days, and then a measurement specimen is collected from the container which has been kept standing for 20 minutes in an upright state, to be a measurement specimen.
3. Before the measurement, the particle counter is purged with ultrapure water, and then the measuring apparatus is washed twice with 25 ml of ultrapure water.
4. After washing, ultra pure water is injected into a 10 ml particle counter to measure the number of particles. This operation is performed twice to confirm that the number of particles of 0.2 μm or more is zero (A).
5. Wash the measuring device twice with 25 ml of the measurement sample.
6. After washing, 10 ml is injected into a particle counter from a container (bottle) filled with ultrapure water of the measurement sample, and the number of particles is measured. This operation is performed twice to obtain an average value (B) of the number of particles of 0.2 μm or more.
7. The particle value in 1 ml is calculated from the measured value according to the following equation.
(B (pieces)) ÷ 10 ml = pieces / ml
Conventionally, it has been considered that the quality and yield of semiconductors and liquid crystals can be improved if the degree of cleanliness is less than 500 pieces / ml. It becomes more severe now, and the conventional measurement method often requires 5 or less per ml.
However, recently, the demand for cleanliness has become even higher, and the test container is molded, and the test container is filled with ultrapure water in full water, and the particle size is 0 in 1 ml of ultrapure water after storage for 30 days at 23 ° C. Elution of impure particles with a particle size of 0.2 μm or more in 1 ml of ultrapure water after storage for 30 days at a temperature of 40 ° C. It came to be required that ml) be 10 or less.

  As containers used in the field of spice, cans with a fluorine coating on the inner surface of metal cans and sealer bottles are used in the market. However, in the case of metal cans, there is a problem of dents and rust; The problem of quality deterioration as a perfume is often occurring.

  Therefore, the weight average molecular weight of the raw material resin made of polyethylene or ethylene-α-olefin copolymer is in a certain range, the content of the light shielding pigment and the dispersant in the resin composition is in a certain range, Containers molded from resin compositions consisting of polyethylene or ethylene-α-olefin copolymer whose content of low molecular weight polymer and additive in the product is less than a certain weight has excellent mechanical strength and handling It has been proposed as a light-shielding container for high-purity chemicals (see Patent Document 1) having a light-shielding property, which is easy and extremely low in leaching of impure fine particles into stored chemicals.

  However, this container satisfies the cleanliness of less than 500 pcs / ml by the conventional measurement method, but it does not become less than 5 pcs / ml, and also has oxygen barrier properties etc. There was a problem such as not having.

  A container containing a high purity solvent of methyl alcohol, ethyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, acetone, ethyl acetate, toluene, dimethylformamide, ethylene glycol acetate, methoxypropyl acetate or butyl cellosolve, the container Of at least the inner surface of a polyethylene or ethylene-.alpha.-olefin copolymer resin of density 940 to 970 Kg / m.sup.3 and of the neutralizing agent, antioxidant and light stabilizer in the resin determined by liquid chromatography The content is 0.01% by weight or less based on the total weight of the resin, and the weight average molecular weight of the resin measured by gel permeation chromatography is 120,000 to 260,000. Inside the molecule 1,000 of the polymer is less than 2.5% by weight relative to the total weight of the resin high purity solvent container (see Patent Document 2) are proposed.

  However, although the container for high purity solvents described in Patent Document 2 satisfies the cleanliness of less than 500 pcs / ml by the conventional measurement method, the cleanliness does not become 5 pcs / ml or less, and the deterioration of the contained content liquid is prevented. There is also a problem that it is inferior also to the ultraviolet ray blocking property which can be done.

  In addition, at least 0.01 wt% to 5 wt% of a light shielding pigment such as titanium oxide or carbon black and a liquid or gas barrier resin to a resin of polyethylene or ethylene-α-olefin copolymer having a density of 940 to 970 kg / m3. A container for high purity chemicals comprising a resin composition to which 4% by weight to 25% by weight of is added, wherein the weight average molecular weight of the resin is 120,000 to 260,000 as determined by gel permeation chromatography The polymer having a weight average molecular weight of 1,000 or less is less than 5% by weight of the resin, and the α-olefin is selected from propylene, butene-1, 4-methyl-pentene-1, hexene-1 and octene-1. There is proposed at least one type of high purity chemical container (see Patent Document 3).

  However, the container for high purity chemicals of Patent Document 3 also satisfies the cleanliness of less than 500 pcs / ml by the conventional measurement method, and there is a problem that the cleanliness does not fall below 5 pcs / ml.

Also, at least one selected from ethylene, propylene, butene-1, 4-methyl-pentene-1, hexene-1 or octene-1 olefin polymers, and copolymers of ethylene and other olefins. An inner layer comprising a high purity resin containing various types and containing at most 0.01% by weight of each of a neutralizing agent, an antioxidant and a light stabilizer, and a solvent containing poly (ethylene-co-vinyl alcohol) A container in which an intermediate layer of a barrier resin and an outer layer made of a resin composition containing a light shielding material are blow molded, and the minimum absorbance at a wavelength of 400 nm or less of all layers of the container measured by a spectrophotometer is 2. The extinction coefficient at a wavelength of 400 nm which is zero or more and the absorbance of the whole layer of the container divided by the thickness of the whole layer is 1.5 mm ⁻¹ or more at the wavelength of 600 nm A high purity chemical liquid container (see Patent Document 4) characterized in that the absorption coefficient is 1.5 mm ⁻¹ or less is proposed.

  However, the high purity chemical liquid container of Patent Document 4 satisfies the cleanliness of less than 100 pcs / ml in the conventional measurement method, and has a problem that the cleanliness does not become 5 pcs / ml or less.

The present applicant has previously injected, in order from inside to outside of the container, 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, A molded laminated container having a visible light transmittance of 1% or less at a wavelength of 500 to 800 nm, an ultraviolet light transmittance of 200 to 400 nm at a wavelength of 1% or less, and stored in the container from the container side A blow-molded laminated container for ultra-high-purity chemicals without the visibility of the content having a cleanliness of 5 / ml or less as an index indicating the number of impure fine particles to be leached was proposed (see Patent Document 5).
Inner layer: High density having the following characteristics consisting of a homopolymer or copolymer containing at least one selected from ethylene, propylene, butene-1, 4-methyl-pentene-1, hexene-1 and octene-1. Polyolefin resin.
(Characteristic)
No intentionally added neutralizing agent, antioxidant, and light stabilizer, and the maximum content is 0.005% by mass or less,
Clean degree: 5 pcs / ml or less,
Density: 950 to 962 kg / m ³
Weight average molecular weight: 18 to 250,000
Component with 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 ° C, 21.6 kg load g / 10 min): 6.5 to 9.5

Patent Document 1: Patent No. 2805723 Patent Document 2: Patent No. 2749513 Patent Document 3: Patent No. 2805188 Patent Document 4: Patent No. 4167745 Patent Document 5: Japanese Patent Application No. 2015-243798 Specification

  As described above, recently, the demand for cleanliness is further increased, and the test container is molded, and the test container is filled with ultrapure water in full water and stored in 1 ml of ultrapure water after storage for 30 days at 23 ° C. Dissolution amount (number / ml) of impure fine particles with a particle size of 0.2 μm or more is 5 or less, and elution amount of impure particles with a particle size of 0.2 μm or more in 1 ml of ultrapure water after storage at 40 ° C for 30 days It came to be required that (number / ml) was 10 or less.

The applicant has no visibility of the contents previously proposed ultra-high purity chemicals for blow molding the laminated container (see Patent Document 5), such as excellent chemical resistance and mechanical strength, and storage reservoir Leaching of impure particles into medicines and perfumes is low, and the amount of leaching of impure fine particles with a particle size of 0.2 μm or more in 1 ml of ultrapure water after storage for 30 days at 23 ° C (hereinafter referred to as cleanliness) ) (Number / ml) is 5 or less, the transmittance of visible light with a wavelength of 500 to 800 nm is 1% or less and the visible light blocking property is excellent, and the ultraviolet transmittance of a wavelength of 200 to 400 nm is 1% or less It has excellent properties and oxygen barrier properties, but the elution amount (number / ml) of impure fine particles with a particle size of 0.2 μm or more in 1 ml of ultrapure water after storage at 40 ° C for 30 days is 10 There was a problem that it exceeded.

  The object of the present invention is to improve the chemical resistance and mechanical strength, etc., the cleanliness as an index indicating the number of impure fine particles leached from the container side into ultra high purity chemicals etc stored and stored is 23 ° C. And 5 or less after storage for 30 days, and 10 or less after storage for 30 days at 40 ° C., and excellent in oxygen barrier properties, and having a visible light transmittance of 1% at a wavelength of 500 to 800 nm Below is excellent in visible light blocking properties, UV light transmittance of wavelength 200 to 400 nm is 1% or less and excellent in ultraviolet blocking properties, and visibility of contents that can be used as ultrahigh purity chemical containers such as perfumes and photoresist solutions It is an object of the present invention to provide a chemical-resistant blow-molded laminated container having a low amount of elution of impure fine particles.

  The inventors of the present invention have as a result of keen research to solve the conventional problems, 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 sequentially from the inside to the outside of the container. Chemical-resistant blow-molded laminated container in which the inner layer 1 has no adhesive functional group, and the inner layer 2 has an adhesive property to the fluorocarbon resin but has an adhesive property to the other layers. Using a specific fluorocarbon resin which does not have an additive-free heating loss of 0.20% by mass or less and has an adhesive functional group as the inner layer 2, and the fluorocarbon resin and the barrier and adhesive resin layer of the inner layer 1 Containing additives and additives including lubricants and additives intentionally added as a barrier and adhesive resin layer using a specific fluorocarbon resin having an adhesive property and an additive-free heat loss of 0.40 mass% or less Not using polyamide resin Therefore, the amount of elution of impure microparticles (number / ml) after storage at 23 ° C. for 30 days can be 5 or less, and the elution amount of impure microparticles (number / ml) after storage for 30 days at 40 ° C. can be 10 or less. By using an ethylene vinyl alcohol copolymer resin as the resin, the gas barrier properties can be improved, and by using an ultra-high molecular weight high-density polyethylene resin excellent in ultraviolet ray blocking properties and visible light blocking properties and having a large melt tension, drawdown etc. Since it does not occur and the formability and mechanical strength are improved, the visibility of the contents that can be handled as a container for ultra-high-purity chemicals that contain many expensive and dangerous chemicals such as perfumes and photoresist liquids. It has been found that a chemical-resistant blow-molded laminated container can be obtained which has a low amount of elution of impure fine particles without any impurities, and has reached the present invention.

  The invention according to claim 1 of the present invention for solving the above-mentioned problems has the following inner layer 1, inner layer 2, barrier and adhesive resin layer, adhesive layer, barrier layer and outer layer 1 laminated in order from the inside to the outside of the container. Chemical-resistant blow-molded laminated container, the transmittance of visible light having a wavelength of 500 to 800 nm being 1% or less, and the ultraviolet transmittance of 200 to 400 nm having a wavelength of 1% or less, at 23 ° C. The elution amount of impure microparticles characterized in that the elution amount of impure microparticles (number / ml) after storage for 30 days is 5 or less, and the elution amount of impure microparticles (number / ml) after storage for 30 days at 40 ° C. is 10 or less Chemical-resistant blow-molded laminated containers.

Inner layer 1: Additive-free fluorine resin having no adhesive functional group and having adhesive property to the fluorine resin of the inner layer 2 but no adhesive property to the other layers, and the heat loss is 0 It is .20 mass% or less.
Inner layer 2: An additive-free fluorine resin having an adhesive functional group and having adhesiveness to the fluorine resin of the inner layer 1 and the barrier / adhesive resin layer, and the heating loss is 0.40 mass% or less. Barrier-Adhesive Resin Layer: At least one polyamide selected from the group consisting of polyamides obtained by ring-opening polycondensation of caprolactam which do not contain intentionally added additives or additives containing a lubricant.
Adhesive layer: It is a maleic anhydride modified polyolefin resin.
Barrier layer: ethylene vinyl alcohol copolymer resin.
Outer layer 1: an ultra high molecular weight high density polyethylene resin which contains a light shielding pigment and a maleic anhydride-modified polyolefin resin and is excellent in adhesion to the barrier layer.

  The invention of claim 2 of the present invention is formed by laminating the following inner layer 1, inner layer 2, barrier / adhesive resin layer, adhesive layer, barrier layer, adhesive layer and outer layer 2 in order from the inside to the outside of the container. Chemical resistant blow molded laminate container, having a visible light transmittance of 1% or less at a wavelength of 500 to 800 nm, and a UV transmittance of 1% or less at a wavelength of 200 to 400 nm, for 30 days storage at 23 ° C. After that, the amount of elution of impure microparticles (number / ml) is 5 or less, and the elution amount of impure microparticles (number / ml) after storage for 30 days at 40 ° C. is 10 or less. It is a chemical blow molded laminate container.

Inner layer 1: Additive-free fluorine resin having no adhesive functional group and having adhesive property to the fluorine resin of the inner layer 2 but no adhesive property to the other layers, and the heat loss is 0 It is .20 mass% or less.
Inner layer 2: An additive-free fluorine resin having an adhesive functional group and having adhesiveness to the fluorine resin of the inner layer 1 and the barrier / adhesive resin layer, and the heating loss is 0.40 mass% or less. Barrier-Adhesive Resin Layer: At least one polyamide selected from the group consisting of polyamides obtained by ring-opening polycondensation of caprolactam which do not contain intentionally added additives or additives containing a lubricant.
Adhesive layer: It is a maleic anhydride modified polyolefin resin.
Barrier layer: ethylene vinyl alcohol copolymer resin.
Adhesive layer: It is a maleic anhydride modified polyolefin resin.
Outer layer 2: Ultra high molecular weight high density polyethylene resin containing a light shielding pigment.

  The invention of claim 3 of the present invention is the chemical resistant blow-molded laminated container according to claim 1 or 2, wherein 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 ethylene At least one member selected from the group consisting of / chlorotrifluoroethylene / monomer (α) copolymer, and the monomer (α) is a monomer having an adhesive functional group , And it is characterized by being a fluorine resin which has the following characteristic.

(Characteristic)
MFR (265 ° C, 5 kg load g / 10 min): 10 to 40
Specific gravity: 1.7 to 1.9
Melting point (° C): 150 to 200

  The invention according to claim 4 of the present invention is the chemical resistant blow-molded laminated container according to any one of claims 1 to 3, wherein the fluorine resin used for the inner layer 1 is the adhesive functional group It is characterized in that it is a fluorine-free resin having the following characteristics.

(Characteristic)
MFR (297 ° C, 5 kg load g / 10 min): 9 to 35
Specific gravity: 1.7 to 1.9
Melting point (° C): 200 to 240

  The invention according to claim 5 of the present invention is characterized in that, 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 (° C): 170-250
Density (Kg / m3): 1.0 to 1.2

  The invention according to claim 6 of the present invention is the chemical resistant blow-molded laminated container according to any one of claims 1 to 5, wherein the barrier layer is ethylene excellent in oxygen barrier properties having the following characteristics. It is characterized by being a vinyl alcohol copolymer resin.

(Characteristic)
MFR (210 ° C, 2.16 kg load g / 10 min): 2 to 5
Density (Kg / m3): 1.1 to 1.3
Melting point (° C): 170 to 200

  The invention according to claim 7 of the present invention is the chemical resistant blow-molded laminated container according to claim 1, wherein the outer layer 1 is made of polyethylene or ethylene-α-olefin copolymer having the following characteristics. Density polyethylene resin, quinacridone-based, phthalocyanine-based, anthraquinone-based, and monoazo-based organic light-shielding pigments for imparting ultraviolet blocking properties and visible light blocking properties, carbon black, iron oxide, zinc oxide, ultra blue And at least one light-shielding pigment selected from the group consisting of at least one light-shielding pigment selected from inorganic light-shielding pigments such as chromium oxide, titanium oxide and silicon dioxide, and an antioxidant 0.05 to 0.30% by mass, containing 25 to 65% by mass of maleic anhydride-modified polyolefin resin, and having a wavelength of 500 to 800 nm And the transmittance of light is less than 1%, wherein the ultraviolet transmittance of the wavelength 200~400nm is composed of the composition 1 is not more than 1%.

(Characteristic)
Density: 940 to 962 Kg / m ³
Weight average molecular weight: 220,000 to 260,000
Molecular weight distribution (Mw / Mn): 12 or less
Melt tension: 18 to 30 g

  The invention according to claim 8 of the present invention is the chemical resistant blow-molded laminated container according to claim 2, wherein the outer layer 2 is made of polyethylene or ethylene-α-olefin copolymer having the following characteristics. Density polyethylene resin, quinacridone-based, phthalocyanine-based, anthraquinone-based, and monoazo-based organic light-shielding pigments for imparting ultraviolet blocking properties and visible light blocking properties, carbon black, iron oxide, zinc oxide, ultra blue And at least one light-shielding pigment selected from the group consisting of at least one light-shielding pigment selected from inorganic light-shielding pigments such as chromium oxide, titanium oxide and silicon dioxide, and an antioxidant It contains 0.05 to 0.30% by mass, has a transmittance of visible light having a wavelength of 500 to 800 nm of 1% or less, and has a violet wavelength of 200 to 400 nm. Wherein the linear transmittance is constituted from a composition 2 is 1% or less.

(Characteristic)
Density: 940 to 962 Kg / m ³
Weight average molecular weight: 220,000 to 260,000
Molecular weight distribution (Mw / Mn): 12 or less
Melt tension: 18 to 30 g

The invention according to claim 1 of the present invention is a chemical-resistant blow formed 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 sequentially from the inside to the outside of the container. It is a self-forming laminated container, the transmittance of visible light having a wavelength of 500 to 800 nm is 1% or less, the ultraviolet transmittance of a wavelength of 200 to 400 nm is 1% or less, and impure fine particles after storage for 30 days at 23 ° C. Elution amount (number / ml) is 5 or less, and impure fine particle elution amount (number / ml) after storage for 30 days at 40 ° C. is 10 or less. Molded laminated container,
The inner layer 1 has no adhesive functional group, and the fluorine resin of the inner layer 2 has adhesiveness but does not have adhesiveness to other layers. And the additive-free heat loss of the fluorine-containing resin of the inner layer 1 and the adhesive property of the barrier and adhesive resin layer is 0.40% by mass as the inner layer 2 using the specific fluorine resin which is By using a specific fluororesin which is the following, and using a polyamide resin which does not contain an additive or an additive containing a lubricant intentionally added to the barrier and adhesive resin layer, the cleanliness is 30 at 23 ° C. Clean degree equivalent to a glass bottle of 5 or less after day storage and 10 or less after 30 days storage at 40 ° C can be obtained, chemical resistance can be improved, and deterioration of odor component can be reduced as much as possible. Play a remarkable effect That.

  Further, by providing a barrier layer made of ethylene vinyl alcohol copolymer resin excellent in oxygen barrier property, the oxygen barrier property is improved, while the melt tension of the fluorocarbon resin, the polyamide resin and the adhesive resin is reduced at once. As a result, problems such as drawdowns occur during blow molding, and for example, there is a problem that a container with uniform thickness can not be molded or a defective product is generated and the yield is deteriorated. The use of ultra-high molecular weight, high-density polyethylene resin with excellent UV blocking properties and visible light blocking properties and mechanical strength improves moldability and UV blocking properties, so it is expensive and dangerous for perfumes and photoresist solutions. Can be used as a container for ultra-high-purity chemicals that contain many highly volatile chemicals, and has low-impact fine particle elution levels without visible contents It can provide blow molded multilayer containers, a marked effect of.

  Moreover, since the chemical-resistant blow-molded laminated container of the present invention contains a maleic anhydride-modified polyolefin resin as the outer layer 1 and uses the outer layer having excellent adhesiveness with the barrier layer, the outer layer 1 and the barrier layer There is a remarkable effect that there is no need to provide an adhesive layer (maleic anhydride-modified polyolefin resin) between them, and the workability and economy become better.

In addition, the chemical-resistant blow-molded laminated container of the present invention is resistant to breakage, has excellent mechanical strength, and is provided with a barrier layer, as compared with a heavy, easily broken, and unsafe glass bottle. Improves the oxygen barrier properties, so that it can be used as a perfume bottle etc., and can be used for various contents as well, it can be used safely and safely in terms of taste and odor etc. It produces a remarkable effect of being able to.
Since the chemical resistant blow-molded laminated container of the present invention has the above-mentioned characteristics, it is easy for the environment and health, contributes to environmental problems and health problems, and reduces costs, so it is economical. It produces a remarkable effect of

The invention according to claim 2 of the present invention comprises the inner layer 1, the inner layer 2, the barrier / adhesive resin layer, the adhesive layer, the barrier layer, the adhesive layer and the outer layer 2 sequentially from the inside to the outside of the container. Chemical resistant blow molded laminate container, having a visible light transmittance of 1% or less at a wavelength of 500 to 800 nm, and a UV transmittance of 1% or less at a wavelength of 200 to 400 nm, for 30 days storage at 23 ° C. After that, the amount of elution of impure microparticles (number / ml) is 5 or less, and the elution amount of impure microparticles (number / ml) after storage for 30 days at 40 ° C. is 10 or less. A chemical blow molded laminate container,
The chemical resistance blow molded laminate container according to claim 2 of the present invention is within the acceptable range of economic efficiency by providing the adhesive layer (maleic anhydride modified polyolefin resin) between the outer layer 2 and the barrier layer. Although it slightly lowers, the adhesion between the two is assured, so it is used depending on the application and purpose. Except this point, it has the same configuration as the chemical resistant blow-molded laminated container of claim 1 of the present invention. The effect is the same as that of the chemical resistant blow-molded laminated container of claim 1 of the present invention.

The invention of claim 3 of the present invention is the chemical resistant blow-molded laminated container according to claim 1 or 2, wherein 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 ethylene At least one member selected from the group consisting of / chlorotrifluoroethylene / monomer (α) copolymer, and the monomer (α) is a monomer having an adhesive functional group , And the fluorine resin having the above-mentioned characteristics,
By using for the inner layer 2 a fluorine resin obtained by copolymerizing a monomer (α) having an adhesive functional group, the fluorine resin of the inner layer 1 and the barrier and adhesive resin layer (polyamide resin) have excellent adhesion. In addition, coextrusion molding can be performed at a molding temperature comparable to that of the polyolefin, which produces a further remarkable effect.

  The invention according to claim 4 of the present invention is the chemical resistant blow-molded laminated container according to any one of claims 1 to 3, wherein the fluorine resin used for the inner layer 1 has the adhesive functional group. Furthermore, it is a fluorine resin having the above-mentioned characteristics, and it is characterized in that it has excellent adhesion to the fluorine resin of the inner layer 2 and that coextrusion molding becomes possible at a molding temperature comparable to that of polyolefin. It produces remarkable effects.

The invention according to claim 5 of the present invention is characterized in that, in the chemical resistant blow-molded laminated container according to any one of claims 1 to 4, the polyamide resin has the above-mentioned characteristics. And
The adhesion of the inner layer 2 to the fluorocarbon resin is improved, and by making the additive and the lubricant free, the amount of elution of impure particles caused by the additive can be greatly reduced, and the cleanliness equivalent to a glass bottle can be obtained. It produces a further remarkable effect.

The invention according to claim 6 of the present invention is the chemical resistant blow-molded laminated container according to any one of claims 1 to 5, wherein the barrier layer is excellent in oxygen barrier properties having the above-mentioned characteristics. Ethylene vinyl alcohol copolymer resin,
A further remarkable effect is exerted that the oxygen barrier properties are surely further improved.

The invention according to claim 7 of the present invention is the chemical resistant blow-molded laminated container according to claim 1, wherein the outer layer 1 is made of polyethylene or ethylene-α-olefin copolymer having the above-mentioned characteristics. Density polyethylene resin, quinacridone-based, phthalocyanine-based, anthraquinone-based, and monoazo-based organic light-shielding pigments for imparting ultraviolet blocking properties and visible light blocking properties, carbon black, iron oxide, zinc oxide, ultra blue And at least one light-shielding pigment selected from the group consisting of at least one light-shielding pigment selected from inorganic light-shielding pigments such as chromium oxide, titanium oxide and silicon dioxide, and an antioxidant 0.05 to 0.30% by mass, containing 25 to 65% by mass of maleic anhydride-modified polyolefin resin, and having a wavelength of 500 to 800 nm Transmittance of light is less than 1%, which is characterized in that ultraviolet transmittance at a wavelength of 200~400nm is composed of the composition 1 is 1% or less,
Melt tension of the fluorocarbon resin, polyamide resin and adhesive resin is reduced immediately after melting, which causes problems such as drawdown in blow molding, for example, a container of uniform thickness can not be molded or defective products are generated. There is a problem that the yield is deteriorated, but by using the ultra high molecular weight high density polyethylene resin with large weight average molecular weight and melt tension for the outer layer 1, problems such as draw down are eliminated and the formability and mechanical strength etc. Improved
By using a suitable amount of light-shielding pigment, visible light blocking properties and ultraviolet blocking properties are surely improved, and the visible light transmittance of wavelengths 500 to 800 nm is 1% or less, and the ultraviolet transmittance of wavelengths 200 to 400 nm is reliable. Since it can achieve 1% or less, it can be used as a container for ultra-high purity chemicals containing many expensive and dangerous chemicals such as perfumes and photoresist liquids. Further, the use of the antioxidant within the above range can prevent the burning of the resin, and can prevent the deterioration of physical properties and the deterioration of the appearance due to the burning resin.

  Moreover, since the chemical-resistance blow-molded laminated container of the present invention contains a maleic anhydride-modified polyolefin resin as the outer layer 1 and uses the outer layer having excellent adhesion to the barrier layer, the outer layer 1 and the barrier layer There is a further remarkable effect that there is no need to provide an adhesive layer (maleic anhydride-modified polyolefin resin) between them, and the workability and economy become better.

  In addition, the chemical-resistant blow-molded laminated container of the present invention is resistant to breakage, has excellent mechanical strength, and is provided with a barrier layer, as compared with a heavy, easily broken, and unsafe glass bottle. Improves the oxygen barrier properties, so that it can be used as a perfume bottle etc., and it can be used safely and safely in terms of taste and odor as a universal plastic container that can also be used for various contents. It produces a further remarkable effect of.

The invention according to claim 8 of the present invention is the chemical resistant blow-molded laminated container according to claim 2, wherein the outer layer 2 is made of polyethylene or ethylene-α-olefin copolymer having the following characteristics. Density polyethylene resin, quinacridone-based, phthalocyanine-based, anthraquinone-based, and monoazo-based organic light-shielding pigments for imparting ultraviolet blocking properties and visible light blocking properties, carbon black, iron oxide, zinc oxide, ultra blue And at least one light-shielding pigment selected from the group consisting of at least one light-shielding pigment selected from inorganic light-shielding pigments such as chromium oxide, titanium oxide and silicon dioxide, and an antioxidant Transmittance of visible light having a wavelength of 500 to 800 nm, containing 0.05 to 0.30% by mass, is 1% or less, and violet having a wavelength of 200 to 400 nm It is characterized in that the linear transmittance is constituted from a composition 2 is 1% or less,
Melt tension of the fluorocarbon resin, polyamide resin and adhesive resin is reduced immediately after melting, which causes problems such as drawdown in blow molding. For example, a container having a uniform thickness can not be molded or a defective product is generated. There is a problem that the retention is deteriorated, but by using the ultra high molecular weight high density polyethylene resin with large weight average molecular weight and melt tension for the outer layer 2, problems such as draw down are eliminated and the formability and mechanical strength are improved. The visible light blocking property and the ultraviolet blocking property are surely improved by using a proper amount of the light shielding pigment, and the visible light transmittance of the wavelength 500 to 800 nm is 1% or less reliably, and the ultraviolet transmission of the wavelength 200 to 400 nm Can achieve a rate of 1% or less, so containers for ultra-high-purity chemicals containing many expensive and dangerous chemicals such as perfumes and photoresist solutions Even if the amount of impure fine particles that can be handled can be reduced, a chemical-resistant blow-molded laminated container can be provided more reliably, and by using an antioxidant within the above range, burning of the resin is prevented, and physical properties attributed to the burning resin. It has the further remarkable effect of being able to prevent deterioration or deterioration of the appearance.

By providing an adhesive layer (maleic anhydride-modified polyolefin resin) between the outer layer 2 and the barrier layer, the economy is slightly reduced within the allowable range, but the adhesion between the two is ensured, so According to the purpose, it has the same configuration as the outer layer 1 except for this point, and the action and effect are the same as the chemical resistant blow-molded laminated container of the present invention using the outer layer 1 It produces a further remarkable effect.
That is, the chemical resistant blow-molded laminated container of the present invention is hard to be broken, has excellent mechanical strength, and is provided with a barrier layer as compared with a heavy, easily broken, and unsafe glass bottle. Improves the oxygen barrier properties, so that it can be used as a perfume bottle etc., and it can be used safely and safely in terms of taste and odor as a universal plastic container that can also be used for various contents. It produces a further remarkable effect.

BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing which illustrates typically the cross section of one example of the chemical-resistant blow-molded laminated container of this invention. It is explanatory drawing which illustrates typically the cross section of the other example of the chemical-resistant blow-molded laminated container of this invention. It is a graph which shows the result of the infrared spectroscopy analysis of the inner layer 1 of the chemical-resistant blow-molded laminated container of this invention. It is a graph which shows the result of the infrared spectroscopy analysis of the inner layer 2 of the chemical-resistant blow-molded laminated container of this invention.

Hereinafter, the present invention will be described in detail using the drawings.
FIG. 1 is an explanatory view for explaining a cross section of one example of the 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 made of the above-mentioned fluorocarbon resin having an adhesive functional group, the inner layers 1 and 1B consisting of the fluorocarbon resin not having an adhesive functional group. Inner layers 2 and 2 are 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, 5 is An adhesive layer comprising a maleic anhydride modified polyolefin resin, 6A is an ultrahigh molecular weight high density polyethylene having a transmittance of 1% or less for visible light with a wavelength of 500 to 800 nm and 1% or less for ultraviolet light with a wavelength of 200 to 400 nm The outer layer 2 which consists of resin is shown, respectively. 7 shows the ultra-high purity drug which is the content.

FIG. 2 is an explanatory view for explaining the 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 made of the above-mentioned fluorocarbon resin having an adhesive functional group, the inner layers 1 and 1B consisting of the fluorocarbon resin having no adhesive functional group. Inner layers 2 and 2 are 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, 6B is Ultrahigh molecular weight comprising a maleic anhydride modified polyolefin resin having a transmittance of 1% or less for visible light with a wavelength of 500 to 800 nm and an ultraviolet transmittance for a wavelength of 200 to 400 nm with a good adhesion to the barrier layer 4 The outer layer 1 which consists of high density polyethylene resin is shown, respectively. 7 shows the ultra-high purity drug which is the content.
Since the outer layer 1 contains 25 to 65% by mass of a maleic anhydride-modified polyolefin resin, it is excellent in the adhesion between the outer layer 1 and the barrier layer 4 and has no problems such as drawdown, and the formability and machineability Excellent in mechanical strength etc. However, if the amount of maleic anhydride-modified polyolefin resin is less than 25% by mass, adhesion between the outer layer 1 and the barrier layer 4 may be insufficient. If the amount of maleic anhydride-modified polyolefin resin exceeds 65% by mass, drawdown And other problems may occur.

The fluorine resin used for the inner layer 2 is not particularly limited. 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 / monomer (α) copolymer, chlorotrifluoroethylene / tetrafluoroethylene / monomer (α) copolymer, and ethylene / chlorotrifluoroethylene / monomer (α) copolymer The inner layer 2 is a fluorine resin of the inner layer 1 when it is a fluorine resin which is at least one selected from the group consisting of polymers and which is obtained by copolymerizing a monomer (α) having an adhesive functional group having the above-mentioned properties. And the barrier / adhesive resin layer (polyamide resin) have excellent adhesiveness, and coextrusion molding becomes possible at a molding temperature comparable to that of a polyolefin, so that they can be preferably used.
As the fluorine resin used for the inner layer 2 in the present invention, it is preferable to use an additive-free, additive-free grade fluorine resin.

  The fluorine resin used for the inner layer 1 in the present invention is a fluorine resin which does not copolymerize the monomer (α) having an adhesive functional group and does not have the adhesive functional group, and has no additive free It is preferable to use an addition grade fluorine resin.

And the fluorine resin used for the inner layer 1 in the present invention is 0.20 mass% or less, preferably 0.15 or less, of the heating loss measured by the following heating loss measurement method, and the fluorine resin used for the inner layer 2 is the same measurement The heating loss measured by the method should be 0.40% by mass or less, preferably 0.30 or less. Within this range, the cleanliness can be 5 or less after 30 days storage at 23 ° C. and 10 or less after 30 days storage at 40 ° C. However, the cleanliness can not be achieved outside the above range There is a fear.

(Heating weight loss measurement method)
The aluminum cup is precisely weighed to a weight of 0.1 mg with a balance (WO).
Place 5.00 ± 0.01 g of the sample in an aluminum cup and precisely weigh the total mass to 0.1 mg (W).
After adjusting the temperature of the electric furnace to 260 ° C. ± 1 ° C., the sample is heated for 240 minutes.
After heating, the sample is taken out and cooled in a desiccator, and the sample is precisely weighed to 0.1 mg (W1).
Then, the heating loss is calculated by the following equation.
Weight loss on heating (mass%) = [(W-W1) / (W-W0)] x 100

(About the desirable characteristic of inner layer 2)
MFR (265 ° C., 5 kg load g / 10 min) (measurement method: 265 ° C., ASTM D1238) is preferably 10 to 40, more preferably 20 to 30, and if it is less than 10, the melt viscosity is high and the blow molding formability is If it exceeds 40, the melt tension is too low and problems such as draw down may occur during blow molding.

The specific gravity (measurement method: ASTM D-792) may be 1.7 to 1.9, and more preferably 1.72 to 1.76 of the specific gravity of a commercially available product. If the specific gravity is less than 1.7, there may be a problem that the adhesion is reduced, and if it exceeds 1.9, the strength of the container may be insufficient.
The melting point (° C.) (measurement method: ASTM D 792) varies depending on the amount and type of the copolymerized monomer (α), but it may be 150 to 200 ° C. of melting point of a commercially available product. Preferably it is 190-200 degreeC. If the melting point is less than 150 ° C., a difference in melting point with other resins may occur to cause problems in adhesive strength and moldability, and when the melting point exceeds 200 ° C., it may be difficult to laminate with other resins .

The monomer (α) to be copolymerized is not particularly limited as long as it is a monomer that has an adhesive functional group and can be copolymerized, but controlling the amount and type in consideration of melt molding It is preferable that the fluorine resin in the inner layer 2 be in the melting point (° C.) range, and that the fluorine resin in the inner layer 1 and the barrier and adhesive resin layer (polyamide resin) have excellent adhesion.
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. can be mentioned, for example. As a specific example of this copolymer, ethylene-tetrafluoroethylene-hexafluoropropylene-ethylene carbonate copolymer EFEP (for example, RP5000 manufactured by Daikin Industries, Ltd.) used in Example 1 can be mentioned.

(About the desirable characteristic of inner layer 1)
MFR (297 ° C., 5 kg load g / 10 min) (measurement method: 265 ° C., ASTM D1238) is preferably 9 to 35, more preferably 15 to 25. If it is less than 9, the melt viscosity is high and the blow molding formability is If it exceeds 35, the melt tension is low, and problems such as draw-down may occur during blow molding.

The specific gravity (measurement method: ASTM D-792) may be 1.7 to 1.9, and more preferably 1.83 to 1.89, as the specific gravity of a commercially available product. If the specific gravity is less than 1.7, there may be a problem that the adhesion is reduced, and if it exceeds 1.9, 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., which is the melting point of a commercially available product. If the melting point is less than 200 ° C., a difference in melting point with other resins may occur to cause problems in adhesive strength and moldability, and when the melting point exceeds 240 ° C., it may be difficult to laminate with other resins .

The polyamide resin of the barrier and adhesive resin layer used in the present invention is an additive-free polyamide resin to which no additive or additive containing a lubricant and which is usually added intentionally is added or formulated. Specific examples thereof include Z 4887 manufactured by Daicel Evonik Co., Ltd.
Among them, at least one polyamide selected from nylon 6, nylon 11, nylon 12, nylon 66, etc., obtained by ring-opening polycondensation of caprolactam, and which does not contain an additive or an additive containing a lubricant is It can be used preferably.

(Characteristic)
Melting point (° C) (according to ISO11357): 170-250
Density (Kg / m ³ ) (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.
If the melting point is less than the lower limit value, adhesion may be insufficient, and if the upper limit value is exceeded, moldability may be deteriorated.
If the density is less than the lower limit value, adhesion may be insufficient, and if the upper limit value is exceeded, the formability may be deteriorated.

  The maleic anhydride-modified polyolefin resin of the adhesive layer used in the present invention has excellent adhesion to the barrier-cum-adhesive resin layer (the polyamide resin) and the barrier layer (ethylene vinyl alcohol copolymer resin). Furthermore, the maleic anhydride-modified polyolefin resin of the adhesive layer has excellent adhesion to the barrier layer (ethylene vinyl alcohol copolymer resin) and the outer layer (ultrahigh molecular weight high density polyethylene resin), Both of them are adhered to form an adhesive layer, and they may be melt-molded as long as they can be melt-molded. Commercially available commercial products can be used.

The maleic anhydride-modified polyolefin resin of the adhesive layer for adhering the barrier layer and the outer layer (ultrahigh molecular weight high density polyethylene resin) to the inner layers 1 and 2 (fluororesin), as long as the adhesiveness is not impaired Compounded with recovered material including barrier / adhesive resin layer (the above polyamide resin), adhesive layer (maleic anhydride modified polyolefin resin), barrier layer (ethylene vinyl alcohol copolymer resin) and outer layer (ultra high molecular weight high density polyethylene resin) can do.
Since the maleic anhydride-modified polyolefin resin compounded with the recovered product of the adhesive layer is separated from the fluorocarbon resin of the inner layer 1 to be the liquid-contacting surface, there is practically no risk of loss of cleanliness. .

  A maleic anhydride-modified polyolefin resin having excellent adhesion to a barrier-cum-adhesive resin layer (the polyamide resin) and a barrier layer (ethylene-vinyl alcohol copolymer resin), and a barrier layer (ethylene-vinyl alcohol copolymer resin) The maleic anhydride-modified polyolefin resin having excellent adhesiveness to the outer layer (ultrahigh molecular weight high density polyethylene resin) may be the same as or different from, and is preferably determined by testing in advance.

  The ethylene vinyl alcohol copolymer resin (ethylene 24 to 44 mol% copolymer) of the barrier layer used in the present invention is a resin which is almost completely saponified by hydrolysis of ethylene vinyl alcohol copolymer, Have excellent gas barrier properties and are widely used in containers and packaging materials for medicines and cosmetics, etc., and have high resistance to oils, organic solvents, etc., and in particular ethylene vinyl alcohol copolymer having the following characteristics By using a polymer resin, oxygen barrier properties can be secured, and MFR, melting point, and the like are close to those of the ultrahigh molecular weight high density polyethylene resin, and are preferably used because they are excellent in stability moldability. As an example of ethylene vinyl alcohol copolymer resin of a barrier layer, F171B (Ethylene 32 mol% copolymerization, Melting point 183 ° C, Saponification rate 99.99%) manufactured by Kuraray Co., Ltd. is specifically mentioned, for example. be able to.

(Characteristic)
MFR (210 ° C, 2.16 kg load g / 10 min): 2 to 5
Density (Kg / m3): (according to ISO1183) 1.1 to 1.3
Melting point (° C): (according to ISO 1346): 170 to 200
The MFR is preferably 2 to 5, more preferably 3 to 5, and 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, and more preferably 190 to 200. When the MFR, density, and melting point are in the above ranges, gas barrier properties, strength, stable moldability, and the like are all excellent, but outside the above ranges, at least one of these properties may be impaired.

  As the ultrahigh molecular weight high density polyethylene resin of the outer layers 1 and 2 used in the present invention, as described above, the density (measurement method: in accordance with JIS K7112) is preferably 940 to 962 kg / m3, more preferably 944 to 946 kg / m3. The weight average molecular weight (measurement method: described later) is preferably 22 to 260,000, more preferably 24 to 260,000, and the molecular weight distribution (Mw / Mn) (measurement method: described later) is preferably 12 or less, more preferably 11 or less, melt tension (Measuring method: Nippon polyethylene method, using Capillograph made by Toyo Seiki Seisakusho, 210 ° C, orifice: L: 8 mm, D: 2.095 mm, piston descent speed 10 mm / min, winding speed 3.9 mm / min Ultra-high molecular weight high density polyethylene which is preferably 18 to 30 g, more preferably 22 to 26 g The use of the ultrahigh molecular weight high density polyethylene resin as the outer layers 1 and 2 improves moldability and mechanical strength, eliminates problems such as draw down, and improves yield and the like.

  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 as narrow as 12 or less, multilayer molding blow molding under the usual molding processing conditions of melt processing and rapid cooling Since the outer layers 1 and 2 of the laminated container are formed of compact small crystal aggregates, mechanical strength is improved.

  The (Mw / Mn) of the ultrahigh molecular weight high density polyethylene resin forming the outer layers 1 and 2 is preferably 12 or less, more preferably 11 or less, and melt processing and rapid cooling when (Mw / Mn) exceeds 12 The crystals of the outer layer of the blow-molded laminated container formed in a multi-layered manner under such normal forming processing conditions may become large or disperse, and may not be composed of fine small crystal aggregates, resulting in a lack of mechanical strength.

  When the weight average molecular weight of the ultrahigh molecular weight high density polyethylene resin is less than 220,000, the high density polyethylene resin forming the outer layers 1 and 2 may lack mechanical strength, and the weight average molecular weight exceeds 260,000. Since the melt viscosity of the resin is high, the moldability is deteriorated, and molecular cutting due to shear stress may occur.

  If 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, while if the upper limit is exceeded, the bottle surface May cause melt fracture problems.

Ultra high molecular weight polyethylene resin used in the outer layer 1, ethylene Ren, propylene, butene-1,4-methyl - pentene-1, hexene-1, homopolymers containing at least one selected from octene-1 Alternatively, a commercial product which is a copolymer and has the above-mentioned properties can be used. Among them, ethylene homopolymers and copolymers of ethylene and α-olefins such as propylene, butene-1, 4-methyl-pentene-1, hexene-1 and octene-1 are preferably used. The content of α-olefin in the copolymer is preferably 15% by mass or less. If a polymer or copolymer having the above characteristics such as a density of 940 to 962 Kg / m ³ is obtained, the molecular structure of the copolymer is atactic, isotactic, syndiotactic or the like. Any of the mixtures may be used without particular limitation, and for example, the low pressure method or the medium pressure method may be used.

The outer layers 1 and 2 used in the present invention have at least one light-shielding pigment selected from organic light-shielding pigments and / or inorganic light-shielding pigments and have a visible light transmittance of 1 to 500 nm. It is preferable to mix | blend a predetermined amount so that it is% or less (by the measuring method mentioned later), and the ultraviolet-ray transmittance | permeability of wavelength 200-400 nm becomes 1% or less (by the measuring method mentioned later).
As an organic light-shielding pigment and an inorganic light-shielding pigment, the visible light transmittance of a wavelength of 500 to 800 nm is 1% or less, and the ultraviolet transmittance of a wavelength of 200 to 400 nm is a mixture by incorporating a predetermined amount in the outer layer. It is not particularly limited as long as it can be 1% or less and does not impair the other properties of the outer layer.

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

  Specific examples of quinacridone-based light-shielding pigments include TET 48183 and TET 78310 (manufactured by Toyo Color Co., Ltd.).

  Specific examples of phthalocyanine-based light-shielding pigments include 7F2854 (manufactured by Dainichi Seika Kogyo Co., Ltd.), TET58335 (manufactured by Toyo Color Co., Ltd.) and EPH-525328 (manufactured by Polycor Kogyo Co., Ltd.). Can.

  Specific examples of the monoazo light-shielding pigment include TET 38013 (manufactured by Toyo Color Co., Ltd.) and ECE-6293 (manufactured by Polycor Kogyo 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 Kogyo Co., Ltd.).

  Specific examples of the iron oxide-based light-shielding pigment include EPH-C-1045 (manufactured by Polycol Kogyo Co., Ltd.) and TET 68473 (manufactured by Toyo Color Co., Ltd.).

  Specific examples of ultramarine based light-shielding pigments include EPH-B-46662 (manufactured by Polycol Kogyo Co., Ltd.) and TET26146 (manufactured by Toyo Color Co., Ltd.).

  Specific examples of titanium oxide-based light-shielding pigments include EB-1427 (manufactured by DIC Corporation), EPH-H-2481 (manufactured by Polycor Kogyo Co., Ltd.), and TET 28318 (manufactured by Toyo Color Co., Ltd.). It can be mentioned.

In the use of these light-shielding pigments, it is preferable to avoid pigments having poor dispersibility and pigments that promote the oxidative degradation of containers.
In the present invention, after the types of the ultrahigh molecular weight high density polyethylene resin and the light shielding pigment forming the outer layers 1 and 2 and the like are determined, the compounding amount of the light shielding pigment is tested in advance and visible at a wavelength of 500 to 800 nm The transmittance of light is preferably 1% or less, and the transmittance of ultraviolet light having a wavelength of 200 to 400 nm is preferably 1% or less.
When the transmittance of visible light of wavelength 500 to 800 nm can be 1% or less and the transmittance of ultraviolet light of wavelength 200 to 400 nm can be 1% or less, there is no visibility of the contents and deterioration of the contained contents can be prevented. For example, it can be used as an ultra-high-purity chemical container such as a chemical or fragrance which can be provided with an ultraviolet blocking property and which is denatured and hardened by ultraviolet rays such as a photoresist solution.

  As a specific example of the light-shielding pigment and the compounding amount, an example in which 2 mass% of phthalocyanine-based light-shielding pigment (trade name: 7F2854: manufactured by Dainichi Seika Kogyo Co., Ltd.) is mixed in the outer layer in Example 1 described later is given be able to. Since 7F2854 is a masterbatch containing 6% by mass of phthalocyanine, 0.012% by mass of phthalocyanine is blended in the outer layer in the above example, and the ultraviolet transmittance is 1% or less and the visible light transmittance is 1% or less I got the result of.

The outer layers 1 and 2 used in the present invention are blended with a predetermined amount of at least one antioxidant selected from the group consisting of phenol type, phosphorus type and sulfur type antioxidants (0.05 to 0.30 mass% It is preferable to prevent the burning of the resin and to prevent the deterioration of the appearance due to the burning resin.
The phenol-based antioxidant, the phosphorus-based antioxidant, and the sulfur-based antioxidant are not particularly limited as long as they have a high antioxidant action and do not impair the other properties of the outer layers 1 and 2.

Specific examples of the phenolic antioxidant include Adekastab AO60 manufactured by ADEKA Corporation.
Specific examples of the phosphorus-based antioxidant include Adekastab 2112 manufactured by ADEKA Corporation.
Specific examples of the sulfur-based antioxidant include DSTP manufactured by Yositomi Mitsubishi Chemical Co., Ltd.

  It is preferable to mix | blend 0.05-0.30 mass% of these antioxidant with respect to the ultra-high molecular weight high-density polyethylene resin which forms the outer layers 1 and 2, 0.10-0.25 mass% It is more preferable to do. If the amount is less than 0.05% by mass, the antioxidant performance may be degraded, and if it exceeds 0.30% by mass, the additive may bleed out on the surface of the container.

  The outer layers 1 and 2 used in the present invention contain a light-shielding pigment, an antioxidant and the like which can become impure fine particles, but since the outer layers 1 and 2 are separated from the inner layers 1 and 2 which become liquid contact surfaces, The impervious fine particles caused by the light-shielding pigment, antioxidant, etc. are prevented from leaching into the content liquid by the barrier / adhesive resin layer 2, the adhesive layers 3, 5, the barrier layer 4, etc. Do not leach into chemicals such as

In the present invention, light-shielding stabilizers such as benzotriazole-based light stabilizers and triazine-based light stabilizers may be suitably used in the outer layers 1 and 2 as well as the light-shielding pigments.
By using a benzotriazole light stabilizer or a triazine light stabilizer, UV-B (200 to 320 nm) and UV-A (320 to 400 nm) can be blocked, respectively, and other properties can be obtained by using both in combination. It is possible to significantly improve the ultraviolet blocking properties without loss.

Examples of light stabilizers 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-tert-butyl-cresol, 2- (3,5-di-tert-amino-2-hydroxyphenyl) Ben zo triazole, 2- (2H-benzotriazol-2-yl)-p-benzotriazole light stabilizer, such as cresol, 2- [4,6-di (2,4-xylyl) -1,3,5 Triazin-2-yl] -5,2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine, 2- (4,6-dipheny) Triazine-based light stabilizers such as 1,3,5-triazin-2-yl) -5- [2- (2-ethylhexaneuroxy) 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) And-tetramethyl-4-piperidyl) imino} hexamethylene (2,2,6,6-tetramethyl-4-piperidyl) imino}] include hindered amine light stabilizers.

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

In the method of measuring the molecular weight of the resin of the container, the resin composition cut off from the container is dissolved in a solvent (orthodichlorobenzene) to form a sample solution, and the molecular weight and molecular weight distribution are measured by GPC. The weight average molecular weight and the number average molecular weight are calculated by the following equation.
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.

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

  The molding method is not particularly limited as long as it can mold the chemical-resistant blow-molded laminated container excellent in transparency of the present invention by the blow molding method, and a commercially available blow-molded laminated container is used. It can also be used by selecting from a molding machine.

  The above description of the embodiment is intended to explain the present invention, and does not limit the scope of the invention described in the claims. Further, the configuration of each part of the present invention is not limited to the above embodiment, and various modifications are possible within the technical scope described in the claims.

  EXAMPLES The present invention will next be described in detail by way of examples, which should not be construed as limiting the invention without departing from the spirit of the present invention.

Example 1
Additive-free fluorocarbon resin (EP-610 manufactured by Daikin Industries, Ltd.) with an MFR of 25 g / 10 min, a specific gravity of 1.86, a melting point of 223 ° C. and a heating loss of 0.16 mass% is used as the inner layer 1. Additive-free fluorocarbon resin (RP-5000 manufactured by Daikin Industries, Ltd.) with a specific gravity of 1.74 and a melting point of 195 ° C and a heating loss of 0.35% by mass is used as a barrier and adhesive resin layer. Additive-free polyamide resin (product of Daicel Evonik Co., Ltd. Z4887, relative viscosity 1) which has an adhesive function with the fluorocarbon resin of the inner layer 2 and does not contain an additive containing an additive or lubricant intentionally added. Maleic anhydride-modified polyolefin resin (Nippon Polyethylene Co., Ltd.) as an adhesive layer having an adhesive function between the polyamide resin and the barrier layer using Using T71A) and using a barrier resin (ethylene-vinyl alcohol copolymer resin F171B: manufactured by Kuraray Co., Ltd., saponification ratio 99.99%) as a barrier layer, and as an outer layer 1, ultrahigh molecular weight high density polyethylene Maleic anhydride-modified polyolefin for resin (HB111R manufactured by Japan Polyethylene Corp.) (HL-MFR (measurement method: JIS K7112) 6 g / 10 min, density 946 Kg / m ³ , weight average molecular weight 250,000, melt tension 25 g) 30% by mass of resin (Japan polyethylene FT71A), phthalocyanine-based light-shielding pigment (trade name: 7F2854: product of Dainichi Seika Kogyo Co., Ltd., phthalocyanine 6% by mass) for improving visible light blocking property and ultraviolet blocking property Containing masterbatch) 2% by mass, Phenolic antioxidant as an antioxidant (trade name: Adécasta AO60: manufactured by ADEKA Co., Ltd.) and a phosphorus-based antioxidant (trade name: Adekastab 2112: manufactured by ADEKA) manufactured by using an ultra-high molecular weight high-density polyethylene resin containing 0.2% by mass in total There are no problems with draw down under molding conditions, and the chemical resistant blow molded laminate container of the present invention consisting of 6 layers (total weight 400 g, inner layer 1 50 μm, inner layer 2 100 μm, barrier and adhesive resin layer 50 μm, adhesion 50 μm of the layer, 50 μm of the barrier layer, 1500 μm of the outer layer 1, an average total thickness of 1.8 mm, and a capacity of 3750 ML).

(Molding condition)
A blow molding machine (6 types and 6 layers made by Bluns Co., Ltd.) (a type in which six types of extruders are used to laminate six layers with one die head) was used.
Fluorine resin of inner layer 1: Screw diameter 40 mm 設定 Setting temperature: 260 ° C
Fluoro resin in inner layer 2: Screw diameter 20 mm 設定 Setting temperature: 240 ° C
Polyamide resin layer: Screw diameter 20 mm 設定 Setting temperature: 200 ° C
Maleic anhydride-modified polyolefin resin layer: Screw diameter 20 mmΦ Setting temperature: 220 ° C.
Ethylene-vinyl alcohol copolymer resin layer: Screw diameter 40 mm 設定 Setting temperature: 230 ° C.
Ultrahigh molecular weight high density polyethylene resin of outer layer 1: Screw diameter 50 mm 50 Setting temperature: 220 ° C
Die head temperature: Set temperature: 235 ° C
The polyamide resin and the barrier resin having hygroscopic property were dried at 80 ° C. using a drier to remove water.

And, immediately after the extraction at 23 ° C and stored for 30 days, the elution amount of impure fine particles (number / ml) after extraction and the immediately after the extraction at 40 ° C and the elution amount of impure fine particles after extraction after storage for 30 days (number / ml) Measure using the sample bottle by the following test method, evaluate oxygen permeability and visibility by the following test method, cut out a sample of 4 cm × 4 cm × 1.8 mm from the wall of the bottle barrel, and use it to measure The ultraviolet ray transmittance and the visible light transmittance are evaluated by the test method in the following, and the container is filled with pure water, the metal elution is evaluated by the following test method, and the drop strength and the perfume suitability are evaluated by the following test method. Ataishi commentary loss on heat of layers of an inner layer 1, 2 and Se'ekimen the test method described above, for the economy, without the use of expensive materials, high marketability if economically possible to provide a container ○ Due to the use of expensive materials, depending on the application market Although there are, economic efficiency is evaluated to be ×, and carried out a comprehensive decision are collectively. The results are shown in Tables 1 and 2.
The heating loss described in Table 1 is the heating loss of the inner layer 1 or the layer to be the liquid contact surface.

  The fluorine resin of the inner layer 1 of the chemical resistant blow-molded laminated container of the present invention obtained by molding in Example 1 (EP-610 manufactured by Daikin Industries, Ltd.) and the fluorine resin of the inner layer 2 (Daikin Industries, Ltd.) The infrared spectroscopy analysis was performed on the following measurement conditions using RP-5000 manufactured by Japan.

(Infrared spectroscopy measurement conditions)
Measurement device: IR Affinity-1 manufactured by Shimadzu Corporation
Measurement sample: A 50 μm thick film sheet of the inner layers 1 and 2 was prepared and used using a 240 ° C. press.
Measurement wavelength: 600 to 4000 cm ^-1

FIG. 3 shows the results of infrared spectroscopy of the inner layer 1, where the vertical axis is absorbance (%) and the horizontal axis is wavelength (cm ⁻¹ ).
FIG. 4 shows the results of infrared spectroscopy of the inner layer 2, where the vertical axis shows absorbance (%) and the horizontal axis shows wavelength (cm ⁻¹ ).
When FIG. 3 and FIG. 4 are superimposed, it can be seen that they have substantially the same waveform except for the sharp absorption at the wavelength 1800 (cm ⁻¹ ) of FIG. 4.

Large sharp absorption at a wavelength of 1800 (cm ^-1) of FIG. 4 (indicated by arrows) is the absorption peak of the carbonate group, the fluorine resin inner layer 2 is seen to have an adhesive officer functional group (carbonate group) .
The fluorine resin of the inner layer 2 is manufactured by copolymerizing the monomer (α) having the adhesive functional group as described above, and the fluorine resin of the inner layer 2 is selected depending on the amount of the monomer (α) to be copolymerized. The amount of adhesive functional groups can be controlled, thereby controlling the adhesiveness of the inner layer 2 fluorocarbon resin and the like, so that the inner layer 2 adheres well to the inner layer 1 fluorocarbon resin and the barrier / adhesive resin layer. At the same time, the melting point can be controlled to be within the predetermined range.
Not seen the large sharp absorption peak in the wavelength 1800 of FIG. 3 (cm ^-1), fluororesin of the inner layer 1 indicates that no adhesion officer functional group (carbonate group). The inner layer 1 has good adhesion to the fluorocarbon resin of the inner layer 2 but no 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)
(Method of measuring impure fine particles (particles))
The following measurements are performed in a clean room (class 100).
1. Measuring device: Particle counter "KL-26" made by Rion Co., Ltd. RION KL-26 is used.
2. Measurement sample: Fill ultrapure water in a molded container with full water, store immediately after extraction at 23 ° C and after storage for 30 days, or after extraction at 40 ° C after storage after storage for 30 days and after erection, 20 What collected the measurement sample from the container left still for a minute is taken as a measurement sample.
3. Before the measurement, the particle counter is purged with ultrapure water, and then the measuring apparatus is washed twice with 25 ml of ultrapure water.
4. After washing, ultra pure water is injected into a 10 ml particle counter to measure the number of particles. This operation is repeated twice to confirm that the number of particles of 0.2 μm or more is zero (A).
5. Wash the measuring device twice with 25 ml of the measurement sample.
6. After washing, 10 ml is injected into a particle counter from a container (bottle) filled with ultrapure water of the measurement sample, and the number of particles is measured. This operation is performed twice to obtain an average value (B) of the number of particles of 0.2 μm or more.
7. The particle value in 1 ml is calculated from the measured value according to the following equation.
(B (pieces)) ÷ 10 ml = pieces / ml

Oxygen permeability [cm ^{3 / (} pkg.24h.atm)]:
Using a 3.75 L container (wall thickness at the center of the bottle: 1.8 mm) and according to JIS K 7126-2, using (OX-TRAN 2/21) (made by MOCON) from the outside of the container The inward oxygen permeation was measured. Temperature and humidity: outside 1 atmosphere, 23 ° C., 50% RH oxygen. Inside 1 atm, 23 ° C, dry nitrogen.

(UV transmittance)
The transmittance in the ultraviolet region of 200 to 400 nm is determined using JASCO V-670.

(Visible light transmittance)
Using JASCO Corporation V-670, the transmittance in the visible light region of 500 to 800 nm is determined.

(Visibility)
In a room of 750 lux, put the tap water into the container, and observe the tap water with the naked eye with 3 persons from outside the container. Then, the following three evaluations are made.
Rating:
×: Tap water can be confirmed.
:: It can be confirmed if you look at the tap water well.
○: We can not confirm tap water.

(Fall strength)
The container is filled with 80% of water by volume, dropped from the height 1.2 m to the concrete surface 5 times with the bottom of the container down, dropped once with the container side down, and visual evaluation of cracks and leaks Do.

(Perfuming appropriate)
Typical examples of perfumes are limonene (trade name: orange oil, purity 96.4%, manufactured by Hasegawa perfume), citrus fruits (trade name: lemon essence, produced by Hasegawa perfume), crab oil (15%) Dimethyl sulfide, propylene glycol solution, manufactured by Hasegawa Perfume Co., Ltd., rice salad (trade name: rice oil, produced by Hasegawa Perfume Co., Ltd.), ethyl butyrate (trade name: esters, purity 100%, Hasegawa perfume C) Made using trans-2-hexenal (trade name: aldehydes, 99.7% purity, manufactured by Hasegawa Fragrance Co., Ltd.), 1 kg of each flavor is filled and sealed separately, and one month at normal temperature and pressure, I left for three months. However, only crab oil (15% dimethyl sulfide, propylene glycol solution) was stored refrigerated at normal temperature and normal pressure for 1 month and 3 months.
After standing for 3 months, for each sample, measure the container weight and check whether the contents have dissipated, and do 10 panel members perform a sensory test to check whether or not the material has been altered, and specific gravity and refractive index It was measured and checked whether or not it fluctuates, and for samples which can be analyzed, components were checked by gas chromatograph and evaluated according to the following evaluation criteria.

Evaluation criteria:
○: There is no dissipation, deterioration, fluctuation, etc., storage stability is high, and there is marketability.
:: slightly inferior to 、, but practically no dissipation, deterioration, fluctuation, etc., practically practical, storage stability is high and marketable.
X: Dissipation, deterioration, fluctuation, etc., storage stability is low and there is no marketability.

(Metal elution)
Filled with pure water full level in the sample container, 23 ° C. and allowed to stand for 30 days in heated state at 40 ℃, ICP-MASS the pure water as the specimen (Agilent Technologies Co., Ltd. 8800) using the ppb level Measure up to. The measurement is performed in a clean room (class 1000). 23 of the elements Li, Na, Mg, Al, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Ag, Cd, Sn, Ba, W, Au, Pb Measure the element. Pass if 10 ng / L or less.

(Comprehensive judgment)
The particle value after 30 days at 23 ° C is 5 particles / ml or less, and the particle value after 30 days at 40 ° C is 10 particles / ml or less,
Oxygen permeability is 0.003 [cm ^{3 / (} pkg.24h.atm)] or less,
UV transmittance less than 1%,
Visible light transmittance less than 1%,
Visibility is ○ (cannot confirm the tap water inside),
Drop strength: no destruction,
O-、, appropriate for perfume
Metal elution is less than 10 (ng / L).
If all pass, the comprehensive judgment is 判定. If any of these is inferior to the above, it is determined that the overall determination is x.

(Comparative example 1)
In place of the additive-free polyamide resin (Z 4887 manufactured by Daicel Evonik Co., Ltd.) (barrier and adhesive resin, relative viscosity 1.87) used in Example 1, an antioxidant (hindered phenolic antioxidant, A blow-molded laminated container for comparison was made and evaluated in the same manner as in Example 1 except that the same polyamide resin (relative viscosity 1.87) containing 2000 ppm) was used. The results are shown in Tables 1 and 2.

(Comparative example 2)
Instead of the inner layers 1 and 2 used in Example 1, a component having a density of 956 kg / m 3, HL-MFR (measurement method: JIS K 7112, load 21.6 kg) 8 g / 10 min, Mw / Mn = 11, and a molecular weight of 1000 or less A blow-molded laminated container for comparison was produced and evaluated in the same manner as in Example 1 except that a wetted layer using 0.2% by mass of high density polyethylene (9D01A manufactured by Tosoh Corp.) was used. . The results are shown in Tables 1 and 2.

(Comparative example 3)
Comparative Example 1 is the same as Example 1 except that the inner layer 1 used in Example 1 is not used, and the inner layer 2 used in Example 1 is used as the wetted layer of 0.35% by mass. The blow molded laminate containers were made and evaluated. The results are shown in Tables 1 and 2.

(Comparative example 4)
Except that the fluorine resin of the liquid contact layer used in Comparative Example 3 was heated at a temperature of 260 ° C. ± 1 ° C. for 120 minutes to reduce the heating loss (heating loss of 0.31 mass%). In the same manner as in Comparative Example 3, a blow-molded laminated container for comparison was made and evaluated. The results are shown in Tables 1 and 2.

(Comparative example 5)
For comparison, evaluation was performed in the same manner as in Example 1 except that a glass bottle (Fuji Film Electronics Materials, volume 2500 ML) was used. The results are shown in Tables 1 and 2.

(Comparative example 6)
For comparison, evaluation was performed in the same manner as in Example 1 except that a commercially available plastic sealer bottle (commercially available perfume container, manufactured by Kitai Acid Co., Ltd., 1 L) was used. The results are shown in Tables 1 and 2.

  From Tables 1 to 2, the chemical resistant blow-molded laminated container of Example 1 had particle values, oxygen permeability, ultraviolet transmittance, visible light transmittance, visibility, drop strength, spice suitability, metal elution It is understood that the container for comparison of Comparative Examples 1 to 6 is inferior in any one of these, while the overall judgment is ○, which is excellent in all of the above.

The chemical-resistant blow-molded laminated container of the present invention does not have an adhesive functional group as the inner layer 1 and has adhesiveness to the fluorine resin of the inner layer 2 but does not have adhesiveness to other layers. Additive-free heat loss is 0.20% by mass or less using a specific fluorine resin, and as the inner layer 2, it has an adhesive functional group, and the adhesiveness to the fluorine resin of the inner layer 1 and the barrier and adhesive resin layer is Said polyamide which does not contain the additive and the additive containing the additive and the lubricant intentionally added to the barrier-cum-adhesive resin layer using a specific fluorine resin which has no additive and which has a heating loss of 0.40 mass% or less By using the resin, a degree of cleanliness equivalent to a glass bottle is obtained which is 5 or less after storage for 30 days at 23 ° C. and 10 or less after storage for 30 days at 40 ° C. While improving the drugability, it also has an odor component The remarkable effect of reducing the deterioration as much as possible, the oxygen barrier property is improved by providing the barrier layer made of ethylene vinyl alcohol copolymer resin excellent in the oxygen barrier property, and the outer layer has a high melt tension and an ultraviolet blocking property and visible since moldability and ultraviolet blocking properties are improved by using the light shielding sectional resistance and mechanical strength such as excellent ultra high molecular weight high density polyethylene resin, high chemical expensive and the risk of such perfumes and photoresist liquid It has the remarkable effect of being able to provide a chemical-resistant blow-molded laminated container with a low amount of impure fine particle elution without visibility of the contents that can be handled as a container of too many ultra-high-purity chemicals. Is high.

1A inner layer 1
1B inner layer 2
2 barrier / adhesive resin layer 3 adhesive layer 4 barrier layer 5 adhesive layer 6 A outer layer 2
6B Outer layer 1
7 Ultra High Purity Chemicals 8A, 8B Chemical resistant blow-molded laminated containers

Claims (8)

A chemical-resistant blow-molded laminated container comprising an inner layer 1, an inner layer 2, a barrier and adhesive resin layer, an adhesive layer, a barrier layer, and an outer layer 1 laminated in this order from the inside to the outside of the container. The transmittance of visible light of ~ 800 nm is 1% or less, the UV transmittance of wavelength 200 to 400 nm is 1% or less, and the amount of leached impure fine particles (number / ml) after storage for 30 days at 23 ° C is 5 or less And a chemical-resistant blow-molded laminated container with a small amount of elution of impure microparticles, characterized in that the amount of elution of impure microparticles (number / ml) after storage for 30 days at 40 ° C. is 10 or less.
Inner layer 1: Additive-free fluorine resin having no adhesive functional group and having adhesive property to the fluorine resin of the inner layer 2 but no adhesive property to the other layers, and the heat loss is 0 It is .20 mass% or less.
Inner layer 2: An additive-free fluorine resin having an adhesive functional group and having adhesiveness to the fluorine resin of the inner layer 1 and the barrier / adhesive resin layer, and the heating loss is 0.40 mass% or less.
Barrier and adhesive resin layer: containing no additive comprising an additive pressurizing and lubricants, at least one polyamide selected from the group consisting of polyamides obtained by ring-opening polycondensation of caprolactam.
Adhesive layer: It is a maleic anhydride modified polyolefin resin.
Barrier layer: ethylene vinyl alcohol copolymer resin.
Outer layer 1: an ultra high molecular weight high density polyethylene resin which contains a light shielding pigment and a maleic anhydride-modified polyolefin resin and is excellent in adhesion to the barrier layer. A chemical-resistant blow-molded laminated container obtained by laminating the following inner layer 1, inner layer 2, barrier / adhesive resin layer, adhesive layer, barrier layer, adhesive layer and outer layer 2 in order from the inside to the outside of the container. Transmittance of visible light with a wavelength of 500 to 800 nm is 1% or less, ultraviolet transmittance of a wavelength of 200 to 400 nm is 1% or less, and the amount of leached impure fine particles after storage for 30 days at A chemical-resistant blow-molded laminated container with a small amount of elution of impure fine particles characterized in that the amount of leaching of impure fine particles (number / ml) after storage for 30 days at 40 ° C. is 10 or less.
Inner layer 1: Additive-free fluorine resin having no adhesive functional group and having adhesive property to the fluorine resin of the inner layer 2 but no adhesive property to the other layers, and the heat loss is 0 It is .20 mass% or less.
Inner layer 2: An additive-free fluorine resin having an adhesive functional group and having adhesiveness to the fluorine resin of the inner layer 1 and the barrier / adhesive resin layer, and the heating loss is 0.40 mass% or less.
Barrier and adhesive resin layer: containing no additive comprising an additive pressurizing and lubricants, at least one polyamide selected from the group consisting of polyamides obtained by ring-opening polycondensation of caprolactam.
Adhesive layer: It is a maleic anhydride modified polyolefin resin.
Barrier layer: ethylene vinyl alcohol copolymer resin.
Adhesive layer: It is a maleic anhydride modified polyolefin resin.
Outer layer 2: Ultra high molecular weight high density polyethylene resin containing a light shielding pigment. 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, At least one selected from the group consisting of chlorotrifluoroethylene / tetrafluoroethylene / monomer (α) copolymer, and ethylene / chlorotrifluoroethylene / monomer (α) copolymer, The chemical resistance according to claim 1 or 2, wherein the monomer (α) is a monomer having an adhesive functional group and is a fluorine resin having the following characteristics: Blow-molded laminated container.
(Characteristic)
MFR (265 ° C, 5 kg load g / 10 min): 10 to 40
Specific gravity: 1.7 to 1.9
Melting point (° C): 150 to 200 4. The chemical-resistant resin according to any one of claims 1 to 3, wherein the fluorine resin used for the inner layer 1 is a fluorine resin which does not have the adhesive functional group and has the following characteristics. Molded laminated container.
(Characteristic)
MFR (297 ° C, 5 kg load g / 10 min): 9 to 35
Specific gravity: 1.7 to 1.9
Melting point (° C): 200 to 240 The said polyamide resin has the following characteristic, The chemical-resistant blow-molded laminated container of any one of the Claims 1-4 characterized by the above-mentioned.
(Characteristic)
Melting point (° C): 170-250
Density (Kg / m ³ ): 1.0 to 1.2 The said barrier layer is ethylene-vinyl alcohol copolymer resin excellent in oxygen barrier property which has the following characteristics, The chemical-resistant blow molding of any one of the Claims 1-5 characterized by the above-mentioned. Stacked containers.
(Characteristic)
MFR (210 ° C, 2.16 kg load g / 10 min): 2 to 5
Density (Kg / m ³ ): 1.1 to 1.3
Melting point (° C): 170 to 200 The outer layer 1 is an ultrahigh molecular weight high density polyethylene resin comprising polyethylene or ethylene-α-olefin copolymer having the following characteristics, and quinacridone, phthalocyanine and anthrales for imparting ultraviolet ray blocking property and visible light blocking property. quinone, and the light-shielding pigment of organic monoazo, carbon black, iron oxide, zinc oxide, ultramarine blue, chromium oxide, titanium oxide, at least one light-shielding selected from shielding pigment of inorganic dioxide silicofluoride-containing Pigment containing at least one light-shielding pigment selected from the group consisting of inorganic pigments, 0.05 to 0.30 mass% of an antioxidant, 25 to 65 mass% of a maleic anhydride-modified polyolefin resin, and a wavelength of 500 A group in which the transmittance of visible light of ~ 800 nm is 1% or less and the UV transmittance of wavelengths 200 to 400 nm is 1% or less Chemical resistance blow molding laminated container according to claim 1, characterized in that it is constituted from the object 1.
(Characteristic)
Density: 940 to 962 Kg / m ³
Weight average molecular weight: 220,000 to 260,000
Molecular weight distribution (Mw / Mn): 12 or less Melt tension: 18 to 30 g The outer layer 2 is an ultrahigh molecular weight high density polyethylene resin consisting of polyethylene or ethylene-α-olefin copolymer having the following characteristics, and quinacridone, phthalocyanine and anthrales for imparting ultraviolet ray blocking property and visible light blocking property. quinone, and the light-shielding pigment of organic monoazo, carbon black, iron oxide, zinc oxide, ultramarine blue, chromium oxide, titanium oxide, at least one light-shielding selected from shielding pigment of inorganic dioxide silicofluoride-containing Pigment containing at least one light-shielding pigment selected from the group consisting of inorganic pigments, 0.05 to 0.30 mass% of an antioxidant, and having a visible light transmittance of 1% or less at a wavelength of 500 to 800 nm The chemical resistance according to claim 2, characterized in that the composition 2 is composed of a composition 2 having a UV transmittance of 1% or less at a wavelength of 200 to 400 nm. Blow molding laminated container.
(Characteristic)
Density: 940 to 962 Kg / m ³
Weight average molecular weight: 220,000 to 260,000
Molecular weight distribution (Mw / Mn): 12 or less Melt tension: 18 to 30 g