JP2015123351A - Chemical resistance blow molding laminated container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a chemical resistance blow molding laminated container in which the deterioration of perfume ingredients is not caused and the container can be used as a super high purity medicine container such as a photoresist solution, the blow molding laminated container that is superior in chemical resistance or mechanical strength, and the percolation of impure particles to the inside such as a stored medicine or perfume is reduced.SOLUTION: A chemical resistance blow molding laminated container to solve problems is characterized by sequentially laminating the following inner layers from the inside to the outside of the container, the inner layers that are a barrier-cum-adhesive resin layer, an adhesive layer, a barrier layer, an adhesion layer and an outer layer, where the inner layer is a fluorinated carbon resin, the barrier- cum- adhesive resin layer is a special polyamide resin, the adhesive layer is a maleic anhydride modified polyolefins resin, the barrier layer is an ethylene vinyl alcohol copolymer resin, the adhesion layer is a maleic anhydride modified polyolefins resin and the outer layer is an ultra high molecular weight high-density polyethylene resin.

Description

  The present invention relates to a chemical-resistant blow-molded laminated container. More specifically, the present invention is excellent in chemical resistance and mechanical strength, and impregnation of impure particles into stored chemicals and fragrances. Blow molding (blow molding) laminated container with low cleanliness, that is, good cleanliness (very small amount of impure particle elution), chemical resistant blow that can be used as an ultra high purity chemical container The present invention relates to a molded laminated container.

  Generally, as a container for storing chemicals, fragrances, etc., a glass container, a plastic container such as a sealer bottle, or a container obtained by coating the inner surface of a metal container is used.

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

  On the other hand, a molded container made of a polyethylene resin is advantageous in that it is difficult to break during handling and is lightweight. However, high-purity chemicals used for etching and cleaning in semiconductor manufacturing, such as sulfuric acid, nitric acid, hydrogen peroxide water, and high-purity solvent-based resists and dilution solvents used for semiconductor processes, 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. High purity solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, etc. while being stored, impure fine particles into the chemical stored from the resin composition and additives that form the container Leached, compromising the purity of the drug. For this reason, there is a problem in that the quality and yield of semiconductors and liquid crystals are significantly adversely affected, and the storage period of chemicals is shortened.

In addition, during the long-term storage of the chemical in the container, the degree to which the impure fine particles are leached out from the resin composition forming the container into the chemical that is the content, and the impure fine particles impair the content. There is a cleanness as an index indicating.
The degree of cleanness is that once a test container is molded and ultrapure water is stored in the test container for a certain period of time, there are several fine particles having a particle size of 0.2 μm or more in 1 ml of water stored in the resin container. It is calculated and calculated.

(Measurement method of impure particles)
1. Measuring apparatus: A particle counter “KL-26” RION KL-26 manufactured by Rion Co., Ltd. is used.
2. Sample to be measured: A sample obtained by collecting a sample to be measured from a container which is filled with ultrapure water in a molded container and is allowed to stand for 20 minutes in an upright state is used as a sample to be measured.
3. Before the measurement, purge the particle counter with ultrapure water, and then wash the measuring device twice with 25 ml of ultrapure water.
4). After washing, ultrapure water is poured into a 10 ml particle counter and the number of particles is measured. This operation is performed twice to confirm that the number of particles of 0.2 μm or more is zero (A).
5. Wash the measuring device twice with 25 ml measurement sample.
6). After washing, 10 ml is injected into a particle counter from a bottle filled with ultrapure water as a measurement sample, and the number of particles is measured. This operation is performed twice to obtain an average value (B) of the number of particles of 0.2 μm or more.
7). The particle value in 1 ml is calculated from the measured value by the following formula.
(B (pieces)) ÷ 10 ml = pieces / ml
Conventionally, it has been said that the quality and yield of semiconductors and liquid crystals can be improved when the cleanness is less than 500 / ml. However, it is becoming more severe at present, and there are many cases where 5 pieces / ml or less is required.

  Cans and seal bottles with fluorine coating on the inner surface of metal cans are used on the market as containers used in the perfume field, but metal cans have problems of dents and rust. The quality of the fragrance has been increasing frequently.

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, and the resin composition A container molded from a resin composition composed of polyethylene or ethylene-α-olefin copolymer with a low molecular weight polymer in the product and an additive content of less than a certain weight is excellent in mechanical strength and handling. It has been proposed as a light-shielding container for high-purity chemicals having a light-shielding property (see Patent Document 1), which is easy and has very little leaching of impure fine particles into stored and stored chemicals.
The impure fine particles leached into the stored chemical from the resin composition or additive made of polyethylene or ethylene-α-olefin copolymer forming the container, and there was a risk of impairing the purity of the chemical.

Japanese Patent No. 2805723

  The object of the present invention is excellent in chemical resistance, mechanical strength, etc., and there is little leaching of impure particles into stored chemicals and fragrances, that is, the degree of cleanliness is good (impure particles). (Elution amount is very small) Blow-molding (blow-molding) laminated containers that can avoid the alteration of perfume ingredients, and can be used as ultra-high-purity chemical containers such as perfumes and photoresist solutions. It is to provide a multi-layered laminated container.

  In order to solve the conventional problems, the present inventors have intensively studied, and as a result, by using a fluororesin resin as an inner layer serving as a liquid contact surface, preferably by using an additive-free fluororesin resin. The chemical properties can be improved, the alteration of odor components can be reduced as much as possible, and by using a special polyamide resin with free additives and lubricants, the cleanliness equivalent to glass bottles (impure particle elution) By using ethylene vinyl alcohol copolymer resin as the barrier layer, the gas barrier property can be improved. On the other hand, after melting the fluororesin, polyamide resin and adhesive resin, the melt tension decreases at once. As a result, problems such as draw-down occur in blow molding. For example, a uniform-thickness container cannot be molded, or defective products are generated, resulting in poor yield. However, using an ultra-high molecular weight high-density polyethylene resin with a high melt tension in the outer layer prevents drawdown and improves moldability and mechanical strength, making it expensive and dangerous. The present inventors have found that a chemical-resistant blow-molded laminated container that can be used as a container for ultra-high-purity chemicals with a large amount of high chemical substances can be obtained.

  Claim 1 of the present invention for solving the above-mentioned problems is formed by laminating the following inner layer, barrier-adhesive resin layer, adhesive layer, barrier layer, adhesive layer and outer layer in order from the inside to the outside of the container. This is a chemical-resistant blow-molded laminated container.

Inner layer: Fluorine resin barrier-cumulative resin layer: Special polyamide resin Adhesive layer: Maleic anhydride modified polyolefin resin barrier layer: Ethylene vinyl alcohol copolymer resin adhesive layer: Maleic anhydride modified polyolefin resin outer layer: Ultra high molecular weight high density It is a laminate blow container of polyethylene resin.

Claim 2 of the present invention is the chemical resistant blow molded laminated container according to claim 1,
The fluororesin used for the inner layer is tetrafluoroethylene / hexafluoropropylene / monomer (α) copolymer, tetrafluoroethylene / perfluoro (alkyl vinyl ether) / monomer (α) copolymer 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 a polymer, a chlorotrifluoroethylene / tetrafluoroethylene / monomer (α) copolymer, and an ethylene / chlorotrifluoroethylene / monomer (α) copolymer. The monomer (α) is a monomer having an adhesive functional group, and is a fluororesin having the following characteristics.

(Characteristic)
MFR (5 kg load g / 10 min): 10 to 40
Specific gravity: 1.7 to 1.9
Melting point (° C): 150-220

Claim 3 of the present invention is the chemical resistant blow-molded laminated container according to claim 1 or 2,
The special polyamide resin is intentionally free of additives including additives and lubricants, and the maximum content of the additives is 0.01% by mass or less.

Claim 4 of the present invention is the chemical resistant blow-molded laminated container according to any one of claims 1 to 3,
The ultra high molecular weight high density polyethylene resin is made of polyethylene or an ethylene-α-olefin copolymer, and is an ultra high molecular weight high density polyethylene resin having the following characteristics.

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

Claim 1 of the present invention is a chemical resistance characterized by laminating the inner layer, the barrier / adhesive resin layer, the adhesive layer, the barrier layer, the adhesive layer and the outer layer in order from the inner side to the outer side of the container. A blow molded laminated container,
By using a fluororesin resin as the inner layer on the wetted surface, chemical resistance can be improved, alteration of odor components can be reduced as much as possible, and by using a special polyamide resin with free additives and lubricants, glass The degree of cleanliness equivalent to a bottle is obtained (the impure particle elution amount is very small), and by using ethylene vinyl alcohol copolymer resin as the barrier layer, the gas barrier property can be improved. The melt tension of special polyamide resin and adhesive resin decreases at once after melting, so problems such as draw-down occur in blow molding, for example, it is impossible to mold a uniform wall thickness container, defective products occur, and yield increases There were problems such as deterioration, but by using ultra-high molecular weight high-density polyethylene resin with high melt tension for the outer layer, moldability and mechanical strength, etc. Improved, also exhibits a remarkable effect of providing a compatible chemical resistance blow molding the laminated container as a container for expensive and highly hazardous chemicals often ultra high purity chemicals.

  Further, a six-layer chemical-resistant blow-molded laminate using a fluororesin resin as an inner layer that becomes a wetted surface, preferably an additive-free fluororesin resin, and an ethylene vinyl alcohol copolymer resin as a barrier layer By making it a container, it is hard to break, unlike a glass bottle that is heavy, easy to break, and lacks safety, has excellent mechanical strength, and has performance as a universal container as a fragrance bottle, As a versatile plastic container that can also be used for various other contents, it has a remarkable effect that it can be used safely and securely with respect to taste and smell.

  Since the chemical-resistant blow molded laminated container of the present invention has the characteristics as described above, it is easy for the environment and health, so it contributes to environmental problems and health problems, and it also reduces costs and is economical. It has the remarkable effect of being.

Claim 2 of the present invention is the chemical resistant blow molded laminated container according to claim 1, wherein the fluororesin used for the inner layer is a 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 / chlorotri At least one selected from the group consisting of a fluoroethylene / monomer (α) copolymer, the monomer (α) is a monomer having an adhesive functional group, and the characteristics With foot It is characterized by being a base resin,
By using a fluororesin resin copolymerized with a monomer (α) having an adhesive functional group as an inner layer that becomes a wetted surface, coextrusion molding can be performed at a molding temperature comparable to polyolefin, and an adjacent barrier function There is a further remarkable effect that adhesion with the adhesive resin layer (special polyamide resin) is improved.

Claim 3 of the present invention is the chemical resistant blow-molded laminated container according to claim 1 or 2, wherein no additive or additive containing a lubricant is intentionally added to the special polyamide resin. The maximum content of the additive is 0.01% by mass or less,
By using a special polyamide resin that does not intentionally add additives or lubricants, and the maximum content of the additives is below a specified value, the amount of impure particle elution caused by the additives is greatly reduced. And a further remarkable effect is obtained in that a cleanliness equivalent to a glass bottle can be obtained.
When the maximum content of the additive exceeds 0.01% by mass, the impure fine particles are leached into the chemical and the cleanliness is 5 / ml or more, and cannot be used as a light-shielding container for high-purity chemicals.

A fourth aspect of the present invention is the chemical resistant blow molded laminated container according to any one of the first to third aspects, wherein the ultra high molecular weight high density polyethylene resin is polyethylene or ethylene-α-olefin. It consists of a copolymer and is characterized by being an ultra-high molecular weight high-density polyethylene resin having the above characteristics,
By using an ultra-high molecular weight high-density polyethylene resin having a high melt tension for the outer layer, the moldability and mechanical strength are further improved, and problems such as the above-mentioned draw-down are eliminated, and the yield and the like are further improved. .

FIG. 1 is an explanatory view schematically illustrating a wall cross section of a chemical-resistant blow-molded laminated container of the present invention.

Hereinafter, the present invention will be described in detail with reference to the drawings.
FIG. 1 is an explanatory view illustrating a cross section of a chemical-resistant blow-molded laminated container of the present invention.
1 is an inner layer made of a fluororesin, 2 is a barrier / adhesive resin layer made of a special polyamide resin, 3 is an adhesive layer made of a maleic anhydride-modified polyolefin resin, and 4 is made of an ethylene vinyl alcohol copolymer resin. Barrier layers 5 are adhesive layers made of maleic anhydride-modified polyolefin resin, and 6 is an outer layer made of ultrahigh molecular weight high-density polyethylene resin.

The fluororesin used in the present invention is not particularly limited, but specifically, for example, tetrafluoroethylene / hexafluoropropylene / monomer (α) copolymer, tetrafluoroethylene / perfluoro (Alkyl vinyl ether) / monomer (α) copolymer, ethylene / tetrafluoroethylene / monomer (α) copolymer, ethylene / tetrafluoroethylene / hexafluoropropylene / monomer (α) Copolymer, chlorotrifluoroethylene / monomer (α) copolymer, chlorotrifluoroethylene / tetrafluoroethylene / monomer (α) copolymer, and ethylene / chlorotrifluoroethylene / monomer ( α) At least one selected from the group consisting of copolymers, and a fluororesin obtained by copolymerizing a monomer (α) having an adhesive functional group having the above characteristics, at a molding temperature comparable to polyolefin. Since co-extrusion molding becomes possible and the adhesiveness with the adjacent barrier / adhesive resin layer (special polyamide resin) is improved, it can be preferably used.
As the fluororesin used in the present invention, an additive-free non-addition grade fluororesin resin is preferably used.

The MFR (5 kg load g / 10 min) (265 ° C., 5 kg load, ASTM D1238) is preferably 10 to 40, more preferably 20 to 30. If it is less than 10, the melt viscosity is high, and the blow melt moldability is deteriorated and driven. The energy may also increase. If it exceeds 40, the melt tension is low, and problems such as draw-down may occur during blow molding.
The specific gravity (measuring method: ASTM D-792) may be a commercially available specific gravity of 1.7 to 1.9, and preferably 1.72 to 1.76.
Melting point (° C.) (Measurement method: DSC manufactured by PerkinElmer Co., Ltd.) varies depending on the amount and type of monomer (α) to be copolymerized, but it is usually 150 to 220 ° C. with a melting point of a commercially available product. It may be, Preferably it is 190-200. If the melting point is less than 150 ° C., a difference in melting point from other laminated resins may occur, which may cause problems of adhesive strength and moldability. If the melting point exceeds 220, it may be difficult to laminate with other resins. is there.

  The monomer (α) to be copolymerized is not particularly limited as long as it is a monomer having an adhesive functional group and can be copolymerized, but the amount and type are controlled in consideration of melt molding. The melting point (° C.) is preferable, and specific examples include ethylene fluoride. In this case, a copolymer EFEP of ethylene and fluoroethylene (for example, manufactured by Daikin Industries, Ltd.) RP-5000) is used as the fluororesin.

The special polyamide resin of the barrier / adhesive resin layer used in the present invention is an additive-free grade polyamide resin in which no additive is blended. Specifically, for example, Z4887 manufactured by Daicel Eponic Co., Ltd. Can be mentioned.
Free polyamide resins such as additives and lubricants that do not contain additives or lubricants can be preferably used.

The maleic anhydride-modified polyolefin resin of the adhesive layer used in the present invention has excellent adhesion to the barrier / adhesive resin layer (special polyamide resin) and the barrier layer (ethylene vinyl alcohol copolymer resin). Furthermore, the maleic anhydride-modified polyolefin resin of the adhesive layer has excellent adhesion to the barrier layer (ethylene vinyl alcohol copolymer resin) and the outer layer (ultra high molecular weight high density polyethylene resin). The adhesive layer and the adhesive layer are formed by bonding them together, and any commercially available product can be used as long as it can be melt-molded.
The maleic anhydride-modified polyolefin resin of the adhesive layer has an inner layer (fluorine resin), a barrier / adhesive resin layer (special polyamide resin), and an adhesive layer (maleic anhydride-modified polyolefin resin) as long as the adhesiveness is not impaired. ), A barrier layer (ethylene vinyl alcohol copolymer resin), an adhesive layer (maleic anhydride modified polyolefin resin) and an outer layer (ultra high molecular weight high density polyethylene resin) can be blended.
Since the maleic anhydride-modified polyolefin resin containing the recovered material of the adhesive layer is separated from the fluororesin resin of the inner layer that becomes the wetted surface, there is no possibility that the degree of cleanliness is impaired practically. is there.

  Maleic anhydride-modified polyolefin resin having excellent adhesion to the barrier / adhesive resin layer (special polyamide resin) and the barrier layer (ethylene vinyl alcohol copolymer resin), and the barrier layer (ethylene vinyl alcohol copolymer) Resin) and the outer layer (ultra high molecular weight high density polyethylene resin) may have the same or different maleic anhydride-modified polyolefin resin having excellent adhesion, and is preferably determined by testing in advance. .

  The barrier layer ethylene vinyl alcohol copolymer resin (ethylene 24-44 mol% copolymer) used in the present invention is a resin obtained by hydrolyzing ethylene vinyl alcohol copolymer and almost completely saponified, and has an aroma retaining property. It has excellent gas barrier properties and is widely used in containers and packaging materials for chemicals, cosmetics, etc., and has high resistance to oils and organic solvents. By using a polymerized resin, oxygen barrier properties can be secured, and since MFR, melting point, etc. are close to ultra high molecular weight high density polyethylene resin and excellent in stable moldability, it can be preferably used. As an example of the ethylene vinyl alcohol copolymer resin of the barrier layer, specifically, for example, F171B (ethylene 32 mol% copolymerization, melting point 183 ° C., saponification rate 99.99%) manufactured by Kuraray Co., Ltd. Can be mentioned.

(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 (ISO 1346)
The MFR is preferably 2 to 5, more preferably 3 to 5, the density is preferably 1.1 to 1.3, more preferably 1.2 to 1.3, and the melting point (° C.). Is preferably 170 to 200, and more preferably 190 to 200.
If the melting point is less than the lower limit, the adhesiveness may be insufficient, and if it exceeds the upper limit, the moldability may be deteriorated. If the MFR, density, and melting point are within the above ranges, gas barrier properties, strength, stability Although moldability and the like are all excellent, at least one of these characteristics may be impaired outside the above range.

The outer layer ultra high molecular weight high density polyethylene resin used in the present invention preferably has a density (measurement method: JIS K7112) of preferably 940 to 962 Kg / m ³ , more preferably 944 to 946 Kg / m ³ , and a weight average molecular weight (measurement). Method: described later) is preferably 220,000-260,000, more preferably 240,000-260,000, molecular weight distribution (Mw / Mn) (measurement method: described later) is preferably 12 or less, more preferably 11 or less, preferably melt tension (measurement method: Japanese polyethylene method, measured at 210 ° C. using a capillograph manufactured by Toyo Seiki Seisakusho), preferably 18-30 g, more preferably 22-26 polyethylene or ethylene-α-olefin copolymer. The moldability and mechanical strength are improved by using it for the outer layer. Problem is eliminated, also improved, such as yield.

  If the weight average molecular weight of the raw ultra-high molecular weight high density polyethylene resin is less than 220,000, the mechanical strength may be insufficient. If the weight average molecular weight exceeds 260,000, the resin has a high melt viscosity, so that the moldability is high. May worsen and molecular breakage due to shear stress may occur.

  If the density and melt tension are less than the lower limit, it may be difficult to draw down and control the wall thickness. On the other hand, if the density and melt tension are more than the upper limit, a problem of melt fracture (rough skin) may occur on the bottle surface. is there.

A commercially available product can be used as the ultra-high molecular weight high-density polyethylene resin used in the present invention. As the α-olefin copolymerized with ethylene, propylene, butene-1,4-methyl-pentene-1, hexene-1 and octene-1 are used. The content of α-olefin in the copolymer is preferably 15% by mass or less. The polymerization method may be either the low pressure method or the medium pressure method as long as a high-density polymer of 940 to 962 Kg / m ³ is obtained.

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

The container molecular weight is measured by dissolving the resin composition cut out from the container in a solvent (orthodichlorobenzene) to form a sample solution, and measuring the molecular weight and molecular weight distribution by GPC. The weight average molecular weight and the number average molecular weight are calculated by the following equations.
Weight average molecular weight = Σ (M × w) / Σw (1)
Number average molecular weight = Σw / Σ (w / M) (2)
However, M is molecular weight and w is a weight fraction.

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

  The molding method is not particularly limited as long as it can form the chemical-resistant blow-molded laminated container of the present invention consisting of the above six layers by a blow-molding method, and is not limited to a commercially available blow-molded laminated container. It can also be used by selecting from a molding machine.

  The description of the above embodiment is for explaining the present invention, and does not limit the invention described in the claims or reduce the scope. Moreover, each part structure of this invention is not restricted to the said embodiment, A various deformation | transformation is possible within the technical scope as described in a claim.

EXAMPLES Next, although an Example demonstrates this invention in detail, unless it deviates from the main point of this invention, it is not limited to these Examples.
The% described below indicates mass%.

Example 1
As an inner layer, a fluororesin (RP-5000 manufactured by Daikin Industries, Ltd.) having an MFR of 25 g / 10 min, a specific gravity of 1.74, and a melting point of 200 ° C. is used, and an additive-free special polyamide resin having an adhesive function with the fluororesin ( Z4887 manufactured by Daicel Evonik Co., Ltd.) (barrier and adhesive resin), and the adhesive function between barrier resin (ethylene-vinyl alcohol copolymer resin F171B: manufactured by Kuraray Co., Ltd.) and special polyamide resin Maleic anhydride-modified polyolefin resin (Nippon Polyethylene Co., Ltd. FT71A) is used as the adhesive layer, and the outermost layer is used to compensate for the decrease in melt tension of the barrier resin and the fluororesin or polyamide resin. Ultra high molecular weight high density polyethylene resin (HB111R manufactured by Nippon Polyethylene Co., Ltd.) (HL-MFR6g / 10mi , Density 946Kg / m ^3, weight average molecular weight 250,000, using a melt tension 25 g) and the adhesive layer as a maleic anhydride-modified polyolefin resin having an adhesive function (Japan Polyethylene (Ltd.) FT71A), the molding under the following conditions There are no problems such as drawdown, and the chemical-resistant blow molded laminated container of the present invention consisting of 6 layers (mass 122 g, inner layer 50 μm, special polyamide resin layer 400 μm, adhesive layer 40 μm, barrier-resin layer 40 μm, adhesive layer 500 μm) , Outer layer 750 μm, total wall thickness 1.42 mm, capacity 1300 CC). However, the maleic anhydride-modified polyolefin resin (Nippon Polyethylene Co., Ltd. FT71A) of the adhesive layer contains 30% by mass of the recovered material of the chemical-resistant blow-molded laminated container of the present invention based on the entire adhesive layer. .

(Molding condition)
A blow molding machine (6 types, 6 layers, manufactured by Brenzu Co., Ltd.) (a type in which 6 types of extruders are used to laminate 6 layers with one die head) was used.
Inner layer fluororesin: Screw diameter 40mmΦ Setting temperature: 240 ℃
Special polyamide resin layer: Screw diameter 20mmΦ Setting temperature: 260 ℃
Maleic anhydride-modified polyolefin resin layer of adhesive layer: Screw diameter 20 mmΦ Setting temperature: 240 ° C.
Ethylene-vinyl alcohol copolymer resin layer: Screw diameter 20 mmΦ Setting temperature: 230 ° C
Maleic anhydride-modified polyolefin resin layer of adhesive layer: Screw diameter 40 mmΦ Setting temperature: 220 ° C.
Ultra high molecular weight high density polyethylene resin of outer layer: Screw diameter 50mmΦ Setting temperature: 210 ℃
Die head temperature: Set temperature: 220 ° C
In addition, the hygroscopic special polyamide resin and the barrier resin were used after drying at 80 ° using a dryer to remove moisture.

In the thus obtained laminated container of the present invention, as examples of typical fragrances, limonene (trade name: orange oil, purity: 96.4%, manufactured by Sakai Co., Ltd.), citrus fruits (trade name: lemon essence) , Made by Sakai Co., Ltd.), crab oil (15% dimethyl sulfide, propylene glycol solution, produced by Sakai Co., Ltd.), acid (butyric acid: trade name: acids, purity 96.4%, produced by Sakaisha), rice salad ( Product name: rice oil, manufactured by Sakai Co., Ltd.), ethyl butyrate (trade name: ester, purity 100%, manufactured by Sakai Co., Ltd.), trans-2-hexenal (trade name: aldehydes, purity 99.7) %, Manufactured by Sakaisha Co., Ltd.), each 1 kg was filled and sealed, left at room temperature and normal pressure for 1 month and 3 months, and then the performance was tested by the following test method. However, only crab oil (15% dimethyl sulfide, propylene glycol solution) was refrigerated at room temperature and pressure for 1 month and 3 months.
The test results are shown in Table 1.

(Test method)
For each sample, the container mass is measured to check whether the contents have been dissipated, a sensory test is conducted with 10 panel members to check whether it has been altered, and the specific gravity and refractive index are measured to vary. The components that can be analyzed are checked with a gas chromatograph, and the results are compared with the case where each sample is placed in a glass bottle (Fuji Film Electronics Materials Co., Ltd.).

  From Table 1, it can be seen that even if the laminated container of the present invention is allowed to stand at room temperature and normal pressure for 1 month or 3 months, the quality of any fragrance does not change and is equivalent to the case of a glass bottle.

(Example 2)
As an inner layer, a fluororesin (RP-5000 manufactured by Daikin Industries, Ltd.) having an MFR of 25 g / 10 min, a specific gravity of 1.74 and a melting point of 195 ° C. is used, and an additive-free special polyamide resin having an adhesive function with the fluororesin Z4887 manufactured by Daicel Evonik Co., Ltd., barrier / adhesive resin, relative viscosity 1.87), and barrier resin (ethylene-vinyl alcohol copolymer resin F171B: manufactured by Kuraray Co., Ltd., saponification rate 99. 99%) and a maleic anhydride-modified polyolefin resin (Nippon Polyethylene Co., Ltd. FT71A) having an adhesive function with a special polyamide resin, and reducing the melt tension of the barrier resin, the fluororesin and the polyamide resin. Ultrahigh molecular weight high-density polyethylene resin (HB111R manufactured by Nippon Polyethylene Co., Ltd.), which is the outermost layer used to make up HL-MFR (measurement method: JIS K7112) 6g / 10min, density 946Kg / m ^3, weight average molecular weight 250,000, melt tension 25 g) and maleic anhydride-modified polyolefin resin having an adhesive function (Japan Polyethylene (Ltd.) FT71A) The chemical-resistant blow-molded laminated container (total mass 400 g, inner layer 100 μm, barrier) of the present invention consisting of 6 layers and having no problems such as draw-down under the same molding conditions as in Example 1 was used. And an adhesive resin layer 40 μm, an adhesive layer 40 μm, a barrier layer 40 μm, an adhesive layer 40 μm, an outer layer 1540 μm, an average total thickness of 1.8 mm, and a capacity of 3750 CC).
The degree of cleanliness (number / cc), metal elution (ppb), drop strength (1.2 m height), oxygen permeability (cc / one container) of the laminated container of the present invention thus obtained was determined. It measured by the following test method.
For comparison, a glass bottle (Fuji Film Electronics Materials Co., Ltd., capacity 3750CC) and high-density polyethylene resin (Nippon Polyethylene Co., Ltd. HB111R) were used in the same manner as in Example 2 for blowing. For a blow container consisting of one layer formed by molding (number / cc), metal elution (ppb), drop strength (1.2 m height), oxygen permeability (cc / one container) are as follows. It was measured.
The results are shown in Table 2.

(Test method)
Clean degree (number / cc):
1. Measuring apparatus: A particle counter “KL-26” RION KL-26 manufactured by Rion Co., Ltd. is used.
2. Sample to be measured: An ultra-pure water filled in a molded container and a sample to be measured collected from a container placed in an upright state for 20 minutes is used as a sample to be measured.
3. Before the measurement, purge the particle counter with ultrapure water, and then wash the measuring device twice with 25 ml of ultrapure water.
4). After washing, ultrapure water is poured into a 10 ml particle counter and the number of particles is measured. This operation is performed twice to confirm that the number of particles of 0.2 μm or more is zero (A).
5. Wash the measuring device twice with 25 ml measurement sample.
6). After washing, 10 ml is injected into a particle counter from a bottle filled with ultrapure water as a measurement sample, and the number of particles is measured. This operation is performed twice to obtain an average value (B) of the number of particles of 0.2 μm or more.
7). The particle value in 1 ml is calculated from the measured value by the following formula.
(B (pieces)) ÷ 10 ml = pieces / ml
Conventionally, it has been said that the quality and yield of semiconductors and liquid crystals can be improved when the cleanness is less than 500 / ml. However, it is becoming more severe at present, and there are many cases where 5 pieces / ml or less is required.

Oxygen permeability (cc / one container):
A 3.75 L container (wall thickness at the center of the bottle: 1.8 mm) is measured according to JIS K7126-2, using an OX-TRAN2 / 21) (manufactured by MOCON) measuring oxygen from the outside of the container to the inside. Transmission was measured. Temperature and humidity: outside: 1 atm, 23 ° C., 50% RH oxygen, inside 23 ° C., dry nitrogen.

Metal elution (ppb):
Metal elution (ppb):
5% dilute hydrofluoric acid was added and the cap was capped and left at room temperature and normal pressure for 5 weeks. This sample is measured to the pp level using IPC-MASS (SEIKO SPQQ9000) on a 0.1 NHNO ₃ basis. However, about Fe and Na, it measures using Hitachi atomic absorption Z5700 using the sample before concentrating 100 times. Measured elements Ti, V, Mn, Co, Ni, Cu, Zn, As, Sr, Zr, Mo, Ru, Ag, Cd, Sn, W, Au, TI, Pb, U, Na, Mg, Al, K , 27 elements of Ca, Cr, Fe.

Drop strength (1.2m height):
Fill a 3.75 L container (wall thickness at the center of the bottle: 1.8 mm) with 80% of its capacity and drop it 5 times from a height of 1.2 m onto the concrete surface with the container bottom down. , Drop once, and visually check for cracks and leaks.

表２から、硝子瓶は全てにおいて劣り、ＨＤＰＥ単層容器は硝子瓶よりややよいが、いずれかの試験項目において、不満足な点があるのに対して、本発明の積層容器は優れており、クリ−ン度（個数/ｃｃ）、金属溶出（ｐｐｂ），落下強度（１．２ｍ高さ）、酸素透過率（ｃｃ/容器１本）のいずれも超高純度薬品用容器として使用可能な性能を有することが判る。
なお、実施例２のブロー容器に超純水を満水に充填し、１ケ月間常温、常圧のクリーンルームに放置した後、同様にしてパーテイクル個/ＣＣを測定した。測定結果は０．６個/ＣＣであった。

From Table 2, glass bottles are inferior in all, HDPE single-layer containers are slightly better than glass bottles, but there are unsatisfactory points in any of the test items, the laminated container of the present invention is excellent, Any of cleanliness (number / cc), metal elution (ppb), drop strength (1.2m height), oxygen permeability (cc / one container) can be used as a container for ultra-high purity chemicals. It turns out that it has.
The blow container of Example 2 was filled with ultrapure water and left in a clean room at room temperature and pressure for 1 month, and the number of particles / CC was measured in the same manner. The measurement result was 0.6 / CC.

(Comparative Example 1)
Using a 1.3L sealer bottle (trade name, manufactured by North Acid Co., Ltd.) on the market, 1 kg of the same fragrance as in Example 1 is filled and sealed, and at room temperature and normal pressure for 1 month and Left for 3 months. After leaving for 1 month and 3 months, the performance was tested in the same manner as in Example 1. The test results are shown in Table 3.

リモネンは1ケ月保存性試験で散逸が認められた。エステル類およびアルデヒドも3ケ月評価で問題点が見いだされた。その他カニオイルやコメサラダについても臭気の変化が多少見られ、シ−ラ−ボトルは性能が劣り、超高純度薬品用容器として不満足であることが判った。

Limonene was found dissipated in a 1 month shelf life test. Esters and aldehydes were also found to be problematic in the 3-month evaluation. Other crab oil and rice salad also showed some change in odor, and the sealer bottle was inferior in performance and was unsatisfactory as a container for ultra-high purity chemicals.

(Comparative Example 2)
Instead of the additive-free special polyamide resin (Z4887 manufactured by Daicel Evonik Co., Ltd.) (barrier and adhesive resin) having the adhesive function used in Example 1, it has the same physical properties as the special polyamide resin. Example 1 except that the same polyamide resin (manufactured by Daicel Evonik Co., Ltd.), which is 0.2% by weight of an antioxidant (hindered phenol-based antioxidant), is added and is not additive-free. Similarly, a blow-molded laminated container consisting of six layers for comparison was molded under the same molding conditions as in Example 1.

The degree of cleanliness (number / cc), metal elution (ppb), drop strength (1.2m height), oxygen permeability (cc / one container) of the laminated containers for comparison thus obtained. Was measured in the same manner as in Example 2.
For comparison, a glass bottle (Fuji Film Electronics Materials Co., Ltd., capacity 3750CC) and high-density polyethylene resin (Nippon Polyethylene Co., Ltd. HB111R) were used in the same manner as in Example 1. A blow container consisting of one layer formed by molding was measured by the above test method.
The test results are shown in Table 4.

表４から、比較例２の容器は、ポリアミド樹脂に添加剤が添加されており、成形時に発煙があり、そしてパ−ティクル溶出量が大幅に増加した。最内層のフッ素樹脂を通して、ポリアミド樹脂に添加された添加物が溶出したものと考えられる。
参考のためにフッ素樹脂内層１００μｍを４００μｍまで増加させて作成した積層容器についても同様にしてクリーン度を測定したが、パ−ティクル溶出量は大幅には改善されなかった。

From Table 4, in the container of Comparative Example 2, an additive was added to the polyamide resin, smoke was generated at the time of molding, and the amount of particle elution was greatly increased. The additive added to the polyamide resin is considered to have eluted through the innermost fluororesin.
For reference, the cleanness was measured in the same manner for a laminated container prepared by increasing the fluororesin inner layer 100 μm to 400 μm, but the particle elution amount was not significantly improved.

(Comparative Example 3)
Without using the ultra high molecular weight high density polyethylene resin (HB111R manufactured by Nippon Polyethylene Co., Ltd.) (HL-MFR 6 g / 10 min, density 946 Kg / m ^3, weight average molecular weight 250,000, melt tension 25 g) used in Example 1, For high-density polyethylene resin (MFR 0.2 g / min, weight average molecular weight 170,000, melt tension 16 g) used in industrial cans (10 to 20 L), otherwise the same as in Example 1 for comparison An attempt was made to form a blow molded laminated container consisting of 6 layers.
Although the container could be formed somehow, it was a container that could not be commercialized due to large drawdown and large thickness variation.

The chemical-resistant blow-molded laminated container having a 6-layer structure of the present invention is formed by laminating the inner layer, the barrier / adhesive resin layer, the adhesive layer, the barrier layer, the adhesive layer, and the outer layer in order from the inner side to the outer side of the container. It is characterized by
Use of a fluororesin resin as the inner layer on the wetted surface can improve chemical resistance, reduce alterations such as odor components as much as possible, and use a barrier / adhesive resin free of additives and lubricants By using the ethylene vinyl alcohol copolymer resin as the barrier layer, it is possible to improve the gas barrier property, while the cleanliness equivalent to a glass bottle is obtained (the impure particle elution amount is very small). Fluorine resin, polyamide resin, adhesive resin, etc. will melt, and the melt tension will drop at a stretch.Therefore, problems such as blow-down will occur in blow molding. Although there was a problem that the yield deteriorated, the moldability and mechanical strength were improved by using ultra high molecular weight high density polyethylene resin with high melt tension for the outer layer. As a result, it is possible to provide a chemical-resistant blow-molded laminated container that can be used as a container for ultra-high-purity chemicals, which is expensive and contains many hazardous chemicals. Is expensive.

DESCRIPTION OF SYMBOLS 1 Inner layer which consists of fluororesins 2 Barrier and adhesion resin layer which consists of special polyamide resin 3 Adhesive layer which consists of maleic anhydride modified polyolefin resin 4 Barrier layer which consists of ethylene vinyl alcohol copolymer resin 5 Maleic anhydride modified polyolefin resin Adhesive layer 6 Outer layer made of ultra high molecular weight high density polyethylene resin

Claims (4)

A chemical-resistant blow-molded laminated container characterized by laminating the following inner layer, barrier-adhesive resin layer, adhesive layer, barrier layer, adhesive layer and outer layer in order from the inside to the outside of the container.
Inner layer: Fluorine resin barrier-cumulative resin layer: Special polyamide resin Adhesive layer: Maleic anhydride modified polyolefin resin barrier layer: Ethylene vinyl alcohol copolymer resin adhesive layer: Maleic anhydride modified polyolefin resin outer layer: Ultra high molecular weight high density Polyethylene resin The fluororesin used for the inner layer is tetrafluoroethylene / hexafluoropropylene / monomer (α) copolymer, tetrafluoroethylene / perfluoro (alkyl vinyl ether) / monomer (α) copolymer 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 a polymer, a chlorotrifluoroethylene / tetrafluoroethylene / monomer (α) copolymer, and an ethylene / chlorotrifluoroethylene / monomer (α) copolymer. 2. The chemical-resistant blow molded laminate according to claim 1, wherein the monomer (α) is a monomer having an adhesive functional group and is a fluororesin having the following characteristics: container.
(Characteristic)
MFR (5 kg load g / 10 min): 10 to 40
Specific gravity: 1.7 to 1.9
Melting point (° C): 150-220   The special polyamide resin is not intentionally added with an additive or a lubricant, and the maximum content of the additive is 0.01% by mass or less. Item 3. A chemical-resistant blow-molded laminated container according to Item 2. The ultra high molecular weight high density polyethylene resin is made of polyethylene or an ethylene-α-olefin copolymer, and is an ultra high molecular weight high density polyethylene resin having the following characteristics. A chemical-resistant blow-molded laminated container according to claim 1.
(Characteristic)
Density: 940 to 962 kg / m ³
Weight average molecular weight: 220,000-260,000
Molecular weight distribution (Mw / Mn): 12 or less Melt tension: 18-30 g

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