TWI613124B - Excellent transparency and chemical resistance blown laminated container - Google Patents

Abstract

The present invention provides a blown laminated container with excellent chemical resistance and chemical resistance. It has excellent chemical resistance or mechanical strength, has few foreign matter particles oozing out, has visibility comparable to transparent glass bottles, and has ultraviolet blocking properties. It has excellent oxygen barrier properties and can also be used as a container for perfume ingredients or photoresist liquids. The present invention is a chemically resistant blow-molded laminated container formed by stacking an inner layer, a barrier rib and a resin layer, an adhesive layer, a barrier layer, an adhesive layer, and an outer layer described below in order from the inside to the outside of the container. It is a blow-molded laminated container which is excellent in chemical resistance and has excellent transparency in each of the aforementioned layers, which can solve the problem. Inner layer: fluororesin, barrier and resin layer: special polyamide resin, adhesive layer: maleic anhydride modified polyolefin resin, barrier layer: ethylene-vinyl alcohol copolymer resin, adhesive layer: maleic acid Anhydride modified polyolefin resin, outer layer: ultra high molecular weight high density polyethylene resin.

Description

Blown laminated container with excellent chemical resistance and chemical resistance

The present invention relates to a blown laminated container with excellent chemical resistance and chemical resistance, and more specifically, it relates to a chemical or fragrance that is excellent in chemical resistance or mechanical strength, etc. Medium, that is, good cleanliness (very small amount of dissolved particles of impurities) blow-molded (blow-molded) laminated container, which has visibility comparable to that of transparent glass bottles, and can visually confirm the contained content liquid from the outside, and has ultraviolet blocking properties. 2. It has excellent oxygen barrier properties and can also be used as an ultra-high-purity chemical container with excellent transparency and chemical resistance.

Generally, as a container for storing chemicals, perfumes, and the like, a plastic container such as a glass container or a sealed bottle or a container with a coating film on the inner surface is used.

In the field of semiconductors, it is necessary to maintain high-purity chemicals while storing high-purity chemicals. The glass container is heavy due to the container itself, is inconvenient to handle, and may break due to dropping.

In addition, a molded container made of a polyethylene resin is less likely to break during handling, and has the advantage of being lightweight. However, in semiconductor manufacturing, high-purity chemicals used for etching or cleaning, such as sulfuric acid, nitric acid, hydrogen peroxide, etc., and high-purity solvent-based resists or dilutions used in semiconductor processes and liquid crystal displays, etc. Solvents such as methanol, ethanol, isopropanol, isobutanol, ethylene glycol, acetone, ethyl acetate, toluene, dimethylformamide, ethylene glycol acetate, propyl methoxyacetate, butyl Cellulose, etc., and high-purity solvents such as methanol, ethanol, isopropanol, etc. used for sterilization, disinfection, preparation materials, etc. During the storage period, foreign particles exuded from the resin composition or additives forming the container. To the stored chemicals, the purity of the chemicals is impaired. As a result, problems that cause significant adverse effects on liquid crystal quality and yield, or shorten the storage period of chemicals, occur.

In addition, the cleanliness is an index indicating the degree of impurities in the content caused by impurities particles oozing out from the resin composition forming the container into the chemicals when the chemicals are stored in the container for a long time.

Cleanliness is formed by temporarily molding an inspection container. After ultrapure water is stored in the inspection container for a certain period of time, it is calculated that there are several particles having a particle diameter of 0.2 μm or more in 1 ml of water in a resin container.

(Method for measuring foreign particles (particles))

1. Measuring device: RION KL-26, a particle counter "KL-26" manufactured by RION Corporation.

2. Measurement specimen: Fill the formed container with ultrapure water to full water, collect the measurement sample from the container after standing for 20 minutes in an upright state, and use it as the measurement specimen.

3. Before the measurement, rinse the particle counter with ultrapure water, and then wash the measurement device twice with 25 ml of ultrapure water.

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

5. Wash the measuring device twice with a 25 ml test specimen.

6. After washing, inject 10 ml from a bottle filled with ultrapure water for measuring the sample into a particle counter to measure the number of particles. This operation was performed twice, and the average value (B) of the number of particles of 0.2 μm or more was obtained.

7. From the measured value, calculate and find the particle value in 1 ml using the following formula.

(B (pieces)) ÷ 10 ml = pieces / ml

In the past, if the cleanliness was less than 500 cells / ml, it was considered to improve the quality and yield of semiconductors and liquid crystals. But now it is more stringent, and the number of cases below 5 / ml is increasing.

Containers used in the field of perfume use commercially available cans or sealed bottles with fluorine coating on the inner surface of the metal can. However, metal cans have the problem of dents or rust. If sealed bottles are used, the perfume ingredients will deteriorate and the quality of the perfume will repeatedly occur. .

Therefore, a container molded from a resin composition containing polyethylene or an ethylene-α-olefin copolymer has been proposed, which is excellent in mechanical strength, easy to handle, and has few particles of foreign matter exuding into chemicals stored and stored. And a light-shielding container for high-purity chemicals with light-shielding properties (refer to Patent Document 1); wherein the weight average molecular weight of the raw resin composed of the aforementioned polyethylene or ethylene-α-olefin copolymer is within a certain range, and the light-shielding in the resin composition is light-shielding; The content of the neutral pigment and the dispersant is in a certain range, and the content of the low molecular weight polymer and the additive in the resin composition is set to be less than a certain weight (refer to Patent Document 1).

The problems include the leakage of foreign particles from the resin composition or additives containing polyethylene or ethylene-α-olefin copolymer into the storage container into the storage chemicals, lest the purity of the chemicals be impaired, and there is no visual confirmation from the outside. The contained liquid is the visibility or oxygen barrier that is comparable to transparent glass bottles.

Advance technical literature

Patent literature

[Patent Document 1] Japanese Patent No. 2805723

Problems to be solved by the invention

An object of the present invention is to provide a blown laminated container having excellent chemical resistance and chemical resistance, which is excellent in chemical resistance or mechanical strength, and has few particles of impurities exuding into chemicals or fragrances, etc. Good cleanliness (very small amount of impurity particles dissolved out) blown (blow-molded) laminated container, which has visibility comparable to that of transparent glass bottles, and can visually confirm the contents of the contained liquid from the outside, and has ultraviolet blocking and oxygen barrier properties Excellent, can also be used as an ultra-high purity chemical container such as perfume or photoresist.

Technical means to solve problems

The present inventors made intensive research in order to solve the problems in the past, and found that the aforementioned layers of the blow-molded container have transparency, so they have visibility comparable to that of a transparent glass bottle, and the contents of the liquid can be visually confirmed from the outside. By using fluororesin as the inner layer of the wetted surface, it is more suitable to use fluororesin without additives, which can improve chemical resistance and minimize the deterioration of odor components. By using special additives without additives or lubricants, Ammonium resin can obtain the cleanliness equivalent to that of glass bottles (the amount of dissolved particles of impurities is very small). A barrier layer composed of an ethylene-vinyl alcohol copolymer resin with excellent oxygen barrier properties is provided to improve the oxygen barrier properties. Since the melting tension of fluororesin, polyamide resin or adhesive resin is reduced immediately after melting, problems such as sags occur during blow molding, such as failure to form containers with uniform meat thickness, defective products, and yield deterioration. And other problems, but by using a large melt tension in the outer layer, it has excellent ultra-high molecular weight and high density, such as ultraviolet blocking properties, transparency, and mechanical strength. Polyethylene resin can improve the moldability or ultraviolet blocking property, so it is possible to obtain a blown laminated container with excellent chemical resistance and chemical resistance, and it can also correspond to ultra-high-purity chemical containers that are mostly expensive and dangerous chemicals , And finally complete the present invention.

In order to solve the aforementioned problems, a first aspect of the present invention is a chemically resistant blow-molded laminated container with excellent transparency, characterized in that the aforementioned chemical-resistant blow-molded laminated container is sequentially laminated from the inside to the outside of the container. The inner layer, the barrier rib, and the resin layer, the adhesive layer, the barrier layer, the adhesive layer, and the outer layer described above are formed; and each of the foregoing layers has transparency.

Inner layer: fluororesin;

The barrier and resin layer: the following special polyamide resin;

Adhesive layer: maleic anhydride modified polyolefin resin;

Barrier layer: ethylene-vinyl alcohol copolymer resin;

Next layer: maleic anhydride modified polyolefin resin;

Outer layer: UHMWPE resin;

Special polyamide resin: at least one polyamine selected from the group consisting of polyamines obtained by ring-opening polycondensation of caprolactam, does not contain additives containing additives or lubricants, and has the following Mentioned characteristic.

(characteristic)

Melting point (° C): 170 ～ 250

Density (Kg / m ³ ): 1.0 ～ 1.2

The second aspect of the present invention is a blow-molded laminated container having excellent transparency and chemical resistance as described in the first aspect of the present invention, which is characterized in that:

The fluororesin used in the inner layer includes a tetrafluoroethylene / hexafluoropropylene / monomer (α) copolymer, a tetrafluoroethylene / perfluoro (alkyl vinyl ether) / monomer (α) copolymer, and ethylene / Tetrafluoroethylene / monomer (α) copolymer, ethylene / tetrafluoroethylene / hexafluoropropylene / monomer (α) copolymer, trifluorochloroethylene / monomer (α) copolymer, trifluorochloroethylene / tetrafluoro At least one selected from the group of an ethylene / monomer (α) copolymer and an ethylene / trifluorochloroethylene / monomer (α) copolymer, the aforementioned monomer (α) represents a monomer having a bonding functional group; The aforementioned fluororesin has the following characteristics.

(characteristic)

MFR (5 Kg load g / 10 min): 10 ～ 40

Specific gravity: 1.7 ～ 1.9

Melting point (° C): 150 ～ 220

A third aspect of the present invention is a blow-molded laminated container having excellent transparency and chemical resistance as described in the first or second aspect of the present invention, wherein the barrier layer is an oxygen barrier having the following characteristics: Excellent ethylene-vinyl alcohol copolymer resin.

(characteristic)

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

Density (Kg / m ³ ): 1.1 ～ 1.3

Melting point (° C): 170 ～ 200

The fourth aspect of the present invention is a blow-molded laminated container having excellent transparency and chemical resistance as described in any one of the first to third aspects of the present invention, which is characterized by the aforementioned ultra-high molecular weight polyethylene resin. It is composed of a resin composition containing at least the following components: an ultra-high molecular weight polyethylene resin composed of polyethylene or an ethylene-α-olefin copolymer and having the following characteristics; a benzotriazole light-resistant stabilizer and a triazine 0.05 to 0.30 mass% of each light-resistant stabilizer; and at least one nucleating agent selected from the group consisting of a carboxylic acid-based nucleating agent, a phosphate metal salt-based nucleating agent, and a sorbitol-based nucleating agent 0.5 to 0.5 2.5 mass%.

(characteristic)

Density: 940 ～ 962 Kg / m ³

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

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

Melt tension: 18 ～ 30g

Effect of the invention

A first aspect of the present invention is a chemically resistant blow-molded laminated container with excellent transparency, characterized in that the aforementioned chemical-resistant blow-molded laminated container is sequentially laminated from the inside of the container to the outside, The barrier wall is composed of a resin layer, an adhesive layer, a barrier layer, an adhesive layer and an outer layer; and the foregoing layers are transparent; since the foregoing layers of the blow-molded container are transparent, they have visibility comparable to that of a transparent glass bottle You can visually confirm the contained content liquid from the outside. By using fluororesin as the inner layer of the wetted surface, the chemical resistance can be improved, and the deterioration of odor components can be minimized. By using a special polymer without additives or lubricants, Ammonium resin can obtain the cleanliness equivalent to that of glass bottles (the amount of dissolved particles of impurities is very small). A barrier layer composed of an ethylene-vinyl alcohol copolymer resin with excellent oxygen barrier properties is provided to improve the oxygen barrier properties. Since the melting tension of fluororesin, polyamide resin or adhesive resin is reduced immediately after melting, problems such as sags occur in blow molding, such as The method of forming a container with a uniform thickness of the meat may cause problems such as defective products and deterioration of yield. However, the outer layer uses an ultra-high molecular weight high-density polyethylene resin with high melt tension, excellent ultraviolet blocking properties, transparency, and mechanical strength. It can improve the moldability, mechanical strength or ultraviolet blocking property, so it can provide a significant effect that can provide a blown laminated container with excellent chemical resistance and good chemical resistance, and the blown laminated container with excellent chemical resistance can also be used. Containers for ultra-high-purity chemicals with high price and high-risk chemicals.

By using a special polyamide resin with the aforementioned characteristics, the adhesion of the fluororesin is improved, and then by making it without additives or lubricants as described above, the amount of impurity particles caused by the aforementioned additives can be greatly reduced, and the potential Obtain a more significant effect of cleanliness comparable to glass bottles.

In addition, by using a fluororesin as the inner layer of the wetted surface, it is more appropriate to use an additive-free fluororesin and an ethylene-vinyl alcohol copolymer resin as a barrier layer, which is excellent in ultraviolet blocking properties, transparency, and mechanical strength. Ultra-high-molecular-weight high-density polyethylene resin, made of 6-layer chemical-resistant blow-molded laminated container. Compared with glass bottles that are heavy and easy to break and lack safety, they are less likely to break and have excellent mechanical properties. The strength and oxygen barrier properties are improved, so it can also be used as a spice bottle, etc., and has the performance of a universal container. In addition, as a universal plastic container that can be used for various contents, it can be used safely for taste or smell ‧Significant effect for peace of mind.

Since the blow-molded laminated container with excellent transparency and chemical resistance of the present invention has the aforementioned characteristics, it is friendly to the environment or health, contributes to environmental problems or health problems, and can also reduce funds, so it has economic benefits. Significant effect.

The second aspect of the present invention is a blow-molded laminated container with excellent chemical resistance and chemical resistance as described in the first aspect of the present invention, wherein the fluororesin used in the inner layer includes a tetrafluoroethylene / Hexafluoropropylene / monomer (α) copolymer, tetrafluoroethylene / perfluoro (alkyl vinyl ether) / monomer (α) copolymer, ethylene / tetrafluoroethylene / monomer (α) copolymer, ethylene / quad Fluoroethylene / hexafluoropropylene / monomer (α) copolymer, trifluorochloroethylene / monomer (α) copolymer, trifluorochloroethylene / tetrafluoroethylene / monomer (α) copolymer, and ethylene / trifluoro At least one selected from the group of vinyl chloride / monomer (α) copolymers, the aforementioned monomer (α) represents a monomer having a bonding functional group, and the aforementioned fluororesin has the following characteristics; Copolymerized fluororesin is used as the inner layer of the wetted surface. It can be co-extruded at the molding temperature equivalent to that of polyolefin, and also adheres to the resin barrier (adjacent polyimide) with the adjacent barrier wall. Resin) adhesion is more significant.

The third aspect of the present invention is the blow-molded laminated container having excellent transparency and chemical resistance as described in the first or second aspect of the present invention, wherein the barrier layer is excellent in oxygen barrier properties having the aforementioned characteristics. Ethylene-vinyl alcohol copolymer resin; exerts a more significant effect of indeed further improving oxygen barrier properties.

The fourth aspect of the present invention is a blow-molded laminated container having excellent transparency and chemical resistance as described in any one of the first to third aspects of the present invention, which is characterized by the aforementioned ultra-high molecular weight polyethylene resin. It is composed of a resin composition containing at least the following components: an ultra-high molecular weight polyethylene resin composed of polyethylene or an ethylene-α-olefin copolymer and having the aforementioned characteristics; a benzotriazole-based light-resistant stabilizer and a triazine-based 0.05 to 0.30 mass% of each light-resistant stabilizer; and at least one nucleating agent selected from the group consisting of carboxylic acid-based nucleating agent, phosphate metal salt-based nucleating agent and sorbitol-based nucleating agent 0.5 to 2.5 mass%; By blending light-resistant stabilizers and nucleating agents in a predetermined amount, transparency and ultraviolet blocking properties are significantly improved, and by using an ultra-high molecular weight polyethylene resin with a large melt tension in the outer layer, the moldability or mechanical strength is further improved. Improvement, the aforementioned problems such as sags disappeared, and more prominent effects such as yield rate have also been improved.

1‧‧‧ inner layer composed of fluororesin

2‧‧‧ Barrier made of special polyamide resin and resin layer

3‧‧‧ Adhesive layer composed of maleic anhydride modified polyolefin resin

4‧‧‧ Barrier layer composed of ethylene-vinyl alcohol copolymer resin

5‧‧‧ Adhesive layer composed of maleic anhydride modified polyolefin resin

6‧‧‧ Outer layer composed of ultra-high molecular weight high-density polyethylene resin

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

Forms used to implement the invention

Hereinafter, the present invention will be described in detail using drawings.

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

Respectively, 1 indicates an inner layer composed of a fluororesin, 2 indicates a barrier and adhesive resin layer composed of a special polyamide resin, 3 indicates an adhesive layer composed of maleic anhydride modified polyolefin resin, 4 Indicates a barrier layer composed of an ethylene-vinyl alcohol copolymer resin, 5 indicates an adhesive layer composed of maleic anhydride modified polyolefin resin, and 6 indicates an outer layer composed of an ultra-high molecular weight high-density polyethylene resin. The aforementioned outer layers each have excellent transparency.

The fluororesin used in the present invention is not particularly limited, and specifically includes, 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, trifluorochloroethylene / monomer (α) copolymer , Trifluorochloroethylene / tetrafluoroethylene / monomer (α) copolymers, and ethylene / trifluorochloroethylene / monomer (α) copolymers, at least one selected from the group consisting of the following characteristics: The fluororesin copolymerized with functional monomer (α) can be co-extruded at the molding temperature equivalent to polyolefin, and the adhesion with the adjacent barrier and resin layer (special polyamide resin) is improved. Therefore, it can be suitably used.

The fluororesin used in the present invention is preferably a non-additive grade non-additive fluororesin.

MFR (5 Kg load g / 10 min) (measurement method: 265 ° C, ASTM D1238) should preferably be 10 to 40, and more preferably 20 to 30. If it is less than 10, the melt viscosity is high, and the blow molding melt moldability is deteriorated. There is also a possibility that the energy will increase. If it exceeds 40, the melt tension will be low, and problems such as falling will occur during blow molding.

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

The melting point (° C) (measurement method: ASTM D792) varies depending on the amount or type of the monomer (α) to be copolymerized. The melting point may be 150 to 220 ° C., and more preferably 190 to 200. If the melting point is lower than 150 ° C, a melting point difference with other resins may occur, and problems such as adhesion strength or moldability may occur. If the melting point exceeds 220, it may be difficult to laminate with other resins.

The copolymerized monomer (α) is not particularly limited as long as it has a functional group that can be copolymerized with a bonding functional group. In consideration of melt molding, the amount or type may be controlled so as to fall within the aforementioned melting point (° C) range. Specifically, Examples include fluorinated ethylene. At this time, for example, a copolymer of ethylene and fluorinated ethylene EFEP (for example, RP5000 manufactured by Daikin Industries Co., Ltd.) is used as the fluororesin.

The special polyamide resin having a barrier rib and a resin layer used in the present invention is a non-additive grade polyamide resin having no blended additives. Specific examples include Z4887 manufactured by Daicel-Evonik Co., Ltd.

Among them, it is particularly suitable to use at least one kind of polyamine obtained from ring-opening polycondensation of caprolactam, which is selected from Nylon 6, Nylon 11, Nylon 12, Nylon 66, and does not contain Polyamines as additives or lubricant additives.

(characteristic)

Melting point (° C) (ISO1346): 170 to 250

Density (Kg / m ³ ) (ISO1183): 1.0 ～ 1.2

Melting point (℃) should be 170 to 250, 175 to 190 and further desirable density (Kg / m ³⁾ should be 1.0 to 1.2, and thus should be 1.00 to 1.03.

If the melting point is less than the lower limit value, adhesion may be insufficient, and if it exceeds the upper limit value, moldability may deteriorate.

If the density is less than the lower limit value, adhesion may be insufficient, and if it exceeds the upper limit value, moldability may deteriorate.

The maleic anhydride-modified polyolefin resin of the adhesive layer used in the present invention has excellent adhesiveness to the barrier and adhesive resin layer (special polyamide resin) and the barrier layer (ethylene-vinyl alcohol copolymer resin). In addition, 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, and they can be melt-molded, and generally commercially available products can be used.

The maleic anhydride-modified polyolefin resin of the aforementioned adhesive layer can be blended to include an inner layer (fluororesin), a barrier and adhesive resin layer (special polyamide resin), and an adhesive layer (without impairing its adhesiveness). Maleic anhydride modified polyolefin resin), barrier layer (ethylene-vinyl alcohol copolymer resin), adhesive layer (maleic anhydride modified polyolefin resin) and outer layer (ultra high molecular weight high density polyethylene resin) Recycled content.

The maleic anhydride modified polyolefin resin provided with the recovered material in the aforementioned adhesive layer has a fluororesin in the inner layer far away from the liquid contact surface, so there is no risk of impairing cleanliness in practice.

For the barrier rib and resin layer (special polyamide resin) and the barrier layer (ethylene-vinyl alcohol copolymer resin), maleic anhydride-modified polyolefin resin having excellent adhesiveness, and for the barrier layer (ethylene-vinyl alcohol) Copolymer resin) and outer layer (ultra-high-molecular-weight high-density polyethylene resin), maleic anhydride-modified polyolefin resin with excellent adhesion, may be the same or different, and should be determined in advance through experiments.

The ethylene-vinyl alcohol copolymer resin (24-44 mol% copolymer of ethylene) for the barrier layer used in the present invention refers to a resin that is substantially completely alkalized by ethylene-vinyl alcohol copolymerization and hydrolyzed. It has good gas barrier properties, so it is widely used in containers and packaging materials for chemicals, cosmetics, etc., and has high resistance to oils, organic solvents, etc., especially by using ethylene-vinyl alcohol copolymer resins with the following characteristics, which can ensure Oxygen barrier properties, and MFR, melting point, etc. are similar to those of ultra-high molecular weight and high-density polyethylene resins. Specific examples of the ethylene-vinyl alcohol copolymer resin for the barrier layer include, for example, F171B (copolymer of ethylene 32 mol%, melting point 183 ° C, and alkalinity rate 99.99%) manufactured by Kuraray Co., Ltd.

(characteristic)

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

Density (Kg / m ³ ): 1.1 ～ 1.3

Melting point (° C): 170 ～ 200

The MFR is preferably 2 to 5, more preferably 3 to 5, the density is preferably 1.1 to 1.3, further preferably 1.2 to 1.3, and the melting point (° C) is preferably 170 to 200, and further preferably 190 to 200. If the MFR, density, and melting point are within the foregoing ranges, any of gas, strength, and stable moldability are excellent. If they are outside the foregoing ranges, at least one of these characteristics may be impaired.

The outer layer of the ultra-high molecular weight and high-density polyethylene resin used in the present invention has a density (measurement method: JIS K7112) of preferably 940 to 962, and more preferably 944 to 946 Kg / cm ³ , and a weight average molecular weight (measurement method: It is preferably 220,000 to 260,000, and more preferably 240,000 to 260,000. The molecular weight distribution (Mw / Mn) (measurement method: described later) is preferably 12 or less, and further preferably 11 or less. Melt tension (measurement method: Japanese polyethylene method, Capillograph manufactured by Toyo Seiki Co., Ltd. (measured at 210 ° C) should preferably be 18 to 30 g, and further preferably 22 to 26 g of polyethylene or ethylene-α-olefin copolymer, and used for outer layer, moldability or mechanical strength As the problems improved, the problems such as sags disappeared, and the yield rate improved.

When the weight average molecular weight of the raw material ultra-high molecular weight high-density polyethylene resin is less than 220,000, the mechanical strength may be insufficient. When the weight average molecular weight exceeds 260,000, the resin has a high melt viscosity, so the moldability is deteriorated, for fear of causing the shear stress. Molecular cutoff, etc.

If the aforementioned density and melt tension are less than the lower limit value, a drop may occur, and it may be difficult to control the thickness of the meat. In addition, if it exceeds the upper limit value, the problem of melt damage (rough texture) on the bottle surface may occur.

Commercially available ultra-high molecular weight and high-density polyethylene resins used in the present invention can be used. As the α-olefin copolymerized with ethylene, propylene, butene-1,4-methyl-pentene-1, hexene-1, and octene-1 are used. The α-olefin content in the copolymer is preferably 15% by mass or less. The molecular structure of the copolymer may be any of a hetero, a co-row or a counter-row. If a high density polymer of 940 to 962 Kg / cm ³ can be obtained by the polymerization method, either a low pressure method or a medium pressure method may be used.

The ultra high molecular weight density polyethylene resin is composed of a resin composition containing at least the following components: an ultra high molecular weight density polyethylene resin composed of polyethylene or an ethylene-α-olefin copolymer and having the aforementioned characteristics; benzotriazole The lightfast stabilizers and the triazine lightfast stabilizers are each preferably 0.05 to 0.30 mass%, more preferably 0.06 to 0.30 mass% each; and from carboxylic acid nucleating agents, phosphate metal salt nucleating agents, and sorbitol systems. The at least one nucleating agent selected in the nucleating agent group is preferably 0.5 to 2.5 mass%, more preferably 0.6 to 2.5 mass% each; thereby, the layered container of the present invention can be given a level that can be visually confirmed and contained from the outside. The content liquid has significantly improved transparency, visibility comparable to that of a transparent glass bottle, and significantly improved UV blocking properties. It can also be used as a photoresist, etc., ultra-high purity chemicals or perfumes that are deteriorated and hardened due to ultraviolet rays. Chemical container.

The combination of benzotriazole-based light-resistant stabilizers and triazine-based light-resistant stabilizers is used to block both UV-B (290-320 nm) and UV-A (320-400 nm). Significantly improves UV blocking without damaging and other properties.

If the aforementioned lightfastness stability and nucleating agent are smaller than the lower limit, there is a risk that transparency and ultraviolet blocking properties cannot be improved significantly. If the upper limit is exceeded, the transparency and cleanliness may be impaired.

Examples of the light-resistant stabilizer include 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2- (3-tertiarybutyl-5-methyl-2-hydroxyphenyl) -5-chloro Benzotriazole, 2- (2-hydroxy-5-methylphenylbenzotriazole), 2- (5-chloro-2-benzotriazole) -6-tertiary butyl-cresol, 2 -(3,5-Di-tertiary amino-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -p-cresol, etc. Agent, 2- [4,6-bis (2,4 stub base) -1,3,5-triazin-2-yl] -5,2,4,6-ginseng (2-hydroxy-4-hexyloxy) Methyl-3-methylphenyl) -1,3,5-triazine, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- [2- ( 2-ethylhexyloxy) ethoxy] phenol and other triazine light stabilizers, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate, poly [{6 -(1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4 -Piperidinyl) iminyl} hexamethylene {(2,2,6,6-tetramethyl-4-piperidinyl) iminyl}] a hindered amine-based light stabilizer.

The content of additives contained in special polyamide resins and other resins is the value obtained by extracting the extract with a Soxler extractor for 8 hours using tetrahydrofuran (THF), and separating and quantifying it by liquid chromatography. The measurement conditions are as follows: the device is GULLIVER (manufactured by JASCO Corporation); the column is Finepak GEL 101 (manufactured by JASCO Corporation); the solvent is THF; the detector is UV-970 (manufactured by JASCO Corporation) And 830-RI (manufactured by JASCO Corporation).

The method for measuring the molecular weight of a container is to prepare a sample solution by dissolving the resin composition cut from the container into a solvent (o-dichlorobenzene), and measuring the molecular weight and molecular weight distribution by GPC. The weight average molecular weight and number average molecular weight are calculated by the following formula.

Weight average molecular weight = Σ (M × w) / wΣ ... (2)

Number average molecular weight = Σw / Σ (w / M) ... (3)

Here, M is a molecular weight, and w is a weight fraction.

The measurement conditions of GPC are as follows: the device is 150 CV (manufactured by Waters); the column is TSKgel GMH-HT (manufactured by TOSOH Co., Ltd.); the solvent is o-dichlorobenzene; the temperature is 138 ° C; the detector is a differential refractometer . In order to control the molecular weight distribution of the container within the aforementioned range, the raw resin must also have a molecular weight distribution within a certain range.

The molding method is not particularly limited as long as it can be formed by a blow molding method including the above-mentioned 6 layers of the present invention having excellent transparency and chemical resistance and blow-molded laminated containers, and can also be formed from commercially available laminated containers. Choose to use the molding machine.

In addition, the description of the above-mentioned embodiment is for explaining the present invention, and does not limit the invention described in the scope of patent application or reduce the scope. In addition, the configuration of each part of the present invention is not limited to the above-mentioned embodiment, and various modifications can be made within the technical scope described in the patent application scope.

[Example]

The present invention is explained in detail by the following examples, but as long as it does not deviate from the gist of the present invention, it should not be limited by these examples.

The following description% means mass%.

(Example 1)

The inner layer uses a fluororesin (FR-5000 manufactured by Daikin Industries Co., Ltd.) with MFR 25g / 10 min, specific gravity 1.74, and melting point 195 ° C, and a special polyamine resin (Daicel-Evonik) with no additives that adheres to the fluororesin. Co., Ltd. Z4887, with barrier and resin, relative viscosity of 1.87), and then used with barrier resin (ethylene-vinyl alcohol copolymer resin F171B: KURARAY Co., Ltd., alkalinity rate 99.99%), and special polyamide resin has Following the functionalization of maleic anhydride modified polyolefin resin (Japan Polyethylene Corporation FT71A), and then use the best with the aforementioned barrier resins, and in order to strengthen the reduction of the melt tension of the fluororesin or the polyamide resin Outer layer ultra high molecular weight high density polyethylene resin with maleic anhydride modified polyolefin resin (Japan Polyethylene Co., Ltd. HB111R) (HL-MFR (Measurement method: JIS K7112) 6 g / 10 min, density 946 Kg / m ³ , weight average molecular weight 250,000, melt tension 25g); and the aforementioned ultra-high molecular weight high-density polyethylene resin is blended with: disazo yellow 0.025 mass%, azo yellow 0.0 7 mass% as pigment; sodium bis (4-third butylphenyl) phosphate (trade name: ADK STAB NA11) 1.5 mass% as nucleating agent; and benzotriazole (UVA), manufactured by ADEKA Co., Ltd. LA32, 0.1 mass% and triazine (UVB), LA-F70, 0.1mass% manufactured by ADEKA Co., Ltd. are used as light-resistant stabilizers; under the following molding conditions, there is no problem such as drop, and the transparency of the present invention will be included in 6 layers Blow-molded laminated container with excellent chemical resistance (full weight 400 g, inner layer 100 μm, barrier layer and resin layer 40 μm, adhesive layer 40 μm, barrier layer 40 μm, adhesive layer 40 μm, outer layer 1540 μm, average Whole meat is 1.8 mm thick and has a capacity of 3750 CC).

(Molding conditions)

A blow molding machine (6 types and 6 layers manufactured by BLENS Co., Ltd.) (a model in which 6 types of extruders are used and 1 die is laminated to 6 layers) is used.

Inner layer of fluororesin: Helix diameter 40 mmΦ Setting temperature 240 ℃

Special polyamide resin layer: spiral diameter 20 mmΦ set temperature 260 ℃

Maleic anhydride modified polyolefin resin layer: Spiral diameter 20 mmΦ Setting temperature 240 ° C

Ethylene-vinyl alcohol copolymer resin layer: Spiral diameter 20 mmΦ Setting temperature 230 ° C

Maleic anhydride modified polyolefin resin layer: Helix diameter 40 mmΦ Setting temperature 220 ℃

Outer layer of ultra-high-molecular-weight high-density polyethylene resin: spiral diameter 50 mmΦ set temperature 210 ° C

Die head temperature: set temperature 220 ℃

In addition, special polyamide resins and barrier resins with hygroscopicity are dried at 80 ° using a dryer, and the water is removed.

Then, the following test method was used to evaluate the chemical resistance and particle dissolution, oxygen permeability, and visibility using a bottle, and a 4 cm × 4 cm × 1.8 mm sample was cut from the bottle wall portion and used for evaluation Ultraviolet light transmittance and visible light transmittance are then aggregated for comprehensive judgment. The results are shown in Tables 1 to 3.

In addition, for comparison, a blown container including one layer, which is formed by blow molding in the same manner as in Example 1, was used only with a glass bottle (FUJIFILM Electronic Materials (capacity 3750 CC)), high-density polyethylene resin (Japan Poly (HB111R manufactured by Ethylene Co., Ltd.).

(Test method)

(Method for measuring foreign particles (particles))

1. Measuring device: RION KL-26, a particle counter "KL-26" manufactured by RION Corporation.

2. Measurement specimen: Fill the formed container with ultrapure water to full water, collect the measurement sample from the container after standing for 20 minutes in an upright state, and use it as the measurement specimen.

3. Before the measurement, rinse the particle counter with ultrapure water, and then wash the measurement device twice with 25 ml of ultrapure water.

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

5. Wash the measuring device twice with a 25 ml test specimen.

6. After washing, inject 10 ml from a bottle filled with ultrapure water for measuring the sample into a particle counter to measure the number of particles. This operation was performed twice, and the average value (B) of the number of particles of 0.2 μm or more was obtained.

7. From the measured value, calculate and find the particle value in 1 ml using the following formula.

(B (pieces)) ÷ 10 ml = pieces / ml

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

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

1 atmosphere inside, 23 ° C, dry nitrogen.

(UV transmittance)

Using V-670 from Japan Spectroscopy Co., Ltd., the transmittance in the ultraviolet region of 200 ～ 400nm.

(Visible light transmittance)

V-670 from Japan Spectroscopy Co., Ltd. is used for transmission in the ultraviolet region of 400 to 800 nm.

(Visibility)

In a 750 lux room, tap water was put into a container, and three people viewed the tap water with the naked eye from the outside of the container. Then, the following four-stage evaluation was performed.

Evaluation:

：: Tap water can be clearly confirmed.

○: Tap water can be confirmed.

△: Tap water can only be confirmed by careful observation.

×: Tap water cannot be confirmed.

(Comprehensive judgment)

The particle value is less than 5 / ml;

The oxygen permeability is below 0.003 [cm ³ /(pkg.24h.atm)];

UV transmittance is below 3%;

Visible light transmittance is above 45%;

Visibility is the same as glass bottle.

In this case, the overall judgment is ◎. When any item is inferior to the foregoing, it is regarded as ×.

[Table 1]

(Number of particles above 0.2μm: number / ml)

[Table 2]

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

[table 3]

(UV transmittance, visible light transmittance, visibility, comprehensive judgment)

From Tables 1 to 3, it can be seen that the present invention has excellent transparency and chemical resistance. The blow-molded laminated container system has good cleanliness, excellent oxygen barrier properties, ultraviolet blocking properties, and visible light transmittance, and has visibility comparable to transparent glass bottles. You can visually check the contents of the liquid from the outside.

(Comparative example 1)

Instead of using the same polyamide resin (relative viscosity 1.87) added with an antioxidant (hindered phenol, 2000 ppm) instead of the special polyamide resin without additives (Z4887 manufactured by Daicel-Evonik Co., Ltd.) Except for (barrier and resin, relative viscosity 1.87), a blow-molded laminated container for comparison was produced in the same manner as in Example 1, and the amount of particles eluted was measured in the same manner as in Example 1. The results are shown in Table 4.

[Table 4]

(Number of particles above 0.2μm: number / ml)

As can be seen from Table 4, in Comparative Example 1, the addition of additives caused smoke during molding, and the number of particles increased sharply.

(Comparative example 2)

Except that the barrier resin ethylene-vinyl alcohol copolymer resin used in Example 1 was not used, it was replaced with a general-purpose high-density polyethylene (density 0.945 g / cc, MFR 0.30 g / 10 min), and was the same as in Example 1. A blow-molded laminated container for comparison was produced, and the oxygen permeability was measured in the same manner as in Example 1. A single-layer blow-molded container having only high-density polyethylene (density 0.945 g / cc, MFR 0.30 g / 10 min) was produced, and the oxygen permeability was measured in the same manner as in Example 1. The results are shown in Table 5.

[table 5]

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

As can be seen from Table 5, Comparative Example 2 in which the ethylene-vinyl alcohol copolymer resin did not use the barrier resin had a poor oxygen permeability.

(Comparative example 3)

Ultra-high-molecular-weight high-density polyethylene resin (HB111R manufactured by Japan Polyethylene Corporation) (HL-MFR (measurement method: JIS K7112)) with a predetermined amount of nucleating agent and light-resistant stabilizer is used for 6 g / 10 min. Density 946 Kg / m ³ , weight-average molecular weight 250,000, melt tension 25 g), instead of the one used in Example 1, an ultra-high molecular weight high-density polyethylene resin (Japan Polyethylene Co., Ltd.) was prepared with a predetermined amount of nucleating agent and light stabilizer. Co., Ltd. HB111R) (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), similar to Example 1 The blow-molded laminated container was subjected to ultraviolet transmittance, visible light transmittance, visibility, and comprehensive judgment in the same manner as in Example 1.

For comparison, a glass bottle (FUJIFILM Electronic Materials (capacity 3750 CC)) was used. The results are shown in Table 6.

[TABLE 6]

According to Table 6, the ultra-high molecular weight and high-density polyethylene resin layer of Comparative Example 3 is opaque, reduces visible light transmittance, and has high ultraviolet transmittance, which is not practical.

(Comparative Example 4)

Ultra-high molecular weight high-density polymer with a predetermined amount of nucleating agent and light-resistant stabilizer was used instead of the general small-density high-density ethylene for blowing with MFR 0.3 g / 10 min and density 0.945 g / cc. Except for vinyl resin (HB111R manufactured by Japan Polyethylene Corporation) (HL-MFR (measurement method: JIS K7112) 6 g / 10 min, density 946 Kg / m ³ , weight average molecular weight 250,000, and melt tension 25 g), Example 1 was molded in the same manner, and as a result, a fall or the like occurred, and a laminated container having a uniform thickness of the meat could not be obtained.

It can be seen that the laminated fluororesin or polyamide resin has a high melting point, and therefore the overall molding temperature must be approximately 50 ° C higher than the general temperature. Therefore, an ultra-high molecular weight high-density polyethylene resin with a large weight average molecular weight and high melt tension is required.

From the above results, according to the foregoing Examples and Comparative Examples, in order to provide excellent chemical resistance and mechanical strength, there are few foreign particles exuding, visibility comparable to that of transparent glass bottles, and ultraviolet blocking properties and oxygen barriers. It has excellent properties and can also be used as a container for perfume ingredients or photoresist liquids. It has excellent transparency and chemical resistance and is a blown laminated container. The following matters are necessary.

1. The innermost layer must use fluororesin. It is more suitable to use fluororesin without additives.

2. Polyamide resin is used as the adhesive layer of the fluororesin. It is very important to use a special polyamide resin without additives.

3. In order to ensure the barrier properties of the container, an ethylene-vinyl alcohol copolymer resin must be used.

4. Ultraviolet blocking must be used in combination, and the specific nucleating agent and specific light resistance stability of the filling liquid can be confirmed from the outside, and it can be formulated in ultra-high molecular weight high-density polyethylene resin.

Industrial availability

The 6-layer structure of the present invention has excellent transparency and chemical resistance. The blown laminated container has the transparency of the aforementioned layers of the blown laminated container, so it has visibility comparable to that of a transparent glass bottle, and can be visually confirmed from the outside. The inner liquid can improve chemical resistance by using a fluororesin as the inner layer of the wetted surface, and can minimize the deterioration of odor components. A special polyamide resin without additives or lubricants is used as a barrier and adhesion resin. Layer, can obtain the cleanliness equivalent to that of a glass bottle (the amount of dissolved particles of impurities is very small). By providing a barrier layer, the oxygen barrier property is improved. In addition, since the fluororesin, polyamide resin, or the subsequent resin is melted, it melts. The tension decreases momentarily. Therefore, problems such as sags occur during blow molding, such as failure to form containers with uniform meat thickness, or defective products, yield deterioration, etc. However, by using the outer layer with a large melt tension, UV blocking properties and Ultra-high molecular weight high-density polyethylene resin with excellent transparency, which can improve moldability or mechanical strength, so it can provide transparency Excellent chemical resistance of the blow molded container laminated significant effect, but the chemical resistance is excellent in transparency blow laminated container may correspond to multiple ultra-high purity chemicals is expensive and high-risk containers of chemicals.

In addition, by using a fluororesin as the inner layer of the wetted surface and an ethylene-vinyl alcohol copolymer resin as the barrier layer, a 6-layer structure with excellent transparency and chemical resistance is blown and laminated. The container is heavy and easily damaged. Compared with glass bottles that lack safety, they are not easy to break, have excellent mechanical strength, and improve the oxygen barrier properties. Therefore, they can also be used as spice bottles, etc., and have the properties of universal containers. High-value and high-dangerous chemical substances, universal plastic containers that can also be used, exert a remarkable effect that can be safely and safely used in terms of taste or smell, so the industrial use value is high.

1‧‧‧ inner layer composed of fluororesin

2‧‧‧ Barrier made of special polyamide resin and resin layer

3‧‧‧ Adhesive layer composed of maleic anhydride modified polyolefin resin

4‧‧‧ Barrier layer composed of ethylene-vinyl alcohol copolymer resin

5‧‧‧ Adhesive layer composed of maleic anhydride modified polyolefin resin

6‧‧‧ Outer layer composed of ultra-high molecular weight high-density polyethylene resin

Claims (4)

A chemically resistant blow-molded laminated container with excellent transparency, characterized in that the aforementioned chemical-resistant blow-molded laminated container is sequentially laminated from the inside to the outside of the container, and the following inner layers, barriers, resin layers, and adhesive properties are sequentially laminated. Layer, barrier layer, adhesive layer and outer layer; and each of the foregoing layers is transparent;
Inner layer: fluororesin;
The barrier and resin layer: the following special polyamide resin;
Adhesive layer: maleic anhydride modified polyolefin resin;
Barrier layer: ethylene-vinyl alcohol copolymer resin;
Next layer: maleic anhydride modified polyolefin resin;
Outer layer: UHMWPE resin;
Special polyamide resin: at least one polyamine selected from the group consisting of polyamines obtained by ring-opening polycondensation of caprolactam, does not contain additives containing additives or lubricants, and has the following Mentioned characteristic.
(characteristic)
Melting point (° C): 170 ～ 250
Density (Kg / m ³ ): 1.0 ～ 1.2 For example, a blown laminated container with excellent chemical resistance and chemical resistance, such as item 1 of the patent application range, in which the fluororesin used in the inner layer includes a tetrafluoroethylene / hexafluoropropylene / monomer (α) copolymer, tetrafluoro Ethylene / perfluoro (alkyl vinyl ether) / monomer (α) copolymer, ethylene / tetrafluoroethylene / monomer (α) copolymer, ethylene / tetrafluoroethylene / hexafluoropropylene / monomer (α) copolymer , Trifluorochloroethylene / monomer (α) copolymer, trifluorochloroethylene / tetrafluoroethylene / monomer (α) copolymer, and ethylene / trifluorochloroethylene / monomer (α) copolymer At least one selected, the aforementioned monomer (α) represents a monomer having a bonding functional group, and the aforementioned fluororesin has the following characteristics;
(characteristic)
MFR (5 Kg load g / 10 min): 10 ～ 40
Specific gravity: 1.7 ～ 1.9
Melting point (° C): 150-220. For example, the blown laminated laminated container with excellent transparency and chemical resistance of item 1 or item 2 of the patent application scope, wherein the aforementioned barrier layer is an ethylene-vinyl alcohol copolymer resin having excellent oxygen barrier properties with the following characteristics;
(characteristic)
MFR (210 ℃, 2.16 Kg load g / 10 min): 2 ～ 5
Density (Kg / m ³ ): 1.1 ～ 1.3
Melting point (° C): 170-200. For example, the blown laminated container with excellent chemical resistance and chemical resistance in any one of claims 1 to 3, wherein the ultra-high molecular weight polyethylene resin is composed of a resin composition containing at least the following components: Ultra-high-molecular-weight-density polyethylene resin composed of polyethylene or an ethylene-α-olefin copolymer and having the following characteristics; benzotriazole-based light-resistant stabilizers and triazine-based light-resistant stabilizers each 0.05 to 0.30 mass%; and from 0.5 to 2.5 mass% of at least one nucleating agent selected from the group consisting of a carboxylic acid-based nucleating agent, a phosphate metal salt-based nucleating agent, and a sorbitol-based nucleating agent;
(characteristic)
Density: 940 ～ 962 Kg / m ³
Weight average molecular weight: 220,000 ～ 260,000
Molecular weight distribution (Mw / Mn): 12 or less Melt tension: 18 to 30 g.