KR100492893B1 - Bag-in-can for high pure chemical agents - Google Patents

Abstract

The present invention relates to a bag-in can system in which a plastic bag having a shape of attaching a port to a heat seal around a film is inserted into a metal can, wherein the film comprises ethylene as a main component and a linear low density polyethylene resin as a comonomer. (A) A polyimide film made of a resin mixture having a melt index (190 ° C., 2.16 Kg) composed of 80 to 90% by weight and 10 to 20% by weight of a high pressure low density polyethylene resin (B) of 0.2 to 20 g / 10 min. A multilayer film obtained by coating a urethane-based adhesive and laminating an outer layer film made of a gas barrier resin (C), or the film is coated with a polyurethane adhesive on the inner layer film, and made of the gas barrier resin (C). The laminated interlayer film, and then the polyurethane-based adhesive was coated on the interlayer film, and then the outer layer film made of the high pressure low density polyethylene resin (B) was prepared. Mineyi is plated on to the high-purity chemicals for the back, it characterized in that the resulting multi-layer film can.

Description

Bag-in cans for high purity chemicals {Bag-in-Can for High Pure Chemical Agents}

The present invention is an environment-friendly high-purity that is used to insert a plastic bag formed of a film having excellent flexibility as well as ultra-cleaning and chemical barrier properties for high-purity chemicals into a metal can. It relates to a medicine bag in can.

As the semiconductor industry and the liquid crystal display (LCD) industry have recently grown rapidly, the demand for high-purity chemical containers is rapidly increasing. Therefore, the size of containers is urgent to improve productivity. In addition, as semiconductors are rapidly increasing in memory capacity, the cleanliness requirements of related chemicals are being demanded, and the cleanliness requirements of containers are being strengthened.

In general, the cleanliness of a container in the semiconductor industry and the liquid crystal display (LCD) industry indicates the degree of impurity of the chemicals by the container during the storage of high purity chemicals, and is mainly evaluated by the number of fine particles and the residual metal content. That is, after storing the ultrapure water in a container for a certain period of time, the number of particulates for calculating how many fine particles having a particle diameter of 0.2 μm or 0.3 μm or more exist in 1 ml of stored water, and the high purity chemicals are stored after storing for a certain period of time. Obtained from residual metal content leached by chemicals.

Meanwhile, in the case of so-called photoresist, which is commercially available in the form of a composition in which photoresist resins and additives are dissolved in a solvent such as propylene glycol methyl ether acetate (PGMEA), when the solvent diffuses out of the container during long-term storage, As the composition is changed, a serious problem of deterioration of quality is required, so that not only the cleanliness but also the barrier to the solvent are required in the container. In this sense, the brown special glass bottle has been used as a good material since ancient times, but it is not only fragile but also has a maximum capacity of only 1 gal, which is a big obstacle to the enlargement of the container. Has been.

Suggested as a means to solve the problem is a light-shielding clean plastic container of Nowaer Technologies of the United States, such as introduced in US Patent Nos. 5,102,010, 5,031,801, for example. This is a container in which a clean fluororesin film is embedded in a polyethylene container prescribed a light-shielding additive, but it has an advantage of not being broken, but it is rarely used at present because it is extremely expensive in terms of fluororesin characteristics. In Japanese Patent Laid-Open No. 7-330074, a manufacturing method of a plastic container using a resin composition in which light-shielding additives such as titanium oxide and carbon black are simply added to high-density polyethylene is presented. In order to solve this problem, there is a problem of poor light-shielding properties and poor cleanliness based on the poor dispersion state of the photo additive, and according to the coextrusion blow processing method as described in Japanese Patent Application Laid-Open No. 11-290420, an inner layer made of polyolefin resin A so-called five-layer layer consisting of an intermediate layer of resin such as polyamide and polyvinyl alcohol having excellent solvent barrier property, an outer layer of resin containing a light-shielding additive, and two adhesive layers to prevent delamination. Although a manufacturing method of a light-shielding clean plastic container has been proposed, all of the above glass bottles and plastic containers Excessive cleaning costs when reused, and even if washed, there is a concern that the cleanliness deteriorated, so it has been classified as a disposable product that is not reused and disposed of as it is.

As a breakthrough method to reduce such environmental burdens, promote productivity through the enlargement of containers, and provide cleanliness without breaking problems, for example, the bag-in can system of the United States, such as introduced in US Patent No. 5,335,821, is proposed. It became. That is, a bag-in-can system in which a plastic bag having a shape of heat-sealing around a film and having a port attached thereto is inserted into and mounted in a metal can. It is a new concept system that injects gas into the space between the bags and pressurizes the inner bag to automatically move through the port to the storage tank. In this case, a metal can is reused and an environmentally friendly container system that can dramatically reduce the environmental burden since only one million plastics are disposed of for single use. However, the plastic bags currently marketed under this system, such as the product name NOWPAK, have been urgently required for improvement due to the complicated manufacturing process, low cleanliness and high price.

As a means to solve this problem, for example, as in the Republic of Korea Patent Application No. 2003-57590 consists of an inner layer consisting of a high-purity polyolefin resin by the inflation coextrusion film processing technology, composed of a composition of a polyolefin resin and an adhesive polyolefin resin It has been proposed to introduce a novel plastic bag made from a three-layer film of an outer layer consisting of an interlayer, polyamide, polyvinyl alcohol, etc. gas barrier resin into a bag in can system. However, the plastic bag used in such a bag-in can system has excellent cleanliness and a very simple manufacturing process, and thus has a low cost advantage. However, due to the system characteristics, the plastic bag is placed on a small diameter mouse attached to the upper part of the metal can. The plastic bag has to be inserted and the flexibility of the plastic bag is so poor that the productivity of the work is significantly reduced, and even the plastic bag is torn and there is a big problem.

Therefore, the present invention has been devised to solve the above problems, and the present inventors have led the present invention as a result of intensive studies.

An object of the present invention is the flexibility required for plastic bag insertion workability as well as excellent barrier properties, cleanliness and economy based on a bag in can system capable of large-sized containers and consisting of disposable plastic bags and reusable metal cans to reduce environmental burden. It is to provide a new plastic bag film superior to this existing.

Still another object of the present invention is to provide a bag-in-can using the plastic bag film having the new physical properties.

It is another object of the present invention to provide a method for producing a bag in can, which is provided with a means such as a connector having a sealing means and a venting means and mounted on the can.

The present invention is a plastic bag molded from a film having excellent flexibility as well as an ultra clean, chemical barrier property suitable for containing high-purity chemicals such as photoresist is inserted into the metal can and used to reuse the metal can and discard the plastic million. It relates to a friendly high purity medicine bag in cans.

That is, the present invention relates to a bag-in can system in which a plastic bag having a shape of heat sealing the film and having a port attached thereto is inserted into a metal can, wherein the film contains ethylene as a main component and has 6 to 6 carbon atoms as a comonomer. 80 to 90% by weight of a linear low density polyethylene resin (A) having a density of 0.860 to 0.925 g / cm ³ and a high pressure compressor of 1,700 kg / cm ² or more prepared by a metalocene catalyst using 12 alpha olefins. Total thickness made of resin mixture having 0.2-20g / 10min melt index (190 ℃, 2.16Kg) composed of 10-20% by weight of high pressure low density polyethylene resin (B) having a density of 0.915-0.925 g / cm ³ A multilayer film obtained by coating a polyurethane-based adhesive on an inner film formed of 70% to 95% of a lamination and laminating an outer film formed of 5% to 30% of the total thickness made of a gas barrier resin (C). Featuring Is to provide a high-purity bag-in can.

Another aspect of the present invention is a bag-in can system in which a plastic bag having a shape that is heat-sealed around a film and has a port attached thereto is inserted into a metal can, wherein the film is composed of ethylene and is used as a comonomer. 80 to 90% by weight of linear low density polyethylene resin (A) having a density of 0.860 to 0.925 g / cm ³ produced by a metalocene catalyst using an alpha olefin having 6 to 12 carbon atoms and at least 1,700 kg / cm ² Manufactured from a resin mixture with a melt index (190 ° C, 2.16Kg) consisting of 10 to 20% by weight of a high pressure method low density polyethylene resin (B) having a density of 0.915 to 0.925 g / cm ³ obtained from a compressor. Polyurethane-based adhesive was coated on the inner layer film formed from 50% to 90% of the total thickness, and the interlayer film formed from 5% to 30% of the total thickness made of the gas barrier resin (C) was then laminated. Interlayer film The outer layer is formed of 5-20% of the total thickness made of a high-pressure processed low-density polyethylene resin has a density of after coating the polyurethane-based adhesive 1,700kg / cm ² or more 0.915~0.925g / cm ³ obtained by the ultra-high pressure compressor It is providing the high purity chemical | medical agent bag in can which is a multilayer film obtained by laminating a film.

An important differentiating object from the prior art in the present invention is securing the flexibility of the film.

The linear low density polyethylene-based resin (A), which is a resin used in the inner layer of the film in the present invention, adopted from this point of view, is an ethylene-alphaolefin-based copolymer containing alpha olefin as a comonomer as a main component. It is not manufactured using a Ziegler-Natta based catalyst, but rather a metallocene based catalyst as disclosed in US Pat. Nos. 5,206,075, 5,241,031, 5,272,236, 5,278,272 and the like. It is manufactured. In the ethylene-alpha olefin copolymer using a metalocene catalyst, alpha olefins, which are comonomers, are arranged in a relatively regular sequence so that the molecular weight distribution is narrow and physical properties are superior to those of the Ziegler-Natta system. In particular, the narrow molecular weight distribution indicates that the low molecular weight, which is the main cause of fine particles due to elution by chemicals, is extremely small.

In addition, the activity of the catalyst is also very high compared to the Ziegler-Natta system, the content of the remaining catalyst is extremely low, so that the leaching of metal components by the chemical is also very small.

Examples of the alpha olefins include alpha olefins having 6 to 12 carbon atoms such as 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene and 1-dodecene. It is suitable and especially the C6-C8 thing is preferable. If the carbon number is less than 6, the mechanical properties are not sufficient, and if the carbon number exceeds 12, there is a high risk that the content of low molecules, which is an important cause of the fine particles, increases.

The density of the resin is largely dependent on the type, content and the like of the alpha olefin which is usually a comonomer, but is preferably 0.860 to 0.925 g / cm ³ . When the density is less than 0.860g / cm ³ , the flexibility is very good, but the adhesiveness is somewhat weakened, and the antiblocking property between the films may be deteriorated, and the injection of chemicals may be difficult. When the density exceeds 0.925g / cm ³ , the film Poor flexibility

That is, the linear low density polyethylene resin (A) used in the present invention basically has a narrow molecular weight distribution, and thus has a very low molecular weight component, so that the amount of fine particles eluted by the chemical is very small, and the catalytic activity is high. Ultra-low purity and flexibility at the same time in plastic bags suitable for containing high purity chemicals as well as very low residual metals due to extremely low constituents as well as extremely low density resins. It is important to be able to assign.

Examples of the linear low density polyethylene resin (A) according to the present invention include, for example, Affinity of The Dow Chemical Company, Moretec of Idemitsu Petrochemical Co., Exceed from ExxonMobil Chemical Co., etc. are mentioned.

However, when the linear low density polyethylene-based resin (A) alone is used as described above, workability is poor during film processing, and a large amount of low molecules, gels, etc. are generated by deterioration, oxidation, crosslinking reaction, etc. in the extruder or die, and thus fine particles by chemicals are produced. An increasing problem has arisen.

As a means to solve this problem, the resin partially introduced for the inner layer film is a high pressure low density polyethylene resin (B) according to the present invention. It is a low-density polyethylene-based resin obtained from an ultra-high pressure compressor of 1,700kg / cm ² or more.It is characterized by the manufacturing method that usually uses air as a catalyst.It is extremely low in the amount of metal extraction due to the extremely low risk of generation of residual metal components. There is a disadvantage that the molecular weight distribution is very wide compared to the polyethylene-based resin (A), but the low molecular weight content is very high, but there is also a very good workability, the density of 0.915 ~ 0.925 g / cm ³ is suitable for the purpose of the present invention. If the density is less than 0.915 g / cm ³ , the flexibility is very good, but the low molecular content is further increased, there is a fear that a large amount of fine particles are generated, if the density exceeds 0.925 g / cm ³ , the flexibility of the film is poor.

The mixing ratio of the linear low density polyethylene resin (A) and the high pressure low density polyethylene resin (B) according to the present invention is 80 to 90% by weight of the linear low density polyethylene crab resin (A). It is suitable to mix at -20 weight%. If the content of the high pressure low density polyethylene-based resin (B) is less than 10% by weight, the generation of low molecular weight, gel, etc. due to poor film processability increases, and if the content exceeds 20% by weight, the linear low density polyethylene crab before the film forming process is basically used. Due to the low molecular weight contained in the resin (A), there is a possibility that the amount of fine particles caused by the chemicals eventually increases, thereby impairing cleanliness.

Melt index (190 degreeC, 2.16Kg) of the resin mixture used for the inner layer film in this invention should just be 0.2-20 g / 10min, and it is more preferable if it is 0.5-10 g / 10min. If the melt index is less than 0.2g / 10min, there is a risk of low molecular weight and gel generation due to deterioration, oxidation, crosslinking reaction, etc. during the extrusion process, whereas if the melt index exceeds 20g / 10min, the fluidity is increased and the melt tension Too low film formation is very difficult and there is a problem that the appearance of the film worsens, such as bone wrinkles after winding.

Such resin mixtures also include neutralizing agents such as calcium stearate, zinc stearate and hydrotalcite, dibutylhydroxytoluene, pentaerythyl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) An antioxidant such as propionate] may be appropriately added or subtracted as necessary, but the total amount of the added additive is preferably 0.1% by weight or less in the resin mixture. If the total amount of the additives exceeds 0.1% by weight, some of these additives may contain metal components, and therefore, they may have a fatal effect on the leaching residual metal content of the high-purity chemicals, and the molecular weight is very low, so that the high-purity chemicals are easily Leaching and eventually acting as particulates is a major cause of poor cleanliness.

In conclusion, the resin mixture of the linear low density polyethylene resin (A) and the high pressure low density polyethylene resin (B) used in the inner layer of the film of the present invention in direct contact with high purity chemicals has a molecular weight of thousands of paraffin waxes. Due to the extremely low extraction amount of oligomers, it is eluted very quickly when chemicals are stored, and the problem of contaminating the chemicals due to the generation of fine particles is extremely suppressed, and the amount of remaining metal in the resin due to catalysts is extremely small, and thus eluted by chemicals. Is also extremely suppressed.

However, the inner layer film made of the resin mixture of the linear low density polyethylene resin (A) and the high pressure low density polyethylene resin (B) according to the present invention has excellent cleanliness, economical efficiency, and good use in a plastic bag suitable for a bag in can system. Provides flexibility but lacks barrier to drug.

For example, chemicals for semiconductor / LCD such as photoresist are composed of solvent such as high purity propylene glycol methyl ether acetate (PGMEA), photoresist and other additives. There is a problem that the physical properties change when coating on a substrate such as. Therefore, excellent barrier properties to solvents are required for long term storage.

In the present invention, in order to satisfy these requirements, the resin having excellent gas barrier properties such as oxygen and carbon dioxide has excellent solvent barrier properties, and the multilayer film structure is considered, and a part of the multilayer film is considered to be composed of such a resin. . In the present invention adopted from this viewpoint, the gas barrier resin (C) is a conventional polyamide resin, a polyvinyl alcohol resin, an ethylene-vinyl alcohol copolymer resin, a polyester resin known to be excellent in gas barrier properties. Or at least one selected from polyacrylonitrile resin, polyvinylidene chloride resin and the like.

Thus, the following two methods were adopted as a method of additionally providing gas barrier properties.

The first method is to coat the polyurethane-based adhesive on the inner layer film made of the resin mixture of the linear low density polyethylene resin (A) and the high pressure low density polyethylene resin (B) according to the present invention, and to the gas barrier resin (C) The outer layer film thus produced is laminated to obtain a multilayer film. When the multilayer film obtained at this time ignores the thickness of an adhesive layer, it is good to set the inner layer film to 70%-95% of the whole thickness, and the outer layer film to 5%-30% of the whole thickness. If the thickness of the outer layer film is less than 5% of the total thickness, the drug barrier property is not sufficient, and if it exceeds 30%, the desired flexibility cannot be secured.

The second method is to coat a polyurethane-based adhesive on the inner layer film made of a resin mixture of the linear low density polyethylene resin (A) and the high pressure low density polyethylene resin (B) according to the present invention, the gas barrier resin (C) The prepared interlayer film is laminated, and then the polyurethane-based adhesive is coated on the interlayer film, and then the outer layer film made of a high pressure low density polyethylene resin (B) is laminated to obtain a multilayer film. The multilayer film obtained at this time is 50% to 90% of the total thickness of the inner layer film, 5% to 30% of the total thickness of the inner layer film, and 5% to 20% of the total thickness of the outer thickness when the thickness of the adhesive layer is ignored. good. If the thickness of the interlayer film is less than 5% of the total thickness, the drug barrier property is not sufficient, and if it exceeds 30%, the desired flexibility cannot be obtained.

Comparing the multilayer film obtained by the first method and the multilayer film obtained by the second method, the multilayer film obtained by the first method is more economical due to the cost advantage due to only one laminating process, but the gas barrier resin ( The outer layer film of C) may have a problem in that the moisture barrier property is slightly weak, and thus, the chemical barrier property of the external air may be inferior in long term storage.However, in the case of the multilayer film obtained by the second method, the lipophilic high-pressure low density polyethylene resin ( The outer layer film of B) becomes a form of protecting the gas barrier intermediate layer, and thus is excellent in long-term chemical barrier properties. Therefore, it is necessary to select the method according to the storage place, method, and type and nature of the drug.

Polyurethane adhesive in the present invention is produced by the usual alcohol or amines and isocyanate, so there is no relationship between the solvent type and solvent-free type, so-called dry lamination adhesive is suitable, and any one-component and two-component type is possible. The two-component type is more preferable. As the polyether-based polyurethane, for example, “SEIKABOND” A-155 / C-90 of Japan Daiil Chemical Co., Ltd., and A-385 / A of the chemically-accepted aliphatic polyester-based polyurethane -50 and the aromatic polyester polyurethane include LX-75A of Nippon Ink.

In the high-purity medicine bag in can according to the present invention, the film forming the bag can be any one such as inflation film molding and casting film molding, but in the case of inflation film molding, the film is formed by a cylindrical bubble to finally form a double-layer film. The film's inner layer, which should be kept the most clean, depends on the cleanliness of the blowing air rather than being exposed to the outside air, so it is very easy to maintain the cleanliness, and the film outer layer is exposed to cooling water or outside air but does not require very high cleanliness. Therefore, the cost of maintaining cleanliness such as a clean room is low, but according to the casting film method, the film is wound in the form of one layer, and since both the inner and outer layers of the film are exposed to the outside air, the entire clean room must maintain high cleanliness, resulting in very high cleanliness maintenance costs. Inflation film molding It is maintained easily and is more economical.

In addition, the thickness of the film may vary somewhat depending on the capacity of the plastic bag, but considering the flexibility, strength, etc. at the same time 150μm ~ 200μm level is appropriate.

The film forming by the inflation method and the bag in can manufacturing method using the same will be described in more detail as follows.

Melt index (190 ° C., 2.16 Kg) composed of 80 to 90 wt% of linear low density polyethylene resin (A) and 10 to 20 wt% of high pressure low density polyethylene resin (B) according to the present invention is 0.2 to 20 g / 10 min. Measuring and preparing a resin mixture; The resin mixture is introduced into an inflation film extruder installed in a clean room with a class of less than 0.5 µm per ft3 through a hopper, and the inner layer film folded in two layers is rolled using a clean air of class 10 or less. Obtaining; Coating a polyurethane-based adhesive on both outer surfaces of the double layer inner film; The outer layer film made of the gas barrier resin (C) is laminated to obtain a two-layered multilayer film.

As another method, a melt index (190 ° C., 2.16 Kg) composed of 80 to 90 wt% of linear low density polyethylene resin (A) and 10 to 20 wt% of high pressure low density polyethylene resin (B) according to the present invention is used. Measuring to prepare a resin mixture of 0.2 to 20 g / 10 min; The resin mixture is introduced into an inflation film extruder installed in a clean room with a class of less than 0.5 µm per ft3 through a hopper, and the inner layer film folded in two layers is rolled using a clean air of class 10 or less. Obtaining; Coating a polyurethane-based adhesive on both outer surfaces of the double layer inner film; Laminating an interlayer film made of a gas barrier resin (C); Coating the polyurethane-based adhesive on the outer surface of the interlayer film; Laminating an outer layer film made of a high pressure low density polyethylene resin (B) to obtain a double layered multilayer film.

Hereinafter, a method of bonding the above-described multilayer film to the pot and mounting on the can will be described. Basically, the cans of the present invention are described based on the known components and forms of the cans described in US Patent No. 5,335,821, and it is apparent to those skilled in the art that the cans may have various forms in addition to the above-cited references.

The multi-layer film obtained as described above was unpacked in a clean room of class 1,000 or less, put into a bag-making molding machine, cut to a suitable size, heat-sealed around except for the portion where the port is to be inserted, and then a double-layered film was opened to open a hole in either side. Inserting a port into the hole, attaching it by heat sealing, and then heat-sealing around the remaining film to form a bag on which the port is mounted; Inserting the obtained plastic bag into a metal can with a mouse; Mounting a diptube having a passage for high purity medicine and inserted into the bag and spanning the port; Mounting a diptube coupling for coupling a metal can with a port of the bag into which the diptube is inserted; A venting means allowing gas flow between the outside of the bag and the inside of the metal can through the diptube coupling and is equipped with sealing means for sealing the upper void and for releasing high purity chemicals when the seal is removed; A high purity drug bag in can is manufactured by mounting a port of a bag into which a dip tube is inserted, a dip tube coupling, and a connector for simultaneously fastening a metal can.

When the description is added with reference to the drawings, the plastic bag 1 having the port 2 attached thereto is obtained as shown in FIG. 1 according to the above-described manufacturing method, and the metal can 3 having the mouse 4 as shown in FIG. When the plastic bag 1 is inserted into the inside and the dip tube 5 is inserted into the port 2 of the bag, the dip tube is spread over the inside of the port. An example of the dip tube 5 is shown in FIG. 3. Next, as illustrated in FIG. 4, the pot 2 of the bag into which the dip tube is inserted and the metal can 3 are fastened by using the dip tube coupling 6. Next, as shown in FIG. 5, the venting means 7 allows gas flow between the outside of the bag and the inside of the metal can through the deep tube coupling 6, and seals the upper space and removes the high purity chemical when the seal is removed. The bag in can according to the present invention is completed by simultaneously fastening the pot, the dip tube coupling and the metal can of the bag into which the dip tube is inserted using the connector 9 equipped with the sealing means 8 to be discharged. . An example of such a state is shown in FIG. 6.

Through the following examples will be described in more detail the present invention. The following examples are merely illustrative and the present invention is not limited to the following examples. The barrier properties (gas permeability, chemical loss rate), cleanliness (particle count, residual metal content) and flexibility of the prepared film and the plastic bag using the same were measured as follows.

(Gas permeability)

As a measure of barrier to high purity chemicals, gas (oxygen) permeability (cc / m 2 · day · atm) at 23 ° C., 65% RH (relative humidity) and 100% RH for film samples was measured according to ASTM D3985.

(Drug loss rate)

Using a film having a thickness of about 160 μm, a bag (for 20 L) having a port width of 55 cm and a length of 65 cm was prepared. As a measure of barrier properties for high-purity chemicals, the percentage of drug loss was determined by filling high-density propylene glycol methyl ether acetate (PGMEA), which is the main solvent of photoresist, into the bag and capping it. After storage for months, the weight loss rate (%) was evaluated.

(Particle count)

The number of fine particles (pieces / ml), which is a measure of cleanliness for high-purity chemicals, was stored for 30 days in ultra-pure water (resistance of 18 kΩ or more) in the bag, and then the fine particles having a particle size of 0.2 µm or more present in 1 ml of stored water were used. It was calculated using the Counter (Model KS-40A manufactured by RION).

(Residual metal content)

Residual metal content (ppb), a measure of cleanliness for high-purity chemicals, was stored in the bag obtained after storing the photoresist (DPR-i5500, manufactured by Dongjin Semichem Co., Ltd.). , model PlasmaQuadII).

(flexibility)

Using a film having a thickness of about 160 μm, a bag having a port width of 55 cm and a length of 65 cm (for 20 L) was prepared and rolled up to evaluate the ease of operation when inserted into the inlet of a metal can. Good, ○ Good △ Normal, Bad X)

[Examples 1 to 4]

Density as a linear low-density polyethylene-based resin ^{(A) 0.918g / cm 3,} 190 ℃ melt index of 1.0g / 10mim meta to the metallocene catalyst system of ethylene-hexane copolymer metallocene linear low-density polyethylene-based resin is ExxonMobil's Exceed 1018C (resin A (1 ), And Dow Chemical, Affinity PL 1850G (resin A (2)), a linear low density polyethylene resin which is a metalocene catalyst based ethylene-octene copolymer having a density of 0.902 g / cm ³ and a melt index of 3.09 g / 10mim at 190 ° C. 431G (resin B (1)) and density of Samsung Total Chemical Co., Ltd., a high pressure low density polyethylene resin having a density of 0.924 g / cm ³ and a 190 ° C melt index of 1.0 g / 10mim, were prepared as a high pressure low density polyethylene resin (B). F235P (resin B (2)) manufactured by Sumitomo Chemical Co., Ltd., a high-pressure method low density polyethylene resin having a 0.924 g / cm ³ and a 190 ° C melt index of 2.0 g / 10 mim, was prepared.

Inflation film extruder (Placo Co., Ltd.) installed in a clean room of 4,000 (particle size of 0.5 µm or more per ft3) of a resin mixture of resin (A) and resin (B) blended in an appropriate ratio as shown in Table 1 below through a hopper. The inner layer film (thickness 145 micrometers) which was thrown in, and was folded in two layers using the clean air of class 2 was obtained by winding in roll state. Aromatic polyester-based polyurethane adhesive (Japan Nippon Ink Chemical Co., Ltd. LX-75A) was coated on both outer surfaces of the obtained double-layered inner layer film, followed by laminating an outer layer film made of a gas barrier resin (C). The multilayer film of 160 micrometers (162 micrometers in thickness containing an adhesive layer) was obtained.

At this time, the outer layer film made of a gas barrier resin (C) is a film of polyamide-6 resin (thickness 15㎛, Kolon AMIDROLL NP, resin C (1)) and the film of ethylene-vinyl alcohol copolymer ( 15 micrometers in thickness, Japanese Kureray EVAL, EF-XL, Resin C (2)) was used.

Then, unpacking the multilayer film obtained in the clean room of class 600, inserting it into bag making machine, cutting it into 55cm length and 65cm length, heat-sealing it except the part where the port is to be inserted, and then spreading the multilayer film in two layers. A hole was inserted into the hole, and the injection hole was inserted into the hole, and then heat-sealed and attached, and then heat-sealed around the remaining multilayer film to obtain a plastic bag for 20 l equipped with the injection hole. The obtained plastic bag was inserted into the inside of the metal can to obtain a high-purity medicine bag in can. Related properties were evaluated for the obtained films, bags and the like, and the results are shown in Table 1.

[Examples 5 to 8]

Using the same resin mixture of Resin (A) and Resin (B) as in Examples 1 to 4, a double-layered inner layer film (thickness of 125 μm) was wound in a roll to obtain a roll. Aromatic polyester-based polyurethane-based adhesive (Japan Nippon Ink Chemical Co., Ltd. LX-75A) was coated on both outer surfaces of the obtained double-layered inner layer film, followed by a gas barrier resin (C) as in Examples 1-4. After laminating the prepared interlayer film, the polyurethane-based adhesive was again coated, and instead of a mixture of resin (A) and resin (B), a single layer of high pressure low density polyethylene system prepared using only resin (B) alone The film (thickness 20 micrometers) was laminated and the multilayer film of 160 micrometers in thickness (164 micrometers in thickness containing adhesive layer) was obtained. Using the obtained multilayer film, the plastic bag for 20 L and the high purity medicine bag in can which inserted this were obtained by the method similar to Examples 1-4. The obtained physical properties of the film and the bag were evaluated, and the results are shown in Table 1.

Comparative Example 1

As in Table 2, the same procedure as in Example 1 was carried out except that only resin B (1) was used instead of the mixture of resin A (1) and resin B (1) in the inner layer film. , Cleanliness and flexibility are shown in Table 2.

Comparative Example 2

Linear medium-density polyethylene, a metalocene catalyst-based ethylene-hexene-based copolymer with a resin density of 0.942 g / cm ³ and a melt index of 0.8 g / 10 mim, instead of a mixture of resin A (1) and resin B (1) on the inner film Except for using only the system resin (Chevron Phillips, mPACT D449, Resin A (3)) was carried out in the same manner as in Example 1, it was shown in Table 2 to evaluate the barrier properties, cleanliness and flexibility of the obtained film and bag.

Comparative Example 3

The same composition as in Example 2 was carried out in the same manner as in Example 2, except that only a single layered film having a thickness of 165 μm in two layers was used. The obtained films and bags were evaluated in terms of barrier properties, cleanliness, and flexibility, and are shown in Table 2. . Compared with Example 2, the cleanliness and flexibility are similar, but the barrier properties are very poor.

[Table 1] Composition of each film layer obtained according to the Example, physical properties of the film and bag

As shown in Table 1, when comparing Examples 1 to 3, the number of fine particles increases somewhat as the content of the resin (B) increases in the resin composition of the resin (A) and the resin (B) constituting the inner layer film. It tends to be, but overall has excellent barrier properties, cleanliness and flexibility. However, when comparing Examples 1 to 3 in which polyamide-based resin was used as the gas barrier resin (C) and Example 4 in which ethylene-vinyl alcohol copolymer system resin was used as the gas barrier resin (C), ethylene-vinyl In the case of using alcohol copolymer resin, the barrier property is very excellent. In any case, when the relative humidity is increased from 65% to 100%, the barrier property is inferior in view of gas permeability and chemical loss rate. However, it can be seen that generally excellent.

Comparing Example 2 and Example 5, it can be seen that when the film layer made of polyethylene-based resin is composed of an outer layer, the gas barrier property is constantly maintained excellent even in a high humidity environment due to moisture resistance. This phenomenon is also observed in Examples 6 to 8, and in any case, it can be seen that the barrier properties, cleanliness and flexibility are very excellent.

[Table 2] Composition of each film layer obtained according to the comparative example, physical properties of the film and bag

As shown in Table 2, Comparative Example 1 has a similar barrier property and flexibility as compared with Example 1, but it can be seen that the cleanliness, in particular, the number of particulates is very poor, and Comparative Example 2 is compared with Example 1 The barrier properties and cleanliness are somewhat similar, but the flexibility is very poor. In addition, Comparative Example 3 has similar cleanliness and flexibility compared to Example 2, but it can be seen that the barrier properties are very poor.

The present invention is a linear low-density polyethylene having a density of 0.860 to 0.925 g / cm 3 produced by a metalocene catalyst using an ethylene-based alpha olefin having 6 to 12 carbon atoms as a comonomer and a content of 2 to 30% by weight. Melt index composed of 10 to 20% by weight of a high-pressure method low density polyethylene resin (B) having a density of 0.915 to 0.925 g / cm 3 obtained from 80 to 90% by weight of the resin (A) and an ultrahigh pressure compressor of 1,700 kg / cm ² or more. 190 ° C., 2.16Kg) is a multilayer film obtained by coating a polyurethane adhesive on an inner layer film made of a resin mixture having 0.2 to 20 g / 10 min, and laminating an outer layer film made of a gas barrier resin, or a polyurethane film on the inner layer film. An adhesive is coated, the interlayer film made of the gas barrier resin is laminated, and then the polyurethane-based adhesive is coated on the interlayer film, followed by the high pressure low density method. Characterized by a multilayer film obtained by laminating an outer layer film made of polyethylene resin (B), a plastic bag having a shape of heat-sealing around the film and having a port attached thereto is manufactured and inserted into a metal can. As an in can, it is expected to be useful in the semiconductor and LCD industry as it has excellent barrier properties and cleanliness in long-term storage of high-purity chemicals and is greatly improved in flexibility. It is a breakthrough to reduce. That is, when the film of the present invention is used as a film of a white can, it has an excellent effect of satisfying gas permeability, chemical resistance, fine particle number, residual metal content and flexibility at the same time.

1 is a photograph showing a plastic bag attached to the port according to the present invention.

Figure 2 is a photograph showing the insertion of the dip tube according to the present invention is inserted into the metal can with a plastic bag across the port mouse.

Figure 3 is a photograph showing an example of a dip tube used in the present invention.

Figure 4 is a photograph showing a state in which the plastic bag, the dip tube, the metal can can be fastened by a deep tube coupling according to the present invention.

5 is a photograph showing a connector having a sealing means and a venting means and a port of a bag into which a dip tube is inserted, a dip tube coupling, and a metal can at the same time.

Figure 6 is a photograph showing a state in which the plastic bag is inserted into the metal can completed according to the invention.

Detailed description of the drawings

1-back 2-port

3-can of metal 4-mouse

5-Diptube 6-Diptube Coupling

7-ventilating means 8-sealing means

9-connector

Claims (8)

In a bag-in can system in which a plastic bag having a shape in which a plastic bag is formed by heat-sealing around a film and having a port attached thereto is inserted into a metal can, the film has ethylene as a main component and an alpha olefin having 6 to 12 carbon atoms as 80 to 90 wt% of linear low density polyethylene resin (A) having a density of 0.860 to 0.925 g / cm ³ produced by the metalocene catalyst used and 0.915 to 0.925 g / obtained in an ultra high pressure compressor of 1,700 kg / cm ² or more 70% to 95% of the total thickness made of a resin mixture having a melt index (190 ° C, 2.16Kg) composed of 10 to 20% by weight of a high pressure method low density polyethylene resin (B) having a density of ³ cm ³ . Polyurethane adhesive is coated on the inner layer film formed of%, polyamide resin, polyvinyl alcohol resin, ethylene-vinyl alcohol copolymer resin, polyester resin, polyacrylonitrile resin, polychlorinated ratio Vinylidene of the can for a high purity medication bag by laminating an outer layer film is formed of 5-30% of the total thickness made of any one or more gas barrier resin (C) is selected from a resin, it characterized in that the resulting multi-layer film. In a bag-in can system in which a plastic bag having a shape in which a plastic bag is formed by heat-sealing around a film and having a port attached thereto is inserted into a metal can, the film has ethylene as a main component and an alpha olefin having 6 to 12 carbon atoms as 80 to 90 wt% of linear low density polyethylene resin (A) having a density of 0.860 to 0.925 g / cm ³ produced by the metalocene catalyst used and 0.915 to 0.925 g / obtained in an ultra high pressure compressor of 1,700 kg / cm ² or more 50% to 90% of the total thickness made of a resin mixture having a melt index (190 ° C, 2.16Kg) composed of 10 to 20% by weight of a high pressure method low density polyethylene resin (B) having a density of ³ cm ³ . Polyurethane adhesive is coated on the inner layer film formed of%, polyamide resin, polyvinyl alcohol resin, ethylene-vinyl alcohol copolymer resin, polyester resin, polyacrylonitrile resin, polychlorinated ratio Laminating an interlayer film formed of 5% to 30% of the total thickness made of at least one gas barrier resin (C) selected from a lidene-based resin, and then coating the polyurethane-based adhesive on the interlayer film 1,700kg A multilayer film obtained by laminating an outer layer film formed of 5% to 20% of the total thickness made of a high-pressure method low density polyethylene-based resin (B) having a density of 0.915 to 0.925 g / cm 3 obtained in an ultra high pressure compressor of / cm ² or more. A high-purity medicine bag in can. delete The high-purity medicine bag in can according to any one of claims 1 to 7, wherein the gas barrier resin (C) is a polyamide-based resin. The high purity medicine bag in can can according to any one of claims 1 to 7, wherein the gas barrier resin (C) is an ethylene-vinyl alcohol copolymer resin. 80 to 90% by weight of a linear low density polyethylene resin (A) having a density of 0.860 to 0.925 g / cm ³ produced by a metalocene catalyst having ethylene as a main component and an alpha olefin having 6 to 12 carbon atoms as a comonomer. And a melt index (190 ° C., 2.16 Kg) composed of 10 to 20% by weight of a high pressure low density polyethylene resin (B) having a density of 0.915 to 0.925 g / cm 3 obtained in an ultra high pressure compressor of 1,700 kg / cm ² or more. Metering a resin mixture of / 10 min; The resin mixture is introduced into an inflation film extruder installed in a clean room with a class of less than 0.5 µm per ft3 through a hopper, and the inner layer film folded in two layers is rolled using a clean air of class 10 or less. Obtaining; Coating a polyurethane-based adhesive on both outer surfaces of the double layer inner film; Laminating an outer layer film made of a gas barrier resin (C) to obtain a double layer multi-layer film; In a clean room with a class of 1,000 or less, the film is unloaded into a bag-making molding machine, cut into appropriate sizes, heat-sealed except for the part where the port is to be inserted, and then a double layered film is opened to form a hole in either side. Inserting the port into the hole and attaching it by heat-sealing and then heat-sealing around the remaining multilayer film to form a port-mounted bag; Inserting the obtained plastic bag into the inside of the metal can; A method for producing a bag in can, characterized in that a high purity medicine bag in can is produced. 80 to 90% by weight of a linear low density polyethylene resin (A) having a density of 0.860 to 0.925 g / cm ³ produced by a metalocene catalyst having ethylene as a main component and an alpha olefin having 6 to 12 carbon atoms as a comonomer. And a melt index (190 ° C., 2.16 Kg) composed of 10 to 20% by weight of a high-pressure method low density polyethylene resin (B) having a density of 0.915 to 0.925 g / cm ³ obtained in an ultra high pressure compressor of 1,700 kg / cm ² or more. Measuring and preparing a resin mixture of 20 g / 10 min; The resin mixture is introduced into an inflation film extruder installed in a clean room with a class of less than 0.5 μm / ft3 through a hopper, and the inner layer film folded in two layers is rolled using a clean air of class 10 or less. Gaining step; Coating a polyurethane-based adhesive on both outer surfaces of the double layer inner film; Laminating an interlayer film made of a gas barrier resin (C); Coating the polyurethane-based adhesive on the outer surface of the interlayer film; Laminating an outer layer film made of a high-pressure method low density polyethylene resin (B) having a density of 0.915 to 0.925 g / cm ³ obtained in an ultrahigh pressure compressor of 1,700 kg / cm ² or more to obtain a double layered multilayer film; In a clean room with a class of 1,000 or less, the film is unloaded into a bag-making molding machine, cut into appropriate sizes, heat-sealed except for the part where the port is to be inserted, and then a double layered film is opened to form a hole in either side. Inserting the port into the hole and attaching it by heat sealing and then heat sealing around the remaining multilayer film to form a bag with the port mounted thereon; Inserting the obtained plastic bag into the inside of the metal can; A method for producing a bag in can, characterized in that a high purity medicine bag in can is produced. A plastic bag having a port manufactured by any one of the manufacturing methods according to claim 6 or 7, a metal can having a mouse into which the bag is inserted, a passage for a high-purity medicine and inserted into the bag and across the port. The dipping tube has a dip tube, a dip tube coupling for coupling the port of the bag into which the dip tube is inserted, and a metal can, and venting means for allowing gas flow between the outside of the bag and the inside of the metal can through the dip tube coupling. A connector for simultaneously tightening a port of the bag into which the tube is inserted, a diptube coupling and a metal can, and a sealing means for sealing the upper space of the connector and allowing the high purity chemical to be released when the seal is removed. High purity medicine bag in cans.