JP2006096851A - Clean film and wrapping bag using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a clean film showing quantitatively a small amount of an organic out gas and to provide a wrapping bag using the same and also to provide an electronic product wrapped with the wrapping bag. <P>SOLUTION: The clean film comprises a sealant layer at least consisting of a polyolefin resin in which a total amount of organic out gases generated by heating at 80°C for 10 min is 1,500 ng/cm<SP>2</SP>or less calculated as hexadecane, and a total amount of a cyclic siloxane generated by heating at 80°C for 10 min is 2.5 ng/cm<SP>2</SP>or less calculated as siloxane hexamer, and a wrapping bag is prepared from the clean film and an electronic product is wrapped with the wrapping bag. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is a semiconductor device such as silicon wafer, IC and LSI, FDD which is a storage device for computer peripheral devices, magneto-optical disk, which extremely dislikes adhesion of dust, dust, etc., and chemical substances such as halogen ions. It is suitably used for packaging bags for electronic components such as FD and HD, which are memory media, such as drives, HDDs, and MR (magnetoresistive) heads. More specifically, the present invention relates to a packaging bag having a small amount of volatile components from the sealant film layer that may come into contact with the contents.

  Electronic components such as silicon wafers, ICs, LSIs and other semiconductor products, computer peripheral devices such as FDDs, magneto-optical disk drives, HDDs, MR (magnetoresistance effect) heads, memory media such as FDs and HDs Corrosion, malfunction, etc. occur due to extremely minute or minute amount of contaminants.

  Taking HDD as an example, the contaminants are (1) ionic substances that cause corrosion, (2) dust that penetrates between the head and the disk and causes damage to the recording / reproducing surface, and (3) droplets. Non-volatile residue that penetrates between head and disk due to scattering or surface movement and causes product sticking, (4) Adhesion to head due to condensation, adsorption, solidification, etc. They are divided into organic outgases that condense between them and cause sticking. In addition to (1) to (4), Sn and Si are known as contraindicated substances because they lead to disk failure.

The organic outgas (4) will be described in more detail. Outgas is a general term for gases generated from various components in a DE (disk enclosure), and can be broadly classified into organic and inorganic materials, but often refers to organic gases. Outgas greatly contributes to the reliability of the HDD, and can be reduced by selecting materials, performing heat treatment after processing, ultra-precision cleaning, and the like. Among the outgas substances, siloxane compounds, tributyltin compounds and the like adhere to the head surface and cause head crashes. Carbohydrates, methacrylate monomers, plasticizers such as DOP (dioctyl phthalate), phenolic substances that are antioxidants, and the like cause the adsorption failure of the head and the medium. The organic acid causes corrosion of the magnetic film of the core material and coil portion of the head and the magnetic medium.
Contamination of a product with such contaminants is called contamination, but it is also called micro-contamination in order to distinguish it from normal contamination because extremely small or trace amounts of contaminants cause failure. .

In addition to the HDD, a packaging bag for packing such electronic components is required to minimize contamination and control micro contamination so as not to adversely affect the contents. However, although packaging materials called clean films and clean packaging bags are widely used in the world, a method that is often implemented as an evaluation method is to attach a packaging material to a clean HDD medium, etc. It is a method to evaluate the transferred substance by surface analysis such as basic inspection machine, X-ray photoelectron spectroscopy (XPS), fluorescent X-ray analysis, etc., this method can not measure the cleanliness of the packaging material alone, A clean medium is difficult to obtain. As for the outgas measurement method, there is a method in which a heating device such as an HDD medium is diverted to the packaging material evaluation and purge and trap gas chromatograph mass spectrometry (GC-MS) is performed, but the analysis itself is complicated. As described above, there are almost no packaging materials that quantitatively define the cleanliness evaluation method of packaging materials and the cleanliness.
JP 2004-108967 A

  The present invention has been made in view of the above-described problems, and provides a clean film quantitatively showing that organic outgas is low and a packaging bag made of the clean film. Moreover, it aims at providing the package which packaged the electronic component using the said packaging bag.

The invention according to claim 1 comprises a sealant layer made of at least a polyolefin resin, and an organic total outgas amount generated when heated at 80 ° C. for 10 minutes is less than 1500 ng / cm ^{2 in} terms of hexadecane, and The total amount of cyclic siloxane generated when heated at 80 ° C. for 10 minutes is less than 2.5 ng / cm ^{2 in} terms of siloxane hexamer.

  The invention according to claim 2 is the clean film according to claim 1, wherein the sealant layer has a thickness of 120 μm or less.

  The invention according to claim 3 is a low-density polyethylene resin having a melt index (MI) of 0.1 to 20 (g / 10 minutes · 190 ° C.) in the polyolefin resin. 2. The clean film according to any one of 2 above.

  The invention according to claim 4 has a multilayer structure in which a gas barrier layer and / or a base material layer is laminated on at least one side of the sealant layer. It is.

  A fifth aspect of the present invention is a packaging bag comprising the clean film according to any one of the first to fourth aspects.

  The invention described in claim 6 is an electronic component package in which an electronic component is packaged using the packaging bag described in claim 5.

  The clean film of the present invention and the packaging bag made of the clean film have little outgas from the packaging bag and have the highest level of cleanliness. In addition, it is most suitable for packaging of electronic components such as HDDs, and can be an electronic component package having the highest level of cleanliness.

  FIG. 1 is a perspective view of a sealant winding 10 for forming a clean film of the present invention, and FIG. 2 (a) is an A of a sealant 11 for forming a clean film of the present invention that has been wound by casting. Fig. 2 (b) is a side cross-sectional view of the A 'surface, and Fig. 2 (b) is a case where resin is extruded into a tube shape by an inflation method, clean air is blown into the extruded tubular sealant, and both ends of the tubular sealant are on the production line. It is side sectional drawing of the sealant 12A-A 'surface which forms the clean film of this invention wound up in strip shape without cutting.

The sealant for forming the clean film of the present invention is preferably made to have a co-extrusion structure. That is, when the required thickness of the sealant is thick, it is possible to adopt a co-extrusion structure of two or more layers. For example, when 90 μm is required as the thickness of the sealant, a thickness of 90 μm may not be obtained as a single layer depending on the processing method. In such a case, a two-layer coextrusion structure of 45 μm and 45 μm may be used, or a three-layer coextrusion structure of 30 μm, 30 μm, and 30 μm may be used.
The resin used in the case of the co-extrusion configuration is not necessarily the same resin, and it is necessary to select a resin that can provide sufficient interlayer strength.

  Examples of the resin used for the sealants 11 and 12 include polyethylene (PE) such as high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), and linear low density polyethylene (LLDPE), polypropylene ( PP), polybutene, polymethylpentene, and other homopolymers, and copolymers of two or more monomers selected from ethylene, propylene, butene, methylpentene, and other olefins such as ethylene-propylene copolymer. It is also possible to use a mixture of two or more of these, as well as graft polymers having certain functional groups introduced therein, such as resins such as maleic anhydride grafted polypropylene, ethylene-α, β unsaturated carboxylic acid copolymers. Use an ethylene-based copolymer with a polymer as the main skeleton. However, from the viewpoint of cleanliness, melt index (MI) = 0.1 to 20 (g / 10 min · 190 ° C) and includes additives such as antioxidants, antiblocking agents and lubricants No LDPE is optimal. The LDPE has a melt index (MI) of 0.1 to 20 (g / 10 min. 190 ° C.) because a low molecular weight component is less when a resin with a low melt index (MI) is used. This is because a laminated material having excellent thermal stability during molding and high cleanness can be obtained.

  FIG. 3A is a cross-sectional view of a laminate in which a gas barrier layer and a base material layer are laminated on one side of the sealant 11 via an adhesive layer. The sealant 11, the adhesive layer 13, the gas barrier layer 14, and the adhesive The layer 15 and the base material layer 16 are sequentially laminated. FIG. 3B is a cross-sectional view of a laminate in which a gas barrier layer and a base material layer are laminated on one side of the sealant via an adhesive layer. The clean film 12, the adhesive layer 13, and the gas barrier layer 14 are laminated. The adhesive layer 15 and the base material layer 16 are sequentially laminated. FIG. 3C is a side sectional view of a laminate in which a gas barrier layer and a base material layer are laminated on both surfaces of the sealant 12 with an adhesive layer interposed therebetween. 13, a gas barrier layer 14, an adhesive layer 15, and a base material layer 16 are sequentially laminated. FIG. 3D is a side sectional view of a laminate in which a gas barrier layer and a base material layer are laminated on both surfaces of the sealant 12 with an adhesive layer interposed therebetween. 13, a gas barrier layer 18, an adhesive layer 15, and a base material layer 16 are sequentially laminated.

As the adhesive used for the adhesive layers 13 and 15, polyurethane, polyester, polyether, and a mixture mainly composed of them are generally used, but do not contain Sn compound and Si compound, An adhesive with a small amount of eluting components is preferable, and the coating amount is preferably the minimum necessary. An adhesive resin can be used, and direct lamination or sand lamination by some surface modification is also preferably performed. In order to increase the activity of the surface to be laminated, surface treatment such as corona treatment, flame treatment, plasma treatment, and ozone treatment may be performed.
As the lamination resin used for the sand lamination, ethylene acrylic acid or methacrylic acid copolymer, ethylene acrylate or methacrylate copolymer, ethylene vinyl acetate copolymer, modified maleic acid copolymer and the like are used. The adhesive may be anchor-coated, but from the viewpoint of cleanliness, sand lamination using polyethylene that does not have an anchor coat and has little decomposition of acid components and the like is preferable.

  Examples of the base material layer 16 include polyester films such as biaxially stretched polyethylene terephthalate film (PET film), biaxially stretched nylon film (ONy film), biaxially stretched polypropylene film (OPP film), and ethylene-vinyl acetate copolymer. A saponified film (EVOH film) or the like is selected, and better adhesion strength can be obtained by applying corona treatment or the like to the surface to which other layers are bonded.

  As the gas barrier layer 14, an aluminum foil or a film provided with a thin film layer made of a metal or a metal compound is used. As a thin film forming material, any one of oxides, nitrides and fluorides selected from magnesium, silicon, aluminum, tin, titanium, zinc, zirconium, calcium, nickel and the like, or a mixture of two or more kinds Among them, aluminum oxide or silicon oxide is particularly preferable because it is excellent in transparency and gas barrier properties of oxygen and water vapor.

  The thickness of the aluminum foil is preferably 7 to 100 μm, and the thickness of the metal aluminum, aluminum oxide, silicon oxide or other thin film layer is preferably about 1 to 300 nm. These metal thin film layers can be formed by a normal vacuum deposition method. In addition, other thin film forming methods such as sputtering, ion plating, and plasma vapor deposition (CVD) can also be used.

  Further, in place of the gas barrier layer 14, a coating formed by applying a coating agent containing at least a water-soluble polymer and drying by heating on a thin film layer made of a metal or a metal compound in order to suppress gas barrier deterioration after lamination. A gas barrier layer 18 provided with a layer is also preferably used.

  The gas barrier layer 18 is formed by sequentially laminating a thin film layer (A layer) and a coating layer (B layer) obtained by applying a coating agent containing at least a water-soluble polymer and drying by heating on at least one surface of the base material layer 17. Or a coating layer (B layer) formed by applying a coating agent containing a thin film layer (A layer) and at least a water-soluble polymer to at least one surface of a base material made of a thermoplastic resin and drying by heating. And a thin film layer (C layer) and a coating layer (D layer) obtained by applying a coating agent containing at least a water-soluble polymer and drying by heating.

  The thin film forming material of the thin film layer (A layer and C layer) is a metal selected from aluminum, magnesium, silicon, tin, titanium, zinc, zirconium, calcium, nickel, etc., or an oxide or nitride of these metals , Any one of fluorides, or a mixture of two or more. In consideration of transparency, it is preferable to use an inorganic compound. In particular, aluminum oxide and silicon oxide are excellent in gas barrier properties such as water vapor and oxygen in a vapor deposition film alone, and have higher transparency, so It is more preferable in that recognition is possible. Further, the thin film forming materials used for the thin film layer A layer and the C layer are not particularly limited, either the same material or different materials, and the combination is not particularly limited depending on the required gas barrier property.

  There are various methods for forming the thin film layers (A layer and C layer), but it is possible to use a thin film forming method such as a vacuum deposition method, a sputtering method, an ion plating method, or a plasma vapor deposition method (CVD). Is possible. In particular, the vacuum deposition method is particularly excellent in terms of production efficiency. Moreover, in order to improve the adhesiveness of a thin film layer and a base material layer, and the denseness of a thin film layer, it is also possible to vapor-deposit using a plasma assist method or an ion beam assist method. Moreover, you may perform the reactive vapor deposition which blows oxygen gas etc. in the case of vapor deposition.

  The minimum thickness of the thin film layer varies depending on the type of vapor deposition material used, but is preferably in the range of 1 to 300 nm. More preferably, it is in the range of 5 to 100 nm. If the thickness of the thin film layer is less than 1 nm, the film may not be formed on the entire surface of the base material layer. Further, when the thickness of the thin film layer exceeds 300 nm, the thin film cannot be kept flexible, and there is a possibility that the thin film may be cracked due to an external factor.

  Examples of the material for forming the coating layers (B layer and D layer) include water-soluble polymer components such as polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, and sodium alginate. In particular, polyvinyl alcohol (PVD) is preferable because of its excellent gas barrier properties. Here, PVD is obtained by saponifying polyvinyl acetate.

  The thickness of the coating layer is preferably in the range of 100 to 5000 nm. If it is 100 nm or less, the coating film may not be uniform, and if it exceeds 5000 nm, the film tends to crack. More preferably, the film thickness after drying is in the range of 200 to 600 nm.

  More preferably, the coating layer (B layer and D layer) is an aqueous solution or a water / alcohol mixed solution containing the water-soluble polymer and one or more kinds of metal alkoxide and a hydrolyzate generated from the metal alkoxide. A layer composed of a coating agent as a main agent is preferable.

  The organic total outgas amount defined quantitatively for the clean film of the present invention will be described.

  A method for measuring the total amount of organic outgas from the clean film of the present invention will be described below.

  In order to measure the total organic outgas amount from the clean film of the present invention, it is preferable to use a purge and trap gas chromatograph mass spectrometer (hereinafter referred to as purge and trap GC-MS).

  Sampling is preferably performed by cutting the clean film into a size that fits in the center of the glass tube for purge and trap. At that time, it is preferable to measure the weight to the 4th decimal place. When sampling, care must be taken not to cause contamination. First, it is preferable to wear PE gloves or GC-MS gloves. Next, the same structure as the clean film to be sampled is placed on the cutting mat. On top of that, the film to be sampled is folded in four. In the case of a single wafer, 3 or more sheets are stacked. Furthermore, it is preferable to sample with a cutter using a dedicated jig. It is preferable to discard the sample in contact with the jig and the underlay film, and take out only the inner sample with clean tweezers. It is also preferable to perform the above operation in a clean room.

  In the purge and trap GC-MS measurement, it is preferable to use a clean glass tube so as not to cause contamination from the glass tube to be used. As a cleaning method, a glass tube is put in a beaker containing acetone, and ultrasonic cleaning is performed for 30 minutes or more. Next, the glass tube is heated in an electric furnace at 500 ° C. for 3 hours. Further, the glass tube is filled with quartz wool, heated in an electric furnace at 350 ° C. for 24 hours, and then sample tube caps are attached to both ends of the glass tube. Furthermore, it is preferable to make one glass tube with aluminum foil.

  The organic total outgas amount is determined by measuring the sample sampled by the above method with purge and trap GC-MS, and then manually integrating the peak area excluding the baseline rise from the total ion chromatogram (TIC). It is preferable to quantify the total peak area value in terms of hexadecane.

  The method for preparing a hexadecane calibration curve is described below. First, a methanol solution of about 50 ng / μl of hexadecane is prepared to prepare a hexadecane standard solution. At this time, it is necessary to measure the exact weight of hexadecane.

  The hexadecane standard solution is preferably subjected to a purge and trap GC-MS measurement using, for example, a glass tube filled with 100 mg of TENAX TA (hereinafter referred to as a TENAX tube). Besides, TENAX GR, Carbotrap, etc. are used as the filler. The TENAX tube is preferably conditioned before measurement. As the procedure, purging with He gas was performed at a flow rate of 30 ml / min. This is done for 3 minutes or more. Take 1 μl of hexadecane standard solution into a TENAX tube that has been conditioned in a zero dead volume syringe, drive it into the TENAX from the end close to the GC inlet during GC-MS measurement of the TENAX tube, attach it to the purge and trap device, and measure GC-MS I do. A calibration curve is prepared by taking the hexadecane weight on the horizontal axis and the peak area on the vertical axis. In order to improve accuracy, it is also preferable to create a multi-inspection quantity curve.

The organic total outgas amount obtained from the hexadecane calibration curve is calculated as the amount per 1 cm ² of the clean film.
Outgas amount per 1 cm ^{2 of} clean film (ng / cm ² ) = Measured sample outgas amount (ng) / Sample area (cm ² )

When the amount of cyclic siloxane was measured by purge and trap GC-MS, the peak area from cyclic siloxane trimer (D3) to cyclic siloxane octamer (D8) was calculated by manual integration in TIC, and the total value was calculated. It is preferable to determine and quantify in terms of siloxane hexamer (D6). When the hydrocarbon peak is large and it is difficult to confirm the cyclic siloxane peak, the mass-to-charge ratio m / z = 207 (D3), 281 (cyclic siloxane tetramer (D4), cyclic siloxane heptamer (D7)) 341 (cyclic siloxane pentamer (D5), D8), 355 (D6) is preferably used as an index. A calibration curve is prepared from the siloxane hexamer, and the total cyclic siloxane value is preferably less than 2.5 ng / cm ² .

  Regarding the amount of cyclic siloxane, a calibration curve is prepared with a siloxane hexamer standard substance and calculated by the same method. It should be noted that hexadecane and siloxane hexamer are free from impurities and it is preferable to use a reagent having high purity.

In order to grasp the contamination in the purge and trap GC-MS measurement, it is preferable to perform a blank measurement only on the glass tube before the sample measurement. Even when using a TENAX tube, the blank measurement should be performed before the standard solution is injected. Preferably it is done. The measured value of the blank is preferably cyclic siloxane and less than 0.5 ng / cm ² . After blank measurement and confirming that the cyclic siloxane is less than 0.5 ng / cm ² , it is preferable to measure by putting a sample in the same tube.

  If there is contamination in the laboratory environment, pre-measurement is preferably performed before sample or standard solution measurement. Pre-measurement is performed according to the following procedure. After pre-measurement once with the purge and trap GC-MS, the main measurement is performed with the same tube without opening the purge and trap apparatus to the atmosphere.

  The thermal desorption temperature condition of the purge and trap is preferably 80 ° C. and 10 minutes for the main sample measurement, and 250 ° C. and 10 minutes for the standard solution. The cold trap temperature is preferably −135 ° C. or lower. In the case of pre-measurement, the thermal desorption temperature condition of the purge and trap may be a minimum condition that can be set at 30 ° C. for 10 minutes for the sample and standard solution. Alternatively, the sample outgas may be adsorbed on a glass cube coated with a filler such as TENAX or polydimethylsiloxane and then desorbed in the purge and trap GC-MS.

  The temperature conditions of GC-MS are as follows. In the case of sample measurement, the initial temperature is 40 ° C., held for 5 minutes, and the heating rate is 5 ° C./min. The maximum temperature is preferably 300 ° C. for 5 minutes. As standard GC-MS measurement conditions, the ionization method is an electron impact method (EI), the ionization voltage is 70 eV, the ion source temperature is 230 ° C., the quadrupole temperature is 150 ° C., and the mass range is 45 to 550. SCAN measurement is preferable, and it is preferable to perform data acquisition finely. The column used is preferably 5% Phenyl, 95% Poly Dimethyl Siloxane, length 30 m × diameter 0.25 mm × liquid phase thickness 0.25 μm.

  Examples of the present invention will be described below, but the technical scope of the present invention is not limited to these examples.

An additive-free LDPE resin (MI = 2.0) was used as a raw material, and a film (thickness 90 μm) was obtained by a casting method.
Then, the obtained film was bonded together in the shape of a three-sided seal bag with an inner size of 40 × 40 cm to obtain a packaging bag of Example 1.
Extrusion molding and bag making were performed in a clean environment of class 10000 or less.

By the inflation method, additive-free LDPE (MI = 0.8) resin (thickness 80 μm), adhesive resin, and Ny (thickness 25 μm) were laminated in this order from the sealant side. At this time, the LDPE layer was extruded at a resin temperature of 170 ° C., and clean air was blown.
The obtained tube-shaped laminate was folded on a line, and a band-like clean film was obtained without cutting off the ears.
The film was bonded to a bottom seal bag shape with an inner size of 25 × 35 cm to obtain a packaging bag of Example 2. The bag making process was performed in a clean environment of class 10,000 or less.

A tubular sealant having a thickness of 40 μm made of an additive-free LDPE resin (MI = 0.8) was obtained by an inflation method. The outer surface of the sealant and a laminate obtained by laminating a PET film (thickness 12 μm), an adhesive, and an Al foil (thickness 7 μm) in this order are bonded together with an adhesive so that the Al foil surface becomes the adhesive surface. A film was obtained.
The clean film was bonded in a three-sided sealed bag shape with an inner size of 40 × 40 cm to obtain a packaging bag of Example 3. The bag making process was performed in a clean environment of class 10,000 or less.

By dry lamination, a film obtained by laminating PET (thickness 12 μm), an adhesive, and PET having a silicon oxide thin film layer (thickness 12 μm) in this order was obtained. Further, an adhesive was laminated on the PET layer having the silicon oxide thin film layer, and an additive-free LDPE resin (MI = 2.0) (thickness 80 μm) was further laminated by a casting method to obtain a clean film.
The clean film was bonded in a three-sided sealed bag shape with an inner size of 40 × 40 cm to obtain a packaging bag of Example 4. The dry lamination process, extrusion process, and bag making process were performed in a clean environment of class 10000 or less.

A 90 μm thick film made of additive-free LDPE resin (MI = 1.0) was obtained by the inflation method. At this time, a tube-like sealant obtained by extruding at a resin temperature of 160 ° C. and blowing clean air was woven on the line to obtain a belt-like sealant in which the inner surface layer was in close contact without cutting off the ears.
Moreover, the film formed by laminating in order of Al foil (thickness 7 μm), adhesive, stretched Ny (thickness 25 μm), adhesive, and PET (12 μm) having an Al thin film layer was obtained by dry lamination.
Next, the sealant, the adhesive, and the laminated film were laminated in this order by dry lamination to obtain a clean film. Under the present circumstances, it bonded together so that the PET layer surface and sealant which have Al thin film layer of this laminated film may stick.
The obtained clean film was bonded in a three-sided sealed bag shape with an inner size of 40 × 40 cm to obtain a packaging bag of Example 5.

  As a base material 17, metal aluminum is evaporated on one side of a biaxially stretched PET film having a thickness of 12 μm by a vacuum vapor deposition apparatus using an electron beam heating method, oxygen gas is introduced therein, and aluminum oxide having a thickness of 15 nm is vapor deposited. Thus, a thin film layer (A layer) was formed. Next, a coating agent having the following composition was applied by a gravure coating method and then dried at 120 ° C. for 1 minute to form a coating layer (B layer) having a thickness of 400 nm. Further, metal aluminum was evaporated on the coating layer by a vacuum deposition apparatus using an electron beam heating method, oxygen gas was introduced therein, and aluminum oxide having a thickness of 15 nm was deposited to form a thin film layer (C layer). . Further, a coating agent having the following composition was applied on the thin film layer by a gravure coating method, and then dried at 120 ° C. for 1 minute to form a coating layer (D layer) having a thickness of 350 nm.

The composition of the coating agent for forming the coating layers (B layer and D layer) is obtained by mixing the following (a) liquid and (b) liquid at a blending ratio (wt%) of 65/35.
(I) Liquid: A hydrolyzed solution having a solid content of 3 wt% (SiO ₂ equivalent) obtained by adding 89.6 g of hydrochloric acid (0.1N) to 10.4 g of tetraethoxysilane and stirring for 30 minutes.
(B) Liquid: 3 wt% water / isopropyl alcohol solution of polyvinyl alcohol (water: isopropyl alcohol = 90: 10 (weight ratio))

  Further, a sealant made of PE having a thickness of 80 μm was obtained by an inflation method.

  An ONy film (25 μm) is laminated on the coating layer (D layer) via the adhesive layer, and a sealant is laminated on the PET substrate via the adhesive, and the clean of Example 6 shown in FIG. A film was obtained.

<Comparative Example 1>
A sealant (thickness: 90 μm) was obtained by casting using LDPE resin (MI = 2.0) as a raw material. A clean film was obtained by laminating the obtained sealant in the order of Ny film (25 μm), adhesive layer, and LDPE film layer from the outer surface by dry lamination.
The obtained clean film was bonded in a three-sided sealed bag shape with an inner size of 40 × 40 cm to obtain a packaging bag of Comparative Example 1. Extrusion molding and bag making were performed in a general environment.

<Comparative example 2>
A single-site LLDPE resin (MI = 2.5) was used as a raw material, and a sealant (thickness 80 μm) was obtained by a casting method. A clean film was obtained by laminating the obtained sealant from the outer surface in the order of a Ny film (25 μm), an adhesive layer, and the LLDPE film by dry lamination.
The obtained clean film was bonded in a three-sided sealed bag shape with an inner size of 40 × 40 cm to obtain a packaging bag of Comparative Example 2. Extrusion molding and bag making were performed in a general environment.

About the packaging bag of Examples 1-6 and Comparative Examples 1-2, it cut | judged to the magnitude | size of 2 * 12 mm so that it might fit in the glass tube for purge and dripping GC-MS measurement, and measured the weight to 4th place decimal place. The glass tube used was cleaned. The cleaning method was performed as described above. First, blank measurement of only a glass tube was performed. As the GC-MS measurement conditions, the ionization method was EI, the ionization voltage was 70 eV, the ion source temperature was 230 ° C., the quadrupole temperature was 150 ° C., and the mass range was 45 to 550. The column used was 5% Phenyl, 95% Poly Dimethyl Sioxane, 30 m long × 0.25 mm diameter × d × liquid phase thickness of 0.25 μm. The GC-MS temperature conditions were an initial temperature of 40 ° C. and a 5-minute hold, a temperature increase temperature of 5 ° C./min, a maximum temperature of 300 ° C. and a 5-minute hold. The purge and trap heat desorption temperature condition was 80 ° C. for 10 minutes, and the cold trap temperature was −150 ° C. After confirming that the measured value of the blank was less than 0.5 ng / cm ² in the cyclic siloxane, the sample was put in the same tube, and then the sample was measured. The purge and trap heat desorption temperature condition was 80 ° C. for 10 minutes, and the cold trap temperature was −150 ° C. The GC-MS measurement conditions were the same as the blank measurement described above.
For the organic total outgas, the peak area of the portion excluding the increase in baseline of the obtained TIC was manually integrated to determine the total peak area value. Regarding cyclic siloxane, the peak area from cyclic siloxane trimer (D3) to cyclic siloxane octamer (D8) on TIC was calculated by manual integration, and the total value was obtained.

Next, a standard substance was measured for preparing a calibration curve. For organic total outgas, a methanol solution of 50 ng / μl of hexadecane was prepared, and for cyclic siloxane, a methanol solution of 50 ng / μl of siloxane hexamer was prepared. Next, the TENAX tube subjected to conditioning was subjected to blank measurement. The purge and trap thermal desorption temperature condition was 250 ° C. for 10 minutes, and the cold trap temperature was −150 ° C. The GC-MS measurement conditions were the same as in the blank main measurement. Take 1 μl of each standard solution in a zero dead volume syringe, and drive it into TENAX from the side close to the GC inlet of the same TENAX tube for which a blank measurement was performed, and with He gas at 30 ml / min. After purging for 3 minutes, it was attached to a purge and trap apparatus and GC-MS measurement was performed. The purge and trap thermal desorption temperature condition was 250 ° C. for 10 minutes, and the cold trap temperature was −150 ° C. The GC-MS measurement conditions were the same as the blank measurement described above.
The calibration curve was prepared by taking the hexadecane weight or siloxane hexamer weight on the horizontal axis and the peak area on the vertical axis. Using a hexadecane calibration curve, the organic total outgas amount (ng) from the total peak area value of the organic total outgas, and cyclic from the peak area total value of the cyclic siloxane measured from the sample using the siloxane hexamer calibration curve Calculate the amount of siloxane (ng) and divide by the area of one side of the sample to convert it per 1 cm ² of clean film, and calculate the total amount of organic outgas (ng / cm ² ) and the amount of cyclic siloxane (ng / cm ² ). Asked. The results are shown in Table 1.

Further, in the packaging bags of Comparative Examples 1 and 2, silica was generated by the heat generated when the HD media was rotated, and there was a risk of disk crash when sandwiched between the magnetic head and the HD media. This is presumably because the amount of cyclic siloxane is large.
On the other hand, the packaging bags of Examples 1 to 6 were found to have very little outgas and high cleanliness. As is apparent from the results shown in Table 1, the packaging bags of Examples 1 to 6 have an organic total outgas amount of less than 1500 ng / cm ² and a cyclic siloxane amount of less than 2.5 ng / cm ² . It became clear that it was because it had the characteristic of being.

It is a perspective view which shows an example of winding up of a sealant. (A) is an example of a side sectional view of the A-A 'surface of the sealant, and (b) is an example of a side sectional view of the A-A' surface of the tubular sealant. (A), (b), (c), (d) is an example of a sectional side view of the clean film in the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Sealant winding 11,12 Sealant 13,15 Adhesive layer 14,18 Gas barrier layer 16,17 Base material layer A layer Thin film layer B layer Coating layer C layer Thin film layer D layer Coating layer

Claims (6)

It consists of a sealant layer made of at least polyolefin resin, and the total amount of organic outgas generated when heated at 80 ° C. for 10 minutes is less than 1500 ng / cm ^{2 in} terms of hexadecane, and generated when heated at 80 ° C. for 10 minutes. A clean film, wherein the total amount of cyclic siloxanes to be converted is less than 2.5 ng / cm ^{2 in} terms of siloxane hexamer.   The clean film according to claim 1, wherein the sealant layer has a thickness of 120 μm or less.   3. The clean film according to claim 1, wherein the polyolefin resin is a low-density polyethylene resin having a melt index (MI) of 0.1 to 20 (g / 10 minutes · 190 ° C.). .   The clean film according to any one of claims 1 to 3, wherein the clean film has a multilayer structure in which a gas barrier layer and / or a base material layer is laminated on at least one side of the sealant layer.   A packaging bag comprising the clean film according to claim 1.   An electronic component package comprising an electronic component packaged using the packaging bag according to claim 5.

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