JPH09193307A - Laminated film and packaging bag for electronic part - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a laminated film and a packaging bag with excellent strength, moistureproofness and transparency and being suitable as a packaging material for protecting electronic parts from moisture and static electricity. SOLUTION: A laminated film wherein the outermost layer is the drawn nylon film (A) or the metallized film (B) and the innermost layer is the heat seal layer (D) and the metallized film (B) is such a metallized film that is prepd. by forming a transparent inorg. metallized film on at least one face of a transparent polymer film base material and the gas barrier layer (C) is such a gas barrier layer that contains at least one layer of composite metallized film prepd. by forming a water-resistant film prepd. by heat-treating a coating of a mixture contg. polycarboxylic acid or its partly neutralized product and succharides on at least one face of a transparent polymer film base material through a transparent inorg. metallized film, is provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated film, and more particularly to a laminated film excellent in strength, moisture resistance and transparency. The laminated film of the present invention is used as a packaging film for protecting electronic components such as semiconductor devices from moisture and static electricity, and more specifically, as a packaging bag for electronic components (including a packaging bag for electronic component storage containers). In particular, it is particularly suitable.

[0002]

2. Description of the Related Art As electronic devices have become higher in performance and smaller in size, ICs (integrated circuits) and LSIs, which are major electronic components, have been developed.
2. Description of the Related Art Semiconductor devices such as (large-scale integrated circuit) and VLSI (ultra-large-scale integrated circuit) are becoming smaller and thinner, and leads are becoming narrower in pitch and finer. Therefore, the semiconductor device is easily affected by external loads, humidity, static electricity, and the like. Therefore, a packaging material for packaging precision electronic components such as semiconductor devices is also required to have a structure with higher precision and superior protection than ever before.

The electronic components are protected by various packaging means so that the mechanical and electrical characteristics of the electronic components are not deteriorated during the period from the manufacturing to the mounting. When electronic components are attacked by load, vibration, shock, temperature, humidity, harmful gas, static electricity, etc. in the distribution channel, lead deformation, deterioration of solderability, electrostatic breakdown, etc. occur. Therefore,
Individual electronic components are usually stored (packaged) in trays (also called pallets), magazines (also called tubes, sticks or sleeves), reels, etc., and protected from external loads, vibrations, shocks, etc. . The structures of these trays, magazines, reels, etc. are devised so that they can be used as a handling jig in the assembly process.

Further, since these trays and the like are moisture-proof,
Individually or collectively, put in a packaging bag,
It is generally shipped. If an LSI sealed with a resin such as epoxy resin is left in a humid atmosphere, the resin absorbs moisture. A surface-mount type LSI package is generally soldered to a printed wiring board by infrared reflow, but at that time, the package is heated to about 200 to 240 ° C. Therefore, if soldering is performed while the resin absorbs moisture, the package The internal water vaporizes and expands to increase the internal pressure, causing reflow cracks. Therefore, for example, in tray packaging, electronic components such as semiconductor devices are protected from external loads and vibrations and are easily handled before being mounted on equipment after manufacturing. Are stored together in a plastic tray provided with a large number of pockets for storing one by one. This tray is usually made by stacking multiple sheets as one pack (for example, 11 sheets are stacked about 2 kg per pack),
It is shipped in a moisture-proof packaging bag.

The packaging bag for electronic parts is required to have a moisture-proof effect lasting for at least about 1 to 2 years in view of the storage situation in the market. In addition, the packaging bag is required to have antistatic properties in order to prevent destruction of electronic components and deterioration of quality due to static electricity. Therefore,
Conventionally, a composite material in which a metal foil such as aluminum is laminated is used as a packaging bag for electronic parts. Examples of such a composite material include Japanese Patent Application No. 58-64963.
The publication discloses a bag for packaging electronic parts in which a metal thin film layer is provided on the inner surface of a plastic film having heat sealing properties.

However, the conventional packaging bag for electronic parts using a composite material laminated with metal foil is effective in protection from static electricity but insufficient in puncture strength. That is, in the conventional packaging bag, the aluminum foil layer is cut at the edge of the bottom of the tray or the like in some cases, for example, when packaging or packing the tray, or when packing and transferring the tray, and in some cases, an external impact is applied. When received, the bag may break due to the tray or external protrusions.
In this way, if the piercing strength of the packaging bag is insufficient,
The probability of bag breakage during transportation and storage is high, and the reliability of moisture-proof distribution of electronic components is impaired. As a result, it is necessary to introduce a step of heating and drying the electronic components taken out from the packaging bag before mounting.

On the other hand, an unstretched nylon film, for example, is laminated on one side with a metal foil sandwiched therebetween, and a stretched nylon film, for example, is laminated on the other side by extrusion lamination. There has been proposed a laminated film for packaging electronic parts having a structure in which the above are laminated (JP-A-7-76375). According to this laminated film, it is possible to produce a practical packaging bag for electronic parts, which is excellent in puncture resistance and practical, even if the thickness of each layer is not so large.

However, metal foil such as aluminum foil is
Although it has excellent moisture resistance and antistatic properties, it is opaque, and therefore, when a packaging bag made of a composite material laminated with metal foil is used, the contents after packaging cannot be confirmed.
In recent years, electronic parts are often handled in an automated process, and it is required that they can be managed and inspected by a sensor or a CCD camera. However, it is difficult to identify the contents of an opaque packaging bag. I have a problem. Further, since the metal foil is usually a metal layer having a thickness of about 5 to 15 μm, when the composite material is incinerated like plastic, the metal foil remains as an incombustible substance in the incinerator. Therefore, a substitute for the metal foil is required from the viewpoints of transparency and the problem of waste incineration.

Recently, a vapor deposition film in which a transparent vapor deposition film is formed on a polymer film by a vacuum vapor deposition method, a plasma vapor deposition method, a sputtering method or the like using a metal oxide such as silicon oxide, magnesium oxide or aluminum oxide. Attention has been paid. In addition, a metal such as aluminum, copper, silver, tin, or zinc is deposited on the polymer film to a thickness of 15 nm by a vacuum deposition method, a plasma deposition method, a sputtering method, or the like.
It is also proposed that the following thin film is formed to impart conductivity without impairing transparency. These transparent inorganic vapor-deposited films are not usually used alone, but used by laminating with various resin layers.However, although transparent vapor-deposited films are transparent and moisture-proof, they are packaged or packed. At times, the vapor-deposited thin layer is cracked at the edges of the tray, etc., and the moisture resistance is reduced. In addition, the transparent inorganic vapor deposition film does not have sufficient moisture resistance. In the packaging of electronic parts, vacuum packaging is required to maintain the dry state. Therefore, the packaging bag has excellent pinhole resistance (puncture resistance) during and after vacuum packaging. Is required.

[0010]

An object of the present invention is to provide a laminated film having excellent strength, moisture resistance, transparency and the like. Another object of the present invention is to provide a laminated film suitable as a packaging material for protecting electronic components such as semiconductor devices from moisture and static electricity.
Another object of the present invention is to perform tray packing of electronic parts storage containers such as trays, magazines, reels, etc., where electronic parts are stored in a moisture-proof packaging bag, or when the packaging bag is further boxed and transferred. It is an object of the present invention to provide a packaging bag suitable for use as a packaging bag for precision electronic component storage containers, which is excellent in practicality, in which damage to the packaging bag due to edges or the like and deterioration in moisture resistance are suppressed.

Further, the object of the present invention is to greatly improve the problem of incineration by laminating a transparent film mainly made of plastic and making a bag without using a thick metal foil. It is to provide a packaging material suitable for packaging for precision electronic components such as. As a result of intensive research to overcome the above-mentioned problems of the prior art, the inventors have combined a strength layer, a conductive layer, a gas barrier layer, a heat seal layer, etc. with various transparent films mainly composed of plastic. It was found that a packaging material suitable for packaging precision electronic components such as semiconductor devices can be obtained by stacking layers, and the present invention has been completed based on the findings.

[0012]

According to the present invention, a stretched nylon film (A), a vapor deposited film (B), a gas barrier layer (C) containing at least one composite vapor deposited film, and a heat seal layer (D). ) Are laminated films each having an adhesive layer interposed therebetween, and (1)
The outermost layer is a stretched nylon film (A) or a vapor deposited film (B), and (2) the innermost layer is a heat seal layer (D).
(3) The vapor deposition film (B) is a vapor deposition film in which a transparent inorganic vapor deposition film b2 is formed on at least one surface of a transparent polymer film substrate b1, and
(4) The gas barrier layer (C) deposits polycarboxylic acid or its partially neutralized product and saccharides on at least one surface of the transparent polymer film substrate c1 via the transparent inorganic vapor deposition film c2. It is a gas barrier layer containing at least one composite vapor deposition film (C ₁ ) having a water resistant film c3 formed by heat-treating a coating film of a mixture containing 95: 5 to 20:80 by weight. A laminated film is provided.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Examples of the stretched nylon film (A) stretched nylon film (ONy film) include nylon-6, nylon-66, nylon-6.
66 copolymer, nylon 6/12 copolymer, nylon M
Mention may be made of uniaxially or biaxially stretched films of nylon (polyamide) such as XD-6. The stretched nylon film functions as a strength imparting layer in the laminated film of the present invention. Therefore, as a stretched nylon film, in accordance with the JAS method (standard for retort food packaging materials in Japanese agricultural and forestry standards), 23 ° C., 60% relative humidity (R
It is desirable that the puncture strength measured in H) is usually in the range of 8 to 25 N, preferably 10 to 15 N.
When the stretched nylon film (A) is laminated adjacent to the vapor deposition film (B), it also functions as a protective layer for the inorganic vapor deposition film b2 of the vapor deposition film (B). When the stretched nylon film (A) is arranged as the outermost layer, it also serves as a printing layer.

Vapor Deposition Film (B) The vapor deposition film (B) is a transparent polymer film substrate b1.
Is a vapor deposition film having a transparent inorganic vapor deposition film b2 formed on at least one surface thereof. Examples of the transparent polymer film substrate b1 include polyethylene terephthalate (PET), polybutylene terephthalate (PBT),
The film is formed of polyester such as polyethylene naphthalate (PEN); polyolefin such as polyethylene and polypropylene; polyamide such as nylon-6 and nylon-66; polyimide and the like. These films are unstretched films or stretched films,
Among these, stretched PET film and ONy film are preferable.

These transparent polymer film base materials b1
Aluminum, copper, silver, tin, on at least one side,
A metal such as zinc is deposited by vacuum deposition, plasma deposition, or sputtering.
Thin film of 15 nm or less (transparent
By forming (half vapor deposition) on the machine vapor deposition film b2),
Vapor deposition while maintaining the transparency of the polymer film substrate b1.
The surface resistance value of the surface (measured at 23 ° C and 60% RH)
Usually 10¹-10⁸Ω / □, preferably 10^Two -10⁶Ω /
Adjust within the range of □ and attach the vapor-deposited film (B) to conductivity
It is desirable to function as a layer.

The inorganic vapor deposition film b2 such as aluminum (Al) has a total light transmittance (T%) of usually 20 to 9.
5%, preferably 20-85%, more preferably 25-
It is desirable to form it to a thickness of 75%. T
If the percentage is less than 20%, it becomes difficult to identify the contents, and 9
When it exceeds 5%, the metal film thickness of the conductivity-imparting layer becomes too thin and the conductivity performance deteriorates. The thickness of the inorganic vapor deposition film b2 is usually 15 nm or less, preferably 10 nm or less, more preferably 8 nm or less.

The total thickness of the vapor deposited film (B) is usually
It is 10 to 25 μm. Among these vapor deposition films (B), A1 half vapor deposition stretched PET film and A1 half vapor deposition ONy are particularly preferable. In the case of Al half vapor deposition, T% is usually about 30 to 40% and is semitransparent. Therefore, the vapor deposition film (B) is preferably a film on which a transparent or semitransparent metal vapor deposition film is formed. That is, the transparent inorganic vapor deposition film b2 includes a semitransparent film.

Gas Barrier Layer (C) The gas barrier layer (C) is a transparent polymer film substrate c.
1, a coating film of a mixture containing a polycarboxylic acid or a partially neutralized product thereof and a saccharide in a weight ratio of 95: 5 to 20:80 is heat-treated on at least one surface of 1 through a transparent inorganic vapor deposition film c2. It is a layer containing at least one layer of the composite vapor deposition film (C ₁ ) on which the water resistant film c3 is formed, and in the laminated film, it mainly functions as a moisture-proofing layer.

As the transparent polymer film substrate c1,
For example, nylon-6, nylon-66, nylon-1
2. Polyamide such as nylon-6.66 copolymer, nylon 6/12 copolymer, polyester such as PET, PBT, PEN, polypropylene, polyolefin such as poly-4-methylpentene-1, polymer such as polyphenylene sulfide Mention may be made of films formed from the material. These films are unstretched films or stretched films.

The polymer film substrate c1 is preferably one having a heat resistance sufficient to withstand the heat treatment conditions at the time of manufacturing the water resistant film. Polymer film base material c1 having heat resistance
The crystalline melting point (JIS K-7121) or the Vicat softening point (JIS K-7206) is usually 100 to
The temperature is preferably 380 ° C, preferably 150 to 380 ° C, more preferably 180 to 380 ° C. Among the above-mentioned polymer films, heat-resistant films such as polyamide, PET, PEN having a crystal melting point or a Vicat softening point of 180 ° C. or higher are particularly preferable.

As the inorganic material used as the vapor deposition source, aluminum (Al), aluminum oxide (Al
₂ O ₃ ), silicon oxide (SiO _x ; x = 1 to 2), silicon oxynitride (SiO _x N _y ; x = 0.6 to 0.8, y = 0.
7 to 0.9) and the like, but from the viewpoint of transparency,
Silicon oxide (SiO _x ) is particularly preferred. The thickness of the inorganic vapor deposition film c2 is usually 10 to 300 nm, preferably 1
The thickness is 0 to 150 nm, and more preferably 10 to 100 nm. The vapor deposition method may be either a physical vapor deposition method or a chemical vapor deposition method, but a vacuum vapor deposition method of the physical vapor deposition method is preferable.

A transparent inorganic vapor-deposited film c2 is formed on at least one surface of the transparent polymer film substrate c1, and polycarboxylic acid or its partially neutralized product and saccharides are formed on the inorganic vapor-deposited film c2. Is applied in a weight ratio of 95: 5 to 20:80, dried to form a film, and then the film is heat-treated at a temperature of 100 ° C. or higher to give a water resistant film c3. Let it form.

The polycarboxylic acid used in the present invention is a polymer having at least two carboxyl groups in the molecule, and specific examples thereof include polyacrylic acid, polymethacrylic acid, and acrylic acid-methacrylic acid copolymer. , Polymaleic acid, and mixtures of two or more of these. Among these, homopolymers of acrylic acid or methacrylic acid, and copolymers of both are preferable, and further, homopolymers of acrylic acid and copolymers with methacrylic acid in which acrylic acid is the predominant amount are gas barrier properties. It is particularly suitable. The number average molecular weight of the polycarboxylic acid is usually 2,000 to 250,000.

The partially neutralized product of polycarboxylic acid is obtained by partially neutralizing the carboxyl group of polycarboxylic acid with an alkali such as sodium hydroxide, lithium hydroxide, potassium hydroxide or ammonia to form a carboxylate salt. It can be obtained by From the viewpoint of gas barrier properties, the degree of neutralization of the partially neutralized polycarboxylic acid is preferably more than 0% and 20% or less, and more preferably 1 to 20%. The degree of neutralization can be determined by the following equation. Neutralization degree = (A / B) × 100 (%) A: Number of moles of neutralized carboxyl groups in 1 g of partially neutralized polycarboxylic acid. B: Number of moles of carboxyl group in 1 g of polycarboxylic acid before partial neutralization. Examples of saccharides (also referred to as sugars) used in the present invention include monosaccharides, oligosaccharides, and polysaccharides.
These sugars also include sugar alcohols and various substitution products and derivatives. These saccharides are preferably soluble in water.

<Monosaccharide> A monosaccharide is a basic substance among saccharides that does not become a simpler molecule by hydrolysis, and is a constituent unit of oligos and polysaccharides.
The monosaccharide is usually represented by the general formula C _n (H ₂ O) _n ,
Among them, carbon number (n) is 2, 3, 4, 5, 6, 7,
Those that are 8, 9 and 10 are called diose, triose, tetrose, pentose, hexose, heptose, octose, inose, and decose, respectively. Monosaccharides are classified into those having an aldehyde group as aldoses and those having a ketone group as ketose. Those having n = 3 or more have asymmetric carbon atoms, and there may be many stereoisomers depending on the number of asymmetric carbon atoms, but naturally known ones are a part thereof. Naturally occurring pentoses and hexoses are common. As the monosaccharide used in the present invention, n =
Aldose, which is an aldehyde of a chain polyhydric alcohol of 6 or more, is preferable because it is naturally abundant. Examples of such monosaccharides include glucose, mannose, and galactose. Among them, glucose and galactose are more preferable. Monosaccharides can be used alone or in combination of two or more.

<Sugar Alcohol> Sugar alcohol is a polyhydroxyalkane obtained by reducing aldose or ketose. As the sugar alcohol used in the present invention, a chain polyhydric alcohol is preferable. Such sugar alcohols may be represented by the general formula _{C n H 2n + 1 O n} .
When n is 3, 4, 5, 6, 7, 8, 9 and 10, they are called trititol, tetritol, pentitol, hexitol, heptitol, octitol, nonitol and decitol, respectively. Each sugar alcohol has a number of stereoisomers depending on the number of asymmetric carbon atoms. In the present invention, it is preferable to use a sugar alcohol having n = 4 to 6. Specific examples of the sugar alcohol include sorbitol, mannitol, dulcitol, xylitol, erythritol, glycerin and the like. The sugar alcohols can be used alone or in combination of two or more.

<Oligosaccharides> Oligosaccharides (oligosaccharides) have a structure in which 2 to 10 monosaccharides are linked by glycosidic bonds. Depending on the number of monosaccharides, they are classified into disaccharides, trisaccharides, tetrasaccharides, pentasaccharides and the like. Specific examples include sucrose, lactose, trehalose, cellobiose, maltose, raffinose, stachyose and the like. Further, those obtained by alcoholizing the ends of these oligosaccharides (terminal alcohol or oligosaccharide) can also be used.

<Polysaccharides> Polysaccharides is a general term for high molecular compounds (polymerization degree of 10 or more) in which monosaccharides are polyglycosylated, and homopolysaccharides (homoglycans) are used when the number of constituent sugars is one. More than one species are called heteropolysaccharides (heteroglycans). Polysaccharides widely exist in the animal, plant, and microbial communities as storage polysaccharides (such as starches), structural polysaccharides (such as cellulose), and functional polysaccharides (such as heparin). A natural polysaccharide is a polymer compound mainly composed of aldohexose and aldpentose, which are connected in a linear, branched or cyclic manner by glycosidic bonds. Aldpentose and aldohexose form a 6-membered ring structure called a pyranose ring by an intramolecular hemiacetal bond between an aldehyde at the C ₁ position and an alcohol at the C ₅ position. Aldohexose and aldopentose in natural polysaccharide molecules mainly adopt this pyranose ring structure.

Aldohexose and aldopentose, which are constituent units of natural polysaccharides, include neutral monosaccharides as well as sulfates, phosphates, other organic acid esters, methyl ethers, and primary alcohol groups of neutral monosaccharides. C _{2 of} uronic acid and aldohexose which are oxidized to carboxyl groups
Hexosamine in which the hydroxyl group at the C-position has been substituted with an amino group, and derivatives thereof include N-acetylhexosamine, and 3,6-anhydride aldhexose in which an ether is formed between the hydroxyl groups at C ₃ and C ₆ . Natural polysaccharides are widely distributed in the animal and plant kingdoms, and exist in plants as cell wall constituents of higher plants and seaweeds, those not involved in cell composition, and cell constituents of microorganisms. Those not involved in the cell wall composition of higher plants and seaweeds include storage substances such as mucous and starch contained in the cell fluid. In animals, it is present as a constituent of storage substances such as glycogen and mucus such as heparin and chondroitin sulfate.

When natural polysaccharides are classified according to their constituents, they are classified into neutral polysaccharides, acidic polysaccharides and basic polysaccharides.
Neutral polysaccharides include mannan and glucan as homopolysaccharides. Heteropolysaccharides include konjak and guaran, which are composed only of hexose, xylan and araboxylan, which are composed only of pentose, and tamarind and pear, which are composed of hexose and pentose. Examples of acidic polysaccharides include those containing only uronic acid, trouroois and pectin as those containing galacturonic acid and neutral sugars, and those containing glucuronic acid and neutral sugars such as chamomile and Xanthus quail, and other neutral sugars. Of sulfuric acid ester, phosphoric acid ester, organic acid ester,
There are acidic polysaccharides including methyl ether and 3,6 anhydride.
Basic polysaccharides include those containing glucosamine and galactosamine as constituent monosaccharides. The polysaccharides used in the present invention include, in addition to these natural polysaccharides, these polysaccharides in the solid phase, liquid phase, or solid phase using an organic acid or an inorganic acid and a hydrolase of the polysaccharide as a catalyst. In the liquid mixed phase, by applying heat as necessary, those obtained by hydrolysis, natural polysaccharides and those obtained by subjecting them to the above-mentioned hydrolysis treatment, and those further processed further are also available. included.

Examples of the processing treatment for natural polysaccharides and their hydrolysates include the following. Esterification treatment such as esterification treatment with inorganic acid or organic acid, allyl etherification, methyl etherification, carboxymethyl etherification and the like. Cationization treatment: For example, natural polysaccharides and their hydrolysates, 2-diethylaminoethyl chloride and 2,2
A method of reacting with 3-epoxypropyltrimethylammonium chloride is exemplified. Cross-linking treatment: For example, a method of cross-linking using formaldehyde, epichlorohydrin, phosphoric acid, acrolein and the like can be mentioned. Grafting treatment: For example, a method in which various monomers are graft-polymerized to a natural polysaccharide or a hydrolyzate thereof. Examples of the monomer include vinyl acetate, vinyl propionate, t-butyl vinyl ether, (meth) acrylamide, (meth) acrylic acid, alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, and (meth) acryl. Ethoxyalkyl acid acid, methoxypolyethylene glycol (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl methacrylate, acrylonitrile, styrene, anhydrous Maleic acid, itaconic acid and the like can be mentioned.

Among these natural polysaccharides, their hydrolysis products and their processed products, those soluble in water are preferred. Among the water-soluble natural polysaccharides, their hydrolysis products, and their processed products, homopolysaccharides whose constituent monosaccharide is glucose are more preferable. Examples of glucose homopolysaccharides include starches, celluloses, dextran, pullulan, water-soluble chitins and chitosans. In the present invention, sugar sugars thereof may be used in place of the natural polysaccharides and the hydrolysis products thereof and the chemically modified products thereof. The sugar alcohols of the natural polysaccharides and their hydrolysis products and their chemically modified products referred to here are those obtained by reducing the carbonyl group at the C ₁ -position at their reducing terminals to give alcohols. In addition, in the present invention, a saccharide such as cyclodextrin in which the molecular chains of the saccharide are cyclically connected can also be used. The polysaccharides used in the present invention can be used alone or in combination of two or more.

<Starches> Starches are included in the above-mentioned polysaccharides, and the starches used in the present invention will be described in more detail below. As the starches used in the present invention,
Wheat starch, corn starch, waxy corn starch,
Raw starch (unmodified starch) such as potato starch, tapioca starch, rice starch, sweet potato starch, sago starch, and various processed starches are available.

Examples of the modified starch include pregelatinized starch, separated and purified amylose, separated and purified amylopectin, physically modified starch such as heat-moisture treated starch, hydrolyzed dextrin, enzyme-degraded dextrin, enzyme-modified starch such as amylose, and acid-treated starch. , Chemically decomposed modified starch such as hypochlorous acid oxidized starch, dialdehyde starch, etc., esterified starch (acetic acid esterified starch, succinic acid esterified starch,
Nitric acid esterified starch, phosphoric acid esterified starch, urea phosphoric acid esterified starch, xanthogenic acid esterified starch, acetoacetic acid esterified starch, etc., etherified starch (allyl etherified starch, methyl etherified starch, carboxymethyl etherified starch) Starch, hydroxyethyl etherified starch, hydroxypropyl etherified starch, etc.), cationized starch (reaction product of starch and 2-diethylaminoethyl chloride, reaction product of starch and 2,3-epoxypropyltrimethylammonium chloride, etc.), Chemically modified starch such as cross-linked starch (formaldehyde cross-linked starch, epichlorohydrin cross-linked starch, phosphoric acid cross-linked starch, acrolein cross-linked starch, etc.), grafted starch obtained by graft-polymerizing various starches with a monomer (for example, vinyl acetate, propion Acid vinyl Le, t- butyl vinyl ether, (meth) acrylamide, (meth) acrylic acid,
(Meth) acrylic acid alkyl ester, (meth) acrylic acid hydroxyalkyl ester, (meth) acrylic acid ethoxyalkyl ester, (meth) acrylic acid methoxy polyethylene glycol ester, (meth) acrylic acid 2-hydroxy-3-chloropropyl ester , (Meth) acrylic acid dimethylaminoethyl ester, methacrylic acid glycidyl ester, acrylonitrile, styrene, maleic anhydride, itaconic acid and the like. And the like. Among these starches, processed starches soluble in water are preferred. The starches may be hydrated. These starches can be used alone or in combination of two or more.

The mixing ratio (weight ratio) of the polycarboxylic acid or its partially neutralized product and the saccharide is 95: 5 to 20: 8.
It is 0, preferably 90:10 to 40:60, and more preferably 85:15 to 50:50. Within these ranges, good gas barrier properties can be obtained. A mixture of a polycarboxylic acid or a partially neutralized product thereof and a saccharide is generally used as an aqueous solution (concentration: 5 to 30% by weight). The aqueous solution is applied onto the transparent inorganic vapor deposition film c2 formed on at least one surface of the transparent polymer film substrate c1 by a casting method or the like and dried to form a film. Then, the film is heat-treated at a temperature of 100 ° C. or higher. The heat treatment temperature is 100 ° C. or higher, preferably 100 to 350 ° C., more preferably 160 to 250 ° C. The heat treatment time may be appropriately selected according to the heat treatment method and the heat treatment temperature. The film acquires water resistance by heat treatment and becomes insoluble in water and boiling water.

The thickness of the water resistant film c3 thus formed is usually 0.1 to 5 μm, preferably 0.
The thickness is 2 to 5 μm, more preferably 0.5 to 3 μm. For example, the thickness of the polymer film substrate c1 is 12μ
m, the thickness of the inorganic vapor deposition film c2 is 30 to 50 nm, and the thickness of the water resistant film c3 is 2 μm, the moisture vapor transmission rate at 40 ° C. and 90% RH of the composite vapor deposition film (C ₁ ) is:
Usually, 0.5 g / m ² · 24h or less, preferably 0.3
g / m ² · 24h or less, more preferably 0.2 g / m ²
・ It will be 24 hours or less. The composite vapor deposition film (C ₁ ) is a transparent inorganic vapor deposition film c2 on one side of the polymer film substrate c1.
Although the water resistant film c3 may be formed via the above, curling can be prevented by forming these layers on both sides.

The thickness of the composite vapor deposition film (C ₁ ) is usually about 10 to 30 μm. Gas barrier layer (C)
The composite deposited film (C ₁₎ may be a single layer only, but a plurality of composite deposited film (C ₁₎ may be a stack through an adhesive layer. However, when a plurality of composite vapor deposition films (C ₁ ) are laminated, a transparent polymer film c is used as a buffer layer between the composite vapor deposition films (C ₁ ).
4 is preferably interposed. For example, the gas barrier layer (C) includes two layers of the composite vapor deposition film (C ₁ ), and each of these composite vapor deposition films (C ₁ ) is a transparent polymer film c4 via an adhesive layer. Those having a structure laminated on both sides are preferable.

By interposing such a transparent polymer film c4, when the packaging bag for electronic parts formed from the laminated film is bent or impacted, the inorganic vapor deposition film c2 or the water resistant film c3 is formed. It functions as a buffer layer that prevents cracks and breaks from occurring. The thickness of the transparent polymer film c4 is 10 to 50 μm.
And the tensile elastic modulus is 0.3 to 3 GPa, preferably 0.3.
A material having an elastic modulus of 1 GPa to 1 GPa is preferable, and specific examples thereof include polyamide, polypropylene, polyethylene, ethylene-vinyl acetate copolymer, ionomer, polyvinyl chloride, polyvinylidene chloride, and saponified product of ethylene-vinyl acetate copolymer. Can be mentioned. The elastic modulus is in accordance with JIS K-7127 at 23 ° C. and 60%.
With RH, a sample with a width of 20 mm and a length of 100 mm is tested at a tensile speed of 10 mm / min, and the tensile secant elastic modulus (1% secant modulus) at a strain of 1% is measured and obtained.

4 to 6 show specific examples of the laminated constitution of the composite vapor deposition film (C ₁ ) which becomes the gas barrier layer (C) or is contained in the gas barrier layer (C). FIG. 4 shows a water resistant film c3 / inorganic vapor deposition film c2 / polymer film substrate c1.
5 is a laminated structure of water resistant film c3 / inorganic vapor deposition film c2 / polymer film substrate c1 / inorganic vapor deposition film c2 / water resistant film c3, and FIG. 6 is a polymer film c4 of a buffer layer. A water resistant film c3 / inorganic vapor deposition film c2 / polymer film base material c1 is laminated through the respective layers.

Heat Seal Layer (D) Materials for forming the heat seal layer include low density polyethylene, linear low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-α-olefin copolymer, ethylene-acryl. Known products such as acid copolymers, ethylene-alkyl acrylate copolymers, ionomer resins and the like can be used. The thickness of the heat seal layer is usually 10 to 1
The thickness is 00 μm, and it is preferable that it is laminated on another layer by an extrusion lamination method or a dry lamination method. Further, an antistatic agent is applied to the outer surface of the heat seal layer to have a surface resistance value of 10 at 23 ° C. and 60% RH.
It is preferable to adjust the resistance to ⁷ to 10 ¹¹ Ω / □, typically about 10 ⁹ Ω / □ to impart antistatic property.

Laminated film In the laminated film of the present invention, a stretched nylon film (A), a vapor deposited film (B), a gas barrier layer (C) and a heat seal layer (D) are laminated via an adhesive layer, respectively. The outer layer is a stretched nylon film (A) or a vapor-deposited film (B), the innermost layer is a heat seal layer (D), and more preferably, an antistatic agent is applied to each outer surface of the outermost layer and the innermost layer. It has a structured structure. Further, when laminating, each film may be subjected to a surface treatment for improving the wettability, if necessary, within a range not hindering the present invention.

1 to 3 show specific examples of the laminated structure (however, the adhesive layer is omitted). In Fig. 1, (A) / (B) /
(C) / (D) laminated structure, FIG. 2 shows (B) / (A) /
(C) / (D) laminated structure, (B) / (C) / in FIG.
The laminated structure of (A) / (D) is shown. The stretched nylon film (A) can be disposed between either the outermost layer or the middle layer. When the stretched nylon film (A) is the outermost layer, the vapor-deposited film (B) serving as the conductivity-imparting layer is preferably arranged immediately below it, and in other cases, it is preferably arranged in the outermost layer. The material of the adhesive may be a resin usually used in dry lamination or the like, and examples thereof include urethane adhesives, polyester adhesives, acrylic adhesives, epoxy adhesives, and the like. These resins can be used alone or in combination of two or more.

The antistatic agent applied to the inner and outer layers has a surface resistance value of 10 ⁷ to 10 ¹¹ Ω / □, typically about 10 ⁹ Ω / □, at 23 ° C. and 60% RH by antistatic treatment. Use one that can be adjusted. For example, a surfactant-type antistatic agent such as Statiside manufactured by US ACL Co. is preferable.
The layer of the antistatic agent is usually about 0.01 to 1 μm. If the thickness of the antistatic treatment layer is too thick, for example,
Inconveniences such as deterioration of heat sealability are likely to occur. The laminated film of the present invention has an overall thickness of 50 to 28.
It is 0 μm, preferably 70 to 200 μm. The laminated film of the present invention, when used as a packaging material, withstands harsh packaging such as vacuum packaging of contents with protrusions, and is suitable for packaging electronic component storage containers such as semiconductor devices.

The laminated film of the present invention typically has the following features. It has transparency. Total light transmittance (T%) is 20-
95%. Low water vapor transmission rate. The moisture vapor transmission rate is 0.5 g / m ² · 24 h or less. Strong piercing strength. A puncture strength value of 20 N or more can be obtained. Strong impact strength. An impact strength value of 230 N or more can be obtained. It has a conductive layer. The surface resistance value of the vapor deposition film (B) (measured at 23 ° C. and 60% RH) can be 10 ¹ to 10 ⁸ Ω / □. Has antistatic properties. By the antistatic treatment, the surface resistance value of the inner and outer layers can be adjusted within the range of 10 ⁷ to 10 ¹¹ Ω / □.

[0045]

The present invention will be described more specifically below with reference to examples and comparative examples. In addition, the measuring method of physical properties is
It is as follows. <Transparency> Σ80 Color M made by Nippon Denshoku Industries Co., Ltd.
The total light transmittance (T%) of the laminated film was measured using an easuring system. <Moisture Permeability> In order to make a practical evaluation as a packaging bag for a container for storing electronic components such as semiconductor devices, a packaging bag with a size of 250 mm × 500 mm is formed by folding back three-way seals, and a semiconductor is manufactured using a vacuum forming machine MULUTIVAC. The device and other electronic component storage trays were vacuum packaged. Then, with respect to a peripheral area of 50 cm ^{2 including} a place where the protrusion at the bottom of the tray bottom hits, the moisture permeability before and after vacuum packaging was measured. Measuring equipment is Modern Con
PERMATRAN-W 3/31 type manufactured by troll,
The measurement conditions are 40 ° C. and 90% RH. <Puncture strength> Measured at 23 ° C. and 60% RH according to the JAS method (standard for retort food packaging materials in Japanese agricultural and forestry standards). Specifically, a piercing jig having a tip curvature radius of 0.5 mm is applied to the center of the laminated film set in a hollow table having a ring inner diameter of 44 mmφ with a speed of 50 mm /
Puncture was performed from the inner layer side to the outer layer side in minutes. <Impact strength> According to ASTM D3763, 23 ° C,
Punching was performed from the inner layer side to the outer layer side at a punching speed of 333 cm / sec toward the center of the laminated film set at a hollow base having a ring inner diameter of 25.4 mmφ at 60% RH. <Surface resistance> Measuring method: MONROE ELECTRO
NICS, INC. Made, portable measuring instrument MODEL
262A was used. Parallel electrodes were used and a measuring voltage of 100V was used. Surface resistance (JIS K-6911) is
It is a numerical value obtained by dividing the direct current applied between the two electrodes of the test piece by the current flowing through the surface layer, and is also called sheet resistance. The unit is Ω, but it is expressed as Ω / □ to distinguish it from mere resistance.

Example 1 A stretched PET film having a thickness of 12 μm
On one side of the film, silicon oxide (SiO_x) Vacuum deposition
By vapor deposition to form a transparent inorganic vapor deposition film (thickness 30n
m) was formed. Manufactured by Wako Pure Chemical Industries, Ltd.
Using soluble starch, as polyacrylic acid (PAA),
Wako Pure Chemical Industries, Ltd. PAA aqueous solution (25 wt%)
Using. Sodium hydroxide was added to this PAA aqueous solution.
E. Partially neutralized PAA (PAANAn) with a degree of neutralization of 10%
Prepared. The above starch and PAANA are converted into starch: PAANA
= Aqueous solution containing 30:70 (wt%) (concentration
10% by weight of the SiO 2_xEvaporated PET SiO_xsurface
Coating to a film thickness of 2 μm after drying at 150 ° C
did. Then, heat treatment in an oven at 200 ° C. for 15 minutes
I understood. In this way, a water resistant film was formed
Composite vapor deposition film (C₁) Was produced. This composite deposition film
Film (C ) Was used as the gas barrier layer (C). What
Oh, this composite vapor deposition film (C₁) 40 ℃, 90% R
Water vapor transmission rate at H is 0.2 g / m^Two・ 24h
Was.

On one surface of a stretched PET film having a thickness of 12 μm, a thin aluminum (Al) layer was formed by a vacuum vapor deposition method so as to have a T% of 30%, and the vapor deposition film had a thickness of 5 nm. Half vapor deposition (H-Al) PET
(B) was obtained. Urethane adhesive [AD-953, C, manufactured by Toyo Morton Co., Ltd.]
AT-10] was used. The thickness of the adhesive layer was 2 μm. First, a 15 μm thick ONy film (A) [Emblem ONBC manufactured by Unitika Ltd .: Puncture strength 11
N] was laminated on the A1 surface of the vapor-deposited film (B) by a dry laminating method. Next, the water-resistant film surface of the composite vapor deposition film (C ₁ ) and P of the vapor deposition film (B)
The ET surface was laminated by a dry laminating method. Furthermore,
PET surface of composite vapor deposition film (C ₁ ) and thickness 50 μm
The low density polyethylene (LDPE) film of was laminated by the dry lamination method. Finally, an antistatic agent was applied to each of the surfaces of the outermost ONy film and the innermost LDPE film to a thickness of 25 nm. The transparency, puncture strength, impact strength, and moisture permeability before and after vacuum packaging of the obtained laminated film (thickness 97 μm) were evaluated. The laminated constitution is shown in Table 1 (Constitution 1), and the measurement results of physical properties are shown in Table 2. The surface resistance of the inner and outer surfaces was 10 ⁹ Ω / □.

[Example 2] The thickness of the SiO _x layer of SiO _x vapor deposited PET in the composite vapor deposited film (C ₁ ) was 50 nm.
A laminated film (thickness: 97 μm) was prepared in the same manner as in Example 1 except that vapor deposition was performed so that an antistatic agent was applied to both surfaces. Table 1 (Structure 2)
Table 2 shows the measurement results of physical properties. The surface resistance of the inner and outer surfaces was 10 ⁹ Ω / □.

[Example 3] Example 3 except that the laminated position of the ONy film (A) was between the PET surface of the vapor deposition film (B) and the water resistant film surface of the composite vapor deposition film (C ₁ ). Laminated film (thickness 97μ
m) was prepared, and then an antistatic agent was applied to both surfaces.
The laminated constitution is shown in Table 1 (Constitution 3), and the measurement results of physical properties are shown in Table 2. The surface resistance of the inner and outer surfaces was 10 ⁹ Ω / □.

[Example 4] The laminated position of the ONy film (A) was changed from the PET surface of the composite vapor deposition film (C ₁ ) to the LDP.
A laminated film (thickness: 97 μm) was produced in the same manner as in Example 1 except that it was placed between the E film and
An antistatic agent was applied to both sides. The laminated constitution is shown in Table 1 (Constitution 4), and the measurement results of physical properties are shown in Table 2. The surface resistance of the inner and outer surfaces was 10 ⁹ Ω / □.

Example 5 SiO was formed on both sides of the stretched PET.
_{x A} laminated film (thickness: 99 μm) was prepared in the same manner as in Example 1 except that a composite vapor-deposited film (C ₁ ) having a water-resistant film made of a mixture of soluble starch and PAANA was formed through the vapor-deposited film. Was prepared, and then an antistatic agent was applied to both surfaces. The laminated structure is shown in Table 1 (structure 5).
Table 2 shows the measurement results of the physical properties. The surface resistance of the inner and outer surfaces was 10 ⁹ Ω / □.

[Example 6] Two composite vapor-deposited films (C ₁ ) prepared in Example 1 were used as a buffer layer in terms of a water-resistant film.
Film; Rayfan NO manufactured by Toray Synthetic Film Co., Ltd.]
A laminated film (thickness: 135 μm) was prepared in the same manner as in Example 1 except that the gas barrier layer (C) was dry-laminated as above, and then an antistatic agent was applied to both surfaces. The laminated constitution is shown in Table 1 (Constitution 6), and the measurement results of physical properties are shown in Table 2. The surface resistance of the inner and outer surfaces is 1
It was ⁰⁹ Ω / □.

[Comparative Example 1] An ONy film having a thickness of 25 μm, an Al foil having a thickness of 7 μm, and an LDPE having a thickness of 40 μm
Three layers of the film were extruded and laminated by a lamination method using LDPE as an adhesive to obtain a laminated film of 112 μm. Then, an antistatic agent was applied to both sides. The laminated constitution is shown in Table 1 (Constitution 11), and the measurement results of physical properties are shown in Table 2. The surface resistance of the inner and outer surfaces is 10 ⁹ Ω /
It was □.

[Comparative Example 2] Four layers of an ONy film having a thickness of 15 µm, an Al foil having a thickness of 7 µm, a CNy film having a thickness of 25 µm, and an LDPE film having a thickness of 50 µm were extruded, and LDPE was used as an adhesive. And laminated by a lamination method to obtain a 147 μm laminated film.
Then, an antistatic agent was applied to both sides. Table 1 shows the stacking structure
Table 2 shows the measurement results of physical properties in (Structure 12). In addition,
The surface resistance of the inner and outer surfaces was 10 ⁹ Ω / □.

[Comparative Example 3] A laminated film (thickness: 95 μm) was obtained in the same manner as in Example 1 except that SiO _x vapor-deposited stretched PET was used instead of the composite vapor-deposited film (C ₁ ).
m) was prepared, and then an antistatic agent was applied to both surfaces.
The laminated constitution is shown in Table 1 (Constitution 13), and the measurement results of physical properties are shown in Table 2.
Shown in The surface resistance of the inner and outer surfaces was 10 ⁹ Ω / □.

[Comparative Example 4] A of the vapor deposition film (B)
The 1-side and an ONy film (A) having a thickness of 15 μm were laminated by a dry laminating method. Next, a vapor deposition surface of SiO _x vapor deposition PET vapor-deposited so that the thickness of the SiO _x layer was 30 nm was laminated on both surfaces of the CNy film by a dry lamination method. Furthermore, the P of one of the SiO _x vapor deposition PET
The ET surface and the PET surface of the vapor deposition film (B) are laminated by a dry laminating method, and the other SiOx vapor deposition PET is laminated.
The PET surface and the LDPE film having a thickness of 50 μm are laminated by a dry lamination method to form a laminated film (thickness 131
μm) was prepared. Then, an antistatic agent was applied to both sides. The laminated constitution is shown in Table 1 (Constitution 14), and the measurement results of physical properties are shown in Table 2. The surface resistance of the inner and outer surfaces is 10 ⁹ Ω /
It was □.

[Comparative Example 5] A laminated film (thickness: 80 µm) was prepared in the same manner as in Example 1 except that the ONy film (A) was not laminated, and then an antistatic agent was applied to both surfaces. . The laminated constitution is shown in Table 1 (Constitution 15), and the measurement results of physical properties are shown in Table 2. The surface resistance of the inner and outer surfaces was 10 ⁹ Ω / □.

[Comparative Example 6] A laminated film (thickness: 118 µm) was prepared in the same manner as in Example 6 except that the ONy film (A) was not laminated, and then an antistatic agent was applied to both surfaces. . The laminated constitution is shown in Table 1 (Constitution 16), and the measurement results of physical properties are shown in Table 2. The surface resistance of the inner and outer surfaces was 10 ⁹ Ω / □.

[0059]

[Table 1]

[0060]

[Table 2]

[0061]

According to the present invention, a laminated film excellent in strength, moisture resistance, transparency and the like is provided. The laminated film of the present invention is suitable as a packaging material for protecting electronic components such as semiconductor devices from moisture and static electricity. Further, the laminated film of the present invention, due to the edge of the tray, etc., when packaging electronic component storage containers such as trays containing electronic components in a moisture-proof packaging bag or when packaging and transporting the packaging bag further. It is particularly preferable as a packaging material for producing a packaging bag suitable as a packaging bag for a precision electronic component storage container, which is excellent in practicality, in which the moisture resistance of the packaging bag is suppressed from being deteriorated. Since the laminated film and the packaging bag of the present invention do not use thick metal foil, the problem of incineration can be greatly improved. Furthermore, since the packaging bag is transparent, for example, if a desiccant such as silica gel is used as an indicator together with the contents, it is possible to check the degree of moisture absorption of the contents without opening the packaging bag.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a specific example of a laminated structure of a laminated film of the present invention.

FIG. 2 is a cross-sectional view showing a specific example of the laminated constitution of the laminated film of the present invention.

FIG. 3 is a cross-sectional view showing a specific example of the laminated constitution of the laminated film of the present invention.

FIG. 4 is a cross-sectional view showing a specific example of a laminated structure of a composite vapor deposition film.

FIG. 5 is a cross-sectional view showing a specific example of a laminated structure of a composite vapor deposition film.

FIG. 6 is a cross-sectional view showing a specific example of a laminated structure in which two composite vapor deposition films are laminated on both sides of a polymer film serving as a buffer layer.

[Explanation of symbols]

 A: Stretched nylon film B: Vapor deposition film C: Gas barrier layer D: Heat seal layer c1: Polymer film base material c2: Inorganic vapor deposition film c3: Water resistant film c4: Polymer film

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location B32B 27/28 102 B32B 27/28 102 27/30 27/30 C 101 101 27/32 27/32 C 27/34 27/34 B65D 30/02 B65D 30/02 65/40 65/40 A 85/86 C23C 14/10 C23C 14/10 C08J 7/04 CFGB // C08J 7/04 CFG 0333-3E B65D 85 / 38 D

Claims (12)

[Claims] 1. A stretched nylon film (A), a vapor-deposited film (B), a gas barrier layer (C) containing at least one composite vapor-deposited film, and a heat-sealing layer (D) are laminated via an adhesive layer, respectively. (1) The outermost layer is a stretched nylon film (A) or a vapor deposition film (B), (2) the innermost layer is a heat seal layer (D), and (3) a vapor deposition film. (B)
A vapor-deposited film in which a transparent inorganic vapor-deposited film b2 is formed on at least one surface of a transparent polymer film substrate b1, and (4) the gas barrier layer (C) is a transparent polymer film substrate. Coating film of a mixture containing a polycarboxylic acid or a partially neutralized product thereof and a saccharide in a weight ratio of 95: 5 to 20:80 on at least one surface of the material c1 via a transparent inorganic vapor deposition film c2. A laminated film which is a gas barrier layer containing at least one composite vapor-deposited film (C ₁ ) having a water-resistant film c3 formed by heat treatment. 2. The laminated film according to claim 1, wherein an antistatic agent is further applied to each outer surface of the outermost layer and the innermost layer. 3. The stretched nylon film (A) has a thickness of 1
The thickness of the vapor deposition film (B) is 0 to 30 μm, and the thickness is 10 to 2
The thickness of the composite vapor deposition film (C ₁ ) is 5 to 5 μm and is 10 to 3
0 μm, the thickness of the heat seal layer (D) is 10 to 100
The laminated film according to claim 1, wherein the laminated film has a thickness of 50 μm and a total thickness of 50 to 280 μm. 4. The stretched nylon film (A) has a puncture strength of 8 to 25 N.
The laminated film according to item. 5. The laminated film according to claim 1, wherein the gas barrier layer (C) contains one layer of the composite vapor deposition film (C ₁ ). 6. The laminated film according to claim 1, wherein the gas barrier layer (C) contains two layers of the composite vapor deposition film (C ₁ ). 7. The gas barrier layer (C) comprises two layers of a composite vapor deposition film (C ₁ ), and each of these composite vapor deposition films (C ₁ ) is a transparent polymer film via an adhesive layer. The laminated film according to claim 6, which has a structure laminated on both surfaces of c4. 8. The transparent polymer film c4 has a thickness of 1
The laminated film according to claim 7, which has a tensile modulus of 0 to 50 µm and a tensile modulus of 0.3 to 3 GPa. 9. The group of transparent polymer film c4 consisting of a saponified product of polyamide, polypropylene, polyethylene, ethylene-vinyl acetate copolymer, ionomer, polyvinyl chloride, polyvinylidene chloride, ethylene-vinyl acetate copolymer. The laminated film according to claim 7, which is a film formed from at least one resin selected from the following. 10. The laminated film has a total light transmittance of 20 to 20.
The laminated film according to any one of claims 1 to 9, which is 95%. 11. The laminated film according to claim 1, which is a film for packaging electronic parts. 12. A packaging bag for electronic parts, comprising the laminated film according to any one of claims 1 to 11.