JP3251694B2 - Elastic metallized film and production method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a metallized film and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Metallic coatings ranging in thickness from sub-nanometers to several microns in thickness are applied to sheet materials to provide a luxurious appearance and / or various physical properties (e.g.,
Electrical conductivity, electrostatic resistance, chemical resistance, heat reflection or heat radiation and optical reflection). Alternatively, instead of metallizing the product itself, a part or all of the product may be provided with a metallized sheet material or a metallized sheet material may be incorporated. Such methods are, for example, very effective for products that are large, sensitive to heat and vacuum, difficult to apply metallization methods, or have complex shapes.

Heretofore, limitations on substrate sheets have often limited such use of metallized sheet materials. Heretofore, metal coatings have generally been applied to sheet-like substrates that are relatively inextensible and inelastic. This is because the sheet-like substrate is not deformed and the metal coating is not peeled off. For this reason, the flexibility, elasticity, softness and / or drape properties of such metallized materials have been insufficient for use in many applications. For example, U.S. Pat. Nos. 4,999,222 and 5,057,351 describe metallized polyethylene.
A plexifilament film fibril sheet is disclosed. This sheet is inelastic and has relatively low drape and softness. Therefore, it is not suitable for applications requiring elasticity, drape and softness. EP 392,082-A2 discloses a method for producing a metal porous sheet suitable for an electrode plate of a battery. According to this publication, the metal is vacuum deposited,
It is deposited on a porous sheet (foam sheet, nonwoven web, mesh film or a mixture thereof) using a method such as electroplating or electroless plating.

Thus, there is still a need for an elastomeric metallized sheet material having desirable flexibility, elasticity, drape and softness. further,
What is needed is an elastomeric metallized sheet material that has the desirable properties described above and is inexpensive enough to be discarded after a single use. Although inexpensive sheet materials have ever been metal-coated, such inexpensive metallized sheet materials have less flexibility, elasticity, drape and softness in the original sheet material, Applications were limited.

[0005]

Definitions The terms "elastic" and "elastomer" as used herein refer to the following materials.
That is, a material that can be extended to an extension length of at least about 125% of its original length when an urging force is applied, and recovers at least 40% of its elongation when the urging force is released. As a hypothetical example, a 1-inch sample can be extended to at least 1.25 inches, and when released from this extended state, recovers to a length of 1.10 inches or less. Most of the elastic material is 25
% (Ie, 125% or more of the original length), for example, 200% or more.
Many of these recover to almost their original length when the stretching force is released. For example, it recovers to within 105% of the original length.

[0006] As used herein, the term "inelastic" refers to a material that does not fall under the definition of "elastic" above.

[0007] As used herein, the term "recovery" refers to the contraction of an elongated material when the bias is released after the material is stretched by applying a bias. For example, if a 1-inch long material stretches 50% to 1.5 inches, then this material is 50% (0.5 inches).
It will elongate and have an elongation length of 150% of its original length. Assuming that the stretched material contracts upon release of the bias to a length of 1.1 inches, the material recovers 80% (0.4 inches) of the 0.5 inch stretch. Become. The recovery rate is represented by the following equation. [(Maximum extension length-final length) / (maximum extension length-original length)] x 100

[0008] As used herein, the term "thermoset material" refers to a polymer that cures irreversibly when heated. This property generally involves a crosslinking reaction of the molecular components caused by heating or thermal radiation.
Phenolics, alkyds, amino resins, polyesters, epoxides, silicones and the like are considered thermosetting. The term also includes materials capable of inducing cross-linking inductively, such as natural rubber in a cross-linked structure. One way to determine whether a material has a "cross-linked" structure, i.e., whether it is a thermosetting material, is to dissolve the material in boiling toluene, xylene, or other solvent. To soak the material for 40 hours. If at least 5% residue (% by weight) remains, the material can be considered as a crosslinked structure and thus a thermosetting material. Other methods for determining whether a polymer has a crosslinked structure and the degree of crosslinking include ASTM-D-2765-68 (1
978 reapproved). Yet another method for determining whether a material is a cross-linked structure is described in ASTM-
According to D-1238-79, at 230 degrees Celsius 2
To determine the melt flow of the material under a load of 1600 grams. Materials with melt flow values greater than 75 grams / 10 minutes are non-crosslinked structures and are not considered thermoset materials. This method is used to supplement the "gel" method when less than 5% of undissolved gel remains. Some of the crosslinked materials
% (% By weight) or less of the remaining gel. Not surprisingly, the term "thermoset material"
In addition to mixtures of two or more thermosetting materials, mixtures containing at least 50% (% by weight) of thermosetting material are also included.

The term "thermoplastic material" as used herein refers to a high polymer that softens when heated and returns to its original state when cooled to room temperature. Natural materials exhibiting such properties are natural rubber and many waxes. Examples of other thermoplastics include polyvinyl chloride, polyester, nylon, fluorocarbon, linear polyethylene such as linear low density polyethylene, polyurethane prepolymer, polystyrene, polypropylene, polyvinyl alcohol, caprolactam and cellulosic and acrylic resins. .

[0010] As used herein, the term "naturally occurring polymeric material" refers to a naturally occurring polymeric material. The term also includes materials such as materials that can be regenerated from naturally occurring materials (eg, cellulose) (eg, cellophane regenerated from cellulose). Examples of naturally occurring polymer materials include (1) starch, cellulose, pectin, seaweed gum (e.g., persimmon), vegetable gum (arabic, guar (g)
ua)), (2) polypeptides, (3) hydrocarbons such as rubber and gutta percha (polyisoprene), and (4) regenerated materials such as cellophane and chitosan. It will be appreciated that the term "naturally occurring polymeric material" includes at least 50% (by weight) of "naturally occurring polymeric material" as well as a mixture of two or more of these naturally occurring polymeric materials. As well as mixtures comprising "a polymeric material present in".

The term "hole" as used herein generally refers to a straight hole or passage.
A "hole" is distinct from and does not include a hole or passage having large tortuous passages, such as those found in membranes.

As used herein, the term "micropore" refers to a pore having an area of less than about 100,000 square micrometers. The area of the micropore is measured at the narrowest point in a straight passage or hole.

As used herein, the term "extensibly adaptable" refers to a material that has both measurable softness and recoverable elongation. The extensible conformable material has about 2.75 c in at least one direction.
m and has a drape stiffness of not more than m. For example, a compatible material can have a drape stiffness of no more than about 1.5 and up to about 2.75 cm in at least one direction. Draped stiffness is Testing M
The stiffness can be measured using a stiffness tester commercially available from Aches. The test results are ASTM
It can be obtained using the method of option A (cantilever) according to standard test D1388-64. Compatible materials have a softness characterized by cup rupture test results of about 200 grams or less. For example, compatible materials may have cup rupture test results of up to about 150 and up to 200 grams. This cup destruction test
The peak load required to break a 9 inch x 9 inch piece of film formed into an inverted cup shape with a diameter of about 6.5 cm and a height of 6.5 cm using a 4.5 cm diameter hemispherical foot. Is measured, and the stiffness of the film is measured. During fracture, the cup-shaped film is surrounded by a cylinder about 6.5 cm in diameter, maintaining uniform deformation. The foot and the cup are aligned to avoid contact between the cup wall and the foot, which could affect peak load. The peak load is Sc
Model FTD-G-500 load cell (500 gram range) marketed by Haevitz Company
Measured while the foot is descending at a rate of about 0.25 inches / second (15 inches / minute).

As used herein, the term "breathable" refers to a Frazier porosity of at least about 25 cubic feet per minute per square foot [cfm / ft ² ].
Refers to a material that is For example, Fraz of a breathable material
The ier porosity is about 25-100 [cfm / ft ² ]. The Frazier porosity is the Frazier P
precision Instrument Compa
measured using a Frazier breathability tester commercially available from ny. The Frazier porosity is determined by Federal Test Method 5450, Standard No. 191A.
However, the size of the sample was 8 inches × 8 inches instead of 7 inches × 7 inches.

"Polymer" as used herein
The term includes homopolymers, copolymers (eg, block, graft, random and substituted copolymers, etc.), terpolymers, and mixtures or modifications thereof. However, it is not limited to these. Further, unless otherwise specified, the term "polymer" includes all possible geometric shapes of the material. Examples include, but are not limited to, isotactic, synditactic and random symmetry.

As used herein, "basically ...
The word "comprising" does not exclude the presence of additional substances that do not significantly affect the desired properties of the given composition or product. Examples of such substances include, but are not limited to, picture elements, surfactants, waxes, flow enhancers, substances added to improve the processability of the particles and compositions thereof.

[0017]

SUMMARY OF THE INVENTION The present invention solves the above problems by providing an elastic metallized film. The elastic metallized film comprises an elastic film and a metal coating substantially covering at least a portion of at least one side of the elastic film.

According to the present invention, the elastic film component of the elastic metallized film can be a thermosetting elastic material, a thermoplastic elastic material or a naturally occurring elastic polymer film. Further, the elastic film may be a porous (micropore) elastic film and / or an elastic film in which micropores are formed.

The elastic film can be made from a synthetic elastomeric polymer. Synthetic elastomeric polymers include, for example, elastic polyesters, elastic polyurethanes,
Elastic polyamides, elastic copolymers of ethylene and at least one vinyl monomer and elastic ABA 'block copolymers (A and A' are the same or different thermoplastic polymers and B is an elastic polymer block)
and so on. These elastic polymers may be mixed with a processing accelerator such as, for example, a polyolefin. Alternatively, an adhesive resin may be mixed with the elastic polymer. It may also be desirable to make the elastic film from a naturally occurring elastomeric polymer such as rubber or gutta percha.

The elastic film used in the present invention can have a thickness ranging from about 0.25 to about 10 mils. For example, the elastic film can have an average thickness ranging from about 0.8 to about 5 mils. More specifically, the elastic film can have an average thickness ranging from about 1 to about 2 mils. In one embodiment of the present invention, the thickness of the elastic film is at least 10 mils (eg, 30 mils or more).

One or both surfaces of the elastic film may be embedded with one or more of other materials such as, for example, wood pulp, inelastic fibers and particles.
Examples of inelastic fibers include polyester fibers, polyamide fibers, glass fibers, polyolefin fibers, cellulosic fibers, multicomponent fibers, natural fibers, absorbent fibers, conductive fibers or two or more of these fibers. And mixtures. Examples of particles include activated carbon, clay, starch, metal oxides, superabsorbent materials and mixtures thereof.

Generally, the thickness of the metal coating applied to the elastic film ranges from about 1 nanometer to about 5 microns. For example, the metal coating can have a thickness ranging from about 5 nanometers to about 1 micron. More specifically, the metal coating can have a thickness ranging from about 10 nanometers to about 500 nanometers.

In the present invention, the elastic metallized film is capable of maintaining substantially all of the metal coating when stretched at least about 25%. For example, the elastic metallized film is capable of maintaining substantially all of the metal coating when stretched by 35% or more. More specifically, the elastic metallized film is capable of maintaining substantially all of the metal coating when stretched 100% or more.

The metal coating may cover substantially the entire surface on one or both sides of the elastic film, or the metal coating may cover only a part of one or both sides of the elastic film. For example, the elastic film can be masked by a metal coating process to create a partially metallized elastic coating. One or more identical or different metal layers can be coated on the elastic film. The coating can be any metal that can be deposited on the elastic film and that can bond to the elastic film to form a permanent coating. Examples of such metals include aluminum, copper, tin, gold, silver, and the like. The elastic metallized film may be given a known film finish. For example, a lacquer or sealant may be applied to the elastic metallized film.

The present invention also includes a multilayer material that includes at least one layer that is an elastic metallized film. For example,
The elastic metallized film can also be laminated with one or more other films or nonwoven webs. The elastic metallized film can also be sandwiched between layers of other materials.

According to the present invention, the elastic metallized film is made by a method having the following steps. (1) A step of preparing an elastic film and (2) metalizing at least one side of the elastic film so that at least a part of the elastic film is almost covered with a metal coating.

Metallizing the elastic film can be performed by any method that is used to deposit metal on the film and that can bind the metal onto the film. .
This metallization step can be performed by techniques such as metal deposition, metal sputtering, plasma treatment, electron beam treatment, and chemical oxidation or reduction reaction. Before applying the metal coating to the elastic film, the surface of the elastic film is modified by using a technique such as flame treatment, plasma discharge or corona discharge treatment so as to enhance the adhesion of the metal coating of the elastic film. You can also.

According to one embodiment of the method according to the invention,
The elastic film may be stretched during the metallization step. For example, the elastic film can be stretched at a rate of 10% or more. More specifically, the elastic film can be stretched to about its elastic limit. Further, the elastic film may be subjected to embossing or pattern bonding before or after the metallizing step.

[0029]

FIG. 1 shows an example of a method 10 for manufacturing an elastic metallized film according to the present invention inside a vacuum chamber 12. Metal deposition occurs inside chamber 12 at an absolute pressure of about 10 ^-6 to about 10 ^-4 millimeters of mercury. Inside the chamber 12, there is a supply roll 14 of an elastic film 16, which is unwound. The elastic film 16 advances in the direction of the arrow as the supply roll 14 rotates in the direction of the arrow in FIG. Elastic film 16
Pass through the nip of the S-shaped roll mechanism 18 composed of two stack rollers 20 and 22. The elastic film 16 can be made by a film forming method such as a film extrusion method. In this case, it is not necessary to first accumulate the elastic film on the supply roll, and it is necessary to directly store the elastic film on the S-shaped roll. The nip of the mechanism 18 can be passed.

From the reverse S-shaped path of the S-shaped roll mechanism 18, the elastic film 16 passes through the idle roller 24 and contacts a part of the chill roll 26, during which the elastic film 16 is dissipated from the molten metal tank 30. Exposure to steam 28. Metal vapor 28 condenses on elastic film 16 to form elastic metallized film 32. Although the chill roll 26 is not necessarily required for implementing the present invention, it is effective for preventing the quality of the elastic film 16 from being deteriorated while the elastic film 16 is exposed to the metal vapor 28. For example, if the elastic film 16 is exposed to metal vapor for a relatively long time, it is desirable to have the chill roll 26. It is also possible to arrange a plurality of molten metal tanks and a chill roll mechanism (not shown) in series to perform multiple coatings of the same or different metals. Further, the present invention relates to other types of metallization methods,
For example, it includes metal sputtering, electron beam metal evaporation, and the like. It is also possible to deposit the metal on the elastic film using a chemical reaction, for example a chemical reduction reaction. Generally, a method that can deposit metal on the elastic film while minimizing deterioration of the quality of the elastic film is used. In carrying out the present invention, it is also possible to use a combination of the above-mentioned metallization methods.

The metal coating is applied so as to cover at least a part of at least one surface of the elastic film 16.
For example, the metal coating can cover substantially all of one or both sides of the elastic film 16. It is also possible to mask the elastic film 16 in one or more patterns during exposure to the metallization 28 so that only one or both desired portions of the elastic film are metallized. It is.

The elastic metallized film 32 passes through an idler roller 34 and through a nip of a drive roller mechanism 36 consisting of two drive rollers 38,40. Since the linear velocity on the circumference of the roller of the S-shaped roll mechanism 18 is controlled to be smaller than the linear velocity on the circumference of the roller of the drive roller mechanism 36, the elastic film 16 is in contact with the S-shaped roll mechanism 18. The tension between the driving roller mechanism 36 and the driving roller mechanism 36 is maintained. By adjusting the speed difference between the two rollers, the elastic film 16
6, while the elastic film 16 is exposed to the metal vapor 28, the tension can be adjusted to extend by a desired amount and maintain such an extended state.
In general, the elastic film 16 can be stretched by an arbitrary amount within its elastic limit.
8, such an extended state can be maintained. For example, JPS Elastome
product name “Thes”
Elastic polyurethane films commercially available under the name "rmoplastic Polyurethane" (thermoplastic polyurethane) can be stretched in the range of about 5% to about 100% or more, depending on the material. More specifically, this "ThermoplasticPolyur
Ethane "films can be stretched in the range of about 25% to 200%. More specifically, a 1 mil Thermoplastic Polyuretha
ne XPR-824 "film is about 30 to about 90%
Can be extended. Of course, it is not necessary to stretch elastic film 16 throughout the metallization process to form elastic metallized film 32.

If necessary, the elastic film 16 is stretched by a first amount, for example 5% or more,
In that state, it is also possible to expose the metal film 28 to deposit a metal coating on the elastic film 16. Next, the elastic film 16 is subjected to a second elongation, for example, about 5
0% elongation (from the same or different molten metal bath)
Exposure to metal vapor 28 deposits a second metal coating. This process can be repeated several times with different combinations of elongation and molten metal bath to form elastic metallized films with different types of metal coatings.

When the tension applied by the S-shaped roll mechanism 18 and the drive roller mechanism 36 is released, the elastic metallized film 32 contracts immediately, and then the elastic metallized film 32 is retracted by the winder 42. It is wound up.

A post-treatment of the film (known in the art) may be applied to the elastic metallized film provided that the metal coating is not destroyed. For example, shellac or sizing may be applied.

In general, the elastic film is any elastic film that can withstand the metallization process and can form an elastic metallized film with good elongation and recovery properties. It may be. For example, as the elastic film, a thermoplastic elastic film, a thermosetting elastic film, or a naturally occurring polymer elastic film can be used. These elastic films may be porous (micropores) and / or formed with micropores.

Preferably, the elastic film component of the elastic metallized film is a thermoplastic elastic film. Generally, a suitable elastic film forming resin or a mixture containing the same is used to form the nonwoven web of the elastic film of the present invention. For example, useful elastic film-forming resins include block copolymers having the general formula of ABA 'or AB (where A and A' are thermoplastic polymer endblocks containing styrene moieties such as poly (vinyl allene)). Where B is a binding gene or an elastomeric polymer midblock such as a lower alkene polymer). The ABA 'type block copolymers can have the same or different thermoplastic block copolymers for the A and A' blocks, where the block copolymers used are linear, branched and radial block copolymers. Including. In this regard, radial block copolymers are represented by (AB) mX. Here, X is a polyfunctional molecule, and [(AB) m-] is emitted from X such that A is an endblock. In the radial block copolymer, X is an organic or inorganic polyfunctional molecule, and m is an integer having the same value as the functional group originally present in X. m is usually at least 3, and may be 4 or 5, but is not limited thereto. Thus, in the present invention,
The expression "block copolymer" and especially "AB-A '" and "AB" are meant to include all block copolymers having a rubbery block and a thermoplastic block as described above, which are extruded. Possible (e.g., by meltblowing) and, furthermore, there is no limit on the number of blocks. The elastic nonwoven web is
For example, an elastomer (polystyrene / poly (ethylene-butylene) / polystyrene) block copolymer (S
(available under the trade name "KRATON G" by the company Chemical Chemical Company). One such block copolymer is, for example, KRATON G-1657.

Other examples of elastomeric materials that can be used to make elastic films include, for example,
F. Goodrich & Co. Polyurethane elastomeric materials marketed under the trade name "ESTANE", such as Rilsan Company, are sold under the trademark "PEBA
X ", a commercially available polyamide elastomer material under the trade name" E. I. DuPont De Nemo
urs & Company include polyester elastomer materials marketed under the trade name "HYTREL®". For making elastic sheets from polyester elastic materials, see, for example, Morman
No. 4,741,949, which is incorporated herein by reference. The elastic film can also be made from an elastic copolymer of ethylene and at least one vinyl monomer (eg, vinyl acetate, unsaturated aliphatic monocarboxylic acids, esters of such monocarboxylic acids, etc.). The production of elastic copolymers and elastomeric nonwoven webs from these elastic copolymers is described, for example, in US Pat. No. 4,803,117.

Processing accelerators may be added to the elastomeric polymer. For example, a polyolefin can be mixed with an elastomeric polymer (eg, an ABA elastomer block copolymer) to enhance the processability of the elastomeric polymer. Extrudable mixtures of elastomeric polymers and polyolefins are described, for example, in Wisnes.
Ki et al., US Pat. No. 4,663,220. This description incorporates the description of this U.S. patent and replaces part of this description.

The elastic film may be a pressure-sensitive elastomer adhesive film. For example, the elastic material itself may be tacky, or a suitable tacky resin may be added to the extrudable elastomeric composition described above to provide an elastomeric film that can act as a pressure-sensitive adhesive, for example, when tension is applied. While acting, it can add the property of bonding to a reversibly necking inelastic web, or it can add the property of increasing the toughness of the metal coating. For tacky resins and extrudable tacky elastomeric compositions, see the resins and compositions described in U.S. Patent No. 4,787,699. This description incorporates the description of this U.S. patent and replaces part of this description.

Any tacky resin can be used as long as it is compatible with the elastomeric polymer and can withstand high processing temperatures (eg, the temperature during extrusion). The adhesive resin must also be able to withstand the environment encountered while the elastic film is being metallized. For example, when using a physical vapor deposition method, the adhesive resin is relatively stable even when exposed to high temperature and high vacuum for a short time so as not to generate a large amount of vapor that may hinder the metallization process. It is necessary to be. Elastomer polymer (for example, AB
When a processing accelerator (for example, polyolefin or extended oil) is mixed with the (A-elastomer block copolymer), the adhesive resin must be compatible with these processing accelerators.

The elastic film may be a multilayer material having two or more individual films and / or nonwoven webs. Further, the elastic film may be a multilayer material, wherein one or more of the layers is a nonwoven web comprising a mixture of elastic and inelastic fibers or particles. can do.
An example of the latter elastic web is US Pat. No. 4,209,
No. 563, which is incorporated herein by reference and replaces a portion of the description herein. In this example, elastomeric and non-elastomeric fibers are mixed to form a single cohesive web with randomly interspersed fibers. Other examples of such elastic compositions are disclosed in U.S. Pat. Nos. 4,741,949 and 4,100,32.
No. 4 and No. 4,803,117. This specification recites these U.S. patents and replaces part of the description herein. It is also possible to use other types of nonwoven elastomeric composition webs. For example, hydraulically entangled nonwoven elastomeric composition webs such as those described in Radwanski U.S. Pat. Nos. 4,879,170 and 4,939,016 may be used. This specification recites these U.S. patents and replaces part of the description herein.

The elastic film of the present invention has a thickness of at least about 0.5.
It can have an average thickness of 25 mils. For example, the average thickness of the elastic film can be from about 0.25 mil to about 10 mil. More specifically, the average thickness of the elastic film can be from about 0.25 mil to about 5 mil. Even more specifically, the average thickness of the elastic film can be from about 0.5 mil to about 1 mil. In general, the average thickness of the elastic film before metal coating is determined by arbitrarily selecting five points in the sheet material and setting the thickness of the sheet material at those points to .0.
Measure to one mil and average 5 measurements (5
Divided by 5).
The thickness at each point was measured using a dial thickness gauge No. commercially available from Mitoyo Seiki (Japan). Performed using 2804-10.

The elastic film used in the method according to the present invention can be a porous (micropore) elastic film and / or an elastic film having micropores formed therein. From these porous and / or microporous films, materials that require physical properties, such as, for example, air and / or vapor permeability, can be made and are therefore useful in some applications. In general, any method of forming a porous and / or microporous film can be used to treat the elastic film prior to metal coating the elastic film.

Various porous (microporous) films and methods for making such films are known. For example, porous (microporous) films are disclosed in US Pat.
No. 7,367 and No. 3,795,720, which are incorporated herein by reference, and which are incorporated in their entirety by reference.

Many types of microporous films and methods for forming micropores have been developed so far, all of which can be used in the practice of the present invention. For example, the film is a thin thermosetting sheet material in which micropores are formed by hydraulic sound waves in US Patent Application No. 07 / 769,050, and a film is formed by using hydraulic sound waves in US Patent Application No. 07 / 769,047. Thin Thermoplastic Sheet Material ", US Patent Application 07
U.S. Patent Application No. 07 / 769,045, entitled "Naturally Existing Thin Polymer Sheet Materials Having Micropores Formed by Hydraulic Acoustic Waves and Methods of Producing the Same" How To Form A Hole "
And so on. Each of these applications is incorporated herein by reference and forms a part of the description of this specification.

In general, such a film in which micropores are formed by hydraulic sound waves can be produced by a method including a step of applying ultrasonic vibrations to a material. The liquid is supplied to the area where the ultrasonic vibration is applied. The extent of the supply is such that the gap between the tip of the ultrasonic horn and the surface of the material is filled with a sufficient amount of liquid. The method of forming micropores by hydraulic sound waves includes the following steps: (1) A method of forming an elastic film on a pattern anvil having a pattern-shaped convex region (the height of the convex region is larger than the thickness of the elastic film). (2) passing the elastic film through a region for supplying liquid to the elastic film while keeping the elastic film on the pattern anvil; (3) applying ultrasonic vibration to the elastic film in the region. By this method, micropores are formed in the elastic film in substantially the same pattern as the pattern-shaped convex region on the pattern anvil.

The area of the micropores of the elastic film in which the micropores are thus formed can be in a range of at least about 10 square micrometers to about 100,000 square micrometers. For example, the area of each of the micropores is at least about 10 square micrometers to about 5,000.
It can be square micrometers. More specifically, the area of each of the micropores can range from at least about 10 square micrometers to about 1,000 square micrometers. Even more particularly, the area of each of the micropores can range from at least about 10 square micrometers to about 100 square micrometers.

The density of the micropores formed in the elastic film can be at least about 1,000 per square inch. For example, the density of the micropores formed in the elastic film can be at least about 5,000 per square inch. More specifically, the density of the micropores formed in the elastic film can be at least about 20,000 per square inch. Even more particularly, the density of the micropores formed in the elastic film can be at least about 90,000 per square inch. Even more particularly, the density of the micropores formed in the elastic film is at least about 16 per square inch.
It can be 0000. When forming the micropores in the elastic film, it is desirable to form the micropores in a predetermined region of the elastic film.

Other films that can be used in the present invention include those with a valve system that can respond to pressure changes. For example, US patent application Ser.
No./768,782, "Pressure-sensitive valve system and method of making the system". Films that are thin but include portions that have not yet been perforated can also be used in the present invention. Such films include, for example, those described in U.S. patent application Ser. No. 07 / 767,727, entitled "Method for Thinning Thin Sheet Materials with Hydraulic Acoustic Waves." Other films that can be used include, for example, films having fibers or particles embedded on at least one side. Examples of soft materials include, but are not limited to, certain thermoset film materials and certain materials made from natural materials. If the material is too hard, fibers and / or particles cannot be embedded in the material, and confirmation experiments are needed. Conversely, if the elasticity of the material is too large, fibers or particles cannot be embedded. This is because fibers and particles bounce off the material during the hydrosonic method. Useful embedding films include, for example, those described in U.S. patent application Ser. No. 07 / 768,494, entitled "Soft and Thin Film Materials Embedd by Hydraulic Acoustic Waves and Methods of Making Same".

The elastic film may be subjected to a pretreatment before the metallizing step. For example, the elastic film can be calendered with a flat roll, point bonded, or pattern bonded to obtain desired physical and / or hand characteristics. Further, at least a part of the surface of the elastic film can be modified using various known surface modification techniques to change the degree of adhesion of the metal coating to the elastic film. Examples of surface modification techniques include, for example, chemical etching, chemical oxidation, ion bombardment, plasma treatment, flame treatment, heat treatment, corona discharge treatment, and the like.

One important feature of the present invention is that the elastic metallized film, when stretched at least about 25%,
It is intended to be able to hold almost all of the metal coating. That is, when using the elastic metallized film of the present invention covered with a metal coating at least in a range from a low level to a moderate level under normal conditions, as far as the visual observation, the peeling or falling off of the metal is almost, Or not at all. For example, about 5 nanometers ~
Elastic metallized films having a metal coating in the range of about 500 nanometers are adapted to retain substantially all of the metal coating when stretched in the range of about 30% to 100% or more. More specifically, the elastic metallized film is adapted to retain substantially all of its metal coating when stretched in the range of about 35% to about 75%.

The thickness of the deposited metal depends on various factors. The factors include, for example, exposure time, pressure inside the vacuum chamber, temperature of the molten metal, surface temperature of the film,
The size of the metal vapor “cloud”, the distance between the elastic film and the molten metal bath, the number of times the metal vapor “cloud” has passed, the moving speed of the film, etc. In general, the lower the processing speed, the heavier and thicker the metal coating on the elastic film tends to be, but conversely, the lower the processing speed, the lower the metal vapor at a temperature that reduces the quality of the elastic film. Exposure time becomes longer.
Depending on the processing conditions, the exposure time is about 1 second or less, for example,
It can be less than about 0.75 seconds or less than about 0.5 seconds. The number of passes through the metal vapor "cloud" can be increased to increase the thickness of the metal coating.

[0054] Generally, the thickness of the metal applied to the elastic film ranges from about 1 nanometer to about 5 microns. The thickness of the metal coating is about 5 nanometers to about 1
Preferably it is microns. More specifically, the thickness of the metal coating can be from about 10 nanometers to about 500 nanometers.

Any metal suitable for physical vapor deposition or metal sputtering can be used for metal coating on the elastic film. Examples of such metals include, for example, aluminum,
Copper, tin, zinc, lead, nickel, iron, gold, silver and the like. Examples of suitable metal alloys include copper-based alloys (eg,
Bronze, monel, capro-nickel, aluminum bronze, etc., aluminum-based alloys (aluminum-silicon, aluminum-iron and their ternary metals, etc.), titanium-based alloys, iron-based alloys and the like. Useful metal alloys also include magnetic materials (e.g., nickel-iron and aluminum-nickel-iron) and corrosion and / or scratch resistant alloys.

FIGS. 2 to 5 are scanning electron micrographs of an example of the elastic metallized film according to the present invention. The elastic metallized films shown in FIGS. 2 to 5 are commercially available elastic films. Metal coating on the web was performed by conventional methods. Scanning electron micrographs were obtained directly from metal-coated films without the pre-treatments normally performed in scanning electron microscopy.

More specifically, FIG. 2 shows an elastic natural rubber film 88 coated with metallic aluminum.
It is a micrograph of 8 times. This sample was metallized in the non-stretched state, and the micrograph is also in the non-stretched state. FIG. 3 is a 888 × micrograph of a portion of the film shown in FIG. 2 taken while the film was stretched about 100%.

FIG. 4 is a 888 × photomicrograph of an elastic urethane film having a metallic aluminum coating. The elastic nonwoven web is coated in the non-stretched state, and the micrograph is when the elastic metallized film is in the non-stretched state. FIG. 5 is a 888 × photomicrograph of a portion of the film shown in FIG. 4 taken while elongating the film by about 100%.

FIGS. 6 to 8 are dislocation electron micrographs of an example of the elastic metallized film of the present invention. These dislocation electron micrographs were taken by operating a JEOL 1200EX dislocation electron microscope at 100 kV. Micrographs were made from extremely thin sections of the metal-coated sample.

FIG. 6 is a 7500-fold dislocation electron micrograph of a urethane film coated with aluminum. The aluminum coated urethane sample only partially dissolves in the epoxy bed used to cut the sample into very thin sections. FIG. 7 is a 30,000 × photomicrograph of a portion of the film shown in FIG. As can be seen from the cross sections of FIGS. 6 and 7, a dense continuous surface aluminum coating having a thickness of about 10 nanometers is visible. The urethane film itself has a thickness of about 100 to about 200 nanometers.

FIG. 8 is a dislocation electron micrograph of a natural rubber film coated with aluminum. This metallized natural rubber sample could only be roughly cut in the process of obtaining an extremely thin cross section. Obviously, there is a collapsed region consisting of a plurality of fine layers of metal.

[Experimental Example] [Experimental Example A] A sample of a natural rubber elastic film was
Aluminum metal was coated using conventional small-scale vacuum metallization. The elastic film had an average thickness (before coating) of about 4 mils and was formed into a sample measuring about 7 inches by 7 inches. This elastic film sample was obtained from NRC Corp. Was placed in an NRC-3176 laboratory vacuum metallizer commercially available from Sigma-Aldrich, Inc. The sample was taped to the side of the vacuum chamber of the instrument. The vacuum chamber containing this sample was sucked by a pump to about 10 ^-4 Torr (mm of mercury), a current was passed through the aluminum wire, and aluminum vapor was generated in the vacuum chamber. This aluminum vapor condensed on the surface of the sample, forming a metal coating. The amount of metal deposited on the sample (ie,
For the degree of deposition, a piece of a transparent film (eg, polyvinyl chloride) was placed on a viewing glass port of a vacuum chamber and the degree of deposition on the transparent film was observed. The device was turned off when the metal had sufficiently covered the transparent film and was no longer observable through the view glass port. Generally, by this metal deposition method,
The transparent film is covered with the metal in a relatively short time, that is, a few minutes. After turning over the sample, the above steps may be repeated to deposit metal on both sides of the sample. When the resilient metallized film is removed from the vacuum chamber, there is little or no metal flakes or shedding within the visible range. 2, 3 and 8 are micrographs of the elastic metallized film made according to Experimental Example A.

[Experimental example B] JPS Elastomer
ics Corporation "Thermopl
asic Polyurethane XPR-82
The procedure of Experimental Example A was repeated using a 1 mil thick elastic polyurethane commercially available under the trade name 4 "film. Samples of the elastic metallized film were examined using a scanning electron microscope and photographs were taken of the film when it was stretched and when it was not stretched. FIGS. 4, 5, 6, and 7 are micrographs of the elastic metallized film made according to Experimental Example B.

Although the present invention has been described with reference to the preferred embodiments, the present invention is not limited to these embodiments. On the contrary, the invention is intended to cover all alternatives, modifications, and equivalents.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a method for producing an elastic metallized film.

FIG. 2 is a micrograph showing the shape of a fiber in a non-stretched state of an elastic metallized film coated in a non-stretched state.

FIG. 3 is a photomicrograph when a part of the elastic metallized film shown in FIG. 2 is maintained in an extended state.

FIG. 4 is a micrograph showing the shape of a fiber in a state where an elastic metallized film is not stretched.

FIG. 5 is a photomicrograph when a part of the elastic metallized film shown in FIG. 4 is maintained in an extended state.

FIG. 6 is a micrograph showing a fiber shape in a cross section of an example of an elastic metallized film.

FIG. 7 is an enlarged micrograph of a part of the elastic metallized film shown in FIG.

FIG. 8 is a micrograph showing a fiber shape in a cross section of an elastic metallized film of another example.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 Manufacturing method 12 Vacuum chamber 14 Supply roll 16 Elastic film 18 S-shaped roll mechanism 20 Stack roller 22 Stack roller 24 Idle roller 26 Chill roll 28 Metal vapor 30 Molten metal tank 32 Elastic metallized film 34 Idler roller 36 Drive roller climate 38 Drive Roller 40 Drive roller 42 Winder

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C23C 14/34 C23C 14/34 (56) References JP-A-3-140156 (JP, A) JP-A-60-205831 (JP) JP-A-64-31961 (JP, A) JP-A-63-227762 (JP, A) JP-A-59-157275 (JP, A) JP-A-4-174777 (JP, A) 60-139877 (JP, A) JP-A-3-130393 (JP, A) JP-B-1-60410 (JP, B2) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 15/00 -15/20

Claims (21)

(57) [Claims] 1. A multilayer elastomeric metallized material having a mean thickness in the range of about 0.25 to about 30 mils.
An adhesive film, a metal coating covering at least a portion of at least one side of the pressure-sensitive elastomeric adhesive film, and an elastic non-woven web, and applying a tensile force to the multilayer elastic metallized material by about 30 to 10
When stretched by 0% or more,
Multi-layer elastic metallized material characterized in that the whole is retained
Fees . 2. The multilayer elastic metallized material according to claim 1, wherein said pressure-sensitive elastomeric adhesive film is a thermosetting film. 3. The multilayer elastic metallized material according to claim 1, wherein said pressure-sensitive elastomeric adhesive film is a thermoplastic film. 4. The multilayer elastic metallization of claim 1 wherein said pressure sensitive elastomeric adhesive film is a microporous film.
Material . 5. The multi- layered pressure-sensitive elastomer film according to claim 1, wherein the pressure-sensitive elastomer adhesive film is a film in which micropores are formed.
Layer elastic metallized material . 6. The pressure-sensitive elastomer adhesive film comprises an elastic polyester, an elastic polyurethane, an elastic polyamide, an elastic copolymer of ethylene and at least one vinyl monomer, and an elastic ABA ′ block copolymer (A and A ′ are The same or different thermoplastic polymers,
The multilayer elastic metallized material according to claim 1, wherein B is an elastomeric polymer selected from the group consisting of: 7. The multilayer elastic metallized material according to claim 6, wherein said elastomeric polymer is mixed with a processing accelerator. 8. The multilayer elastic metallized material according to claim 6, wherein said elastomeric polymer is mixed with a tacky resin. 9. The multilayer elastic metallized material according to claim 8, wherein said mixture further comprises a processing accelerator. Wherein said pressure sensitive elastomer adhesive film is a multilayer elastic metallization material of claim 1 having at least one comminuted other material embedded in at least one surface of the elastic film. 11. The finely ground material is wood pulp,
The multilayer elastic metallized material according to claim 10, wherein the material is selected from the group consisting of inelastic fibers, particles and mixtures thereof.
Fees . 12. The inelastic fiber is a polyester fiber, a polyamide fiber, a glass fiber, a polyolefin fiber, a cellulosic fiber, a multicomponent fiber, a natural fiber, an absorbent fiber, a conductive fiber, or two of these inelastic fibers. 12. The multilayer elastic metallized material according to claim 11, selected from the group consisting of a mixture of three or more. Wherein said particulate material is activated carbon, clays, starches, multilayered elastic metallized material according to claim 11 which is selected from the group consisting of metal oxides and superabsorbent material
Fees . 14. The multilayer elastic metallized material of claim 1, wherein said pressure sensitive elastomeric adhesive film has an average thickness in the range of about 0.8 to about 10 mils. 15. The multilayer elastic metallized material of claim 14, wherein said pressure sensitive elastomeric adhesive film has an average thickness in the range of about 1 to about 2 mils. 16. The metal coating is selected from the group consisting of aluminum, copper, tin, zinc, lead, nickel, iron, silver, copper based alloys, aluminum based alloys, titanium based alloys and iron based alloys. 1
Multilayer elastic metallized material . 17. The multilayer elastic metallized material according to claim 16, wherein said metal coating comprises a plurality of layers. 18. The multilayer elastic metallized material of claim 1, wherein said metal coating is between about 1 nanometer and about 5 microns thick. 19. The multi according to claim 18 metallic coating has a thickness of about 5 nanometers to about 1 micron
Layer elastic metallized material . 20. The metal coating according to claim 19, wherein said metal coating is between about 10 nanometers and about 500 nanometers thick.
A multilayer elastic metallized material according to claim 1 . 21. The multilayer elastic metallized material of claim 1, wherein the pressure sensitive elastomeric adhesive film retains substantially all of its metal coating when stretched from about 35 to about 75% .