JP4413412B2 - Inclined laminate - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a resin laminate. In particular, the present invention relates to an inclined laminate useful for pressure-sensitive adhesiveness, electrical conductivity, antifogging property, gas permeability and the like.
[0002]
[Prior art]
Conventionally, laminates have been widely used to produce laminates such as films and sheets by combining a plurality of resins in order to impart properties that cannot be obtained with a single resin, most of which are made of a plurality of resins. This is a form of laminating parallel to the thickness direction. These laminates are often used to obtain the intermediate properties of a plurality of resins, but are layers of layers spread in a direction perpendicular to the thickness, and the resin is a sheet in the thickness cross-sectional direction. In many cases, the film is laminated in a form that does not penetrate the front and back of the film, so that the functions are not fully utilized.
[0003]
For example, Japanese Patent Application Laid-Open No. 8-90700 discloses a film or sheet laminated in a unidirectional oblique line shape. Adhesiveness, conductivity, antifogging property, gas permeation by gradient lamination is disclosed. It is known that improvements in properties and mechanical properties can be measured.
However, the above-described unidirectional inclined lamination technique has problems such as low tear strength and bending strength, and a laminate having excellent performance cannot be obtained because a cross-sectional arrangement cannot be obtained.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a graded laminate that is excellent in a number of properties such as pressure-sensitive adhesiveness, electrical conductivity, antifogging property, and gas permeability, which has solved the conventional problems.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventor has made the present invention.
That is, the present invention is as follows.
1) Two or more kinds of resins are laminated in a V shape in one of the cross sections having an angle with respect to the surface.
2) An inclined laminate in which a bonding layer is disposed on at least one side of the inclined laminate of 1) above.
3) The inclined laminate according to 1) or 2), wherein at least one layer of the inclined laminate is made of a pressure-sensitive adhesive resin.
4) The inclined laminate according to 1) or 2) above, wherein at least one layer of the inclined laminate is made of a conductive resin.
5) The inclined laminate according to 1) or 2) above, wherein at least one layer of the inclined laminate is made of a resin having antifogging properties.
6) The inclined laminate according to 1) or 2) above, wherein at least one layer of the inclined laminate is made of a resin having gas permeability.
[0006]
The most different point of the present invention from the prior art is that the present invention has a substantially V-shaped laminated section, whereas the conventional technique is an inclined laminated section having a unidirectional oblique shape as shown in FIG. The role of the constituent elements of the present invention, which is different from the above-described prior art, is that it is excellent in tearing and bending strength, and further has many excellent performances as a laminate.
[0007]
The present invention will be specifically described below.
In the inclined laminate of the present invention, two or more kinds of resins are laminated in a V shape in one of the cross sections having an angle with respect to the surface. FIG. 1a shows a laminated body and a cross-sectional shape of an example of the present invention, and the cross-sectional shape of one cross section in FIG. 1c shows a V-shape. The V shape means a shape substantially similar to the letter V in the alphabet, and does not have to be exactly V itself. For example, V is horizontal, left-right asymmetrical, close to U, or low. There is no hindrance. FIG. 2c shows an example of an asymmetrical V shape. Compared to the conventional parallel laminated laminate, the conventional unidirectional oblique-shaped inclined laminated body can reflect the characteristics of each resin constituting the laminated body on the surface. Laminating the inclined laminated body in the V-shape is a solution to the first inferior to bending and tearing of the conventional unidirectional inclined laminated shape, and bending, peeling, tearing, etc. by making it into the V-shape In addition, the conventional unidirectional inclined shape is a solution to the problem that the position of the resin layer is shifted obliquely on the front and back surfaces of the laminate, and by making it V-shaped The positional deviation between the front surface and the back surface is almost eliminated, and as a result, the use area for applications utilizing the function is remarkably expanded. For example, when using a laminate that uses a conductive resin and has a conductive property from the front to the back, it can be used as an electrical resistor or battery separator. In order to maintain the uniformity of the current-carrying characteristics at the end faces of the battery separator, it may be required to match the positions of the conductive resins on the front and back of the laminate symmetrically. Thus, the laminated body excellent in performance is obtained by V shape.
[0008]
Any resin can be used as the resin used for the resin laminate of the present invention as long as it is a generally known thermoplastic resin. Usually, at least two resin layers are arranged and laminated according to the purpose of use of the laminate, but selection of the resin naturally selects resins having different properties according to the purpose of use.
In the present invention, the meaning that two or more kinds of resins are laminated generally means that, for example, a two-layered repetitive laminate of two kinds of resins is obtained, or a bonding layer between the resins is provided for three layers, For example, an inclined laminated body having four layers is repeatedly obtained. The number of layers to be repeated may be limited by the size of the die, but there is no limit on the total number of stacked layers in order to achieve the purpose with any number of layers.
[0009]
The resin laminate of the present invention provides a material suitable for many purposes using the properties of resins in different layers, such as a pressure-sensitive adhesive film, a conductive film, an antifogging film, Its function is utilized in applications such as gas permeable films.
[0010]
Known thermoplastic resins used in the present invention include, for example, polyethylene, polypropylene, polystyrene, vinyl chloride, vinylidene chloride, methacryl, polyethylene terephthalate, ethylene vinyl alcohol, ionomer, styrene acrylate, Styrene butadiene series, styrene acrylonitrile series, acrylate butadiene styrene series, polyamide series, polyacetal series, polycarbonate series, polyphenylene ether series, polybutylene phthalate series, polysulfone series, polyether sulfone series, polyphenylene sulfide series, polyarylate series, polyimide , Polyetheretherketone, liquid crystal polymer, fluororesin, syndiotack polystyrene, polymer alloy, thermoplastic elastomer, heat Resins such 塑 polyurethane systems. These resins are selected in consideration of mutual affinity according to the purpose of use. There is no problem even if some of these resins are crosslinked or uncrosslinked before or after lamination. These resins can be used alone or in combination. In addition, known additives such as heat stabilizers, antioxidants, ultraviolet absorbers, surfactants, microballoons, metal powders, and inorganic powders are blended in the resin within the range that gives the requirements and characteristics of the present invention. I can do it.
[0011]
The meaning of using a pressure-sensitive adhesive resin for at least one layer of the inclined laminate of the present invention is to a pressure-sensitive adhesive film having such a property that the film adheres to an adherend by applying pressure to the surface of the film. This is to obtain a V-shaped inclined laminated body that is preferably used. Since the adhesiveness is imparted to the laminate by disposing the pressure-sensitive adhesive resin in at least one layer, it can be used for an adhesive film, a pressure-sensitive adhesive film, or the like that covers a tray or a container. Adhesive performance can be adjusted by selecting resins, blending resins, or blending additives into the resin. In addition, it is possible to form unevenness on the surface of the laminate by selecting the viscosity of the resin. For example, by arranging an adhesive resin in the concave portion, the degree of adhesion can be adjusted by changing the shape of the unevenness. .
[0012]
The pressure-sensitive adhesive resin used in the resin laminate of the present invention is a resin having the property of a dry and sticky adhesive, such as a cellophane tape adhesive, and any known thermoplastic resin adhesive Can be used alone or in combination. For example, vinyl acetate, polyvinyl alcohol, polyvinyl acetal, vinyl chloride, acrylic, polyamide, polyethylene, cellulose, polyisobutylene, polyvinyl ether, chloroprene (neoprene), nitrile rubber, styrene rubber Type, polysulfide type, butyl rubber type, silicone rubber type adhesive and the like, and these are appropriately selected depending on the purpose and the lamination partner resin. Among these, a pressure sensitive adhesive type and a hot melt adhesive type are more preferable in view of ease of use.
[0013]
The meaning of using a conductive resin for at least one layer of the inclined laminate of the present invention is to obtain a V-shaped inclined laminate suitably used for a conductive film, a conductive container or the like. By providing a conductive resin in at least one layer, conductivity is imparted to the laminate, so that it can be used for precision electronic devices, semiconductor conductive packaging containers, conductive packaging films, and the like. In addition, the conductive performance can be adjusted by selecting a resin, blending resins, or blending an additive such as metal powder or carbon into the resin. In addition, unevenness can be formed on the surface of the laminate by selecting the viscosity of the resin, and the degree of conductivity can be adjusted.
[0014]
As the conductive resin used in the resin laminate of the present invention, any known resin can be used, and it can be used alone or in combination. Examples thereof include polyacetylene-based, polyarylene-based, polyarylene vinylene-based, polythiophene-based, polyisothianaphthene-based, polypyrrole-based, polyaniline-based, polyphenylene sulfide-based, polyacene-based, and polyperiphthalene-based resins. Moreover, generally well-known electroconductive filler can also be disperse | distributed to resin. Examples of the conductive filler include carbon black, graphite, carbon fiber, metal powder, metal fiber, metal flake, and metal plating inorganic substance.
[0015]
The meaning of using an antifogging resin for at least one layer of the inclined laminate of the present invention is to obtain a V-shaped inclined laminate suitably used for an antifogging film or the like. Since the anti-fogging property is imparted to the laminate by disposing the anti-fogging resin in at least one layer, it can be used for a wrapping film to be placed on a tray or a container. Further, the antifogging performance can be adjusted by selecting a hydrophilic resin, blending resins, or blending an additive such as a surfactant with the resin. In addition, unevenness can be formed on the surface of the laminate by selecting the viscosity of the resin, and the degree of anti-fogging can be adjusted.
[0016]
The antifogging resin used in the laminate of the resin of the present invention can be any known resin, and can be used alone or in combination. For example, the hydrophilic resin includes polyvinyl alcohol, polyacrylic acid, polyvinyl pyrrolidone and the like. The antifogging property is achieved by appropriately adding a known antifogging agent to the resin. Antifogging agents include polyethylene glycol monostearate, polyethylene glycol monolaurate, polyethylene glycol monooleate, polyoxyethylene lauryl ether, polyoxyethylene stearylamine, polyoxyethylene cocoamine, polyoxyethylene soyamine, polyoxyethylene Ethylene lauryl amide, polyoxyethylene cocoamide, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan trioleate, glycerin mono Oleate, sorbitan monolaurate, diglycerin monooleate, glycerin monopalmitate, pentaerythri Over monostearate, propylene glycol monooleate, sucrose monopalmitate, ethylene glycol monostearate, dipentaerythritol monolaurate, pentaerythritol monooleate, sorbitan monostearate, and the like. The addition amount can be appropriately selected according to the purpose and the type of resin.
[0017]
The meaning of using a gas permeable resin for at least one layer of the inclined laminate of the present invention is to obtain a V-shaped inclined laminate suitably used for packaging films such as fermentation and breathing foods, packaging containers and the like. is there. Gas permeability is imparted to the laminate by disposing a gas permeable resin in at least one layer, so that gases such as carbon dioxide, oxygen gas, nitrogen gas, and water vapor in cheese, lettuce, and fungi can be passed. It can be used for a ventilation packaging container and a ventilation packaging film. Further, the gas permeation performance can be adjusted by selecting the kind of the gas permeable resin, blending the resins, or blending the resin with additives such as microballoons and inorganic powders. In addition, unevenness can be formed on the surface of the laminate by selecting the viscosity of the resin, and the degree of gas permeation can be adjusted.
[0018]
The gas permeable resin used for the resin laminate of the present invention can be any known resin, and can be used alone or in combination. Examples include polyethylene, polypropylene, polystyrene, Teflon, polycarbonate, polyvinyl acetate, styrene acrylonitrile, polyvinyl fluoride, polyphenylene oxide, polybutadiene, polymethylpentene, and polydimethylsiloxane.
[0019]
The thickness of the inclined laminate of the present invention is determined depending on the purpose of use, but is preferably about 3 μm to 1 cm.
The meaning of arranging the bonding layer on at least one side of the inclined laminated body of the present invention is to laminate one or more other face materials on the V-shaped inclined laminated body, which is used for reinforcement and expression of optimum performance. Is done. One or more bonding layers may be arranged on one side, or may be arranged on both sides. The bonding layer is selected according to the purpose, and examples thereof include a plastic film, a plastic sheet, paper, a board, a corrugated cardboard, a metal plate, a fiber, a cloth fabric, a nonwoven fabric, and an adhesive. Any commonly known material can be used. A plastic film or a plastic sheet is more preferable because of ease of processing. Coating by casting or spraying is also possible. The thickness of the bonding layer varies depending on the purpose of use, but generally about 1 μm to 5 mm is used. It is more preferably about 5 μm to 1 mm.
[0020]
The lamination angle (φ ₁ , φ _{2 in} FIG. 2c) of the cross section perpendicular to the MD direction of the V-shaped resin laminate of the present invention (the cross section within the dotted line where θ is 0 ° in FIG. 2a) is It is particularly important to develop performance (bending strength, tensile strength and application characteristics). If the angle is less than 10 °, the distance between the layers becomes long, and the effect of inclined lamination may not be exhibited. The strength may be insufficient. More preferably, it is 10-80 degrees, More preferably, it is 20-70 degrees, More preferably, it is 30-60 degrees. In this case, 0 ° represents horizontal.
[0021]
An example of how to make the V-shaped resin laminate of the present invention will be described with reference to the spiral die cross-sectional view of FIG. Between the outer surface of the inner mandrel 42 and the inner surface of the outer die ring 41, which are in a cylindrical axial relationship with each other in FIG. 4a, a slit channel gradually increasing in thickness and a plurality of spiral grooves gradually decreasing in depth. Using the dies formed with the flow passages, the resins A and B having different properties are distributed and introduced into the plurality of spiral groove flow passages in a predetermined order, and the cylindrical flow is caused to move along the spiral flow passage grooves in the direction of the die axis. Form. In the cylindrical flow, the resin flow in the spiral groove and the resin flow in the upper spiral groove are alternately overlapped to form a cylindrical body of A and B resins as shown in the resin cross-sectional view of FIG. It is. A film-like or sheet-like laminate is obtained from the cylindrical body by a generally known inflation method. The partial perspective view of the laminate shown in FIG. 1a is obtained in this way, and the states of the surfaces 11, 12 in the vertical direction (thickness direction) with respect to MD (Machine Direction) and TD (Transverse Direction) and the state of the cross-sectional layer are observed. And the following. FIG. 1b is a cross-sectional view parallel to the MD, in which the A and B resin layers are parallel. On the other hand, FIG. 1c is a cross-sectional view of the portion indicated by the dotted line in FIG. 1a. In particular, the stacking angle φ represents the stacking angle of the cross section perpendicular to the MD direction (the cross section within the dotted line where θ is 0 ° in FIG. 1a). . In this way, a horizontal V-shaped laminate in which the cross sections referred to in the present invention are alternating A and B resin layers is obtained. The V-shaped tips 13, 23, 33 of FIGS. 1, 2, and 3 may be acute, obtuse, or arcuate, or may be offset from the center or the center of the thickness cross section. FIG. 2 is an example of the present invention when the V-shaped tip 23 is located below the center of the thickness cross section, and φ ₁ and φ _{2 in} FIG. 2c are cross sections perpendicular to the MD direction of the upper and lower parts (FIG. 2a). Represents a stacking angle of a cross section within a dotted line in which θ is 0 °. This stacking angle is important for the properties of the stack. FIG. 3 is an example in which bonding layers are arranged on both surfaces of the inclined laminate of the present invention.
[0022]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below with reference to examples and comparative examples.
[0023]
【Example】
Using a spiral die having a structure as shown in FIG. 4, A is a styrene rubber-based adhesive resin (product name: Tuftec H1051 manufactured by Asahi Kasei Kogyo Co., Ltd.) as a pressure-sensitive adhesive resin and a petroleum resin having a molecular weight of about 1000. 1% by weight blended, B is styrene resin (Asahi Kasei Kogyo Co., Ltd., product name: Asaflex 810), melt-extruded at 190 ° C. and heated and stretched by the inflation method as shown in FIG. A V-shaped laminated sheet of the present invention having a thickness of 0.2 mm, a width of 1 m, and a length of 30 m was obtained. The lamination angle φ of the sheet was 30 ° as measured from the MD cross section, and the thicknesses of the A layer and the B layer were about 1 mm to 2 mm. As a result of measuring this sheet to a size of 10 cm in width and 20 cm in length and performing a sensory test, the pressure-sensitive adhesiveness was sufficiently confirmed, the bending strength and the tensile strength were sufficiently excellent, There was no destruction at all.
[0024]
[Comparative example]
The same resin as in the above embodiment, except that a conventional spiral die as shown in FIG. 4 of JP-A-8-90700 is used, is performed in the same manner as in the embodiment, and is unidirectional as shown in FIG. An inclined laminated sheet was obtained. The sheet stacking angle φ was 30 ° as measured from the MD cross section, the sheet was 0.2 mm thick, 1 m wide, and 30 m long, and the thicknesses of the A and B layers were approximately 1 mm vs. 2 mm. As a result of measuring this sheet in the same manner as in the example and inspecting it in the same manner, the pressure-sensitive adhesiveness was the same, but the bending strength and tensile strength were problematic in practice, and the misalignment and destruction of the laminated surface were confirmed by microscopic inspection. It was found that there was a problem in performance.
[0025]
【The invention's effect】
The V-shaped inclined laminated body of the present invention has improved tear strength and bending strength, and further reduces the positional deviation of the resin layer on the front and back sides, so that the laminated body for pressure-sensitive adhesion, electrical conductivity, anti-fogging, gas permeation, etc. It is suitable as.
[Brief description of the drawings]
FIG. 1 shows an example of a schematic diagram of a substantially symmetric V-shape of a laminate of the present invention, in which a is a perspective view of the laminate, b is a sectional view in the MD direction, and c is a sectional view of a dotted frame.
FIG. 2 shows an example of a schematic diagram of a substantially asymmetric V-shape of a laminate of the present invention, in which a is a perspective view of the laminate, b is a sectional view in the MD direction, and c is a sectional view of a dotted frame portion.
FIG. 3 shows an example of a schematic diagram in which a resin or the like is arranged on the surface of a substantially asymmetric V-shaped laminate of the present invention, where a is a perspective view of the laminate, b is a sectional view in the MD direction, and c is Sectional drawing of a dotted-line frame part.
4A and 4B show an example of a schematic view of a method for producing a laminate of the present invention, in which a is a cross-sectional view of a spiral die and b is a cross-sectional view of a laminated state of resin extruded from an outlet 13 of the die.
FIGS. 5A and 5B show an example of a schematic diagram of a laminated body according to the prior art, in which a is a perspective view of the laminated body, b is a sectional view in the MD (extrusion) direction, and c is a sectional view of a dotted frame portion.
[Explanation of symbols]
11, 12 Surfaces 21 and 22 of the laminated body Surfaces 31 and 32 of the laminated body Surfaces 51 and 52 of the laminated body 13, 23 and 33 Surfaces of the laminated body 40 Spiral manifold 41 Outer die ring 42 Inner mandrel 43 Dice exit A Inclined laminated constituent resin B Inclined laminated constituent resin C Laminated constituent resin other than inclined laminated resin D Laminated constituent resin other than inclined laminated θ The TD direction on the laminate surface and FIGS. 1c, 2c, 3c, Lamination angle at the cross section perpendicular to the MD direction in the angle φ, φ ₁ , φ ₂ MD formed by the cross section 5c (the cross section within the dotted line where θ in FIGS. 1a, 2a, 3a, 5a is 0 °)

Claims (6)

An inclined laminate, wherein two or more kinds of resins are laminated in a V shape in one of the cross sections having an angle with respect to the surface. An inclined laminate comprising a bonding layer disposed on at least one surface of the inclined laminate of claim 1. The inclined laminate according to claim 1 or 2, wherein at least one layer of the inclined laminate comprises a pressure-sensitive adhesive resin. The inclined laminated body according to claim 1 or 2, wherein at least one layer of the inclined laminated body is made of a conductive resin. The inclined laminate according to claim 1 or 2, wherein at least one layer of the inclined laminate is made of a resin having antifogging properties. The inclined laminate according to claim 1 or 2, wherein at least one layer of the inclined laminate is made of a resin having gas permeability.

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