JP2000297257A - Multi-layered adhesive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a multi-layered adhesive film which comprises halogen-free resins, can readily be adhered by a simple adhering work even in home, can easily be moved also after adhered, can easily be peeled, and does not cause the staining of a substrate with the residual portion of the adhesive, when peeled. SOLUTION: This multi-layered adhesive film comprises a thermoplastic resin layer, an adhesive layer and a peeling layer, has a smoothness degree of 0.3 to 2 on the adhesive side of the adhesive layer and a flexibility (flexural rigidity) of 100 to 5,000 kg/cm2, and is obtained by melt-extruding a halogen-free olefinic polymer such as EVA in a sandwich-like laminate form between a peeling OPP film and a thermoplastic resin film, such as a PET film, preliminarily coated with a dew condensation-preventing agent, and the like, to impart various functions to the film. When the multi-layered adhesive film is used, the peeling layer is peeled, and the adhesive layer is adhered to window glass, or the like, through a lubricant such as water, thereby enabling the exhibition of the functions such as the dew condensation-preventing function.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a multilayer adhesive film having an adhesive layer. More specifically, the present invention relates to a multi-layer pressure-sensitive adhesive film used for attaching a function such as dew condensation prevention to a window glass or the like.

[0002]

2. Description of the Related Art Conventionally, durability, heat insulating properties, anti-fog properties, UV cut properties,
As a method of imparting anti-condensation properties and the like, an adhesive film or sheet having such various functions (hereinafter, simply referred to as an adhesive film) is adhered to the surface thereof.

[0003] Such an adhesive film is usually provided with a coating film such as an anti-fogging agent or an anti-condensation agent on the side opposite to the adhesive side of the substrate made of a synthetic resin film, and the adhesive surface is provided with an adhesive. One provided with a layer is used.

As a method of sticking the pressure-sensitive adhesive film to the substrate, a method of directly sticking to a substrate such as glass with a pressure-sensitive adhesive layer into which a strong pressure-sensitive adhesive is kneaded can be mentioned, but the pressure-sensitive adhesive remains on the substrate after peeling. And may become dirty. Also,
In this form, the adhesive force is too strong, and it is not easy to perform the sticking work at home or the like. Therefore, as a method of sticking, a method of applying water to the sticking side or the sticking side of the base material and bringing them into close contact with each other via water has been adopted.

However, the conventional pressure-sensitive adhesive layer has
When water evaporates, it is difficult to peel off, and the position cannot be freely shifted even if an attempt is made to correct the position after sticking, so that work at home or the like is still not easy. Further, the problem that the pressure-sensitive adhesive remains on the substrate when peeled off is not solved.

In the field of films, films having various functions such as anti-fogging property, durability and dew condensation prevention property have been used as, for example, agricultural soft resin films. It is made of vinyl resin. However, in recent years, there has been an increasing interest in environmental issues, and we would like to develop a film using a resin that has the same flexibility and smoothness as conventional vinyl chloride resins and does not contain halogen such as chlorine. There is a tendency.

Therefore, the adhesive film is an adhesive film made of a halogen-free resin, which is easy to attach and can be easily attached at home, and the position can be easily moved even after attaching. In addition, there has been a demand for the development of a material which does not stain the substrate due to the residual adhesive at the time of peeling.

[0008]

DISCLOSURE OF THE INVENTION The present invention is made of a halogen-free resin, is easy to stick, can be easily stuck at home, can be easily moved after sticking, and can be peeled off. It is an object of the present invention to provide a pressure-sensitive adhesive film which is easy to remove and does not stain the substrate due to the residual pressure-sensitive adhesive at the time of peeling.

[0009]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that by laminating a synthetic resin film having a specific smoothness and softness on the bonding surface of a base film,
The inventors have found that the above problems can be solved, and have completed the present invention.

That is, the present invention relates to a multilayer adhesive film comprising at least a thermoplastic resin layer and an adhesive layer, wherein the adhesive layer is adhered to a substrate surface to form a film layer. A multilayer pressure-sensitive adhesive film comprising a halogen-free polymer and satisfying the following (1) and (2): (1) The smoothness of the side of the pressure-sensitive adhesive layer that adheres to the substrate surface is 0.3 to 2 as measured using a surface roughness meter. (2) The bending stiffness measured according to JIS-K7106 is 100 to 5000 kg / cm ² .

In the present invention, the olefin-based halogen-free polymer may be an ethylene-vinyl acetate copolymer, a low density polyethylene, an ethylene-ethyl acrylate copolymer, an ethylene-methacrylate copolymer, or an ethylene-methyl methacrylate. Copolymer and low crystalline ethylene
The multilayer pressure-sensitive adhesive film is provided, which is selected from the group consisting of α-olefin copolymers.

Further, the present invention provides the multilayer pressure-sensitive adhesive film, wherein a peelable release layer is provided on the surface of the pressure-sensitive adhesive layer. Further, the present invention provides the multilayer adhesive film, wherein the substrate is a glass plate. Further, the present invention is characterized in that a lubricant is present between the multilayer pressure-sensitive adhesive film and the substrate, and the film is formed by adhering to the substrate surface via the lubricant.
The multilayer adhesive film is provided.

Further, the present invention provides the above-mentioned thermoplastic resin layer,
The multilayer adhesive film is characterized by being constituted by polyethylene terephthalate. The present invention also provides the multilayer pressure-sensitive adhesive film, wherein a function-imparting layer is provided on the surface of the thermoplastic resin layer opposite to the side on which the pressure-sensitive adhesive layer is provided. The present invention also provides the multilayer pressure-sensitive adhesive film, wherein the function-imparting layer is a layer that imparts a dew-prevention function.

The present invention also provides a multilayer film comprising a thermoplastic resin layer, an adhesive layer, and a release layer laminated in this order, wherein the multilayer adhesive film is adhered to a substrate surface to form a film layer. In the manufacturing method, between a thermoplastic resin film forming a thermoplastic resin layer and a release film forming a release layer, the olefinic halogen-free polymer forming an adhesive layer is melt-extruded and sandwich-laminated, A method for producing a multilayer pressure-sensitive adhesive film is provided, which comprises a step of forming a pressure-sensitive adhesive layer satisfying the following (1) and (2). (1) The smoothness of the side of the pressure-sensitive adhesive layer that adheres to the substrate surface is 0.3 to 2 as measured using a surface roughness meter. (2) The bending stiffness measured according to JIS-K7106 is 100 to 5000 kg / cm ² .

[0015]

Embodiments of the present invention will be described below. The multilayer pressure-sensitive adhesive film of the present invention is a multilayer structure including at least a thermoplastic resin layer and a pressure-sensitive adhesive layer.

(1) Thermoplastic resin layer The thermoplastic resin layer in the multilayer pressure-sensitive adhesive film of the present invention comprises:
It corresponds to the substrate of the film. In general, the thermoplastic resin film forming the thermoplastic resin layer preferably has a certain degree of weather resistance, but various films can be used depending on the application. For example, a transparent plastic film is usually used, but it is not necessarily required to be transparent depending on the application. Usually, a material having a certain degree of rigidity is used.
One having a weight of about 00 kg / mm ² is used.

Specific examples of such a thermoplastic resin film include polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) film, polypropylene film, polyamide resin film such as nylon-6, nylon-66, polystyrene film, and 4-methyl Penten-1 film, polyacrylonitrile (P
AN) Film, polycarbonate film, polyacrylate film, polymethacrylate film, polyimide film, acetate film, biodegradable resin such as polylactic acid, polybutylene succinate (PBS) and the like. These may be any of a non-stretched film and a stretched film. Among them, polyethylene terephthalate is particularly preferable in the case of a film for preventing dew condensation on a window glass.

The thickness of the thermoplastic resin layer varies depending on the type of the thermoplastic resin and the application of the multilayer adhesive film, but is usually in the range of 0.005 to 0.2 mm, preferably 0.01 to 0.1 mm. In range. If the thickness is less than the above range, the workability when forming a film layer on the substrate surface tends to decrease, so that it is not preferable. If the thickness exceeds the above range, the film holding property on the substrate surface tends to decrease, which is not preferable. .

(2) Adhesive Layer The adhesive layer in the multi-layer adhesive film of the present invention is composed of a resin film having an adhesive property by itself, and is adhered to the surface of a substrate (an object on which the adhesive film is to be attached) by the adhesive property. Can be pasted.

The pressure-sensitive adhesive layer of the multilayer pressure-sensitive adhesive film of the present invention is constituted by a film made of an olefin-based halogen-free resin. The use of an olefin-based resin containing a halogen, such as a polyvinyl chloride resin, may cause stains on the peeled surface due to the effect of the compounded plasticizer or the like, and is not preferable in terms of environmental problems.

Further, the adhesive layer has a smoothness of 0.3 to 2 on the side which adheres to the surface of the substrate.
The smoothness (Rz) mentioned here is measured from a roughness curve in the direction of its center line using a surface roughness meter (lm = 4.
0 mm) and each of the five standard lengths (le =
The difference between the maximum value (peak) and the minimum value (valley) at every 0.8 mm) is defined as Z _i (μm), and Rz is calculated using the following equation (I).
(Μm). FIG. 1 shows an example of a roughness curve for obtaining smoothness.

[0022]

(Equation 1)

In the present invention, by providing the pressure-sensitive adhesive layer having the specific smoothness, the adhesion to the substrate surface is maintained at an appropriate level without being too strong or too low, and the workability of sticking to the substrate is improved. Although it is not easily peeled off after further pasting, if it is to be peeled off, it can be easily peeled off. When the smoothness is less than the above range, when the film is wound into a roll or cut and stacked, the thermoplastic resin layer and the adhesive layer cause blocking and deteriorate the appearance, or are bonded to a substrate. This is not preferable because the workability of the method is extremely reduced. On the other hand, if the smoothness exceeds the above range, the adhesiveness to a sticking surface such as a window glass is low, and it is easy to peel off, which is not preferable. A preferred range of the smoothness is 0.5 to 1.5, and a more preferred range is 0.5 to 1.3. The smoothness (R
z) represents the smoothness on the side of the adhesive layer that adheres to the substrate (adhesive side), and the larger the value of the degree of smoothness, the greater the surface roughness.

Further, the pressure-sensitive adhesive layer is made of JIS-K71
Bending stiffness measured according to 06 is 100 to 5000
kg / cm ² . This bending stiffness is a measure of the softness (softness) of the film. In the present invention, when the pressure-sensitive adhesive layer has the above-mentioned smoothness and a specific softness, the workability of sticking to a substrate is good, and the film is further stuck. After that, it is not easily peeled, but if it is to be peeled, it can be easily peeled. If the softness (flexural stiffness) is less than the above range, the adhesiveness to the sticking surface of the window glass or the like becomes too strong, so that it is difficult to peel off from the substrate when trying to peel off, or to take up a roll. Cutting and stacking are not preferred because the thermoplastic resin layer and the adhesive layer cause blocking and deteriorate the appearance. On the other hand, if the softness exceeds the above range, the adhesiveness to the surface to be adhered to a substrate such as a window glass is low, and it is not easy to peel off. The preferred range of softness (flexural stiffness) is 150 to 3500 kg
/ Cm ² , and a more preferred range is 200 to 2000.
kg / cm ² .

Specific examples of the olefin-based halogen-free resin satisfying both the smoothness and the softness at the same time include ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), and ethylene methacryl. Acid copolymers (EMA), ethylene-methyl methacrylate copolymers (EMMA), low-density polyethylene, elastomers, plastomers, low-crystalline ethylene / α-olefin copolymers and the like can be mentioned.

Of these, particularly preferred are ethylene-vinyl acetate copolymers and ethylene- (meth) acrylate copolymers. Further, ethylene-vinyl acetate copolymers having an ethylene content of 70 to 95% by weight or ethylene- ( Meth) acrylate copolymers are preferred because more appropriate softness can be obtained.

Further, among the low-density polyethylenes, low-density polyethylenes produced with a metallocene catalyst are also preferably used. The low-density polyethylene produced with such a metallocene-based catalyst means that the preferred ethylene content is 70 to
It is a 99% by weight ethylene / α-olefin copolymer. The α-olefin which is a copolymer component preferably has 4 to 10 carbon atoms, more preferably butene-1, hexene-
1, octene-1 and the like. Density is preferably 0.870~0.920g / cm ^3.

MF of the olefin-based halogen-free resin
R (melt flow rate) is not particularly limited, but is preferably 1 to 300 g / 10 min, more preferably 3 to 7 g / min.
0 g / 10 minutes. If the MFR is less than the above range, the extensibility at the time of film processing is low, which is not preferable from the viewpoint of thin-wall workability.

The thickness of the pressure-sensitive adhesive layer varies depending on the use of the multilayer pressure-sensitive adhesive film, but is usually in the range of 0.005 to 0.1 mm, preferably in the range of 0.01 to 0.05 mm. If the thickness is less than the above range, it is not preferable from the viewpoint of smoothness, and if it exceeds the above range, it is not preferable from the viewpoint of adhesion to the substrate. The adhesive strength between the adhesive layer and the thermoplastic resin layer is preferably high to some extent.

(3) Multi-layered pressure-sensitive adhesive film release layer The multi-layered pressure-sensitive adhesive film of the present invention is not particularly limited as long as it contains the thermoplastic resin layer and the pressure-sensitive adhesive layer. be able to.

For example, a peelable release layer can be provided on the surface of the adhesive layer. The release layer has a function of protecting the adhesive surface of the adhesive layer during storage and transportation. Then, at the time of sticking work to the substrate, the peeling layer can be peeled off from the adhesive layer to expose the adhesive surface and stick.

The material constituting the release layer is preferably a biaxially oriented polypropylene film (OPP),
Polypropylene unstretched film, PET stretched film,
A plastic film such as a biaxially stretched nylon film can be used, and OPP is particularly preferable. According to the combination of the pressure-sensitive adhesive layer having smoothness and softness and the release layer made of OPP of the present invention, the release layer can be easily and smoothly released.

The thickness of the release layer is usually in the range of 0.005 to 0.2 mm, preferably 0.01 to 0.05 mm in the case of the above-mentioned plastic film. When the thickness is less than the above range, the peeling workability from the pressure-sensitive adhesive layer is unfavorably deteriorated, and when the thickness exceeds the above range, the peeling workability with the pressure-sensitive adhesive layer is similarly unfavorable, and it is not preferable in terms of economy. As the release layer, in addition to the above-mentioned plastic film, a release film in which a silicone coat layer or the like is provided on the surface of the plastic film can be used. Furthermore, paper / polyethylene /
A release paper having a configuration such as a silicone coat layer can be used as the release layer.

Substrate The substrate on which the multilayer pressure-sensitive adhesive film of the present invention is to be adhered is not particularly limited as long as it has a smooth surface that can be adhered by the above-mentioned pressure-sensitive adhesive layer. Examples include wood, concrete, brick, marble, decorative plywood, and the like. Among them, when the substrate is glass, particularly window glass or a mirror of a house or a vehicle, the effect of the present invention is well exhibited.

Lubricant The multilayer pressure-sensitive adhesive film of the present invention is a resin in which the pressure-sensitive adhesive layer itself has a moderate level of tackiness, compared to a film obtained by simply using a low-molecular-weight pressure-sensitive adhesive or by simply kneading the pressure-sensitive adhesive into the pressure-sensitive adhesive layer. Therefore, even when the adhesive is peeled after being attached to the substrate, the adhesive is not so strong that the peeling becomes difficult and the adhesive does not remain on the substrate. As a preferable method of attaching such a multi-layered pressure-sensitive adhesive film, there is a method in which a lubricant is present between the multi-layered pressure-sensitive adhesive film and the substrate, and the film is formed by adhering to the surface of the substrate through the lubricant. The lubricant is not particularly limited as long as it is a liquid that can be easily evaporated after the film is attached, but preferably includes water or an aqueous solution containing a surfactant or the like, and particularly preferably water.

By applying such a lubricant to the adhesive surface of the multilayer adhesive film or the surface of the substrate in advance, the sticking operation becomes easy, and the sticking can be performed uniformly at home without wrinkling. The degree of adhesion of the film to the substrate is increased. Note that the multi-layered pressure-sensitive adhesive film having a pressure-sensitive adhesive layer of the present invention does not have too high a pressure-sensitive adhesive property to the substrate, so that a moving operation such as shifting the position of the film during the sticking operation can be easily performed. On the other hand, if the lubricant evaporates after the sticking operation,
The multilayer pressure-sensitive adhesive film is uniformly adhered to the substrate and maintains a moderately strong pressure-sensitive adhesive property. Therefore, when the film is to be peeled off, it is easily peeled off, but does not come off spontaneously even when left. Moreover, the peeled multilayer film can be adhered again to the same substrate or another substrate, and can be reused any number of times.

Function-Imparting Layer The multilayer pressure-sensitive adhesive film of the present invention has various functions given to the film, and is attached to a substrate to provide a film layer having the various functions on the substrate. It is often used for the purpose of providing such a function. In such a case, the above-mentioned various function-imparting layers can be provided on the surface of the multilayer adhesive film of the present invention on the surface of the thermoplastic resin layer opposite to the side on which the adhesive layer is provided.

For example, when the multilayer pressure-sensitive adhesive film of the present invention is used for imparting dew condensation preventing properties to a substrate, a layer imparting a dew condensation preventing function (a dew condensation preventing function imparting layer) can be provided as the function imparting layer. . The dew condensation preventing function imparting layer may be, for example, a coating layer containing various conventionally known dew condensation preventing agents. In addition, for example, Japanese Patent No. 26245
A thermally transparent plastic layer using a heat insulating method based on the principle of forming a thermal gradient from a low-temperature surface to a high-temperature surface and preventing heat transfer as described in Japanese Patent No. 75 The application layer can be formed on a thermoplastic resin layer.

That is, Japanese Patent No. 2624575 discloses that a heat conductive layer having a heat capacity and a radiant heat absorption smaller than a heat capacity and a radiant heat absorption of a substrate such as a window glass is adhered to the substrate. A method for preventing the occurrence of dew condensation by increasing the heat insulating property of the entire composite comprising the substrate and the heat conductive layer is described. Such a heat conductive layer comprises the function-imparting layer of the present invention and a thermoplastic resin. It corresponds to the whole multilayer adhesive film including the layer and the adhesive layer. Therefore, in the present invention, the heat capacity and radiant heat absorption of the substrate to be adhered are determined, and the material of the function-imparting layer is selected so that the heat capacity and radiant heat absorption of the entire multilayer adhesive film become smaller than that. Thus, by forming a layer on the thermoplastic resin layer, a multilayer pressure-sensitive adhesive film having a dew condensation preventing function can be obtained. That is, the plastic material that can be used for the function (condensation prevention function) -imparting layer of the present invention can be relatively determined based on the relationship between the heat capacity of the substrate to be attached and the radiation heat absorption. It also depends on the heat capacity and radiation heat absorption of the resin material used for the thermoplastic resin layer and the adhesive layer.

Incidentally, regarding the dew condensation preventing functional layer,
As described above, the relationship that the heat volume and the radiant heat absorption on the high-temperature zone side (the heat conductive layer) are smaller than those on the low-temperature zone side (substrate) may be satisfied.
The thermally transparent layer on the hottest zone side, that is, the dew condensation preventing functional layer forming the hottest zone side surface, has a heat capacity of 10% or less, preferably, 10% or less of the heat volume of the substrate forming the coldest zone side surface on the coldest zone side. It is desirable to have a configuration that has a heat volume of 5% or less and a radiant heat absorption of 60% or less, preferably 50% or less of the radiant heat absorption of the substrate.

As a material capable of providing a heat conductive layer having a smaller heat capacity and radiant heat absorption than a substrate, Japanese Patent No.
Various plastic materials are exemplified in Japanese Patent No. 4575. For example, in the case of radiation where the temperature of the heat source is 200 ° C. or less and the dominant wavelength is about 6 μm or less, the wavelength 4
Thermally transparent plastics showing small absorption in the region of μm or less, such as polyethylene, polypropylene, polyisobutylene, polystyrene, polyvinyl acetate, ethylene / vinyl acetate copolymer, polyvinyl alcohol, polyacrylonitrile, polyvinyl pyrrolidone, and polyacryl Acid, polymethyl methacrylate, methyl methacrylate
Examples include styrene copolymer, polybutyl methacrylate, silicon resin, butadiene rubber, butyl rubber, chloroprene rubber, and the like, and mixtures thereof.

When the temperature of the heat source is about 57
For radiation having a dominant wavelength of about 0.5 μm at a high temperature of 27 ° C., thermally transparent plastics exhibiting small absorption in the wavelength range of 0.3 to 2.5 μm, for example, polystyrene,
Polyvinyl acetate, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, cellulose acetate, diallyl phthalate resin, urea resin, melamine resin, polyvinyl butyral, ethylene / α-olefin copolymer, ethylene / vinyl acetate copolymer, polymethylpentene, Polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylpyrrolidone, polymethyl methacrylate, methyl methacrylate / styrene copolymer, polybutyl methacrylate, nylon 66, epoxy resin, silicon resin, butadiene / styrene resin, polysulfone, polyfluoro Examples include vinylidene fluoride, MBS resin, polybutadiene, polyether sulfone, and the like, and mixtures thereof.

The plastic material which can be used for the dew condensation preventing function-imparting layer of the present invention is preferably a (meth) acrylic acid when the thermoplastic resin layer is a polyethylene terephthalate layer and the adhesive resin layer is an ethylene / vinyl acetate copolymer layer. (Co) polymers containing methyl as a polymerization component, such as polymethyl acrylate, polymethyl methacrylate, ethyl acrylate / methyl methacrylate copolymer, methyl acrylate
Styrene copolymers, methyl methacrylate / styrene copolymers, methyl acrylate / methyl methacrylate / styrene copolymers, etc., are preferred.
Methyl acrylate / methyl methacrylate containing about 0%
Styrene copolymers are exemplified. At this time, the thickness of the dew condensation preventing function-imparting layer is preferably 1 to 10 μm, more preferably 2 to 3 μm.

The method for forming the dew condensation preventing function-imparting layer is not particularly limited, but a method in which a plastic material is dissolved in an appropriate solvent, coated on the thermoplastic resin layer, and dried and solidified, or a dew condensation formed in a film or sheet in advance. Examples of the method include laminating the prevention function-imparting layer on the thermoplastic resin layer by heat fusion or adhesion, extrusion lamination, co-extrusion lamination, and the like.

The present invention is particularly effective when a dew condensation preventing film having such a dew condensation preventing function can be attached to a window glass or the like. It is not limited to film.

For example, the function-imparting layer may be a coating layer containing an antifogging agent. Such an anti-fog layer,
Applying a water-soluble polymer such as polyvinyl alcohol, a hydrophilic polymer mainly containing hydroxyalkyl acrylate, or a composition comprising such a polymer and a surfactant to the surface of the thermoplastic resin layer, hydrophilic acrylic An inorganic sol or a mixture of an inorganic aqueous sol and a surfactant is applied to form a cured film of an acid ester polymer, and an organic / inorganic composite of silica / hydrophilic polymer / organosilicon compound is applied. , Etc. can be formed.

In addition, the function-imparting layer may be a layer having durability, heat insulating property, ultraviolet ray cutting property, and the like. For example, the surface of the thermoplastic resin layer may be coated with a UV absorber in order to impart an ultraviolet cut property (UV cut function). Also, a coating layer containing an insect repellent may be provided as a function imparting layer to provide an adhesive film having an insect repellent effect at night.

Further, a light beam cutting function may be provided on the surface of the thermoplastic resin layer. For example, by using a film having a matte surface as a thermoplastic resin layer (such as a PET film), a light-cutting function can be imparted, or a matte film can be laminated on the surface of the thermoplastic resin layer, Alternatively, a light-cutting functional layer can be provided by performing printing, vapor deposition, or the like on the surface of the thermoplastic resin layer. In addition, a function of a display effect can be provided by printing or the like on the surface of the thermoplastic resin layer or by laminating a film on which printing or the like has been performed.

In a particularly preferred embodiment of the multilayer pressure-sensitive adhesive film of the present invention, a function-imparting layer / thermoplastic resin layer / adhesive layer /
It has a layer structure of a release layer, and more specifically, a dew condensation preventing agent coating layer (function imparting layer) / PET
A multilayer adhesive film having a structure of film (thermoplastic resin layer) / EVA film (adhesive layer) / OPP film (peeling layer) can be given.

Various additives such as known antioxidants, heat stabilizers, lubricants, antiblocking agents, antistatic agents, coloring agents, and ultraviolet absorbers are added to the thermoplastic resin layer, the adhesive layer and the release layer. Agent, if necessary, in an amount that does not significantly reduce the adhesive strength between the thermoplastic resin layer and the adhesive layer, or in an amount that does not significantly impair the releasability of the adhesive layer and the release layer. Can be. The amount of the additive is usually 0.1.
005 to 3% by weight.

(4) Method for Producing Multi-layer Adhesive Film The method for producing a multi-layer adhesive film of the present invention comprises laminating a thermoplastic resin forming a thermoplastic resin layer and an olefin-based halogen-free polymer forming an adhesive layer. The method is not particularly limited as long as the method includes a step of performing lamination, and various lamination molding methods can be adopted. For example, extrusion lamination, dry lamination, sandwich lamination,
A method of forming and laminating each layer by a co-extrusion method (including co-extrusion without an adhesive layer, co-extrusion with an adhesive layer, and co-extrusion with an adhesive resin) is included. Further, at the time of such molding, it is also possible to previously coat an anchor coat agent on the film surface, or to perform a surface treatment such as a corona discharge treatment, a flame treatment, and an ozone treatment.

As described above, the method for producing the multilayer pressure-sensitive adhesive film of the present invention is not particularly limited as long as it includes the step of laminating the thermoplastic resin layer and the pressure-sensitive adhesive layer. In the case of a film formed by laminating a pressure-sensitive adhesive layer and a release layer in this order, a thermoplastic resin film that forms a thermoplastic resin layer, and a release film that forms a release layer, an adhesive layer is formed. It is preferable to use a method in which an olefin-based halogen-free polymer is melt-extruded and sandwich-laminated.

More specifically, PET is used as the thermoplastic resin layer.
When an OPP film is used as a release layer using a film, it is preferable to use a method in which an olefin-based halogen-free polymer such as EVA is melt-extruded between a pre-formed PET film and an OPP film and sandwich-extruded and laminated. .

In this case, on the surface of the thermoplastic resin film, a function-imparting layer is provided in advance by, for example, coating an anti-condensation agent, and further coated with an anchor coat agent, corona discharge treatment, flame treatment, ozone It is preferable to use a material that has been subjected to a surface treatment such as a treatment for lamination.

By using such sandwich extrusion lamination molding, while the thermoplastic resin layer and the adhesive layer are firmly adhered to each other, the smoothness of the surface of the adhesive layer that adheres to the substrate (adhesive side) is improved. Can be kept high. In addition, the blocking phenomenon does not occur, and the productivity is high and the economy is excellent. Conversely, when an OPP film is laminated after extrusion-laminating an olefin-based halogen-free polymer onto a thermoplastic resin film, for example, the smoothness may be impaired because the adhesive side of the adhesive layer contacts the roll. In addition, when the thermoplastic resin film, the olefin-based halogen-free polymer film, and the release film each formed in advance are laminated, a blocking phenomenon may occur between the films, which may make molding difficult.

The molding conditions of the sandwich extrusion laminate are not particularly limited, and conventionally known conditions can be appropriately employed. Preferably, the resin temperature of the olefin-based halogen-free polymer is 150 to 320 ° C., and the laminating speed is 30.
About 200 m / min.

(5) Use The multilayer pressure-sensitive adhesive film of the present invention thus obtained is
Particularly effective when the anti-condensation film provided with a coating layer containing an anti-condensation agent as a function imparting layer on the surface of the thermoplastic resin layer, the multilayer pressure-sensitive adhesive film of the present invention is particularly effective in such an anti-condensation film. It is not limited, and can be used as an anti-fog film, an ultraviolet cut film, an insect-proof film, a light-cut film, a decorative film having a display effect, and the like.

In the case of the anti-condensation film, it is preferable to attach the film to the indoor side of the window glass of a house. In addition, in the case of the anti-fog film, it is preferable that the film is adhered to a mirror such as an automobile window glass or a rearview mirror in addition to a house window glass. In the case of a decorative film, for example, a stained glass pattern may be applied to the surface of the film by printing or the like, and the film may be attached to a window glass of a house.

According to the multilayer pressure-sensitive adhesive film of the present invention, a film having various functions as described above can be easily adhered at home at a simple operation, and it is easy to peel off and no dirt remains.

[0060]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

[0061]

Example 1 Extruder having a diameter of 90 mm and an effective width of 130
Using an extrusion coating (laminating) apparatus equipped with a 0 mm mold (T die), a thermoplastic resin layer was formed on one side from the unreeling portion of one of the base materials as ethyl acrylate.
Methyl methacrylate-styrene copolymer (content of ethyl acrylate component and methyl methacrylate component: 25 each
A 25 μm-thick polyester (PET) film having a dew-condensation prevention function was fed by laminating films (thickness: 5% by weight, styrene component content: 50% by weight). Here, the lamination of the film composed of the ethyl acrylate / methyl methacrylate / styrene copolymer was dissolved in a mixed solvent of toluene and ethyl acetate and applied by a bar coater method. Next, the surface of the PET film opposite to the surface on which the ethyl acrylate / methyl methacrylate / styrene copolymer was laminated was anchored with a polyurethane two-pack primer using a gravure coater and a dryer. Coated.

Next, as a pressure-sensitive adhesive layer, an ethylene-vinyl acetate copolymer (E
VA) [MFR 15 g / 10 min, vinyl acetate content 20 wt%, flexural stiffness 380 kg / cm ² ] was extruded into a thin film. Further, a biaxially oriented polypropylene film (OPP) having a thickness of 30 μm was fed as a release layer from the feeding portion of the other substrate, and the anchor coated surface of the PET and the OPP were sandwiched by the EVA extruded into the thin film. Extrusion lamination was performed to prepare a multi-layer pressure-sensitive adhesive film having a constitution of PET / EVA / OPP. At this time PE
Ozone treatment was performed by blowing ozone gas between T / EVA (ozone treatment conditions; ozone concentration was 15 g / m ³ ,
The processing amount is 5 m ³ / hour / m). The thickness of EVA is 1
5 μm, and the sandwich extrusion laminating speed is 100
m / min.

Table 1 shows the smoothness of the surface of the pressure-sensitive adhesive layer (the surface to be adhered to the substrate) of the multilayer pressure-sensitive adhesive film thus obtained and the results of a test for sticking to a glass plate. The heat capacity of the glass plate (3 mm) used for the adhesion test was 1500 ca
1 / ° C., the radiant heat absorption rate is 95%, the heat volume of the PET film is 33.5 cal / ° C., and the radiant heat absorption rate is 56%.
The heat capacity of the ethyl acrylate / methyl methacrylate / styrene copolymer film was 2.0 cal / ° C, and the radiant heat absorption rate was 30%.

[0064]

Examples 2 to 3 The same procedure as in Example 1 was carried out except that EVA in Table 1 was used instead of EVA. Table 1 shows the smoothness of the surface of the pressure-sensitive adhesive layer (adhesive surface to the substrate) of the obtained multilayer pressure-sensitive adhesive film and the results of an adhesion test on a glass plate.

[0065]

Examples 4 to 5 The same procedures as in Example 1 were carried out except that EVA was changed to the low-density polyethylene shown in Table 1 and the resin temperature was changed to 280 ° C. Table 1 shows the smoothness of the surface of the pressure-sensitive adhesive layer (adhesive surface to the substrate) of the obtained multilayer pressure-sensitive adhesive film and the results of an adhesion test on a glass plate.

[0066]

Examples 6 to 8 In Example 1, EVA was changed to the linear low-density polyethylene shown in Table 1, and the resin temperature was changed to 240 ° C.
Further, the same operation as in Example 1 was performed except that the thickness of the extruded resin was changed to 20 μm. Table 1 shows the smoothness of the surface of the pressure-sensitive adhesive layer (adhesive surface to the substrate) of the obtained multilayer pressure-sensitive adhesive film and the results of an adhesion test on a glass plate.

[0067]

Example 9 In Example 1, EVA was replaced with low-density polyethylene (trade name "Kernel KS560" manufactured by Nippon Polychem Co., Ltd.) produced using the metallocene catalyst shown in Table 1, and the resin temperature was set to 240 ° C. Furthermore, the thickness of the extruded resin is 20 μm
The procedure was performed in the same manner as in Example 1 except that Table 1 shows the smoothness of the surface of the pressure-sensitive adhesive layer (adhesive surface to the substrate) of the obtained multilayer pressure-sensitive adhesive film and the results of an adhesion test on a glass plate.

[0068]

Example 10 In Example 1, EVA was replaced with ethylene-
Example 1 was repeated except that the methyl methacrylate copolymer (EMMA) was used instead. Table 1 shows the smoothness of the surface of the pressure-sensitive adhesive layer (adhesive surface to the substrate) of the obtained multilayer pressure-sensitive adhesive film and the results of an adhesion test on a glass plate.

[0069]

Example 11 The procedure of Example 4 was repeated, except that the biaxially oriented polypropylene film (OPP) having a thickness of 30 μm was replaced with a biaxially oriented nylon film having a thickness of 15 μm. Table 1 shows the smoothness of the surface of the pressure-sensitive adhesive layer (adhesive surface to the substrate) of the obtained multilayer pressure-sensitive adhesive film and the results of an adhesion test on a glass plate.

[0070]

COMPARATIVE EXAMPLE 1 Extrusion lamination was carried out in the same manner as in Example 1 using the same extrusion coating apparatus as in Example 1 except that a mat-like laminate cooling roll having a matte surface was used. However, a two-layer laminated film of PET / EVA was used without using OPP (E / EVA on the opposite side of the PET surface).
VA surface is matte-like mat surface condition). Table 1 shows the smoothness of the surface of the pressure-sensitive adhesive layer (adhesive surface to the substrate) of the obtained multilayer pressure-sensitive adhesive film and the results of an adhesion test on a glass plate.

[0071]

Comparative Example 2 Comparative Example 1 was repeated except that the mat-like laminate cooling roll processed in satin finish was replaced with a semi-matte laminate cooling roll, the EVA was replaced with low-density polyethylene shown in Table 1, and the resin temperature was changed to 290 ° C. It carried out like Example 1. Table 1 shows the smoothness of the surface of the pressure-sensitive adhesive layer (adhesive surface to the substrate) of the obtained multilayer pressure-sensitive adhesive film and the results of an adhesion test on a glass plate.

[0072]

Comparative Example 3 The procedure of Example 1 was repeated, except that EVA was changed to the high-density polyethylene shown in Table 1 and the resin temperature was changed to 280 ° C. Table 1 shows the smoothness of the surface of the pressure-sensitive adhesive layer (adhesive surface to the substrate) of the obtained multilayer pressure-sensitive adhesive film and the results of an adhesion test on a glass plate.

[0073]

[Table 1]

The contents of each symbol in Table 1 are as follows. EVA1: ethylene-vinyl acetate copolymer (MFR = 1
EVA2: Ethylene-vinyl acetate copolymer (MFR = 9, 5 g / 10 min, vinyl acetate (VAC) concentration = 20% by weight)
g / 10 min, VAC concentration = 10% by weight) EVA3: Ethylene-vinyl acetate copolymer (MFR = 1)
LD1: High-pressure low-density polyethylene (MFR = 14 g / min)
LD2: High-pressure low-density polyethylene (MFR = 10 g / 10 minutes, density = 0.918 g / cm ³ )
10 minutes, density = 0.922 g / cm ³ ) LL1: Linear low density polyethylene (MFR = 16 g / cm ³ )
10 minutes, density = 0.921 g / cm ³ ) LL2: Linear low density polyethylene (MFR = 20 g / cm ³ )
10 minutes, density = 0.925 g / cm ³ ) LL3: linear low density polyethylene (MFR = 50 g / cm ³ )
10 minutes, density = 0.928 g / cm ³ ) MLD1: metallocene catalyst-based low-density polyethylene (MF
R = 16.5 g / 10 min, density = 0.988 g / c
m ³ , trade name “Kernel KS560”: Nippon Polychem Co., Ltd.) EMMAl: ethylene-methyl methacrylate copolymer (MFR = 16 g / 10 min, methyl methacrylate concentration = 20% by weight) HD1: high density polyethylene (MFR) = 20g / 10
Min, density = 0.958 g / cm ³ ) (provided that LL1, LL2, LL3, MLD1, and HD1 are each a high-pressure method low-density polyethylene (LD)
1) was mixed at 10% by weight. )

The methods for measuring and evaluating physical properties in the above Examples and Comparative Examples are as follows. (1) Smoothness (Rz) Surface roughness tester [Sumittest 201 Serie manufactured by Mitutoyo Corporation]
s 178] from the roughness curve to the direction of its center line,
A portion of the evaluation length (lm = 4.0 mm) is extracted, and the difference between the maximum value (peak) and the minimum value (valley bottom) for each of the five reference lengths (le = 0.8 mm) is Z _i (μm). Rz (μm) was calculated using the following equation (I). FIG. 1 shows an example of a roughness curve for obtaining smoothness.

[0076]

(Equation 2)

(2) Softness (flexural stiffness) Measured according to JIS-K7106. (3) Adhesion test on glass plate The adhesion test on the glass plate was 3 mm thick, 70 cm x 7
The measurement was performed using a sheet glass having a size of 0 cm. That is, first, the surface of the plate glass is cleaned with acetone to remove dirt such as oils and fats,
Water was applied to the glass surface. On the other hand, 50cm x 50c
The release layer of the multi-layered pressure-sensitive adhesive film having the m dimension was peeled off to expose the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer. Next, the surface of the glass sheet to which water was applied and the adhesive surface of the multilayer adhesive film were bonded together with water interposed therebetween so that air was not entrained. Thereafter, the sheet glass was heated at a temperature of 23 ° C. and a humidity of 50%.
, And the state of adhesion between the glass surface and the multilayer adhesive film surface was visually observed and evaluated according to the following criteria.

(Evaluation method) ：: Even after one month of aging, there is no peeling or air entrapment (floating) between the glass surface and the multilayer adhesive film surface, and the glass surface and the film surface are completely adhered. (Adhesive)
are doing. ：: About 1% of the multilayer adhesive film after one month of aging
Although peeling or air entrainment (floating) occurs in a small area, the glass and the film are bonded (adhesive).
△: About 3% of the multilayer adhesive film after one month of elapse
Although peeling or air entrapment (floating) occurs in a small area, the glass and the film are adhered (adhered). ×: Within 5 days of aging, the multilayer pressure-sensitive adhesive film was separated from the glass sheet and dropped.

[0079]

The multilayer pressure-sensitive adhesive film of the present invention can be easily attached even at home, since the sticking operation is simple, and the position can be easily moved after sticking. In addition, the substrate is easily peeled, and the substrate is less likely to be stained by the residual adhesive or the like during the peeling. Further, since it is made of a halogen-free resin, it is also preferable from the viewpoint of environmental problems.

[Brief description of the drawings]

FIG. 1 is an example of a roughness curve for obtaining smoothness.

[Explanation of symbols]

 1 ... Roughness profile 2 ... Center line

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B32B 27/36 B32B 27/36 31/30 31/30 C09J 123/02 C09J 123/02 157/00 157 / 00 (72) Inventor Hisao Takizawa 93, Iwabe 193, Kurigen-cho, Katori-gun, Chiba Prefecture Inside Narita Plant of Wada Chemical Industry Co., Ltd. (72) Inventor Yoshihiro Ishizaki 2-10-14 Higashikanda, Chiyoda-ku, Tokyo Wada Chemical Industry Co., Ltd.F-term (reference) 4F100 AG00C AK01A AK03B AK06B AK42A AK62B AK68B AK71B BA02 BA03 BA04 BA05 BA07 BA10A BA10C BA10E BA13 CA19D CB05B EH112 EH132 EH172 JA11B JB16A JK04B JK15B JK16D JL05 JL06 JL07E JL13B JL14 YY00B 4J004 AA07 AA09 AA10 AB01 CA03 CA04 CA06 CC02 CC05 CD05 DA02 DA04 DB02 EA01 FA10 4J040 DA021 DA041 DA051 DA061 JA09 JB09 LA06 MA05 MB03 NA12 NA16 PA23

Claims (9)

[Claims] 1. A multilayer adhesive film comprising at least a thermoplastic resin layer and an adhesive layer for adhering to a substrate surface to form a film layer, wherein the adhesive layer is olefin-free and halogen-free. A multilayer pressure-sensitive adhesive film, which is made of a united product and satisfies the following (1) and (2). (1) The smoothness of the side of the pressure-sensitive adhesive layer that adheres to the substrate surface is 0.3 to 2 as measured using a surface roughness meter. (2) The bending stiffness measured according to JIS-K7106 is 100 to 5000 kg / cm ² . 2. The olefin-based halogen-free polymer is an ethylene-vinyl acetate copolymer, a low density polyethylene, an ethylene-ethyl acrylate copolymer, an ethylene-methacrylate copolymer, an ethylene-methyl methacrylate copolymer, The multi-layer pressure-sensitive adhesive film according to claim 1, wherein the multi-layer pressure-sensitive adhesive film is selected from the group consisting of: and a low-crystalline ethylene / α-olefin copolymer. 3. The multi-layer pressure-sensitive adhesive film according to claim 1, wherein a peelable release layer is provided on the surface of the pressure-sensitive adhesive layer. 4. The multilayer pressure-sensitive adhesive film according to claim 1, wherein the substrate is a glass plate. 5. The method according to claim 1, wherein a lubricant is present between the multilayer pressure-sensitive adhesive film and the substrate, and the film is formed by adhering to the surface of the substrate via the lubricant. Item 5. The multilayer pressure-sensitive adhesive film according to any one of Items 1 to 4. 6. The method according to claim 1, wherein the thermoplastic resin layer is made of polyethylene terephthalate.
The multilayer pressure-sensitive adhesive film according to claim 1. 7. The multi-layered pressure-sensitive adhesive according to claim 1, wherein a function-imparting layer is provided on the surface of the thermoplastic resin layer opposite to the side on which the pressure-sensitive adhesive layer is provided. the film. 8. The multilayer pressure-sensitive adhesive film according to claim 7, wherein the function imparting layer is a layer imparting a dew condensation preventing function. 9. A method for producing a multilayer adhesive film comprising a thermoplastic resin layer, an adhesive layer, and a release layer laminated in this order, wherein the multilayer adhesive film is adhered to a substrate surface to form a film layer. , Between a thermoplastic resin film forming a thermoplastic resin layer and a release film forming a release layer, melt-extruding an olefin-based halogen-free polymer forming an adhesive layer and sandwich-laminating;
A method for producing a multilayer pressure-sensitive adhesive film, comprising a step of forming a pressure-sensitive adhesive layer satisfying the following (1) and (2). (1) The smoothness of the side of the pressure-sensitive adhesive layer that adheres to the substrate surface is 0.3 to 2 as measured using a surface roughness meter. (2) The bending stiffness measured according to JIS-K7106 is 100 to 5000 kg / cm ² .