JP4912228B2 - Electronic device laminate - Google Patents

Description

The present invention relates to a laminated body including an element for an electronic device, and relates to an electronic device laminated body capable of suppressing moisture and oxygen that enter and permeate from the outside.

The reliability of various electronic device elements may be reduced by moisture and oxygen contained in the atmosphere. For example, when air, water vapor or the like enters a liquid crystal element or other display device, there is a problem that display defects occur.

The above problem occurs not only in liquid crystal elements but also in organic electroluminescence (hereinafter referred to as organic EL) elements used in various displays and light emitting elements. In the case of an organic EL element, the presence of moisture or oxygen in the element causes modification or oxidation of the organic light emitting material, peeling of the electrode from the organic light emitting material, and the like, and degradation of light emission characteristics due to generation of black spots becomes a problem. .
The above problem also occurs in electronic paper.

Also, in solar cells, when water comes into contact with an ethylene-vinyl acetate copolymer (hereinafter referred to as EVA) that seals solar cell elements, EVA becomes cloudy, so the amount of power generation decreases as the amount of light transmission decreases. Have a problem to do.

In order to solve the problems as described above, it has been proposed to attach a laminate containing a barrier layer for preventing moisture from entering the atmosphere and permeating oxygen to the layers constituting various electronic devices. (For example, refer to Patent Document 1).

JP-A-10-058585

However, since the conventional means for attaching a laminated body is provided only on one surface of layers constituting various electronic devices, there is a problem that moisture permeates from the side surface of the electronic device and oxygen permeates. It was.

An object of the present invention is to provide an electronic device laminate in which moisture permeation and oxygen permeation from the side surfaces of the laminate constituting various electronic devices are improved.
Another object of the present invention is to provide an electronic device laminate having a moisture / oxygen permeation suppressing function for use in liquid crystal elements, organic EL elements, electronic paper, and solar cells.

The electronic device laminate of the present invention includes an electronic device element between an adhesive layer provided on one surface of an organic film and a base material, and is surrounded by the base material and the adhesive layer. An electronic device laminate in which a projection-like continuous body is formed so as to surround the device for use , and a release film is provided on the opposite side of the organic film via an adhesive layer; and The dynamic storage elastic modulus (Ea) of the pressure-sensitive adhesive layer adjacent to the base material and the dynamic storage elastic modulus (Eb) of the pressure-sensitive adhesive layer on the opposite side of the base material through the organic film are “Ea <Eb” ( However, Ea has a relationship of 100 kPa or less), the thickness (Ta) of the adhesive layer adjacent to the substrate, and the thickness (Tb) of the adhesive layer on the opposite side of the substrate via the organic film Has a relationship of “Ta <Tb”.

According to the present invention, an electronic device capable of preventing and preventing moisture from entering from outside and permeation of oxygen by a protruding continuous body formed on a base so as to surround an electronic device element included in a laminate. A device laminate can be provided.

According to the present invention, since a fluororesin film such as poly-3-fluorochlorinated ethylene can be used for the organic film, it is possible to greatly suppress moisture permeation and oxygen permeation from the organic film.

According to the present invention, since the silane coupling agent can be contained in the adhesive layer constituting the laminate, the substrate is excellent in adhesiveness even if it is glass, metal, or film, and after peeling from the substrate. It is also excellent in sticking again (reworkability).

Hereinafter, the present invention will be described in detail with reference to the drawings.
FIG. 1 is a conceptual view of a part of the electronic device laminate according to the present invention in perspective, in which an adhesive layer 20 provided on one surface of an organic film 10 is a continuum 31 of protrusions provided on the surface of a substrate 30. The state where it was stuck to the base material 30 so that the element 40 for electronic devices enclosed by the inside may be included is shown.
FIG. 2 shows a part of the electronic device laminate of the present invention in a cross-sectional view taken along the line AA ′ of FIG. That is, as described above, the adhesive layer 20 provided on one side of the organic film 10 and the substrate in a state where the electronic device element 40 is surrounded by the continuous body 31 of protrusions provided on the surface of the substrate 30. 30 is attached.
In this case, in the step of creating the electronic device laminate of the present invention, a release film is once provided on the pressure-sensitive adhesive layer 20 laminated on the organic film 10, and this is peeled off immediately before being attached to the substrate 30. The material 30 may be attached. Thereby, not only can dust be prevented from adhering to the adhesive layer 20 during the manufacturing process and during conveyance, but also the adhesive force of the adhesive layer 20 can be suitably maintained.

Moreover, the electronic device laminated body of this invention has provided the adhesion layer 21 in the surface on the opposite side to the base material 30 through the organic film 10, as shown in FIG . As shown in FIG. 4, a release film 60 is provided on the adhesive layer 21 . The release film 60 is composed of a release adhesive layer 61 and a resin film 62, and the release adhesive layer 61 is preferably laminated on the adhesive layer 21.
3 and 4, an adhesive layer may be used instead of the adhesive layer 21. Whether the adhesive layer 21 or the adhesive layer is used is determined by sticking to the adhesive layer 21 or the adhesive layer. What is necessary is just to determine with the kind of to-be-adhered body to wear.

The method of attaching the adhesive layer 20 and the base material 30 is not particularly limited, and may be simply pressed by hand, or may be applied with a certain pressure using a machine or an apparatus, and may be appropriately selected. Can do. The protrusion-like continuous body 31 and the organic film 10 are in close contact with each other by pressing the organic film 10 and the substrate 30 by hand. Moreover, although heat processing may be performed if necessary, it is possible to adhere | attach the protrusion-like continuous body 31 and the organic film 10 without performing heat processing.
The protruding continuum 31 may be in close contact with the organic film 10 and sealed so that water and oxygen do not permeate from the side surface of the electronic device laminate of the present invention. The shape of is not limited to the square shape shown in FIGS. 2 to 5, and may be spherical, triangular, or elliptical. Further, the size of the protruding continuous body 31 can be designed as appropriate. Furthermore, the number of the protrusion-like continuous bodies 31 is not limited to one row as shown in FIGS. 1 and 6, and may be provided in any number of rows.

As for the electronic device laminated body 50 after sticking the adhesion layer 20 and the base material 30, it is preferable that the vertex of the protrusion-like continuous body 31 and the organic film 10 adhere | attach as shown in sectional drawing shown in FIG. When the protrusion-like continuous body 31 and the organic film 10 are in close contact with each other, even when water enters from the end face of the adhesive layer 20 or oxygen passes through, the intrusion or oxygen permeation occurs at the contact portion. Can be suppressed.

An example in which a protruding continuous body 31 is provided on the substrate 30 is shown in FIG. The method for forming the protrusion-like continuous body 31 on the base material 30 is not particularly limited, but by forming the protrusion-like continuous body 31 on the frame as shown in FIG. It is necessary to surround the element 40. By adhering the adhesive layer 20 provided on the organic film 10 and the base material 30 provided with the protrusion-like continuous body 31, moisture penetration and oxygen permeation are suppressed from the end face of the adhesive layer 20. Can do. The shape of the frame of the projection-like continuous body may be a square shape as shown in FIG. 6 or a circular shape, and is not particularly limited.
Hereinafter, constituent elements of the present invention will be described focusing on materials.

<Base material>
The base material in the present invention may use an inorganic material or an organic material, and is not particularly limited. For example, a glass plate, a metal plate, a plastic plate, a film, or the like is used. be able to. What is necessary is just to select these base materials suitably by the element for electronic devices to include.
It is preferable to use a glass plate, a plastic plate, a film or the like for the liquid crystal element and the organic EL element.
For the electronic paper, it is preferable to use a plastic plate, a film, or the like.
For the solar cell, it is preferable to use a glass plate, a metal plate, a plastic plate, a film or the like.

<Protruded continuum>
The method for forming a protrusion-like continuous body on a substrate such as a glass plate, a metal plate, a plastic plate, or a film is as follows. 1. An organic film through an adhesive layer is provided in a strip shape on a substrate. 2. Protruding continuous body is formed by solder. 3. Protruding continuum is formed on the substrate by spraying plastic or ceramic. 4. Perform surface printing. Means such as forming by etching is adopted in the present invention.
When using a glass plate as a base material, it is preferable to use a glass paste for formation of a protrusion-like continuous body. Glass paste consists of glass powder, resin components, and a solvent in which these are dispersed and dissolved, and can be formed by volatilizing the solvent and sintering the glass powder after coating on a glass plate. .

<Electronic device>
As an element for electronic devices, a liquid crystal element, an organic EL element, electronic paper, a solar cell etc. can be mentioned, for example.

<Adhesive layer>
The adhesive layer is not particularly limited as long as it can be stuck to a base material having a protruding continuous body, but is not limited to acrylic resin, polyurethane resin, polyester resin, polyvinyl acetate resin, epoxy resin. Etc. can be used.
The pressure-sensitive adhesive layer constituting the present invention preferably uses a pressure-sensitive adhesive layer mainly composed of an acrylic resin. Moreover, the hardness as an adhesion layer can be improved by mix | blending an epoxy resin with an acrylic resin. It is preferable to mix an epoxy resin in the adhesive layer on the side opposite to the substrate through the organic film.

As an acrylic resin, the acrylic resin formed by superposing | polymerizing the acrylic monomer which is illustrated below is mentioned. Examples of the acrylic monomer include alkyl acrylate and alkyl methacrylate (the alkyl group includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group). Groups); hydroxyl group-containing monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate; epoxy group-containing monomers such as glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether; Acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene sulfonic acid and its salts (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.) A monomer containing a carboxy group, a sulfoxy group or a salt thereof; acrylamide, methacrylamide, N-alkylacrylamide, N-alkylmethacrylamide, N, N-dialkylacrylamide, N, N-dialkylmethacrylamide (as alkyl groups, Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, etc.), N-alkoxyacrylamide, N-alkoxymethacrylamide, N, N-dialkoxyacrylamide, N, N-dialkoxymethacrylamide (alkoxy groups include methoxy, ethoxy, butoxy, isobutoxy, etc.), acryloylmorpholine, N-methylolacrylamide, N-methylol Monomers containing amide groups such as clinamide, N-phenylacrylamide, N-phenylmethacrylamide; monomers of acid anhydrides such as maleic anhydride and itaconic anhydride; vinyl isocyanate, allyl isocyanate, styrene, α-methylstyrene, vinyl Methyl ether, vinyl ethyl ether, vinyl trialkoxysilane, alkylmaleic acid monoester, alkyl fumaric acid monoester, alkylitaconic acid monoester, acrylonitrile, methacrylonitrile, vinylidene chloride, ethylene, propylene, vinyl chloride, vinyl acetate, butadiene And the like.

The pressure-sensitive adhesive layer constituting the present invention preferably contains a silane coupling agent. As a result, the adhesive force with the substrate or adherend can be improved, and the reworkability with the substrate or adherend can be improved. The substrate or adherend may be a glass plate, a metal plate, or a film.

The silane coupling agent is not particularly limited as long as it has a structural formula, [R—Si— (OR ′) ₃ ]. As R, a vinyl group, an epoxy group, an amino group, a methacryl group, A reactive group such as a mercapto group or an N-phenylaminopropyl group can be used, and a reactive group such as a methoxy group or an ethoxy group can be used as R ′.

The content of the silane coupling agent contained in the adhesive layer constituting the present invention is preferably 2 parts by weight or less with respect to 100 parts by weight of the resin component. If it exceeds 2 parts by weight, when a release film is provided on the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer is difficult to peel off when the release film is peeled off.

The pressure-sensitive adhesive layer laminated on the organic film is attached to a base material provided with a protruding continuum, so that the gap between the organic film and the protruding continuum is narrow when attached. Is preferred. Therefore, in the laminate of the present invention shown in FIG. 3, the dynamic storage elastic modulus (Ea) of the adhesive layer adjacent to the substrate and the dynamic storage elasticity of the adhesive layer on the opposite side of the substrate via the organic film. The rate (Eb) preferably has a relationship of “Ea <Eb”. By setting Ea <Eb, it becomes easy to stick to the base material provided with the protruding continuous body, and also to stick to the adherend.
In the present invention, Ea is preferably 100 kPa or less. Thereby, even when the adhesive layer laminated on the organic film and the base material provided with the protruding continuum are pressed by hand, the gap between the organic film and the protruding continuum can be reduced. .

The elastic modulus in the present invention means that an adhesive layer sample having an adhesive layer thickness of 1000 μm is placed in a rheo-stress tester (HAAKE Rheo Stress RS75) under conditions of 25 ° C. and an excitation frequency of 1 Hz. This means the value obtained by applying a 3N weight to the adhesive layer sample with a 20 mmφ probe.

Moreover, in the laminated body of this invention shown in FIG. 3, the thickness (Ta) of the adhesion layer adjacent to the said base material, and the thickness (Tb) of the adhesion layer on the opposite side of a base material through an organic film, However, it is preferable to have a relationship of “Ta <Tb”.
Ta in the present invention is preferably 20 μm or less, more preferably 15 μm or less, and particularly preferably 10 μm or less. By setting Ta to 20 μm or less, the gap between the organic film and the protrusion-like continuum is narrowed, so that it is possible to prevent moisture from entering and oxygen to permeate.
Tb is preferably about 5 to 40 μm while maintaining the relationship of “Ta <Tb”.

<Adhesive layer>
In the laminated body of FIG. 3 and FIG. 4, examples of the adhesive layer that can be applied instead of the adhesive layer 21 include various thermosetting resins such as phenol resin, polyester resin, epoxy resin, urea resin, melamine resin, and polyethylene. Various thermoplastic resins such as a resin polypropylene resin can be used. These resins may be used alone or in combination of two or more.

The pressure-sensitive adhesive layer and the adhesive layer constituting the present invention may contain an ultraviolet absorber as necessary.

Examples of the method for applying the adhesive layer and the adhesive layer to the organic film include a roll coating method, a gravure coating method, a roll brush method, a spray coating method, an air knife coating method, an impregnation method, and a curtain coating method. . These methods may be used alone or in combination.

<Organic film>
The organic film constituting the present invention is, for example, polyethylene terephthalate, polyethylene naphthalate, acrylic resin, polycarbonate, polyimide, polyamide, polyamideimide, polyethersulfone, polyphenylene sulfide, polyetherketone, polyetherimide, triacetylcellulose, Silicone rubber, polytetrafluoroethylene, a fluororesin film, a polyvinyl alcohol film, or the like can be used.

In the present invention, it is preferable to use an organic film having a low water vapor transmission rate, and it is particularly preferable to use a fluororesin film. Specifically, polytetrafluoroethylene (PTFE), 4-fluoroethylene-perchloroalkoxy copolymer (PFA), 4-fluoroethylene-6-fluoropropylene copolymer (FEP), 2-ethylene Examples include -4-fluoroethylene copolymer (ETFE), poly-3-fluoroethylene chloride (PCTFE), polyvinylidene fluoride (PVDF), and polyvinyl fluoride (PVF). Among these, it is preferable to use PCTFE because the water vapor transmission rate is extremely small.
The organic film having a small water vapor transmission rate means that the water vapor transmission rate is 2.0 g / m ² · 24 hr or less as a result of measurement according to JIS-K7126.
The film made of PCTFE has a water vapor transmission rate of 23 μm and 1.0 × 10 ⁻⁴ g / m ² · 24 hr or less.
It is also preferable to use a polyvinyl alcohol film having a low oxygen permeability.

Since an adhesive layer is provided on the surface of the organic film constituting the present invention, the surface may be subjected to physical treatment such as corona surface treatment, flame treatment, plasma treatment, etc. as a pretreatment for improving its coating property. preferable.

The thickness of the organic film is preferably 6 to 250 μm, more preferably 10 to 100 μm, and particularly preferably 20 to 50 μm. If it is 6 μm or less, the water vapor transmission rate may be insufficient. If it exceeds 250 μm, the water vapor transmission rate is small, but it is not preferable from the economical aspect.

<Peeling film>
The release film to be laminated on the pressure-sensitive adhesive layer constituting the present invention is not particularly limited as long as the release pressure-sensitive adhesive layer containing a silicone component is laminated on the resin film, and the types of the silicone component and the resin film are particularly limited. Is not to be done. As the silicone component, any of silicone oil, silicone varnish and silicone resin can be used in the present invention. The resin film is not particularly limited, and those described in the organic film can be used. Specifically, a polyethylene terephthalate film can be used.
The release film types are a light release film, a middle release film, and a heavy release film in order from the largest amount of the silicone component contained in the release adhesive layer, but any of them may be used. Use of a light release film is preferable because it easily peels from the adhesive layer.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to this at all.

A glass paste (softening temperature 530 to 560 ° C.) for forming a projection-like continuous body on one surface of a base material made of a soda lime silica glass plate having a thickness of 3.5 mm and a size of 100 mm × 100 mm is as follows: And prepared and applied.
-75 parts by weight of glass powder-15 parts by weight of ethyl cellulose (binder)-10 parts by weight of α-terpioneer (organic solvent) In this application, the glass paste having the above composition is 3 cm and 5 cm from the edges of the four sides of the glass plate. A base material having a protrusion-like continuous body shown in FIG. 6 was prepared at a position of 10 μm in width so as to form a square shape, and this was fired at 670 ° C. for 3 minutes.
In addition, the base material which consists of a glass plate which has the protrusion-shaped continuous body produced as mentioned above was used also in the other Example described below.

After the adhesive layer material having the following composition is dissolved in methyl ethyl ketone and applied on one side of an organic film made of poly (3-fluoroethylene chloride) (trade name: NEOFLON PCTFE, manufactured by Daikin Industries, Ltd.), in a hot-air circulating dryer And dried at 80 ° C. for 5 minutes to produce an organic film having a 5 μm thick adhesive layer. Moreover, the average molecular weight of the said adhesion layer was 900-1.2 million, and the dynamic storage elastic modulus (Ea) was 45 kPa.
・ Butyl acrylate 80 parts by weight ・ Ethyl acrylate 20 parts by weight ・ Silane coupling agent (3-glycidoxypropyltrimethoxysilane) 1 part by weight

Next, after cooling a substrate made of a glass plate having a protruding continuous body to room temperature, a transparent conductive film is formed in the protruding continuous body provided on the frame, and then the transparent conductive film The organic EL was placed on the surface, and the adhesive layer surface of the organic film produced as described above was bonded to the glass plate and brought into close contact with the glass plate by hand to produce a part of the electronic device laminate of the present invention shown in FIG. .

As the organic film, the electronic device laminate of the present invention was manufactured in the same manner as in Example 1 except that a film made of 4-fluoroethylene-6-fluoropropylene copolymer (FEP) having a thickness of 50 μm was used . A part was made. In addition, the thickness of the adhesion layer was 10 micrometers.

A part of the electronic device laminate of the present invention, as in Example 1, except that a film made of 2-ethylene-4-fluoroethylene copolymer (ETFE) having a thickness of 50 μm was used as the organic film. Was made.

In order to use a 100 μm-thick PET film (trade name: Tetron HB manufactured by Teijin DuPont Films Ltd.) as an organic film, an adhesive layer having a thickness of 20 μm is provided on the opposite side of the substrate via the organic film. 3 was produced in the same manner as in Example 1 except that the material for the production was used, and a silicone release film (trade name: PET5001 manufactured by Lintec Co., Ltd.) was laminated on the adhesive layer. The electronic device laminate shown in FIG. 4 was produced.
Moreover, the average molecular weight of the said adhesion layer was 600,000, and the dynamic storage elastic modulus (Eb) was 148 kPa.
-80 parts by weight of butyl acrylate-20 parts by weight of ethyl acrylate-0.05 part by weight of epoxy resin-1 part by weight of silane coupling agent (3-glycidoxypropyltrimethoxysilane)

A piano wire (thickness 1 mm) for forming a projection-like continuous body was laminated on one surface of a base material made of poly-3-fluoroethylene chloride (trade name: NEOFLON PCTFE manufactured by Daikin Industries, Ltd.). By heat-sealing both ends of the piano wire, a base material having a protruding continuous body provided in a frame shape shown in FIG. 6 was produced.
Next, the adhesive layer shown in Example 1 was applied and laminated by the method shown in Example 1 on one side of a polyvinyl alcohol film (trade name: OPL film manufactured by Taisei Kayaku Co., Ltd.) as an organic film.
Subsequently, after forming a transparent conductive film in the projection-shaped continuous body provided on the frame, an organic EL was placed on the transparent conductive film, and the adhesive layer surface of the polyvinyl alcohol film produced as described above was The electronic device laminate of the present invention shown in FIG. 2 was produced by bonding with 3-fluoroethylene chloride and pressing them together by hand.

[Comparative Examples 1 to 4]
Except having used the soda-lime-silica glass plate which did not provide the protrusion-like continuous body, it was set as the electronic device laminated body of Comparative Examples 1-4 respectively similarly to Example 1-4.

The electronic device laminates produced in the examples and comparative examples were left for 24 hours under conditions of 40 ° C. and 90% humidity. After standing, the organic film having the adhesive layer was peeled off from the glass plate, and the respective weights were measured. As a result, the weight increase due to water absorption was less in the Examples than in the corresponding Comparative Examples. Therefore, it was confirmed that moisture permeation can be suppressed by having the example configuration.
Moreover, since the electronic device laminated body produced in the Example can adhere | attach an organic film and a protruding continuous body, it is possible to suppress oxygen permeability. In addition, as shown in Example 5, the oxygen permeability can be further suppressed by using a polyvinyl alcohol film having a low oxygen permeability.

It is a conceptual diagram which shows the electronic device laminated body of this invention. It is sectional drawing which shows the electronic device laminated body of this invention. It is sectional drawing which shows the electronic device laminated body of this invention. It is sectional drawing which shows the electronic device laminated body of this invention. It is a figure which shows an example of the base material which provided the protrusion-like continuous body. It is a figure which shows an example which provided the protrusion-shaped continuous body on the base material.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Organic film 20, 21 Adhesion layer 30 Base material 31 Protruding continuous body 40 Element 50 for electronic devices Electronic device laminated body 61 Peeling adhesion layer 62 Resin film

Claims (4)

An electronic device element is included between the adhesive layer provided on one surface of the organic film and the base material, and is surrounded by the base material and the adhesive layer so as to surround the electronic device element. An electronic device laminate in which a continuous body is formed, wherein a release film is provided on the opposite side of the organic film via an adhesive layer, and the adhesive layer adjacent to the substrate Relationship between the dynamic storage elastic modulus (Ea) and the dynamic storage elastic modulus (Eb) of the adhesive layer on the opposite side of the substrate through the organic film is “Ea <Eb” (where Ea is 100 kPa or less) The thickness (Ta) of the pressure-sensitive adhesive layer adjacent to the base material and the thickness (Tb) of the pressure-sensitive adhesive layer on the opposite side of the base material through the organic film have a relationship of “Ta <Tb” An electronic device laminate comprising:
The electronic device laminate according to claim 1 , wherein the organic film is a fluororesin film.
The electronic device laminate according to claim 2 , wherein the fluororesin film is made of poly-3-fluoroethylene chloride.
Electronic devices laminate according to any one of claims 1 to 3, characterized in that the adhesive layer contains a silane coupling agent.

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