JP6907223B2 - An adhesive composition, an adhesive layer containing the adhesive layer, a support joint, and a gas barrier property evaluation device including the support joint. - Google Patents

Description

The present invention relates to an adhesive composition, an adhesive layer containing the adhesive layer, a support joint, and a gas barrier property evaluation device including the support joint.

In recent years, films having low water vapor permeability and / or oxygen permeability, that is, high gas barrier properties, have been demanded in various fields. Generally, in the development of such a film, a gas barrier property evaluation device for evaluating the gas barrier property of the film is used.

In the gas barrier property evaluation device, a differential pressure method or an isobaric method is adopted as a method for evaluating the gas barrier property of the film. FIG. 3 is a schematic view schematically showing the configuration of a gas barrier property evaluation device using a differential pressure method, which is shown as a reference example. Further, FIG. 4 is a schematic diagram schematically showing the configuration of a gas barrier property evaluation device using the isobaric method, which is shown as a reference example.

First, with reference to FIG. 3, the gas barrier property evaluation device 30 using the differential pressure method includes a tank 31, a sample chamber 32, a detector 33, and a vacuum pump 34. In the sample chamber 32, the film 321 to be measured is supported by a support 322 provided on the base material 323. When measuring the gas barrier property of the film 321, the vacuum pump 34 is operated to generate a differential pressure in the sample chamber 32. Specifically, gas is introduced from the tank 31 side through the film 321 in the sample chamber 32 at an arbitrary pressure to bring the vacuum pump 34 side into an ultra-high vacuum state. Then, water or gas or the like is discharged from the tank 31, and the amount of water or gas or the like that permeates the film 321 is detected by the detector 33.

However, according to the gas barrier property evaluation device 30, a load is applied to the film 321 due to the differential pressure, and the film 321 may be damaged such as bending.

Next, with reference to FIG. 4, the gas barrier property evaluation device 40 using the isobaric method includes a tank 41, a sample chamber 42, and a detector 43. In the sample chamber 42, the film 421 to be measured is supported by a support 422 provided on the base material 423. When measuring the gas barrier property of the film 421, the pressure inside the sample chamber 42 remains normal, water or gas flows out from the tank 41, and the amount of water or gas passing through the film 421 is detected by the detector 43. Detect with. According to the gas barrier property evaluation device 40, the film is not damaged unlike the gas barrier property evaluation device 30 (see FIG. 3) using the differential pressure method. However, the gas barrier property evaluation device 40 has a problem that it takes a longer time for measurement and evaluation than the gas barrier property evaluation device 30.

Therefore, in order to solve the problems of these gas barrier property evaluation devices, the gas barrier property evaluation devices shown in Patent Documents 1 and 2 are disclosed. All of these gas barrier property evaluation devices have a configuration in which the base material and the support in the sample chamber are fixed using an adhesive, and beeswax is an example of the adhesive used at that time. There is.

By the way, in the gas barrier property evaluation device, the temperature in the sample chamber may be raised to, for example, about 80 ° C. to 130 ° C. to remove the water content in the sample chamber. Therefore, the adhesive used in the gas barrier property evaluation device is required to have heat resistance and resistance due to a thermal cycle. However, when beeswax is used as an adhesive, it cannot be said that the heat resistance is sufficient.

Therefore, in the gas barrier property evaluation device, for example, a commonly used thermoplastic adhesive such as polyester (PET, PA, etc.), an acrylic adhesive, and / or a cyanoacrylate adhesive is used as the adhesive. I can think of it. Further, a phenol novolac type epoxy compound used for electronic parts (Patent Document 3) and a hydride phenol novolac type epoxy resin using a cationic polymerization initiator (Patent Document 4) can also be used as an adhesive in a gas barrier property evaluation device. Conceivable.

Japanese Patent Publication "Japanese Unexamined Patent Publication No. 2014-167465 (published on September 11, 2014)" Japanese Patent Publication "Japanese Unexamined Patent Publication No. 2014-167466 (published on September 11, 2014)" Japanese Patent Publication "Japanese Patent Laid-Open No. 8-283688 (published on October 29, 1996)" Japanese Patent Publication "Japanese Patent Laid-Open No. 2006-348308 (published on December 28, 2006)"

However, in the gas barrier property evaluation device, the polyester-based thermoplastic adhesive has poor coatability and must be adhered under high temperature conditions, so that there is a concern about damage to the support. In addition, the acrylic adhesive is also insufficient in terms of heat resistance and adhesiveness. Further, in the case of a cyanoacrylate adhesive, it is difficult to handle because there is a large amount of outgas and a drying time after adhesion is required. Further, when the phenol novolac type epoxy resin disclosed in Patent Document 3 is used as an adhesive, the support that can be used in the sample chamber is limited from the viewpoint of adhesiveness.

Furthermore, when the hydrogenated phenol novolac type epoxy resin disclosed in Patent Document 4 is used as an adhesive, the glass transition temperature of the resin is lowered by hydrogenating the resin, so that the heat resistance is insufficient. ..

The amount of water or gas measured by the gas barrier property evaluation device is very small, and these are easily affected by the outgas generated from the adhesive. Therefore, it is necessary to use a low outgas adhesive especially for the gas barrier property evaluation device.

In addition, in the case of a gas barrier property evaluation device using a differential pressure method, higher adhesiveness to the adhesive is required.

For these reasons, it has been desired to develop an adhesive that can be suitably used in a gas barrier property evaluation device.

The present invention has been made in view of the above problems, and an object thereof is suitable for a gas barrier property evaluation device because it has excellent heat resistance and thermal cycle resistance, is easy to handle, and contributes to low outgas. To provide an adhesive composition for use in.

The present inventors have been diligently researching an adhesive composition that can be suitably used in a gas barrier property evaluation device, and by blending a specific novolak type epoxy resin and a thermal cationic type polymerization initiator in combination. , And have found that the above-mentioned problems can be solved, and have completed the present invention.

式（１）中、ｎは０〜１０の整数を示す。また、Ｒ_１は下記のいずれかの基を示す。

また、式（１）中、Ｒ_２は下記のいずれかの基を示す。

また、式（２）中、ＹはＢＦ_４ ⁻、ＰＦ_６ ⁻、ＳｂＦ_６ ⁻、または、（ＢＸ_４）⁻（ただし、Ｘは、少なくとも２つ以上のフッ素もしくはトリフルオロメチル基で置換されたフェニル基を表す）を対アニオンとする、スルホニウム塩、ホスホニウム塩、第４級アンモニウム塩、ジアゾニウム塩、または、ヨードニウム塩を示す。That is, the adhesive composition according to the embodiment of the present invention contains a novolak type epoxy resin represented by the following formula (1) and a thermal cationic polymerization initiator represented by the following formula (2). Is.

In equation (1), n represents an integer from 0 to 10. Further, R ₁ represents any of the following groups.

Further, in the formula (1), R ₂ represents any of the following groups.

In the formula (2), Y is _{^{BF 4 -, PF 6 -,}} SbF 6 -, or, _(BX 4) ^- (provided that, X is substituted with at least two fluorine or trifluoromethyl group A sulfonium salt, a phosphonium salt, a quaternary ammonium salt, a diazonium salt, or an iodonium salt having (representing a phenyl group) as a counter anion is shown.

The adhesive composition according to one embodiment of the present invention comprises, as novolak type epoxy resin, phenol novolac type epoxy resin, xylene novolac type epoxy resin, dicyclopentadiene (DCPD) phenol novolac type epoxy resin and biphenyl novolac type epoxy resin. It is preferable to contain one or more selected from the group.

Further, the adhesive composition according to the embodiment of the present invention contains 90 to 99.5 parts by weight of the novolak type epoxy resin and 0 of the thermal cationic polymerization initiator with respect to 100 parts by weight of the adhesive composition. It is preferable to contain 5 to 10 parts by weight.

One embodiment of the present invention also provides an adhesive for a gas barrier property evaluation device containing the adhesive composition.

One embodiment of the present invention further provides an adhesive layer containing the adhesive composition.

One embodiment of the present invention further provides a support joint comprising a base material, an adhesive layer laminated on the base material, and a support laminated on the adhesive layer. The adhesive layer in this support joint is the adhesive layer according to the embodiment of the present invention.

An embodiment of the present invention further provides a gas barrier property evaluation device including a support joint according to the embodiment of the present invention.

According to the present invention, it is possible to provide an adhesive composition which is excellent in heat resistance, heat cycle resistance and adhesiveness and contributes to low outgas, and is therefore suitable for use in a gas barrier property evaluation device.

It is a schematic diagram which shows schematic structure of the support joint body which concerns on embodiment of this invention. It is a schematic diagram which shows schematic structure of the gas barrier property evaluation apparatus provided with the support joint which concerns on embodiment of this invention. It is a schematic diagram which shows roughly the structure of the gas barrier property evaluation apparatus using the differential pressure method, which is shown as a reference example. It is a schematic diagram which shows roughly the structure of the gas barrier property evaluation apparatus using the isobaric method, which is shown as a reference example.

Hereinafter, embodiments of the present invention will be described in detail.

[Adhesive composition]
The adhesive composition according to the present embodiment (hereinafter, also simply referred to as “adhesive composition”) contains a novolak type epoxy resin and a thermal cationic type polymerization initiator.

The novolak type epoxy resin used in this embodiment is represented by the following formula (1).

式（１）中、ｎは０〜１０の整数を示し、ｎは０〜５の整数であることが好ましい。

In the formula (1), n represents an integer of 0 to 10, and n is preferably an integer of 0 to 5.

Further, in the formula (1), R ₁ represents any of the groups shown below.

式（１）中、Ｒ_１は水素原子であることが好ましい。

In formula (1), R ₁ is preferably a hydrogen atom.

Further, in the formula (1), R ₂ represents any of the following groups.

式（１）中、Ｒ_２はメチレン基であることが好ましい。

In formula (1), R ₂ is preferably a methylene group.

Preferred examples of the novolac type epoxy resin include phenol novolac type epoxy resin, xylene novolac type epoxy resin, dicyclopentadiene (DCPD) phenol novolac type epoxy resin, biphenyl novolac type epoxy resin and the like. It is preferable to contain one or more selected from these resins. Among these, as a particularly preferable novolak epoxy resin, a phenol novolac type epoxy resin can be mentioned because it is easy to handle and has heat resistance.

The novolak type epoxy resin used in this embodiment is a known compound, and a general commercially available product can be used in this embodiment.

On the other hand, the thermal cationic polymerization initiator means a polymerization initiator that generates a cationic species or a Lewis acid by heat, and is represented by the following formula (2).

式（２）中、Ｙとしては、ＢＦ_４ ⁻、ＰＦ_６ ⁻、ＳｂＦ_６ ⁻、または、（ＢＸ_４）⁻（ただし、Ｘは、少なくとも２つ以上のフッ素もしくはトリフルオロメチル基で置換されたフェニル基を表す）を対アニオンとする、スルホニウム塩、ホスホニウム塩、第４級アンモニウム塩、ジアゾニウム塩、または、ヨードニウム塩等が挙げられる。

In the formula (2), the _{^{Y, BF 4 -, PF 6}} -, SbF 6 -, or, _(BX 4) ^- (provided that, X is substituted with at least two fluorine or trifluoromethyl group Examples thereof include a sulfonium salt, a phosphonium salt, a quaternary ammonium salt, a diazonium salt, and an iodonium salt having (representing a phenyl group) as a counter anion.

Among these, examples of the sulfonium salt include triphenylsulfonium boron tetrafluoride, triphenylsulfonium hexafluoride antimony, triphenylsulfonium arsenic pentafluoride, tri (4-methoxyphenyl) sulfonium arsenic pentafluoride and diphenyl (4-methoxyphenyl). Phenylthiophenyl) Sulfonium Arsenic pentafluoride and the like can be mentioned.

Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoride antimony and tetrabutylphosphonium hexafluoride antimony.

Examples of the quaternary ammonium salt include dimethylphenyl (4-methoxybenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate, and dimethylphenyl (4-methoxybenzyl) ammonium tetrakis ( Pentafluorophenyl) borate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorohexafluorophosphate, dimethylphenyl (4-methylbenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorotetrax (pentafluoro) Phenyl) borate, methylphenyldibenzylammonium, methylphenyldibenzylammonium hexafluoroantimonate hexafluorophosphate, methylphenyldibenzylammonium tetrakis (pentafluorophenyl) borate, phenyltribenzylammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (3,4-Dimethylbenzyl) Ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethyl-N-benzylanilium hexafluoride antimony, N, N-diethyl-N-benzylanilium tetrafluoride, N , N-Dimethyl-N-benzylpyridinium hexafluorinated antimonium and N, N-diethyl-N-benzylpyridinium trifluoromethanesulfonic acid and the like.

The thermal cationic polymerization initiator used in this embodiment is also a known compound, and a general commercially available product can be used in this embodiment.

Commercially available thermal cationic polymerization initiators include, for example, Sun Aid SI-60, Sun Aid SI-80, Sun Aid SI-B3, Sun Aid SI-B3A and Sun Aid SI-B4 (all of which are Sanshin Kagaku Kogyo). CXC1612, CXC1738, CXC1821 (all manufactured by King Industries) and the like.

The adhesive composition according to the present embodiment preferably contains a novolak type epoxy resin in an amount of 90 to 99.5 parts by weight, more preferably 95 to 99.5 parts by weight, still more preferably, based on 100 parts by weight of the adhesive composition. Contains 98 to 99 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, still more preferably 1 to 2 parts by weight of the thermal cationic polymerization initiator.

It is preferable that the novolak type epoxy resin and the thermal cationic type polymerization initiator contained in the adhesive composition are within these ranges from the viewpoint that the outgas by the adhesive composition can be sufficiently reduced.

The adhesive composition according to the present embodiment can be prepared by simply mixing the above two components by a conventional method and homogenizing them.

In the present embodiment, the adhesive composition may be used as it is, or may be optionally mixed with an additive component.

The adhesive composition according to the present embodiment is a thermosetting epoxy resin composition having excellent heat resistance, heat cycle resistance, and adhesiveness. The adhesive composition according to the present embodiment also contributes to low outgassing.

Therefore, the adhesive composition can be used alone or by blending other additive components as an adhesive for a gas barrier property evaluation device, for example, which will be described later.

Examples of known additive components that can be blended in the adhesive for a gas barrier property evaluation device include a curing accelerator, a filler, and a phosphorus compound.

Among these additive components, examples of the curing accelerator include heat curing accelerators such as triphenylphosphine, imidazole, aliphatic amines, and tertiary and secondary amines. Examples of the filler include spherical silica, talc, aluminum oxide and the like. Further, examples of the filler include phosphorus compounds and the like. These additive components can be arbitrarily blended within the range in which the effect of the adhesive composition is exhibited.

The adhesive for the gas barrier property evaluation device may be used as it is, or by simply mixing and homogenizing the adhesive composition and the above-mentioned additive component by a conventional method. It may be prepared.

Subsequently, an adhesive layer containing such an adhesive composition will be described.

[Adhesive layer]
The adhesive layer according to the present embodiment contains the above-mentioned adhesive composition. The method for forming the adhesive layer is not particularly limited, and the adhesive composition may be first applied to a base material or the like, and then heat treatment may be performed, for example. In the present specification, the adhesive layer refers to a state after the adhesive composition is cured by heat treatment or the like.

The amount of the adhesive composition applied to the substrate when forming the adhesive layer is not particularly limited, but is preferably 50 to 200 g / m ² , more preferably 60 to 150 g / m ² , and even more preferably. Is 80 to 100 g / m ² .

The thickness of the adhesive layer is not particularly limited, but is preferably 38 to 154 μm, more preferably 46 to 115 μm, and even more preferably 62 to 77 μm.

The heating temperature at which the adhesive composition is cured is not particularly limited, but is preferably 60 to 150 ° C, more preferably 80 to 120 ° C, and even more preferably 80 to 100 ° C.

Next, a support joint body provided with such an adhesive layer will be specifically described.

[Supported joint]
FIG. 1 is a schematic view schematically showing the configuration of a support joint according to the present embodiment. Explaining with reference to FIG. 1, the support joint 10 includes an adhesive layer 11, a base material 12, and a support 16. The adhesive layer 11 is laminated on the base material 12, and the support 16 is laminated on the adhesive layer 11. The support joint 10 supports, for example, the film 17.

In the present embodiment, a punching metal 15 for preventing deformation of the support 16 is joined to the support joint 10 by welding to the base material 12. However, the support joint 10 may be configured not to include the punching metal 15.

In the present embodiment, the constituent materials of the base material 12 and the support 16 and their shapes are not particularly limited. For example, when the support joint 10 is used in the gas barrier property evaluation device described later, the base material 12 is SUS. It is preferable that it is made of a metal such as. On the other hand, the support 16 is preferably formed of, for example, a film such as polyimide (PI), polyamide (PA), polyethylene terephthalate (PET), or polyethylene naphthalate (PEN). At that time, the thickness of the film is not particularly limited, but is preferably 25 to 200 μm, more preferably 80 to 150 μm, and further preferably 100 to 125 μm.

In the present embodiment, the support bonding body 10 is obtained, for example, by applying the above-mentioned adhesive composition on the base material 12, laminating the support 16 on the base material 12, and then curing the adhesive composition. Be done.

Finally, a gas barrier property evaluation device provided with such a support joint will be specifically described.

[Gas barrier property evaluation device]
FIG. 2 is a schematic view schematically showing the configuration of a gas barrier property evaluation device including the support joint according to the present embodiment. Members having the same functions as the members already described will be designated by the same reference numerals, and the description thereof will be omitted.

Explaining with reference to FIG. 2, the gas barrier property evaluation device 20 is a device for measuring water permeability of a film such as water vapor or gas permeability such as oxygen, and is a support bonding body 10, a tank 21, and a sample. It includes a chamber 22, a detector 23, and a vacuum pump 24.

The support joint 10 is provided in the sample chamber 22, and a film 17 for measurement is placed on the support joint 10. If necessary, the gas barrier property evaluation device 20 may be provided with a holding portion 18 for holding the film 17 in order to stabilize the position of the film 17 at the time of measurement.

Examples of the film 17 used in the gas barrier property evaluation device 20 include a barrier film for organic EL and a film for food.

When measuring the permeability of the film 17 such as water or gas, a vacuum pump 24 creates a differential pressure in the sample chamber 22. Then, gas is introduced from the tank 21 side through the film 17 at an arbitrary pressure to bring the vacuum pump 24 side into an ultra-high vacuum state. Then, water or gas or the like flows out from the tank 21 to the sample chamber 22, and the amount of water or gas or the like that has passed through the film 17 is detected by the detector 23.

According to the present embodiment, the adhesive layer 11 included in the support bonding body 10 contains an adhesive composition having excellent heat resistance and thermal cycle characteristics. Therefore, for example, even if the inside of the sample chamber 22 is raised to a high temperature of, for example, 80 ° C. to 130 ° C. for the purpose of removing water in the sample chamber 22, the heat resistance and the thermal cycle characteristics of the adhesive layer 11 are maintained. , Outgas generation can also be suppressed. Therefore, according to the gas barrier property evaluation device 20, the permeability of the film such as water or gas can be efficiently measured and evaluated.

In the present embodiment, the configuration in which the gas barrier property evaluation device having the specific structure shown in FIG. 2 includes the support joint according to the embodiment of the present invention has been described, but the support joint according to the embodiment of the present invention has been described. , In addition to the gas barrier property evaluation device other than those shown in FIG. 2, it may be adopted for other devices. Further, the gas barrier property evaluation device that can adopt the support joint according to the embodiment of the present invention is not limited to the one using the differential pressure method and the isobaric method.

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. It should be noted that these examples and the like do not limit the present invention at all.

[Manufacturing Example 1]
(1) Preparation of adhesive composition:
The adhesive compositions of Examples 1 to 3 and Comparative Examples 1 to 9 were prepared by mixing the components shown in Table 1. The unit of the numerical value indicating the blending amount of each component is a part by weight. The details of each component are as follows.
Epoxy resin (phenol novolac type): Epicron N-730A manufactured by DIC Corporation
Epoxy resin (Bis-A type): ADEKA, ADEKA REGIN EP-4100
Epoxy resin (PO-added Bis-A type): ADEKA, ADEKA Resin EP-4003S
Acrylic resin (MMA): manufactured by Tokyo Chemical Industry Co., Ltd., methyl methacrylate epoxy resin (naphthalene paraxylene type): manufactured by Nippon Steel Chemical Co., Ltd., Espoxy ESN-185
Epoxy resin (polyfunctional type): Tetraglycidyl diaminodiphenylmethane (YH-434) manufactured by Toto Kasei Co., Ltd.
Epoxy resin (hydrogenated Bis-A type): Oleochemical Shell Epoxy, Epicoat 828EL
Thermal cation type polymerization initiator: manufactured by Sanshin Chemical Co., Ltd., SI-60L
Photocationic polymerization initiator: ADEKA Arkuru's SP-170
Hardener (naphthalene paraxylene novolac resin): manufactured by Nippon Steel Chemical Co., Ltd., SN-180
Hardener (phenol novolac resin): Sumilite resin PR-53195 manufactured by Sumitomo Dures
Curing accelerator (triphenylphosphine): manufactured by Wako Pure Chemical Industries, Ltd., first-class filler (spherical silica): manufactured by Denka Co., Ltd., FB-6S
Phosphorus compound (9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide): SANKO-HCA manufactured by Sanko Chemical Co., Ltd.
(2) Preparation of test piece:
Using a doctor blade YD-3 manufactured by Yoshimitsu Seiki Co., Ltd., a coating film having a thickness of 100 μm was formed by applying the respective adhesive compositions to the base material in Examples 1 to 3 and Comparative Examples 1 to 9. did. Then, the following treatments were performed on Examples 1 to 3, Comparative Examples 1 and 2, and Comparative Examples 3 to 5 to obtain film-shaped test pieces.

(Examples 1 to 3 and Comparative Examples 1 and 2: Thermosetting epoxy resin adhesive)
The substrate on which the coating film was molded was heat-treated at 100 ° C. for 2 hours to cure the coating film, and a film-shaped test piece was obtained.

(Comparative Examples 3 to 5: Photocurable Epoxy Resin Adhesive)
^{The substrate on which the coating film was molded was irradiated with 6000 mJ / cm 2} (365 nm) using a metal halide lamp UVC-1212 manufactured by Ushio, Inc., and the coating film was cured by heating at 80 ° C. for 1 hour to cure the film. A test piece in the shape was obtained.

[Test Example 1]
The following tests were performed on each of the obtained test pieces.

<Heat resistance>
(A) Measurement of heat resistance:
Using a differential scanning calorimeter DSC7000S manufactured by Bruker, the inflection point of the DSC thermogram when heated at a heating rate of 10 ° C./min was measured, and this inflection point was defined as the glass transition temperature.

(B) Evaluation:
If the glass transition temperature is 150 ° C or higher, the heat resistance is "excellent: ◎", if the glass transition temperature is 149 ° C to 130 ° C, the heat resistance is "good: ○", and if the glass transition temperature is less than 130 ° C. The heat resistance was "inferior: x", which was the evaluation result. The results are shown in Table 1.

<Outgas>
(A) Outgas measurement:
1 g of each of the test pieces of Examples 1 to 3 and Comparative Examples 1 to 9 described above was collected in a vial and heated in a headspace at 85 ° C. for 30 minutes by gas chromatography Clarus500 manufactured by Birkin Elmer. The amount of outgas was measured. The outgas amount was calculated from the total area amount of each test piece based on the detected area of the test piece with a known outgas amount.

(B) Evaluation:
If the outgas amount is 100 ppm or less, the outgas amount reduction effect is "excellent: ◎", if the outgas amount is 101 ppm to 500 ppm or less, the outgas amount reduction effect is "good: ○", and if it exceeds 500 ppm, the outgas amount reduction effect is obtained. “Inferior: ×” was used as the evaluation result. The results are shown in Table 1.

[Manufacturing Example 2]
(1) Preparation of adhesive composition:
The adhesive compositions of Examples 1 to 3 and Comparative Examples 1 to 9 were prepared in the same manner as in Production Example 1 described above.

(2) Formation of support joint:
Using each adhesive composition, the base material (manufactured by SUS306) and the film as a support (manufactured by Toray DuPont, thickness 125 μm, polyimide) are bonded and supported so that ^{the bonding area is 1 cm 2.} A joint was formed.

[Test Example 2]
The obtained support joint was subjected to the following tests.

<Adhesiveness>
(A) Observation of the state of destruction:
An autograph AGH-H manufactured by Shimadzu Corporation was used to apply stress to the support joint in the shearing direction at a tensile speed of 5 mm / min in an environment of 25 ° C., and the fracture state at that time was observed.

(B) Evaluation:
If the film as a support breaks, the adhesiveness is "excellent: ◎", if the film as a support aggregates and breaks, the adhesiveness is "good: ○", and the interface from the film or substrate as a support If peeling occurred, the adhesiveness was evaluated as "poor: x" and the evaluation result was obtained. The results are shown in Table 1.

<Heat cycle resistance>
The obtained support joint is heated in a constant temperature bath DNE601 manufactured by Yamato Kagaku Co., Ltd. at 40 ° C. for 1 hour, then heated from 40 ° C. to 150 ° C. at a heating rate of 1 ° C./min, and 150 ° C. for 1 hour for 1 hour. It was set as a cycle, and it was confirmed whether or not any change (wrinkles, peeling, etc.) occurred in the appearance of the sample after each cycle.

(B) The appearance of the evaluation sample changed when the thermal cycle resistance was "excellent: ◎" when it was 10 cycles or more, and when it was 2 to 9 cycles, the thermal cycle resistance was "good: ○", and 1 cycle. If it is as follows, the heat cycle resistance is "poor: x" and the evaluation result is given. The results are shown in Table 1.

From the above results, the adhesive composition of each example has good heat resistance, adhesiveness, and thermal cycle resistance, and contributes to low outgassing. Further, a comprehensive judgment was found that the adhesive composition of Example 1 was the most excellent.

The adhesive composition of the present invention can be used as an adhesive preferably used in a gas barrier property evaluation device.

10 ... Supporting joint 11 ... Adhesive layer 12 ... Base material 16 ... Support 17 ... Film 18 ... Holding part 20 ... Gas barrier property evaluation device 21 ... Tank 22 ... Sample chamber 24 ... Vacuum pump

Claims (6)

A gas barrier property evaluation device containing an adhesive composition containing a novolak type epoxy resin represented by the following formula (1) and a thermal cationic polymerization initiator represented by the following formula (2). Adhesive for.

In equation (1), n represents an integer from 0 to 10. Further, R ₁ represents any of the following groups.

Further, in the formula (1), R ₂ represents any of the following groups.

Further, the thermal cationic polymerization initiator, Y in the formula (2) _{^{is, BF 4 -, PF 6 -}} , SbF 6 -, or, _(BX 4) ^- (provided that, X is at least two It represents a fluorine or represents a phenyl group substituted with a trifluoromethyl group) and a counter anion, a sulfonium salt. As the novolac type epoxy resin, one or more selected from the group consisting of a phenol novolac type epoxy resin, a xylene novolac type epoxy resin, a dicyclopentadiene (DCPD) phenol novolac type epoxy resin and a biphenyl novolac type epoxy resin. The adhesive for a gas barrier property evaluation device according to claim 1, wherein the adhesive is contained. The gas barrier property evaluation apparatus according to claim 1 or 2, wherein 90 to 99.5 parts by weight of the novolak type epoxy resin and 10 to 0.5 parts by weight of the thermal cationic polymerization initiator are contained. glue. An adhesive layer containing the adhesive for a gas barrier property evaluation device according to any one of claims 1 to 3. With the base material
The adhesive layer laminated on the base material and
A support joint including a support laminated on the adhesive layer.
The support joint body, wherein the adhesive layer is the adhesive layer according to claim 4. A gas barrier property evaluation device comprising the support joint according to claim 5.

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