CN112996874B - Adhesive composition - Google Patents

Adhesive composition Download PDF

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Publication number
CN112996874B
CN112996874B CN201980076501.9A CN201980076501A CN112996874B CN 112996874 B CN112996874 B CN 112996874B CN 201980076501 A CN201980076501 A CN 201980076501A CN 112996874 B CN112996874 B CN 112996874B
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mass
adhesive composition
component
resin
manufactured
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CN112996874A (en
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佐藤大河
久保有希
大桥贤
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Ajinomoto Co Inc
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Ajinomoto Co Inc
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Electroluminescent Light Sources (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Abstract

The present invention provides an adhesive composition comprising the following components (a) to (C): an organic binder, (B) a layered clay mineral, and (C) a compound having a maximum absorption wavelength in a wavelength region of 300 to 430nm.

Description

Adhesive composition
Technical Field
The present invention relates to an adhesive composition suitable for forming an adhesive layer in an optical device such as an organic EL display device.
Background
Organic EL devices are light-emitting devices using organic substances as light-emitting materials, and have been drawing attention in recent years because they can emit light with high luminance at low voltage, and display devices (displays) using organic EL devices are beginning to be used in various applications such as mobile phones and televisions. On the other hand, it is known that the organic EL light emitting element has problems such as deterioration, discoloration, and shortened lifetime due to light in a short wavelength region. For example, patent document 1 discloses a method of blocking light having a wavelength of 390nm or less by a window film for a display having a layer containing an ultraviolet absorber in order to suppress deterioration of an organic EL light-emitting element by ultraviolet rays. Patent document 2 proposes a method of suppressing the deterioration of an organic EL element by providing a layer containing an ultraviolet absorber and a dye compound having an absorption spectrum with a maximum absorption wavelength in a wavelength region of 380 to 430nm in an organic EL display device, in order to suppress the deterioration of the organic EL element, in addition to suppressing the transmission of ultraviolet rays and suppressing the transmission (transmittance) of light having a wavelength of 380 to 430nm. Even in other optical devices such as solar cells, deterioration of elements due to light in a short wavelength region is a problem.
Documents of the prior art
Patent document
Patent document 1: japanese patent application laid-open No. 2018-504622
Patent document 2: japanese patent laid-open publication No. 2018-28974.
Disclosure of Invention
Problems to be solved by the invention
An adhesive layer having the ability to absorb light in the wavelength region of 300 to 430nm (hereinafter, sometimes simply referred to as "light absorption ability in the short wavelength region") is formed in an optical device such as an organic EL display device using an adhesive containing a compound having a maximum absorption wavelength in the wavelength region of 300 to 430nm, and this is effective for suppressing light degradation of the optical device. In order to increase the light absorption capacity in the short wavelength region, it is considered to increase the content of the above-mentioned compound in the adhesive.
However, the solubility of the compound in the adhesive is limited, and when the content is too large, problems such as (1) crystallization of the compound, (2) leakage of the compound from the adhesive, and (3) coloring of the adhesive may occur. Therefore, there is a demand for a method of improving the light absorption capacity in the short wavelength region of the adhesive layer, which is different from increasing the content of the above-mentioned compound. In addition, transparency is also required for the adhesive layer in such an optical device.
The present invention has been made in view of the above circumstances, and an object thereof is to provide an adhesive composition which has a capability of absorbing light in a wavelength region of 300 to 430nm and can form an adhesive layer having good transparency.
Means for solving the problems
The present invention which can achieve the above object is as follows;
[1] an adhesive composition comprising the following components (A) to (C):
(A) An organic binder,
(B) A layered clay mineral, and
(C) A compound having a maximum absorption wavelength in a wavelength region of 300 to 430 nm;
[2] the adhesive composition according to the above [1], wherein the component (B) comprises at least one selected from the group consisting of hydrotalcite and layered silicate minerals;
[3] the adhesive composition according to the above [1], wherein the component (B) comprises hydrotalcite;
[4] the adhesive composition according to the above [1], wherein the component (B) comprises a semi-calcined hydrotalcite;
[5] the adhesive composition according to any one of the above [1] to [4], wherein the content of the component (A) is 25 to 95% by mass relative to 100% by mass of nonvolatile components of the adhesive composition;
[6] the adhesive composition according to any one of the above [1] to [5], wherein the content of the component (B) is 1 to 60% by mass relative to 100% by mass of nonvolatile components of the adhesive composition;
[7] the adhesive composition according to any one of the above [1] to [6], wherein the content of the component (C) is 0.05 to 15% by mass relative to 100% by mass of nonvolatile components of the adhesive composition;
[8] the adhesive composition according to any one of the above [1] to [7], wherein the component (A) comprises at least one selected from olefin resins and epoxy resins;
[9] the adhesive composition according to any one of the above [1] to [8], which is used for forming an adhesive layer in an optical device;
[10] the adhesive composition according to the above [9], wherein the optical device is an organic EL display device.
[11] A bonding sheet comprising:
a support, and
an adhesive layer formed of the adhesive composition according to any one of the above [1] to [8] and provided on the support;
[12] the adhesive sheet according to the aforementioned [11], which is used for forming an adhesive layer in an optical device;
[13] the adhesive sheet according to item [12], wherein the optical device is an organic EL display device.
[14] An optical device having an adhesive layer formed of the adhesive composition according to any one of the above [1] to [8 ];
[15] an organic EL display device having an adhesive layer formed of the adhesive composition according to any one of the above [1] to [8 ].
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, an adhesive composition capable of absorbing light in a wavelength region of 300 to 430nm and forming an adhesive layer having excellent transparency can be obtained.
Detailed Description
The adhesive composition of the present invention comprises the following components (a) to (C):
(A) An organic binder,
(B) Layered clay mineral, and
(C) A compound having a maximum absorption wavelength in a wavelength region of 300 to 430 nm;
the present invention is characterized by using the components (B) and (C) in combination. By using both of the components (B) and (C), the light absorption capability in the short wavelength region (i.e., the capability of absorbing light in the 300 to 430nm wavelength region) of the adhesive layer formed from the adhesive composition can be improved while maintaining the transparency as compared with the case of using one of them;
hereinafter, each component will be described in order. In addition, examples, preferable descriptions, and the like described later may be combined as long as they do not contradict each other.
< (A) organic binder
The organic binder as the component (a) is a resin or rubber capable of fixing the component (B) (i.e., the layered clay mineral) and the component (C) (i.e., a compound having a maximum absorption wavelength in a wavelength region of 300 to 430 nm). The component (A) may be used alone in 1 kind, or 2 or more kinds may be used in combination. In addition, only 1 type of resin or 2 or more types of rubber may be used. Further, as the component (a), a resin and a rubber may be used in combination. As the component (a), a resin and/or a rubber which are known organic binders can be used.
The resin may be any of thermoplastic resins or thermosetting resins. Further, as the resin, a tackifier resin (a tackifier resin) may be used. The thermoplastic resin, the thermosetting resin and the tackifier resin may be used alone in 1 kind, or 2 or more kinds may be used in combination. Further, as the resin, a mixture thereof (for example, a mixture of a thermoplastic resin and a tackifier resin) may be used. The resin and the rubber are described below in this order.
(thermoplastic resin)
Examples of the thermoplastic resin include phenoxy resins, acrylic resins, polyvinyl acetal resins, butyral resins, polyimide resins, polyamideimide resins, polyethersulfone resins, polysulfone resins, olefin resins (e.g., vinyl resins, acrylic resins, butene resins, and isobutylene resins), and the like.
The number average molecular weight of the thermoplastic resin is not particularly limited, but is preferably 1000000 or less, more preferably 750000 or less, further preferably 500000 or less, further preferably 400000 or less, from the viewpoint of providing good coatability of the adhesive composition varnish and good compatibility with other components in the composition. On the other hand, from the viewpoint of preventing sagging of the adhesive composition varnish during application (124951247212461. The number average molecular weight is measured by a Gel Permeation Chromatography (GPC) method (polystyrene conversion). The number average molecular weight obtained by the GPC method can be specifically calculated by using LC-9A/RID-6A manufactured by Shimadzu corporation as a measuring apparatus, shodex K-800P/K-804L/K-804L manufactured by Showa Denko K.K., a column, toluene or the like as a mobile phase, measuring at a column temperature of 40 ℃ and using a standard curve of standard polystyrene.
When a thermoplastic resin is used as the component (A), the thermoplastic resin preferably contains an olefin-based resin. The "olefin-based resin" in the present invention is a resin containing a structural unit derived from an olefin (hereinafter, sometimes simply referred to as "olefin unit") and having an amount of the olefin unit of 50 mass% or more with respect to 100 mass% of the total structural units (i.e., the total of the structural units). In the case where the amount of the olefin unit is 50% by mass or more in the entire constituent units, the modified olefin-based resin having a functional group (for example, an epoxy group, an acid anhydride group, or the like) is also included in the "olefin-based resin" of the present invention. Further, even for a resin which can form a crosslinked structure by its functional group as a modified olefin resin, a resin having a thermoplastic property alone is included in the "thermoplastic resin" in the present invention.
The olefin resin may be used alone in 1 kind, or 2 or more kinds may be used in combination. The olefin-based resin is preferably an ethylene-based resin, a propylene-based resin, a butene-based resin, or an isobutylene-based resin. These olefin resins may be homopolymers, or copolymers such as random copolymers and block copolymers. Examples of the copolymer include a copolymer of 2 or more kinds of olefins and a copolymer of "an olefin" and a monomer other than an olefin such as a non-conjugated diene and styrene ". Examples of preferred copolymers include ethylene-nonconjugated diene copolymers, ethylene-propylene-nonconjugated diene copolymers, ethylene-butene copolymers, propylene-butene-nonconjugated diene copolymers, styrene-isobutylene-styrene copolymers, and the like. As the olefin-based resin, for example, an isobutylene-modified resin, a styrene-isobutylene-modified resin, a modified propylene-butene resin, or the like is preferably used.
From the viewpoint of imparting excellent physical properties (e.g., adhesiveness and the like) to the adhesive layer, the olefinic resin preferably contains at least one selected from the group consisting of an olefinic resin having an acid anhydride group (i.e., carbonyloxycarbonyl group (-CO-O-CO-)) and an olefinic resin having an epoxy group, and more preferably contains an olefinic resin having an acid anhydride group and an olefinic resin having an epoxy group.
The olefin-based resin having an acid anhydride group can be obtained, for example, by graft-modifying an olefin-based resin with an unsaturated compound having an acid anhydride group under radical reaction conditions. Further, the unsaturated compound having an acid anhydride group may be subjected to radical copolymerization together with an olefin or the like. Examples of the unsaturated compound having an acid anhydride group include succinic anhydride, maleic anhydride, and glutaric anhydride. Only 1 kind of the unsaturated compound having an acid anhydride group may be used, or 2 or more kinds may be used in combination.
Similarly, the olefin-based resin having an epoxy group can be obtained by, for example, graft-modifying an olefin-based resin with an unsaturated compound having an epoxy group under a radical reaction condition. In addition, an unsaturated compound having an epoxy group may be subjected to radical copolymerization together with an olefin or the like. Examples of the unsaturated compound having an epoxy group include glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, and allyl glycidyl ether. Only 1 kind of the unsaturated compound having an epoxy group may be used, or 2 or more kinds may be used in combination.
The concentration of the acid anhydride group in the olefin-based resin having an acid anhydride group is preferably from 0.05 to 10mmol/g, more preferably from 0.1 to 5mmol/g. The concentration of the acid anhydride group is obtained from the value of the acid value defined as the mg number of potassium hydroxide required for neutralizing the acid present in 1g of the resin in accordance with JIS K2501. The amount of the olefin-based resin having an acid anhydride group in the olefin-based resin is preferably 0 to 70% by mass, more preferably 5 to 50% by mass.
The concentration of the epoxy group in the olefinic resin having an epoxy group is preferably from 0.05 to 10mmol/g, more preferably from 0.1 to 5mmol/g. The epoxy group concentration was determined from the epoxy equivalent obtained according to JIS K7236-1995. The amount of the olefin-based resin having an epoxy group in the olefin-based resin is preferably 0 to 70% by mass, more preferably 5 to 50% by mass.
From the viewpoint of imparting excellent physical properties such as moisture resistance, the olefin-based resin preferably contains both an olefin-based resin having an acid anhydride group and an olefin-based resin having an epoxy group. Such an olefin-based resin can form a crosslinked structure by reacting an acid anhydride group and an epoxy group by heating, and can form an adhesive layer excellent in moisture resistance and the like. The crosslinked structure is preferably formed in advance when the adhesive sheet is manufactured. The ratio of the olefin-based resin having an acid anhydride group to the olefin-based resin having an epoxy group is not particularly limited as long as an appropriate crosslinked structure can be formed, and the molar ratio of the epoxy group to the acid anhydride group (epoxy group: acid anhydride group) is preferably 100:10 to 100:200, preferably 100:50 to 100:150, particularly preferably 100: 90-100: 110.
the number average molecular weight of the olefin-based resin is not particularly limited, and is preferably 1000000 or less, more preferably 750000 or less, further preferably 500000 or less, further preferably 400000 or less, further preferably 300000 or less, particularly preferably 200000 or less, and most preferably 150000 or less, from the viewpoint of providing good coatability of the organic solvent-containing adhesive composition varnish and good compatibility with other components in the adhesive composition. On the other hand, the number average molecular weight is preferably 500 or more, more preferably 700 or more, from the viewpoints of preventing dishing at the time of coating the adhesive composition varnish, expressing the moisture-proof property of the formed adhesive layer, and improving the mechanical strength. The number average molecular weight in the present invention is measured by a Gel Permeation Chromatography (GPC) method (polystyrene conversion). The number average molecular weight obtained by the GPC method can be specifically calculated as follows: LC-9A/RID-6A manufactured by Shimadzu corporation was used as a measuring apparatus, shodex K-800P/K-804L/K-804L manufactured by Showa Denko K.K. 804L/804L was used as a column, toluene or the like was used as a mobile phase, the column temperature was measured at 40 ℃, and the standard curve of standard polystyrene was used for calculation.
The olefin-based resin is preferably amorphous from the viewpoint of suppressing a decrease in fluidity due to thickening of the varnish of the adhesive composition containing an organic solvent. The non-crystallinity here means that the olefin-based resin does not have a clear melting point, and for example, a resin in which a clear peak is not observed when the melting point of the olefin-based resin is measured by DSC (differential scanning calorimetry) can be used.
Next, specific examples of the olefin-based resin will be described. Specific examples of the isobutylene resin include "OPPANOL B100" (viscosity average molecular weight: 1110000) manufactured by BASF corporation and "B50SF" (viscosity average molecular weight: 400000) manufactured by BASF corporation.
Specific examples of the butene-based resin include "HV-1900" (polybutene, number average molecular weight: 2900) manufactured by JXTG energy Co., ltd., and "HV-300M" (modified product of maleic anhydride-modified liquid polybutene ("HV-300" (number average molecular weight: 1400)) manufactured by Toho chemical industries, a number average molecular weight: 2100, the number of carboxyl groups constituting an acid anhydride group: 3.2/1 molecule, an acid value: 43.4mgKOH/g, and an acid anhydride group concentration: 0.77 mmol/g.
Specific examples of the styrene-isobutylene copolymer include "SIBSTAR T102" manufactured by Kaneka corporation (styrene-isobutylene-styrene block copolymer, number average molecular weight: 100000, styrene content: 30% by mass), "T-YP757B" manufactured by Star light PMC corporation (maleic anhydride-modified styrene-isobutylene-styrene block copolymer, acid anhydride group concentration: 0.464mmol/g, number average molecular weight: 100000), "T-YP766" manufactured by Star light PMC corporation (glycidyl methacrylate-modified styrene-isobutylene-styrene block copolymer, epoxy group concentration: 0.638mmol/g, number average molecular weight: 100000), and "T-YP8920" manufactured by Star light PMC corporation (maleic anhydride-modified styrene-isobutylene-styrene copolymer, acid anhydride group concentration: 0.464mmol/g, number average molecular weight: 35800), and "T-YP8930" manufactured by Star light PMC corporation (glycidyl methacrylate-modified styrene-isobutylene-styrene copolymer, epoxy group concentration: 0.638mmol/g, number average molecular weight: 3500 mmol).
Specific examples of the vinyl resin or the propylene resin include "EPT X-3012P" (ethylene-propylene-5-ethylidene) -2-norbornene copolymer manufactured by Mitsui chemical Co., ltd, "EPT1070" (ethylene-propylene-dicyclopentadiene copolymer) manufactured by Mitsui chemical Co., ltd, "TAFMER A4085" (ethylene-butene copolymer) manufactured by Mitsui chemical Co., ltd.
Specific examples of the ethylene-methyl methacrylate copolymer include: "T-YP429" (a 20 mass% toluene solution of a maleic anhydride-modified ethylene-methyl methacrylate copolymer (amount of methyl methacrylate units relative to 100 mass% of the total of ethylene units and methyl methacrylate units: 32 mass%, acid anhydride group concentration: 0.46mmol/g, number average molecular weight: 2300) manufactured by Star light PMC, "T-YP430" (a maleic anhydride-modified ethylene-methyl methacrylate copolymer, amount of methyl methacrylate units relative to 100 mass% of the total of ethylene units and methyl methacrylate units: 32 mass%, acid anhydride group concentration: 1.18mmol/g, number average molecular weight: 4500) manufactured by Star light PMC, "T-YP431" (a 20 mass% toluene solution of a glycidyl methacrylate-modified ethylene-methyl methacrylate copolymer (epoxy group concentration: 0.64mmol/g, number average molecular weight: 2400)) manufactured by Star light PMC, "T-YP432" (a glycidyl methacrylate-modified ethylene-methyl methacrylate copolymer, epoxy group concentration: 1.63mmol/g, number average molecular weight: 3100) manufactured by Star light PMC).
Specific examples of the propylene-butene copolymer include: "T-YP341" (20 mass% Swazole solution of glycidyl methacrylate modified propylene-butene random copolymer (amount of butene unit: 29 mass% relative to total 100 mass% of propylene unit and butene unit; epoxy group concentration: 0.638mmol/g, number average molecular weight: 155000)) manufactured by Star light PMC "," T-YP279 "(maleic anhydride modified propylene-butene random copolymer, amount of butene unit: 36 mass% relative to total 100 mass% of propylene unit and butene unit; acid anhydride group concentration: 0.464mmol/g, number average molecular weight: 35000) manufactured by Star light PMC", "T-YP276" (glycidyl methacrylate modified propylene-butene random copolymer, amount of butene unit: 36 mass% relative to total 100 mass% of propylene unit and butene unit; epoxy group concentration: 0.638mmol/g, number average molecular weight: 57000) manufactured by Star light PMC ", and" T-YP312 "(maleic anhydride modified propylene-butene random copolymer (amount of butylene unit: 100 mass% relative to total of propylene unit and butene unit: 36 mass%, epoxy group concentration: 0.638mmol/g, number average molecular weight: 57000) manufactured by Star light PMC), and" toluene modified propylene-butene random copolymer "(amount of propylene unit: 29-butene unit: 100 mass% relative to total 100 mass% of propylene unit; 20 mass% of propylene unit: 29-butyl unit; toluene modified propylene unit: 29-butyl unit; 30% and toluene unit) (manufactured by Star light PMC).
When the olefin-based resin includes an olefin-based resin having an epoxy group, an olefin-based resin having a functional group other than an acid anhydride group that can react with an epoxy group can be used. Examples of the functional group include a hydroxyl group, a phenolic hydroxyl group, an amino group, and a carboxyl group.
When the olefin-based resin includes an olefin-based resin having an acid anhydride group, an olefin-based resin having a functional group other than an epoxy group that can react with the acid anhydride group can be used. Examples of the functional group include a hydroxyl group, a primary or secondary amino group, a thiol group, and an oxetanyl group.
The content of the thermoplastic resin (particularly, olefin resin) is not particularly limited. In the case of using a thermoplastic resin (particularly an olefin-based resin), the content thereof is preferably 95% by mass or less, more preferably 85% by mass or less, and still more preferably 80% by mass or less, based on 100% by mass of the nonvolatile components of the adhesive composition, from the viewpoint of good coatability of the varnish of the adhesive composition, and the like. The content of the olefin-based resin is preferably 25% by mass or more, more preferably 30% by mass or more, and still more preferably 35% by mass or more, based on 100% by mass of the nonvolatile components in the adhesive composition.
(thermosetting resin)
Examples of the thermosetting resin include epoxy resins, phenol resins, naphthol resins, benzoxazine resins, active ester resins, cyanate ester resins, carbodiimide resins, amine resins, and acid anhydride resins.
When a thermosetting resin is used as the organic binder, the thermosetting resin preferably contains an epoxy resin. As the epoxy resin, a resin having 2 or more epoxy groups per 1 molecule on average can be used. However, even if the resin has an epoxy group, as described above, the resin is included in the "olefin-based resin" of the present invention when the amount of olefin units is 50% by mass or more in the entire structural units. Examples of the epoxy resin include: hydrogenated epoxy resins (hydrogenated bisphenol a epoxy resins, hydrogenated bisphenol F epoxy resins, and the like), fluorine-containing epoxy resins, chain aliphatic epoxy resins, cyclic aliphatic epoxy resins, bisphenol a epoxy resins, biphenyl aralkyl epoxy resins, fluorene epoxy resins, naphthol epoxy resins, naphthalene epoxy resins, bisphenol F epoxy resins, phosphorus epoxy resins, bisphenol S epoxy resins, aromatic glycidyl amine epoxy resins (for example, tetraglycidyl diaminodiphenylmethane, triglycidyl-p-aminophenol, diglycidyl toluidine, diglycidyl aniline, and the like), alicyclic epoxy resins, phenol novolac epoxy resins, alkylphenol epoxy resins, cresol novolac epoxy resins, bisphenol a novolac epoxy resins, epoxy resins having a butadiene structure, diglycidyl etherates of bisphenol, diglycidyl etherates of naphthalenediol, diglycidyl etherates of phenols, and diglycidyl etherates of alcohols, and alkyl substituted products of these epoxy resins, and the like.
The epoxy resin may be used in only 1 kind, or 2 or more kinds may be used in combination. The epoxy equivalent of the epoxy resin is preferably from 50 to 5000, more preferably from 50 to 3000, further preferably from 80 to 2000, particularly preferably from 100 to 1500, from the viewpoint of reactivity or the like. The "epoxy equivalent" refers to the number of grams (g/eq) of a resin containing 1 gram equivalent of epoxy groups, and is measured by a method specified in JIS K7236. The weight average molecular weight of the epoxy resin is preferably 5000 or less.
The epoxy resin may be in any of a liquid state and a solid state, and a liquid epoxy resin and a solid epoxy resin may be used in combination. The terms "liquid" and "solid" as used herein mean the state of the epoxy resin at normal temperature (25 ℃) and normal pressure (1 atm). From the viewpoint of coatability, processability, and adhesiveness, it is preferable that 10% by mass or more of the entire epoxy resin used be a liquid epoxy resin. From the viewpoint of kneading property (mixing property) with hydrotalcite and varnish viscosity, it is particularly preferable to use a liquid epoxy resin and a solid epoxy resin in combination. The mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is preferably 1:2 to 1:0, more preferably 1: 1.5-1: 0.
when a thermosetting resin is used as the component (A), the content thereof is preferably 25 to 95% by mass, more preferably 30 to 95% by mass, and still more preferably 35 to 95% by mass, based on 100% by mass of nonvolatile components in the adhesive composition.
When an epoxy resin is used as the component (A), the content thereof is preferably from 25 to 95% by mass, more preferably from 30 to 95% by mass, even more preferably from 35 to 95% by mass, based on 100% by mass of the nonvolatile matter in the adhesive composition.
When an epoxy resin is used as the component (a), a phenoxy resin as a thermoplastic resin can be further used as the component (a). When the epoxy resin and the epoxy resin are used in combination, the content of the epoxy resin is preferably 25 to 90% by mass, more preferably 30 to 90% by mass, and still more preferably 40 to 90% by mass, based on 100% by mass of the nonvolatile components of the adhesive composition, and the content of the phenoxy resin is preferably 0.1 to 60% by mass, more preferably 3 to 60% by mass, and still more preferably 5 to 50% by mass, based on 100% by mass of the nonvolatile components of the adhesive composition.
When an epoxy resin and a phenoxy resin are used in combination, the weight average molecular weight of the epoxy resin is preferably 5000 or less, and the weight average molecular weight of the phenoxy resin is preferably 10000 to 500000, more preferably 20000 to 300000. These weight average molecular weights were measured by a Gel Permeation Chromatography (GPC) method (polystyrene conversion).
(tackifying resin)
When a thermoplastic resin (particularly, an olefin resin) and/or a rubber is used as the component (a), a tackifier resin is preferably used in order to improve the adhesiveness of the adhesive composition. The tackifier resin may be used alone in 1 kind, or 2 or more kinds may be used in combination.
Examples of the tackifier resin include terpene resins, terpene phenolic resins, rosin tackifier resins, hydrogenated terpene resins, aromatic modified terpene resins, coumarone resins, indene resins, petroleum resins (aliphatic petroleum resins, aromatic petroleum resins, aliphatic aromatic copolymer petroleum resins, alicyclic petroleum resins, dicyclopentadiene petroleum resins, hydrogenated dicyclopentadiene petroleum resins, and the like), saturated aliphatic hydrocarbon resins, and saturated hydrocarbon resins containing a cyclohexane ring.
Commercially available tackifier resins include, for example, the following. Examples of the terpene resin include YS resin PX and YS resin PXN (both manufactured by YASUHARA chemical corporation). Examples of the aromatic modified terpene resin include YS resins of the TO and TR series (both of YASUHARA chemical Co., ltd.). Examples of the hydrogenated terpene resin include CLEARON P, CLEARON M, and CLEARON K series (all manufactured by YASUHARA chemical corporation). Examples of the terpene phenolic resin include YS POLYSTAR 2000, POLYSTAR U, POLYSTAR T, POLYSTAR S, and MightyAce G (both manufactured by YASUHARA Chemicals Co., ltd.). Examples of the saturated aliphatic hydrocarbon resin include Escorez5300 series, 5600 series (both manufactured by Exxon Mobil Co., ltd.), ARKON P100, ARKON P125, and ARKON P140 (both manufactured by Seikagawa chemical Co., ltd.). Examples of the saturated hydrocarbon resin containing a cyclohexane ring include TFS13-030 (manufactured by Mitsukawa chemical Co., ltd.). Examples of the aromatic petroleum resin include ENDEX155 (manufactured by Eastman corporation). Examples of the aliphatic aromatic copolymer petroleum resin include QuintoneD100 (manufactured by Zeon corporation). Examples of the alicyclic petroleum resin include Quintone1325 and Quintone1345 (both manufactured by nippon).
When the adhesive composition is used in a sheet form, the softening point of the tackifier resin is preferably 50 to 200 ℃, more preferably 50 to 180 ℃, and further preferably 50 to 150 ℃ from the viewpoint of softening the sheet in the laminating step of the adhesive sheet and providing desired heat resistance. The softening point was measured by the ring and ball method in accordance with JIS K2207.
The content of the tackifier resin in the adhesive composition is not particularly limited. However, in the case of using a tackifier resin, the content thereof is preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 65% by mass or less, particularly preferably 60% by mass or less, based on 100% by mass of nonvolatile components in the adhesive composition, from the viewpoint of maintaining good moisture permeability resistance of the adhesive composition. On the other hand, in the case of using a tackifier resin, the content thereof is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more, based on 100% by mass of nonvolatile components in the adhesive composition, from the viewpoint of sufficient adhesiveness.
From the viewpoint of the adhesiveness, moisture permeation resistance, compatibility and the like of the composition, the tackifier resin is preferably a saturated aliphatic hydrocarbon resin, an aromatic petroleum resin, an aliphatic aromatic copolymer petroleum resin, an alicyclic petroleum resin, and more preferably a saturated aliphatic hydrocarbon resin (e.g., ARKON P125).
The number average molecular weight of the tackifier resin is preferably 500 or more, more preferably 700 or more, further preferably 2000 or less, further preferably 1500 or less, further preferably 1000 or less. The number average molecular weight is measured by a Gel Permeation Chromatography (GPC) method (in terms of polystyrene).
(rubber)
When a rubber is used as the component (A), the rubber may be any of diene rubbers and non-diene rubbers. Examples of the rubber include butyl rubber (IIR), isoprene Rubber (IR), butadiene Rubber (BR), carboxylated styrene-butadiene rubber-like copolymer (XSBR), chlorinated isobutylene-isoprene rubber-like Copolymer (CIIR), brominated isobutylene-isoprene rubber-like copolymer (BIIR), and the like. Among them, butyl rubber, isoprene rubber and butadiene rubber are preferred, and butyl rubber is more preferred.
From the viewpoint of further improving the adhesiveness, the adhesion heat and humidity resistance, and the like of the adhesive composition, the rubber includes at least one selected from the group consisting of a rubber having an acid anhydride group (i.e., carbonyloxycarbonyl group (-CO-O-CO-)) and a rubber having an epoxy group, and more preferably includes a rubber having an acid anhydride group and a rubber having an epoxy group.
The rubber having an acid anhydride group can be obtained, for example, by graft-modifying a rubber with an unsaturated compound having an acid anhydride group under radical reaction conditions. Further, the unsaturated compound having an acid anhydride group may be subjected to radical copolymerization together with an olefin or the like. Examples of the unsaturated compound having an acid anhydride group include succinic anhydride, maleic anhydride, and glutaric anhydride. Only 1 kind of the unsaturated compound having an acid anhydride group may be used, or 2 or more kinds may be used in combination.
Similarly, the rubber having an epoxy group can be obtained, for example, by graft-modifying the rubber with an unsaturated compound having an epoxy group under a radical reaction condition. In addition, the rubber having an ethylenic double bond may be subjected to radical copolymerization together with an unsaturated compound having an epoxy group. Examples of the unsaturated compound having an epoxy group include glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, and allyl glycidyl ether. Only 1 kind of the unsaturated compound having an epoxy group may be used, or 2 or more kinds may be used in combination.
The rubber having an acid anhydride group is preferably a butyl rubber having an acid anhydride group, an isoprene rubber having an acid anhydride group, or a butadiene rubber having an acid anhydride group, and particularly preferably a butyl rubber having an acid anhydride group. Further, as the rubber having an epoxy group, a butyl rubber having an epoxy group, an isoprene rubber having an epoxy group, and a butadiene rubber having an epoxy group are preferable, and a butyl rubber having an epoxy group is particularly preferable.
The concentration of the acid anhydride group in the rubber having an acid anhydride group is preferably from 0.05 to 10mmol/g, more preferably from 0.1 to 5mmol/g. The concentration of the acid anhydride group is obtained from the value of the acid value defined as the mg number of potassium hydroxide required for neutralizing the acid present in 1g of the rubber in accordance with JIS K2501.
The concentration of the epoxy group in the rubber having an epoxy group is preferably from 0.05 to 10mmol/g, more preferably from 0.1 to 5mmol/g. The epoxy group concentration can be determined from the epoxy equivalent obtained according to JIS K7236-1995.
From the viewpoint of good coatability of the adhesive composition varnish and good compatibility of the rubber with other components, the number average molecular weight of the rubber is preferably 1000000 or less, more preferably 750000 or less, further preferably 500000 or less, particularly preferably 400000 or less. On the other hand, from the viewpoint of preventing the dent or the like of the sealing composition varnish at the time of coating, the number average molecular weight of the rubber is preferably 2000 or more, more preferably 10000 or more, further preferably 30000 or more, particularly preferably 50000 or more. The number average molecular weight is measured by a Gel Permeation Chromatography (GPC) method (polystyrene conversion).
The content of the rubber is not particularly limited. In the case of using a rubber, the content thereof is preferably 80% by mass or less, more preferably 75% by mass or less, further preferably 70% by mass or less, 65% by mass or less, further preferably 60% by mass or less, based on 100% by mass of the nonvolatile component of the adhesive composition, from the viewpoint of good coatability of the adhesive composition varnish, and the like. The content of the rubber is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, further preferably 7% by mass or more, further preferably 10% by mass or more, particularly preferably 15% by mass or more, most preferably 20% by mass or more, based on 100% by mass of the nonvolatile matter in the adhesive composition.
(preferred mode)
Hereinafter, preferred embodiments of the present invention will be described in order for the component (a). In one embodiment of the present invention, the component (a) preferably contains an olefinic resin, and more preferably contains an olefinic resin and a tackifier resin. In one embodiment of the present invention, the component (a) preferably contains a rubber such as butyl rubber, isoprene rubber, or butadiene rubber, and more preferably contains butyl rubber. In addition, as one embodiment of the present invention, the component (a) preferably contains a rubber and a tackifier resin.
When the component (a) contains the olefin-based resin having an acid anhydride group and/or the rubber having an acid anhydride group, the amount of the olefin-based resin having an acid anhydride group and/or the rubber having an acid anhydride group is preferably 1 to 70% by mass, more preferably 10 to 50% by mass, based on the whole component (a). In the case of the embodiment in which the component (a) contains an olefin-based resin having an epoxy group and/or a rubber having an epoxy group, the amount of the olefin-based resin having an epoxy group and/or the rubber having an epoxy group is preferably 1 to 70% by mass, more preferably 10 to 50% by mass, based on the entire component (a).
From the viewpoint of further improving the moisture resistance of the adhesive composition, the present invention is preferably an embodiment satisfying at least one of the following (a) to (d):
(a) The method comprises the following steps The component (A) comprises an olefin resin having an acid anhydride group and an olefin resin having an epoxy group;
(b) The method comprises the following steps The component (A) comprises a rubber having an acid anhydride group and a rubber having an epoxy group;
(c) The method comprises the following steps The component (A) comprises an olefin resin having an acid anhydride group and a rubber having an epoxy group;
(d) The method comprises the following steps The component (A) contains a rubber having an acid anhydride group and an olefin resin having an epoxy group.
In the embodiments (a) to (d), the acid anhydride group and the epoxy group are reacted with each other by heating the component (a) to form a crosslinked structure. Therefore, an adhesive layer having improved moisture permeation resistance and the like can be formed from the adhesive composition of the present invention. The crosslinked structure may be formed when the adhesive layer is formed from the adhesive composition, but it is preferable to form the crosslinked structure in advance in the adhesive layer formed on the support when the adhesive sheet is produced.
The ratio of the "olefin-based resin having an acid anhydride group and/or rubber having an acid anhydride group" to the "olefin-based resin having an epoxy group and/or rubber having an epoxy group" is not particularly limited as long as an appropriate crosslinked structure can be formed, and the molar ratio of the epoxy group to the acid anhydride group (epoxy group: acid anhydride group) is preferably 100:10 to 100:200, preferably 100:50 to 100:150, particularly preferably 100: 90-100: 110.
in one embodiment of the present invention, the component (a) is preferably a mixture of (i) a butyl rubber, (ii) a butyl rubber having an acid anhydride group and a butyl rubber having an epoxy group, or (iii) a mixture of a butyl rubber, a butyl rubber having an acid anhydride group and a butyl rubber having an epoxy group.
In the present invention, when the olefinic resin and the rubber are used together as the component (A), the mixing ratio of the olefinic resin and the rubber (olefinic resin/rubber) is preferably 1/99 to 50/50, more preferably 10/90 to 45/55, in terms of mass ratio.
In one embodiment of the present invention, the component (a) preferably contains at least one selected from the group consisting of an olefin resin and an epoxy resin, and more preferably contains an olefin resin or an epoxy resin. By using such a component (a), the adhesive composition can have low moisture permeability, suppressed occurrence of outgas (out gas), and more excellent transparency.
The content of the component (A) is preferably 25% by mass or more, more preferably 30% by mass or more, further preferably 35% by mass or more, more preferably 95% by mass or less, further preferably 93% by mass or less, further preferably 90% by mass or less, based on 100% by mass of nonvolatile components in the adhesive composition.
(B) layered Clay mineral
One of the characteristics of the adhesive composition of the present invention is that the component (B) contains a layered clay mineral. By using the layered clay mineral, the absorption of light in the wavelength region of 300 to 430nm can be improved while maintaining the transparency of the adhesive layer obtained from the adhesive composition. The component (B) may be used alone or in combination of 2 or more. The layered clay mineral may be a processed layered clay mineral (e.g., semi-calcined hydrotalcite, etc.) as described below, or may be an artificial product.
Examples of the layered clay mineral include hydrotalcite and a layered silicate mineral. Hereinafter, they will be described in order.
(hydrotalcite)
Hydrotalcites can be classified into uncalcined hydrotalcites, semi-calcined hydrotalcites, and calcined hydrotalcites.
The uncalcined hydrotalcite is, for example, a natural hydrotalcite (Mg) 6 Al 2 (OH) 16 CO 3 ・4H 2 O) is a metal hydroxide having a layered crystal structure typified by, for example, a layer [ Mg ] formed into a basic skeleton 1-X Al X (OH) 2 ] X＋ And an intermediate layer [ (CO) 3 ) X/2 ・mH 2 O] X- And (4) forming. The uncalcined hydrotalcite in the present invention is a concept of a hydrotalcite-like compound including synthetic hydrotalcite and the like. As the hydrotalcite-like compound, there is a hydrotalcite-like compound,examples thereof include compounds represented by the following formula (I) and the following formula (II).
[M 2＋ 1-x M 3＋ x (OH) 2 ] x＋ ・[(A n- ) x/n ・mH 2 O] x- (I)
(in the formula, M 2＋ Represents Mg 2＋ 、Zn 2＋ Divalent metal ion of equal valence, M 3＋ Represents Al 3＋ 、Fe 3＋ Iso-trivalent metal ion, A n- Denotes CO 3 2- 、Cl - 、NO 3 - The anion with the valence of n is equal to the anion, x is more than 0 and less than 1, m is more than or equal to 0 and less than 1, and n is a positive number. )
In the formula (I), M 2＋ Preferably Mg 2＋ ，M 3＋ Preferably Al 3＋ ，A n- Preferably CO 3 2- 。
M 2＋ x Al 2 (OH) 2x＋6-nz (A n- ) z ・mH 2 O (II)
(in the formula, M 2＋ Represents Mg 2＋ 、Zn 2＋ An isodivalent metal ion, A n- Represents CO 3 2- 、Cl - 、NO 3 - An n-valent anion, x is a positive number of 2 or more, z is a positive number of 2 or less, m is a positive number, and n is a positive number. )
In the formula (II), M 2＋ Preferably Mg 2＋ ，A n- Preferably CO 3 2- 。
The semi-calcined hydrotalcite is a metal hydroxide having a layered crystal structure in which the amount of interlayer water is reduced or eliminated, which is obtained by calcining an uncalcined hydrotalcite. "interlayer Water", when expressed by the compositional formula, means "H" described in the compositional formula of the uncalcined natural hydrotalcite and hydrotalcite-like compound 2 O”。
On the other hand, calcined hydrotalcite is not only interlayer water (H) obtained by calcining uncalcined hydrotalcite or semi-calcined hydrotalcite 2 O) and a hydroxyl group (OH) which disappears by condensation and dehydration, and has an amorphous structureThe metal oxide of (1).
The uncalcined hydrotalcite, semi-calcined hydrotalcite and calcined hydrotalcite can be distinguished by the saturated water absorption. The saturated water absorption of the semi-calcined hydrotalcite is 1 mass% or more and less than 20 mass%. On the other hand, the non-calcined hydrotalcite has a saturated water absorption of less than 1 mass%, and the calcined hydrotalcite has a saturated water absorption of 20 mass% or more.
The "saturated water absorption" in the present invention is a mass increase rate with respect to an initial mass after measuring the initial mass using a scale of 1.5g of uncalcined hydrotalcite, semi-calcined hydrotalcite or calcined hydrotalcite and allowing the hydrotalcite to stand for 200 hours in a small environmental tester (SH-222 manufactured by ESPEC) set at 60 ℃ and 90% RH (relative humidity) under atmospheric pressure, and can be obtained by the following formula (i),
saturated water absorption (mass%) =100 × (mass after moisture absorption-initial mass)/initial mass (i).
The saturated water absorption of the semi-calcined hydrotalcite is preferably 3 mass% or more and less than 20 mass%, more preferably 5 mass% or more and less than 20 mass%.
Furthermore, the uncalcined hydrotalcite, the semi-calcined hydrotalcite and the calcined hydrotalcite can be distinguished by the rate of thermal weight loss as measured by thermogravimetric analysis. The thermal weight loss rate of the semi-calcined hydrotalcite at 280 ℃ is less than 15 mass%, and the thermal weight loss rate thereof at 380 ℃ is more than 12 mass%. On the other hand, the thermal weight loss rate at 280 ℃ of the uncalcined hydrotalcite is 15 mass% or more, and the thermal weight loss rate at 380 ℃ of the calcined hydrotalcite is less than 12 mass%.
Thermogravimetric analysis can be performed as follows: hydrotalcite 5mg was weighed into an aluminum sample pan using TG/DTA EXSTAR6300 manufactured by Highettech SCIENCE, and heated from 30 ℃ to 550 ℃ at a heating rate of 10 ℃/min in an atmosphere of a nitrogen flow rate of 200 mL/min in an open state without a lid. The thermal weight loss ratio can be determined by the following formula (ii),
thermal weight loss ratio (mass%) =100 × (mass before heating-mass at the time of reaching a predetermined temperature)/mass before heating (ii).
The uncalcined hydrotalcite, semi-calcined hydrotalcite and calcined hydrotalcite can be distinguished by the peak and relative intensity ratio measured by powder X-ray diffraction. The semi-calcined hydrotalcite shows a peak that is split into two peaks in the vicinity of 2 θ of 8 to 18 ° by powder X-ray diffraction, or shows a peak having a shoulder due to the synthesis of the two peaks, and the relative intensity ratio (low-angle side diffraction intensity/high-angle side diffraction intensity) between the diffraction intensity (= low-angle side diffraction intensity) of the peak or shoulder appearing on the low-angle side and the diffraction intensity (= high-angle side diffraction intensity) of the peak or shoulder appearing on the high-angle side is 0.001 to 1000. On the other hand, with the uncalcined hydrotalcite, there is only one peak in the vicinity of 8 to 18 °, or the relative intensity ratio of the diffraction intensity of a peak or shoulder appearing on the low angle side to a peak or shoulder appearing on the high angle side is out of the aforementioned range. The calcined hydrotalcite has no characteristic peak in a region of 8 ° to 18 °, and has a characteristic peak at 43 °. For the powder X-ray diffraction measurement, a powder X-ray diffraction apparatus (PANalytical, empyrean) was used to measure the refractive index of CuK α (1.5405 \8491) as a counter cathode and the refractive index of voltage: 45V, current: 40mA, sampling width: 0.0260 °, scan speed: 0.0657 °/s, measured diffraction angle range (2 θ): 5.0131-79.9711 degree. Peak search (peak search) can be performed by using the peak search function of software attached to the diffraction device, and the peak search function is performed at a "minimum saliency: 0.50, minimum peak tip (peak tip): 0.01 °, maximum peak tip: 1.00 °, peak baseline width: 2.00 °, method: minimum value of second order differential ".
The BET specific surface area of the hydrotalcite (particularly, semi-calcined hydrotalcite) is preferably from 1 to 250m 2 A ratio of the total amount of the acid to be used is preferably 5 to 200m 2 (ii) in terms of/g. The BET specific surface area of hydrotalcite can be calculated by a BET multipoint method using a specific surface area measuring apparatus (Macsorb HM Model 1210, manufactured by MOUNTECH) to adsorb nitrogen gas onto the surface of a sample.
The hydrotalcite (particularly, semi-calcined hydrotalcite) preferably has an average particle diameter of 1 to 1000nm, more preferably 10 to 800nm. The average particle diameter of hydrotalcite is a median particle diameter of a particle size distribution when the particle size distribution is prepared on a volume basis by a laser diffraction scattering particle size distribution measurement (JIS Z8825).
Hydrotalcite (particularly, semi-calcined hydrotalcite) may be surface-treated with a surface treatment agent. As the surface treatment agent used for the surface treatment, for example, higher fatty acids, alkylsilanes, silane coupling agents, and the like can be used, and among them, higher fatty acids and alkylsilanes are preferable. The surface treatment agent may be used in 1 kind or 2 or more kinds.
Examples of the higher fatty acid include higher fatty acids having 14 or more carbon atoms such as stearic acid, montanic acid, myristic acid and palmitic acid, and among them, stearic acid is preferred. These may be used in 1 or 2 or more.
Examples of the alkylsilanes include: methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, dimethyldimethoxysilane, octyltriethoxysilane, n-octadecyl dimethyl (3- (trimethoxysilyl) propyl) ammonium chloride, and the like. These may be used in 1 or 2 or more.
Examples of the silane coupling agent include: epoxy silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyl (dimethoxy) methylsilane and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane; mercapto silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 11-mercaptoundecyltrimethoxysilane; amino silane coupling agents such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane; ureido silane coupling agents such as 3-ureidopropyltriethoxysilane, vinyl silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane and vinylmethyldiethoxysilane; styrene-based silane coupling agents such as p-styryltrimethoxysilane; acrylate-based silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanatopropyltrimethoxysilane; sulfide-based silane coupling agents such as bis (triethoxysilylpropyl) disulfide and bis (triethoxysilylpropyl) tetrasulfide; phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazolesilane, triazinesilane and the like. These may be used in 1 or 2 or more.
The surface treatment of hydrotalcite (particularly, semi-calcined hydrotalcite) can be carried out, for example, by adding a surface treatment agent to untreated hydrotalcite and stirring the mixture for 5 to 60 minutes while dispersing the untreated hydrotalcite in a mixer under stirring at room temperature. As the mixer, known mixers can be used, and examples thereof include mixers such as a V-type mixer (blender), a ribbon mixer (ribbon blender), a double cone mixer (e.g., a mechanical mixer such as a mechanical mixer (e.g., a mechanical mixer). Further, the above-mentioned higher fatty acid, alkylsilane, or silane coupling agent may be added to the hydrotalcite to be subjected to surface treatment when the hydrotalcite is pulverized by a ball mill or the like. The amount of the surface-treating agent to be used varies depending on the kind of hydrotalcite, the kind of the surface-treating agent, etc., and is preferably 1 to 10 parts by mass based on 100 parts by mass of the hydrotalcite which is not subjected to the surface treatment. In the present invention, the hydrotalcite having been subjected to surface treatment is also included in the "hydrotalcite" in the present invention.
When calcined hydrotalcite and/or semi-calcined hydrotalcite is used as component (B), the moisture barrier properties of the resulting adhesive layer are improved because of their excellent moisture absorption properties.
Examples of the semi-calcined hydrotalcite include "DHT-4C" (average particle diameter: 400nm, manufactured by Kyowa chemical Co., ltd.) and "DHT-4A-2" (average particle diameter: 400nm, manufactured by Kyowa chemical Co., ltd.). Examples of the calcined hydrotalcite include "KW-2200" (average particle diameter: 400nm, manufactured by Kyowa chemical industries, ltd.). Examples of the uncalcined hydrotalcite include "DHT-4A" (average particle diameter: 400nm, manufactured by Kyowa chemical industries, ltd.).
(layered silicate mineral)
Phyllosilicate minerals are also commonly referred to as phyllosilicate minerals (phyllosilicate minerals). The layered silicate mineral may be used alone or in combination of two or more. As the layered silicate mineral, a natural substance or a synthetic substance may be used. As the crystal structure of the layered silicate mineral, a crystal structure having a high purity (purity) in which the layered silicate mineral is regularly stacked in the c-axis direction is preferably used, but a so-called mixed layered mineral (mixed layered mineral) in which a plurality of crystal structures are mixed, that is, a non-uniform crystal period (crystal period taken from the front of the body of the wafer 12428).
Examples of the layered silicate mineral include smectite (smectite), kaolinite (kaolinite), halloysite (halloyite), talc, and mica. Among them, mica is preferred.
Smectites are represented by the general formula: x 0.2～0.6 Y 2～3 Z 4 O 10 (OH) 2 ･nH 2 O represents a natural or synthetic substance; wherein, X is at least one selected from K, na, 1/2Ca and 1/2Mg, Y is at least one selected from Mg, fe, mn, ni, zn, li, al and Cr, and Z is at least one selected from Si and Al; note that H 2 O represents a water molecule bonded to an interlayer ion; n represents an integer and varies significantly depending on interlayer ions and relative humidity. Examples of smectites include: hectorite (Hectrite), montmorillonite (montmorillonite), beidellite (beidellite), nontronite (nontronite), saponite (saponite), ferrosaponite (ferrosaponite), sauconite (sauconite), stevensite (stevensite), bentonite (bentonite), or their substitutions, derivatives, or mixtures thereof. Among them, laponite and montmorillonite are preferred.
The layered silicate mineral may be a commercially available one. Examples of commercially available products include: "SURACTON STN", "SURACTON SAN" (organized hectorite) manufactured by KUNMINE industries, or "Orben M" (organized montmorillonite) manufactured by Bainite industries, or "S-BEN NX" (organized montmorillonite) manufactured by HOJUN industries, or "Benton series" (organized montmorillonite) manufactured by Dongminization industries.
The average particle size of the layered silicate mineral is preferably 1nm to 100. Mu.m, more preferably 5nm to 50 μm, still more preferably 10nm to 10 μm. The average particle size of the layered silicate mineral is a median size of a particle size distribution when the particle size distribution is prepared on a volume basis by a laser diffraction scattering particle size distribution measurement (JIS Z8825).
(preferred mode)
Hereinafter, preferred embodiments of the present invention will be described with respect to the component (B) in order. The component (B) preferably contains at least one member selected from the group consisting of hydrotalcite and layered silicate minerals, more preferably contains hydrotalcite, further preferably contains semi-calcined hydrotalcite, and particularly preferably consists of semi-calcined hydrotalcite. The hydrotalcite and the layered silicate mineral in the above embodiment are described above.
The content of the component (B) is preferably 1 mass% or more, more preferably 3 mass% or more, based on 100 mass% of the nonvolatile component of the adhesive composition, from the viewpoint of sufficiently suppressing the decrease in the light absorption ability in the short wavelength region of the adhesive layer. On the other hand, the content of the component (B) is preferably 60% by mass or less, more preferably 55% by mass or less, based on 100% by mass of nonvolatile components in the adhesive composition, from the viewpoint of improving the transparency of the adhesive layer.
< (C) A compound having a maximum absorption wavelength in a wavelength region of 300 to 430nm
One of the characteristics of the adhesive composition of the present invention is that the component (C) contains a compound having a maximum absorption wavelength (λ max) in a wavelength region of 300 to 430nm. Only 1 kind of component (C) may be used, or 2 or more kinds may be used in combination.
The maximum absorption wavelength (λ max) of the component (C) can be determined by preparing a solution of the component (C) having a concentration such that the absorbance at the maximum absorption wavelength in the light absorption spectrum becomes 1.0, and measuring the light absorption spectrum of the solution. Examples of the solvent used for preparing the solution of the component (C) include chloroform and toluene.
The component (C) preferably has a maximum absorption wavelength (. Lamda.max) of 320 to 430nm, more preferably 350 to 430nm.
Component (C) may be treated as an ultraviolet absorber. A known ultraviolet absorber having a maximum absorption wavelength in the wavelength region of 300 to 430nm can be used as the component (C) in the present invention.
Examples of the component (C) include: curcumin (curcuminoid) -based compounds, benzotriazole-based compounds, benzophenone-based compounds, triazine-based compounds, benzoate-based compounds, cyanoacrylate-based compounds, salicylate-based compounds, azomethine (azomethine) -based compounds, indole-based compounds, cinnamic acid-based compounds, pyrimidine-based compounds, porphyrin-based compounds, cyanoacrylate-based compounds, oxybenzophenone-based compounds, polyphenol-based compounds, and the like. The component (C) is preferably at least one selected from curcumin compounds, benzotriazole compounds and benzophenone compounds.
Examples of curcumin compounds include: 1, 7-bis (4-hydroxy-3-methoxyphenyl) -1, 6-heptadiene-3, 5-dione (manufactured by Sanhe chemical Co., ltd., curcumin (curcumin), λ max =420 nm), 1, 7-bis (4-hydroxyphenyl) -1, 6-heptadiene-3, 5-dione (manufactured by Sanhe chemical Co., ltd., HPH,. Lamda. Max =416 nm), and the like.
Examples of the benzotriazole-based compound include: 2- (2-hydroxy-5-methylphenyl) benzotriazole (manufactured by BASF Japan, tinuvin P,. Lamda.max =341 nm), 2- [ 2-hydroxy-3, 5-bis (. Alpha.,. Alpha. -dimethylbenzyl) phenyl ] -2H-benzotriazole (manufactured by BASF Japan, tinuvin234,. Lamda.max =343 nm), 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) 5-chlorobenzotriazole (manufactured by BASF Japan, tinuvin326,. Lamda.max =353 nm), 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole (manufactured by BASF Japan, tinuvin329,. Lamda.max =343 nm), 2 '-methylenebis [6- (benzotriazol-2-yl) -4-tert-octylphenol ] (manufactured by BASF Japan, tinuvin 360. Lamda., sta349 nm), 5-chloro-2- [3- (tert-butyl) -2-hydroxy-5-methylphenyl ] -2H-benzotriazole (manufactured by BASF Japan, ADEK. K = 341), ADEK. Lamda. (manufactured by ADEK. TM.) -36, ADK.' -2-hydroxy-5-phenyl) benzotriazole (manufactured by BASF Japan, ADK =341, ADK. '-27 nm), N. 5' -di-tert-amylphenyl) benzotriazole (product of Tokyo chemical Co., ltd., JF-80,. Lamda.max =306 nm), 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole (product of Tokyo chemical Co., ltd.,), JF-83,. Lamda.max =343 nm), 2 '-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1, 3-tetramethylbutyl) phenol ] (product of North City chemical Co., ltd., JF-832,. Lamda.max =349 nm), 2- (2, 4-dihydroxyphenyl) -2H-benzotriazole (product of Daohand chemical Co., DAINSORB T-0,. Lamda.max =345 nm), 2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole (product of Daohand chemical Co., DAINSORB T-7,. Lamda.max =345 nm), 2- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole (product of Daohand chemical Co., UV-326,. Lamda.max =353 nm), 2- (3-tert-butyl-2-dihydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole (product of SHIPRODUCT chemical Co., SEORB 703,. Lamda.354 nm).
Examples of the benzophenone-based compound include: 2,2',4,4' -tetrahydroxybenzophenone (Dainsorb P-6, λ max =354nm, manufactured by Daihand chemical Co., ltd.), 2- (3-tert-butyl-2-dihydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole (SEESORB 106, λ max =354nm, manufactured by SHIPRO chemical Co., ltd.), 2,2 '-dihydroxy-4,4' -dimethoxybenzophenone (SEESORB 107, λ max =356nm, manufactured by SHIPRO., ltd.), and the like.
Examples of the triazine compound include: 2- [4- (octyl-2-methylacetate)) oxy-2-hydroxyphenyl ] -4,6- [ bis (2, 4-dimethylphenyl) ] -1,3, 5-triazine (manufactured by BASF Japan, tinuvin479,. Lamda. (max =322 nm), 2- [4- (2-hydroxy-3-dodecyloxy-propyl) oxy-2-hydroxyphenyl ] -4,6- [ bis (2, 4-dimethylphenyl) -1,3, 5-triazine (manufactured by BASF Japan, tinuvin400,. Lamda. (max =336 nm), 2, 4-bis (2-hydroxy-4-butoxyphenyl) -6- (2, 4-dibutoxyphenyl) -1,3, 5-triazine (manufactured by BASF Japan, tinuvin460,. Lamda. (max =346 nm), and the like.
Examples of the benzoate-based compound include diethylamino hydroxybenzoyl hexyl benzoate (Uvinul a Plus, λ max =354nm, manufactured by BASF japan).
Examples of the cyanoacrylate-based compound include: ethyl-2-cyano-3,3-diphenylacrylate (Uvinul 3035,. Lamda. Max =302nm, manufactured by BASF Japan), 2-ethylhexyl-2-cyano-3,3-diphenylacrylate (Uvinul 3039,. Lamda. Max =303nm, manufactured by BASF Japan), 2, 4-dihydroxybenzophenone (Uvinul 3030,. Lamda. Max =308nm, manufactured by BASF Japan).
Examples of the salicylate-based compound include phenyl salicylate (λ max =310 nm) and octyl salicylate (λ max =301 nm). Examples of azomethine compounds include BONASORB UA-3701 (trade name,. Lamda.max =378nm, half-value width: 60nm, manufactured by ORIENT Chemicals Co., ltd.).
Examples of the indole-based compound include BONASORB UA-3911 (trade name,. Lamda.max =395nm, manufactured by ORIENT Chemicals Co., ltd.), BONASORB UA-3912 (trade name,. Lamda.max =390nm, manufactured by ORIENT Chemicals Co., ltd.), and the like.
Examples of the cinnamic acid-based compound include ethylhexyl methoxycinnamate (manufactured by BASF japan, uvinul MC80N, λ max =310 nm), octyl p-methoxycinnamate (λ max =308 nm), glyceryl mono-2-ethylhexanoate (λ max =312 nm) di-methoxycinnamate, parsol MCX (product name, λ max =311nm, manufactured by tesleman Nutrition (DSM Nutrition) japan), neo Heliopan AV (product name, λ max =311nm, manufactured by sym corporation), and the like.
Examples of the pyrimidine compound include FDB-009 (trade name, manufactured by Shantian chemical industries, ltd.; λ max =402 nm). Examples of the porphyrin-based compound include FDB-001 (trade name, manufactured by Shanda chemical industries, ltd.; λ max =420 nm).
From the viewpoint of making the light absorption capacity in the short wavelength region of the adhesive layer formed from the adhesive composition sufficient, the content of the component (C) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, particularly preferably 1% by mass or more, based on 100% by mass of the nonvolatile components of the adhesive composition. On the other hand, the content of the component (C) is preferably 15% by mass or less, more preferably 13% by mass or less, and still more preferably 10% by mass or less, based on 100% by mass of the nonvolatile components in the adhesive composition, in order to improve the transparency of the adhesive layer, and to suppress crystallization or leakage of the component (C), coloring of the adhesive layer, and the like.
< other ingredients >
The adhesive composition of the present invention may contain other components different from the components (a) to (C) within a range not impairing the effects of the present invention. Only 1 type of the other component may be used, or 2 or more types may be used in combination. Examples of other components include: a curing agent; a curing accelerator; an organic solvent; softeners such as mineral oil softeners, vegetable oil softeners, rubber substitutes (ointments), fatty acids, fatty acid salts, and synthetic oils; organic fillers such as rubber particles, silicone powder, nylon powder, and fluororesin powder; defoaming or leveling agents; an adhesion imparting agent; thickeners such as Orben, bentonite (Benton), and the like; an antioxidant; a heat stabilizer; light stabilizers, and the like.
When at least one selected from the group consisting of a thermosetting resin (e.g., an epoxy resin), a thermoplastic resin having an epoxy group (e.g., an olefinic resin having an epoxy group), and a rubber having an epoxy group is used as the component (a), the adhesive composition of the present invention preferably contains a curing agent. Only 1 kind of curing agent may be used, or 2 or more kinds may be used in combination.
The curing agent is not particularly limited, and a known curing agent can be used. Examples of the curing agent include tertiary amine compounds, primary or secondary amine compounds, ionic liquids, acid anhydride compounds, imidazole compounds, dimethylurea compounds, amine addition compounds (amine adducts), organic acid dihydrazide compounds, organic phosphine compounds, and dicyandiamide compounds. The curing agent is preferably a tertiary amine compound.
The adhesive composition of the present invention may contain a curing accelerator. The curing accelerator may be used alone in 1 kind, or 2 or more kinds may be used in combination. The curing accelerator is not particularly limited, and a known curing accelerator can be used. Examples of the curing accelerator include tertiary amine compounds, imidazole compounds, dimethylurea compounds, amine addition compounds, and organic phosphine compounds. The curing accelerator is preferably at least one member selected from the group consisting of tertiary amine compounds, imidazole compounds and dimethylurea compounds.
Examples of the tertiary amine compound as the curing agent or the curing accelerator include: DBN (1, 5-diazabicyclo [4.3.0] non-5-ene), DBU (1, 8-diazabicyclo [5.4.0] undec-7-ene), 2-ethylhexanoate of DBU, phenoxide (phenoxide) of DBU, p-toluenesulfonate of DBU, DBU-organic acid salts such as U-CAT SA 102 (manufactured by SANAPRO corporation: octanoate of DBU), formate of DBU, and 2,4, 6-tris (dimethylaminomethyl) phenol (TAP).
Examples of the primary or secondary amine compound as the curing agent include: aliphatic amines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, 1, 3-bisaminomethylcyclohexane, dipropylenediamine, diethylaminopropylamine, bis (4-aminocyclohexyl) methane, norbornenediamine, and 1, 2-diaminocyclohexane; alicyclic amines such as N-aminoethylpiperazine and 1, 4-bis (3-aminopropyl) piperazine; aromatic amines such as diaminodiphenylmethane, m-phenylenediamine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and diethyltoluenediamine. Examples of commercially available primary or secondary amine compounds include Kayahard A-A (manufactured by Nippon chemical Co., ltd.: 4,4 '-diamino-3, 3' -dimethyldiphenylmethane), and the like.
As the ionic liquid as the curing agent, for example: 1-butyl-3-methylimidazolium lactate, tetrabutylphosphonium-2-pyrrolidone-5-carboxylate, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium trifluoroacetate, tetrabutylphosphonium α -lipoate, tetrabutylphosphonium formate, tetrabutylphosphonium lactate, bis (tetrabutylphosphonium) tartrate, tetrabutylphosphonium hippurate, tetrabutylphosphonium N-methylhippurate, benzoyl-DL-alanine, tetrabutylphosphonium N-acetylphenylalanine, 2, 6-di-tert-butylphenylphosphonium, tetrabutylphosphonium L-aspartate, tetrabutylphosphonium glycinate, 1-ethyl-3-methylimidazolium lactate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium formate, 1-ethyl-3-methylimidazolium hippurate, 1-ethyl-3-methylimidazolium N-methylhippurate, 1-ethyl-3-methylimidazolium tartrate, bis (1-ethyl-3-methylimidazolium) N-acetyl-3-methylglycium, 1-ethyl-3-methylimidazolium tartrate, examples thereof include tetrabutylphosphonium caprate, tetrabutylphosphonium N-acetylglycinate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium formate, 1-ethyl-3-methylimidazolium hippurate and 1-ethyl-3-methylimidazolium N-methylhippurate.
Examples of the acid anhydride compound as the curing agent include: tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, dodecenylsuccinic anhydride, and the like. Examples of commercially available acid anhydride compounds include RIKACID TH, TH-1A, HH, MH-700, and MH-700G (all manufactured by NONSHONJA CHEMICAL CO., LTD.).
Examples of the imidazole compound as the curing agent or the curing accelerator include: 1H-imidazole, 2-methyl-imidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methyl-imidazole, 2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2, 4-diamino-6- (2 '-undecylimidazolyl- (1')) -ethyl-s-triazine, 2-phenyl-4, 5-bis (hydroxymethyl) -imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-phenyl-imidazole, 2-dodecyl-imidazole, 2-heptadecylimidazole, 1, 2-dimethyl-imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 4-diamino-6- (2 '-methylimidazolyl- (1') -ethyl-s-triazine, 2, 4-diamino-6- (2 '-methylimidazolyl- (1') -ethyl-triazine, etc. as an addition product of isocyanuric acid, examples thereof include Curezol 2MZ, 2P4MZ, 2E4MZ-CN, C11Z-CN, C11Z-CNS, C11Z-A, 2PHZ, 1B2MZ, 1B2PZ, C17Z, 1.2DMZ, 2P4MHZ-PW, and, 2MZ-A, 2MA-OK (both manufactured by four national chemical industry Co., ltd.), etc.
Examples of the dimethylurea compound as the curing agent or the curing accelerator include aromatic dimethylurea such as DCMU (3- (3, 4-dichlorophenyl) -1, 1-dimethylurea), U-CAT3512T (manufactured by SANAPRO corporation), and aliphatic dimethylurea such as U-CAT3503N (manufactured by SANAPRO corporation). Among them, aromatic dimethylurea is preferred from the viewpoint of curability.
Examples of the amine adduct compound as the curing agent or the curing accelerator include an epoxy adduct compound (epoxy adduct) obtained by stopping an addition reaction of a tertiary amine and an epoxy resin in the middle, and the like. Examples of commercially available products of the amine adduct-based compound include: ajicure (1245011\\\124611251750).
Examples of the organic acid dihydrazide compound as the curing agent include Ajicure VDH-J, ajicure UDH, and Ajicure LDH (all manufactured by Ajinomoto Fine Chemicals Co., ltd.).
Examples of the organic phosphine compound as the curing agent or the curing accelerator include: triphenylphosphine, tetraphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tri-tert-butylphosphonium tetraphenylborate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, triphenylphosphine triphenylborane, and the like. Examples of commercially available products of the organophosphinic compound include TPP, TPP-MK, TPP-K, TTBuP-K, TPP-SCN, and TPP-S (manufactured by Beixing chemical Co., ltd.).
As the dicyandiamide compound as the curing agent, dicyandiamide may be mentioned, for example. Examples of commercially available dicyandiamide products include DICY7 and DICY15 (both manufactured by mitsubishi chemical corporation) which are fine dicyandiamide grinding products.
In the adhesive composition of the present invention, when a thermosetting resin (particularly an epoxy resin) is used as the component (a), the content of the curing agent is preferably 0.1 to 40% by mass, more preferably 0.5 to 38% by mass, and still more preferably 1 to 25% by mass, based on 100% by mass of the nonvolatile components of the adhesive composition, from the viewpoint of balance between curability and storage stability. When the adhesive composition of the present invention contains a curing accelerator, the content thereof is preferably from 0.05 to 10% by mass, more preferably from 0.1 to 8% by mass, even more preferably from 0.5 to 5% by mass, based on 100% by mass of the nonvolatile components of the adhesive composition, from the same viewpoint as above. When a thermosetting resin (particularly an epoxy resin) is used, it is preferable to use a curing agent in combination with a curing accelerator.
In the adhesive composition of the present invention, when a thermoplastic resin having an epoxy group (particularly, an olefin-based resin having an epoxy group) and/or a rubber having an epoxy group is used as the component (a), the adhesive composition of the present invention preferably contains a curing accelerator. The content of the curing accelerator is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on 100% by mass of the nonvolatile components of the adhesive composition.
The adhesive composition of the present invention may contain an organic solvent. The organic solvent may be used alone in 1 kind, or 2 or more kinds may be used in combination. Examples of the organic solvent include: acetone, methyl ethyl ketone (hereinafter also referred to simply as "MEK"), ketones such as cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate (cellosolve acetate), acetic acid esters such as propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve, carbitols such as butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like. The adhesive composition containing an organic solvent may be referred to as an adhesive composition varnish. The amount of the organic solvent is not particularly limited, but from the viewpoint of coatability, it is preferable to use the organic solvent in an amount such that the viscosity (25 ℃) of the adhesive composition varnish becomes 300 to 2000mPa seeds.
< production of adhesive composition >
The adhesive composition of the present invention can be produced by mixing the above components (a) to (C) and, if necessary, other components. The mixing means is not particularly limited, and mixing can be carried out using known equipment (e.g., kneading rolls, rotary mixers, etc.).
< use of adhesive composition >
The adhesive composition of the present invention is preferably used for forming an adhesive layer in an optical device. The optical device in the present invention refers to an electronic device related to light, and examples thereof include an organic EL display device and a solar cell. In particular, the adhesive composition of the present invention can be suitably used for providing an adhesive layer for blocking light such as ultraviolet rays in an organic EL display device in which deterioration of an organic EL element due to light such as ultraviolet rays is a problem. For example, an adhesive layer in an optical device can be formed by applying a varnish of the adhesive composition to a member of the optical device and drying the varnish.
< adhesive sheet >
The present invention also provides an adhesive sheet comprising a support and an adhesive layer formed from the adhesive composition of the present invention provided on the support. The adhesive sheet of the present invention is also preferably used for forming an adhesive layer in an optical device, similarly to the adhesive composition. For example, an adhesive layer in an optical device can be formed by attaching an adhesive sheet to a component of the optical device and then peeling off a support of the adhesive sheet.
The adhesive sheet of the present invention can be produced, for example, by: the adhesive composition varnish is applied to a support, and the resulting coating film is dried to form an adhesive layer on the support. The thickness of the adhesive layer in the adhesive sheet is preferably 10 to 200. Mu.m, more preferably 20 to 180 μm, still more preferably 30 to 150 μm, from the viewpoint of the balance between the light absorption ability in the short wavelength region and the transparency.
The support used for the adhesive sheet is not particularly limited, and a known support can be used. Examples of the support include plastic films made of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes simply referred to as "PET") and polyethylene naphthalate, polycarbonates, and polyimides. As the plastic film, a PET film is particularly preferable. The support may be a metal foil such as an aluminum foil, a stainless steel foil, or a copper foil. The support may be subjected to a mold release treatment in addition to the matting treatment and the corona treatment. Examples of the mold release treatment include mold release treatment using a mold release agent such as a silicone resin mold release agent, an alkyd resin mold release agent, or a fluororesin mold release agent. In the present invention, when the support has a release layer, the release layer is also regarded as a part of the support. The thickness of the support is not particularly limited, but is preferably from 20 to 200. Mu.m, more preferably from 20 to 125 μm, from the viewpoint of handling properties and the like.
In the adhesive sheet, the adhesive layer may be protected with a protective film. The protective film protects the surface of the adhesive layer from adhesion of dust or the like or formation of scratches. The protective film is preferably the same plastic film as the support. The protective film may be subjected to a matting treatment, a corona treatment, a mold release treatment, or the like. The thickness of the protective film is not particularly limited, but is usually 1 to 150. Mu.m, preferably 10 to 100. Mu.m.
< transparency >
The adhesive layer formed from the adhesive composition of the present invention is preferably a layer having transparency. The transparency was evaluated by the total light transmittance (water vapor transmission) at 650nm in the visible light region of an adhesive layer having a thickness of 80 μm. The adhesive layer formed of the adhesive composition of the present invention and having a thickness of 80 μm preferably has a total light transmittance of 650nm of 80 to 100%, more preferably 85 to 100%.
< Haze (Haze) >)
The adhesive layer formed from the adhesive composition of the present invention is preferably a layer having low haze. The adhesive layer formed from the adhesive composition of the present invention and having a thickness of 80 μm preferably has a haze of 30% or less. The haze can be measured by a method according to JIS K7136.
< optical device >
The present invention also provides an optical device having an adhesive layer formed of the adhesive composition. Examples of the optical device include an organic EL display device and a solar cell, and the organic EL display device is preferable.
Examples
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
< evaluation of light absorption Capacity and transparency in short wavelength region >
In order to evaluate the light absorption capacity and transparency in the short wavelength region of the adhesive layer (i.e., the adhesive layer formed of the adhesive composition) of the adhesive sheets prepared in examples and comparative examples, the total light transmittance at wavelengths of 380nm and 400nm and the total light transmittance at wavelength of 650nm were measured.
(1) Preparation of evaluation sample
The adhesive sheets (adhesive layer thickness: 80 μm) prepared in examples and comparative examples were cut to a length of 70mm × a width of 25mm, and the cut sheets were laminated on a glass plate (microscope slide glass having a length of 76mm, a width of 26mm and a thickness of 1.2mm, white slide glass S1112 edging (grinding) No.2 made by Sonlang glass industries, ltd.) by using a batch vacuum laminator (V-160 made by Nichigo-Morton). The lamination conditions were 80 ℃ and 30 seconds of decompression time, and then the pressure was applied at 0.3MPa for 30 seconds. Then, the polyethylene terephthalate (PET) film of the adhesive sheet was peeled off, and the same glass plate as described above was further laminated on the exposed adhesive layer to prepare an evaluation sample (laminate).
(2) Evaluation of light absorption Capacity in short wavelength region (measurement of Total light transmittance at 380nm and 400 nm)
A spectral transmittance of the obtained evaluation sample was measured using a fiber-optic spectrophotometer (MCPD-7700, form 311C, otsuka electronics, external light source unit: halogen lamp MC-2564 (24V, 150W standard)) equipped with a phi 80mm integrating sphere (model SRS-99-010, reflectance 99%), with the distance between the integrating sphere and the evaluation sample set to 0mm and the distance between the light source and the evaluation sample set to 48 mm. The reference (reference) is a glass plate similar to the above. The total light transmittances at 380nm and 400nm were determined from the obtained light transmittance spectrum.
(3) Evaluation of transparency (measurement of total light transmittance at a wavelength of 650 nm)
The total light transmittance at a wavelength of 650nm was determined from the light transmittance spectrum obtained by the foregoing method.
The raw materials used in the examples and comparative examples are as follows;
(A) Organic binder
Seed T-YP341 (manufactured by Star-shine PMC Co., ltd.): a20% by mass toluene solution of a glycidyl methacrylate-modified propylene-butene copolymer (propylene unit/butene unit: 71% by mass/29% by mass, epoxy group concentration: 0.638mmol/g, number average molecular weight: 155000)
Seed HV-1900 (produced by JXTG energy Co., ltd.): polybutene (number average molecular weight: 2900)
Seed HV-300M (manufactured by Dongfeng chemical industry Co., ltd.): maleic anhydride-modified liquid polybutene (acid anhydride group concentration: 0.77mmol/g, number average molecular weight: 2100)
Seed ARKON P125 (manufactured by wasteland and river chemical corporation): tackifying resin (saturated aliphatic hydrocarbon resin, softening point: 125 ℃, number average molecular weight: 750)
Zixi (manufactured by Mitsubishi chemical corporation): liquid hydrogenated bisphenol A type epoxy resin (epoxy equivalent: about 205, weight average molecular weight: 410)
Ziziphora (Ziziphora bungeana) 8040 (manufactured by Mitsubishi chemical corporation): solid hydrogenated bisphenol A type epoxy resin (epoxy equivalent: about 1000, weight average molecular weight: 3000)
Seed YX7200B35 (manufactured by Mitsubishi chemical corporation): a phenoxy resin solution (solvent: MEK, nonvolatile matter: 35% by mass, phenoxy resin number average molecular weight: 10000, phenoxy resin weight average molecular weight: 30000).
(B) Layered clay mineral
As a seed or semi-calcined hydrotalcite (saturated water absorption: 17 mass%, thermal weight loss at 280 ℃ 3.6 mass%, thermal weight loss at 380 ℃ 14.4 mass%, low angle side diffraction intensity/high angle side diffraction intensity in powder X-ray diffraction: 0.6, average particle diameter: 400nm, BET specific surface area: 15m 2 Mole ratio of magnesium oxide/aluminum oxide: 4.16).
(C) Compound having maximum absorption wavelength in 300-430 nm wavelength region
Seed and seed sorb703 (benzotriazole compound manufactured by shiipro chemical corporation): 2- (3-tert-butyl-2-dihydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole (λ max =354 nm)
Seeding and HPH (curcumin-based compound produced by sanhe chemical company): 1, 7-bis (4-hydroxyphenyl) -1, 6-heptadiene-3, 5-dione (λ max =416 nm)
Seed DAINSORB T-0 (benzotriazole compound produced by Dazaochi chemical Co., ltd.): 2- (2, 4-dihydroxyphenyl) -2H-benzotriazole (λ max =345 nm)
Seedtree 107 (benzophenone-series compound manufactured by shiipro chemical company): 2, 2-dihydroxy 4, 4-dimethoxybenzophenone (λ max =356 nm).
(D) Other ingredients
Seeding 2,4, 6-tris (diaminomethyl) phenol (hereinafter referred to simply as "TAP"): curing accelerator
Seeding toluene/Ipzole (\12452125031247812540v) \ 12523100 (manufactured by leucismus-engender company): aromatic mixed solvent
Seedings of Methyl Ethyl Ketone (MEK)
Seed (manufactured by sumitomo chemical corporation): cyclohexanone
Seed U-CAT3512T (manufactured by SANAPRO corporation): curing accelerator
Seeding N-acetyl glycine tetrabutylphosphonium salts: an ionic liquid curing agent.
< example 1 >
A mixture was obtained by mixing 130 parts by mass (78 parts by mass of nonvolatile matter) of a 60% Ipzole # 100 solution of a tackifier resin ("ARKON P125" manufactured by Kawakawa chemical Co., ltd.), 35 parts by mass of a maleic anhydride-modified liquid polybutene ("HV-300M" manufactured by Toho chemical industry Co., ltd.), 60 parts by mass of a polybutene ("HV-1900" manufactured by JXTG energy Co., ltd.), and 100 parts by mass of the above-mentioned half-calcined hydrotalcite as the component (B) with a three-roll mill. To the resulting mixture, 200 parts by mass (40 parts by mass of nonvolatile matter) of a 20% by mass toluene solution of a glycidyl methacrylate-modified propylene-butene copolymer ("T-YP 341" manufactured by starlight PMC corporation), 2.5 parts by mass (0.5 parts by mass of nonvolatile matter) of TAP and 14 parts by mass of toluene were added, and 3.3 parts by mass of SEESORB703 (manufactured by shiipro chemical corporation) as a component (C) were further added, and the obtained mixture was uniformly mixed by a high-speed rotary mixer to obtain an adhesive composition varnish. The resulting varnish was uniformly applied to a polyethylene terephthalate (PET) film treated with a silicone-based release agent by means of a die coater (die coater), and the film was heated at 130 ℃ for 60 minutes and dried to obtain an adhesive sheet having an adhesive layer with a thickness of 80 μm.
In example 1, the content of the component (a) was 67.2 mass%, the content of the component (B) was 31.6 mass%, and the content of the component (C) was 1.0 mass% with respect to 100 mass% of the nonvolatile component of the adhesive composition. The results of the total light transmittance measured as described above are shown in table 1 below.
< comparative example 1a >)
An adhesive sheet was obtained in the same manner as in example 1, except that the component (C) was not blended.
In comparative example 1a, the content of component (a) was 67.9 mass%, the content of component (B) was 31.9 mass%, and the content of component (C) was 0 mass% with respect to 100 mass% of nonvolatile components in the adhesive composition. The results of the total light transmittance measured as described above are shown in table 1 below.
< comparative example 1b >
An adhesive sheet was obtained in the same manner as in example 1, except that the component (B) was not blended and the blending amount of the SEESORB703 as the component (C) was changed to 2.2 parts by mass.
In comparative example 1B, the content of component (a) was 98.7 mass%, the content of component (B) was 0 mass%, and the content of component (C) was 1.0 mass% with respect to 100 mass% of nonvolatile components in the adhesive composition. The results of the total light transmittance measured as described above are shown in table 1 below.
[ Table 1]
Figure DEST_PATH_IMAGE002
。
As is clear from the results shown in table 1, the adhesive layer of the adhesive sheet produced in example 1 has improved light absorption ability in the short wavelength region while maintaining transparency.
< example 2 >
An adhesive sheet was obtained in the same manner as in example 1 except that 330 parts by mass (3.3 parts by mass of nonvolatile matter) of a 99% by mass ANON solution containing HPH (Sanwa chemical Co., ltd.) was added as the component (C) in place of 3.3 parts by mass of SEESORB703 (SHIPRO chemical Co., ltd.).
In example 2, the content of the component (a) was 67.2 mass%, the content of the component (B) was 31.6 mass%, and the content of the component (C) was 1.0 mass% with respect to 100 mass% of nonvolatile components in the adhesive composition. The results of the total light transmittance measured as described above are shown in table 2 below.
< comparative example 2 >
An adhesive sheet was obtained in the same manner as in example 2, except that the component (B) was not blended and the blending amount of the 99 mass% ANON solution of HPH as the component (C) was changed to 220 parts by mass (2.2 parts by mass of nonvolatile component).
In comparative example 2, the content of the component (a) was 98.7 mass%, the content of the component (B) was 0 mass%, and the content of the component (C) was 1.0 mass% with respect to 100 mass% of nonvolatile components in the adhesive composition. The results of the total light transmittance measured as described above are shown in table 2 below.
[ Table 2]
Figure DEST_PATH_IMAGE004
。
As is clear from the results shown in table 2, the adhesive layer of the adhesive sheet produced in example 2 has improved light absorption capability in the short wavelength region while maintaining transparency.
< example 3 >
An adhesive sheet was obtained in the same manner as in example 1 except that 22 parts by mass (3.3 parts by mass of a nonvolatile matter) of a 15 mass% MEK solution containing DAINSORB T-0 (manufactured by DAISORB Chemicals) was added as the component (C) in place of 3.3 parts by mass of SEESORB703 (manufactured by SHIPRO Chemicals).
In example 3, the content of the component (a) was 67.2 mass%, the content of the component (B) was 31.6 mass%, and the content of the component (C) was 1.0 mass% with respect to 100 mass% of nonvolatile components in the adhesive composition. The results of the total light transmittance measured as described above are shown in table 3 below.
< comparative example 3 >
An adhesive sheet was obtained in the same manner as in example 3 except that the amount of the component (B) not added and the daisorb T-0 15 mass% MEK solution as the component (C) were added in an amount of 14.7 parts by mass (2.2 parts by mass as a nonvolatile component).
In comparative example 3, the content of the component (a) was 98.7 mass%, the content of the component (B) was 0 mass%, and the content of the component (C) was 1.0 mass% with respect to 100 mass% of nonvolatile components in the adhesive composition. The results of the total light transmittance measured as described above are shown in table 3 below.
[ Table 3]
Figure DEST_PATH_IMAGE006
。
As is clear from the results shown in table 3, the adhesive layer of the adhesive sheet produced in example 3 has improved light absorption ability in the short wavelength region while maintaining transparency.
< example 4 >
An adhesive sheet was obtained in the same manner as in example 1 except that 16.5 parts by mass (3.3 parts by mass of nonvolatile matter) of a 20% by mass toluene solution of SEESORB107 (manufactured by SHIPRO. CHERO CHEMICAL CO., LTD.) was added as component (C) in place of 3.3 parts by mass of SEESORB703 (manufactured by SHIPRO. CHEMICAL CO., LTD.).
In example 4, the content of the component (a) was 67.2 mass%, the content of the component (B) was 31.6 mass%, and the content of the component (C) was 1.0 mass% with respect to 100 mass% of the nonvolatile component of the adhesive composition. The results of the total light transmittance measured as described above are shown in table 4 below.
< comparative example 4 >
An adhesive sheet was obtained in the same manner as in example 4 except that the 20 mass% toluene solution of SEESORB107 as the component (C) was changed to 11.0 parts by mass (2.2 parts by mass of nonvolatile component) without blending the component (B).
In comparative example 4, the content of the component (a) was 98.7 mass%, the content of the component (B) was 0 mass%, and the content of the component (C) was 1.0 mass% with respect to 100 mass% of nonvolatile components in the adhesive composition. The results of the total light transmittance measured as described above are shown in table 4 below.
[ Table 4]
Figure DEST_PATH_IMAGE008
。
As is clear from the results shown in table 4, the adhesive layer of the adhesive sheet produced in example 4 has improved light absorption ability in the short wavelength region while maintaining transparency.
< example 5 >
60 parts by mass of a liquid hydrogenated bisphenol A-type epoxy resin ("YX 8000" manufactured by Mitsubishi chemical corporation) and 40 parts by mass of the half-calcined hydrotalcite as the component (B) were mixed by a three-roll mill to obtain a mixture. To the obtained mixture, 1.5 parts by mass of a curing accelerator (U-CAT 3512T manufactured by SANAPRO corporation), 57.2 parts by mass of a solution of a phenol resin (YX 7200B35 manufactured by Mitsubishi chemical corporation) (20 parts by mass of a phenoxy resin), and 50 parts by mass of a solution of a solid hydrogenated bisphenol A epoxy resin (YX 8040 manufactured by Mitsubishi chemical corporation) (solvent: MEK, nonvolatile matter: 40% by mass) (20 parts by mass of a solid hydrogenated bisphenol A epoxy resin) were added. To the obtained mixture, 3 parts by mass of an ionic liquid curing agent (tetrabutylphosphonium N-acetylglycine salt) and 1.5 parts by mass of SEESORB107 (manufactured by shipiro chemical company) as the component (C) were further blended, and the obtained mixture was uniformly dispersed by a high-speed rotary mixer to obtain a varnish of the adhesive composition. The resulting varnish was uniformly applied to a polyethylene terephthalate (PET) film treated with a silicone-based release agent by a die coater, heated at 80 ℃ for 5 minutes to dry the film, and then the release PET film was placed on the surface of the resin composition layer as a protective film to obtain an adhesive sheet.
In example 5, the content of the component (a) was 68.5 mass%, the content of the component (B) was 27.4 mass%, and the content of the component (C) was 1.0 mass% with respect to 100 mass% of nonvolatile components in the adhesive composition. The results of the total light transmittance measured as described above are shown in table 5 below.
< comparative example 5 >
An adhesive sheet was obtained in the same manner as in example 5, except that the component (B) was not blended and the SEESORB107 as the component (C) was changed to 1.1 parts by mass.
In comparative example 5, the content of the component (a) was 94.7 mass%, the content of the component (B) was 0 mass%, and the content of the component (C) was 1.0 mass% with respect to 100 mass% of nonvolatile components in the adhesive composition. The results of the total light transmittance measured as described above are shown in table 5 below.
[ Table 5]
Figure DEST_PATH_IMAGE010
。
As is clear from the results shown in table 5, the adhesive layer of the adhesive sheet produced in example 5 has improved light absorption ability in the short wavelength region while maintaining transparency.
Industrial applicability of the invention
The adhesive composition of the present invention can form an adhesive layer having an ability to absorb light in a wavelength region of 300 to 430nm and having good transparency. Such an adhesive layer can prevent optical deterioration of an optical device such as an organic EL element, and is particularly suitable for use in an organic EL display device.
The present application is based on Japanese patent application No. 2018-219682, the contents of which are incorporated in the present specification in their entirety.

Claims (18)

1. An adhesive composition comprising the following components (A) to (C):
(A) An organic binder,
(B) Layered clay mineral, and
(C) A compound having a maximum absorption wavelength in a wavelength region of 300 to 430nm,
wherein the component (B) contains hydrotalcite.
2. The adhesive composition according to claim 1, wherein component (B) comprises a semi-calcined hydrotalcite.
3. The adhesive composition according to claim 1 or 2, wherein the content of the component (a) is 25 to 95% by mass based on 100% by mass of nonvolatile components in the adhesive composition.
4. The adhesive composition according to claim 1 or 2, wherein the content of the component (a) is 30 to 93% by mass with respect to 100% by mass of nonvolatile components of the adhesive composition.
5. The adhesive composition according to claim 1 or 2, wherein the content of the component (a) is 35 to 90% by mass based on 100% by mass of nonvolatile components in the adhesive composition.
6. The adhesive composition according to claim 1 or 2, wherein the content of the component (B) is 1 to 60% by mass based on 100% by mass of nonvolatile components in the adhesive composition.
7. The adhesive composition according to claim 1 or 2, wherein the content of the component (B) is 3 to 55% by mass based on 100% by mass of nonvolatile components in the adhesive composition.
8. The adhesive composition according to claim 1 or 2, wherein the content of the component (C) is 0.05 to 15% by mass based on 100% by mass of nonvolatile components in the adhesive composition.
9. The adhesive composition according to claim 1 or 2, wherein the content of the component (C) is 0.1 to 13% by mass based on 100% by mass of nonvolatile components in the adhesive composition.
10. The adhesive composition according to claim 1 or 2, wherein the content of the component (C) is 0.5 to 10% by mass based on 100% by mass of nonvolatile components in the adhesive composition.
11. The adhesive composition according to claim 1 or 2, wherein the component (a) contains at least one selected from the group consisting of olefin resins and epoxy resins.
12. The adhesive composition according to claim 1 or 2, which is used for forming an adhesive layer of an optical device.
13. The adhesive composition according to claim 12, wherein the optical device is an organic EL display device.
14. A bonding sheet comprising:
a support, and
an adhesive layer comprising the adhesive composition according to any one of claims 1 to 11, provided on the support.
15. The adhesive sheet according to claim 14, which is used for forming an adhesive layer in an optical device.
16. The adhesive sheet according to claim 15, wherein the optical device is an organic EL display device.
17. An optical device having an adhesive layer formed from the adhesive composition according to any one of claims 1 to 11.
18. An organic EL display device having an adhesive layer formed from the adhesive composition according to any one of claims 1 to 11.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018028974A (en) * 2016-08-15 2018-02-22 日東電工株式会社 Adhesive composition for organic el display device, adhesive layer for organic el display device, polarizing film with adhesive layer for organic el display device, and organic el display device
WO2018181664A1 (en) * 2017-03-31 2018-10-04 味の素株式会社 Sealing composition

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5952013B2 (en) * 2011-03-23 2016-07-13 三菱樹脂株式会社 Transparent double-sided pressure-sensitive adhesive sheet for image display device and image display device
JP2013157205A (en) * 2012-01-30 2013-08-15 Sekisui Chem Co Ltd Sealant for organic electroluminescent display element
CN104411790B (en) * 2012-07-05 2019-10-18 三键精密化学有限公司 Sheet adhesive and the organic EL panel for using the sheet adhesive
WO2016076616A1 (en) * 2014-11-11 2016-05-19 삼성에스디아이 주식회사 Window film for display and display device including same
JP6821985B2 (en) * 2015-07-21 2021-01-27 味の素株式会社 Resin composition for sealing
JP6683204B2 (en) * 2015-09-30 2020-04-15 味の素株式会社 Sealing resin composition
WO2018021031A1 (en) * 2016-07-28 2018-02-01 日本ゼオン株式会社 Thermoplastic elastomer laminate and organic electroluminescence device
CN109804035A (en) * 2016-10-04 2019-05-24 味之素株式会社 The resin combination and sealing sheet of sealing
JP6903992B2 (en) * 2017-03-27 2021-07-14 味の素株式会社 Encapsulating resin composition and encapsulating sheet

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018028974A (en) * 2016-08-15 2018-02-22 日東電工株式会社 Adhesive composition for organic el display device, adhesive layer for organic el display device, polarizing film with adhesive layer for organic el display device, and organic el display device
WO2018181664A1 (en) * 2017-03-31 2018-10-04 味の素株式会社 Sealing composition

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