JPWO2020105707A1 - Adhesive composition - Google Patents

Abstract

The present invention comprises 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 the wavelength range of 300 to 430 nm. Provide things.

Description

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.

An organic EL element is a light emitting element that uses an organic substance as a light emitting material, and has been in the limelight in recent years because it can obtain high-intensity light emission at a low voltage. It has come to be used in various applications such as mobile phones and televisions. On the other hand, it is known that an organic EL light emitting device has problems such as deterioration due to light in a short wavelength region, discoloration, and shortening of life. For example, Patent Document 1 discloses a method of blocking light having a wavelength of 390 nm or less by a display window film having a layer containing an ultraviolet absorber in order to suppress deterioration of the organic EL light emitting element due to ultraviolet rays. Further, Patent Document 2 proposes to suppress the transmission of light having a wavelength of 380 to 430 nm in addition to ultraviolet rays in order to suppress deterioration of the organic EL element. A method of suppressing deterioration of an organic EL element by providing a layer containing a dye compound having a wavelength in the wavelength range of 380 to 430 nm in an organic EL display device is disclosed. Deterioration of elements due to light in the short wavelength region is also a problem in other optical devices such as solar cells.

Special Table 2018-504622 JP-A-2018-288974

The ability to absorb light in the wavelength range of 300 to 430 nm (hereinafter, may be abbreviated as "light absorption capacity in the short wavelength range") by an adhesive having a compound having a maximum absorption wavelength in the wavelength range of 300 to 430 nm. Forming the adhesive layer to be formed on an optical device such as an organic EL display device is effective in suppressing light deterioration of the optical device. In order to increase the light absorption capacity in the short wavelength region, it is conceivable to increase the content of the compound in the adhesive.

However, there is also a limit to the solubility of the compound in the adhesive, and if this content becomes too large, (1) the compound crystallizes, (2) the compound leaks from the adhesive, (3). ) Problems such as coloration of the adhesive may occur. Therefore, there is a need for a means for improving the light absorption capacity of the adhesive layer in the short wavelength region, which is different from the increase in the content of the compound. In addition, the adhesive layer in such an optical device also needs to be transparent.

The present invention has been made in view of the above circumstances, and an object of the present invention is an adhesion capable of absorbing light in a wavelength range of 300 to 430 nm and capable of forming an adhesive layer having good transparency. The purpose is to provide an agent composition.

The present invention that can achieve the above object is as follows.
[1] The following components (A) to (C):
(A) Organic binder,
An adhesive composition containing (B) a layered clay mineral and (C) a compound having a maximum absorption wavelength in the wavelength range of 300 to 430 nm.
[2] The adhesive composition according to the above [1], wherein the component (B) contains at least one selected from hydrotalcite and layered silicate minerals.
[3] The adhesive composition according to the above [1], wherein the component (B) contains hydrotalcite.
[4] The adhesive composition according to the above [1], wherein the component (B) contains semi-baked hydrotalcite.
[5] The adhesion according to any one of the above [1] to [4], wherein the content of the component (A) is 25 to 95% by mass with respect to 100% by mass of the non-volatile content of the adhesive composition. Agent composition.
[6] The adhesion according to any one of the above [1] to [5], wherein the content of the component (B) is 1 to 60% by mass with respect to 100% by mass of the non-volatile content of the adhesive composition. Agent composition.
[7] Described in any one of the above [1] to [6], wherein the content of the component (C) is 0.05 to 15% by mass with respect to 100% by mass of the non-volatile content of the adhesive composition. Adhesive composition.
[8] The adhesive composition according to any one of the above [1] to [7], wherein the component (A) contains at least one selected from an olefin resin and an epoxy resin.
[9] The adhesive composition according to any one of the above [1] to [8], which is used to form 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] An adhesive sheet containing a support and an adhesive layer formed on the support from the adhesive composition according to any one of [1] to [8].
[12] The adhesive sheet according to the above [11], which is used to form an adhesive layer in an optical device.
[13] The adhesive sheet according to the above [12], wherein the optical device is an organic EL display device.

[14] An optical device having an adhesive layer formed from the adhesive composition according to any one of the above [1] to [8].
[15] An organic EL display device having an adhesive layer formed from the adhesive composition according to any one of the above [1] to [8].

According to the present invention, it is possible to obtain an adhesive composition having an ability to absorb light in a wavelength range of 300 to 430 nm and capable of forming an adhesive layer having good transparency.

The adhesive composition of the present invention contains the following components (A) to (C):
(A) Organic binder,
The present invention comprises (B) a layered clay mineral and (C) a compound having a maximum absorption wavelength in the wavelength range of 300 to 430 nm, and the present invention is characterized in that the components (B) and (C) are used in combination. By using both components (B) and (C), light absorption in the short wavelength range of the adhesive layer formed from the adhesive composition while maintaining transparency as compared to the case of using one of them. The ability (ie, the ability to absorb light in the wavelength range of 300 to 430 nm) can be improved.
Hereinafter, each component will be described in order. It should be noted that the examples and preferred descriptions described below can 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) (that is, a layered clay mineral) and the component (C) (that is, a compound having a maximum absorption wavelength in the wavelength range of 300 to 430 nm). Means. As the component (A), only one kind may be used, or two or more kinds may be used in combination. Further, as the resin and rubber, only one type may be used, or two or more types may be used in combination. Further, as the component (A), resin and rubber may be used in combination. As the component (A), a resin and / or rubber which is a known organic binder can be used.

The resin may be either a thermoplastic resin or a thermosetting resin. Further, as the resin, a tackifier resin may be used. As the thermoplastic resin, the thermosetting resin, and the tackifier resin, only one type may be used, or two or more types 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. Hereinafter, the resin and rubber will be described in order.

(Thermoplastic resin)
Examples of the thermoplastic resin include phenoxy resin, acrylic resin, polyvinyl acetal resin, butyral resin, polyimide resin, polyamideimide resin, polyethersulfone resin, polysulfone resin, olefin resin (for example, ethylene resin, propylene resin, etc.). Butene-based resin, isobutylene-based resin) and the like can be mentioned.

The number average molecular weight of the thermoplastic resin is not particularly limited, but is 1,000,000 from the viewpoint of providing good coatability of the adhesive composition varnish and good compatibility with other components in the composition. The following is preferable, 750,000 or less is more preferable, 500,000 or less is further preferable, and 400,000 or less is further preferable. On the other hand, from the viewpoint of preventing repelling during coating of the adhesive composition varnish, exhibiting the moisture permeation resistance of the formed adhesive layer, and improving the mechanical strength, 500 or more is preferable, and 700 or more is more preferable. The number average molecular weight is measured by a gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the number average molecular weight by the GPC method was moved by using LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K-804L / K-804L manufactured by Showa Denko Corporation as a column. It can be measured using toluene or the like as a phase at a column temperature of 40 ° C. and calculated using a standard polystyrene calibration curve.

When a thermoplastic resin is used as the component (A), the thermoplastic resin preferably contains an olefin resin. Here, the "olefin-based resin" in the present invention includes a structural unit derived from an olefin (hereinafter, may be abbreviated as "olefin unit"), and the amount of the olefin unit is the total structural unit (that is, each configuration). It means a resin which is 50% by mass or more per 100% by mass (total of units). A modified olefin resin having a functional group (for example, an epoxy group, an acid anhydride group, etc.) is also included in the "olefin resin" in the present invention when the amount of the olefin unit is 50% by mass or more in the total constituent units. Is done. Further, a resin which is a modified olefin resin and can form a crosslinked structure by its functional group and which has thermoplasticity by itself is included in the "thermoplastic resin" in the present invention.

Only one type of olefin resin may be used, or two or more types may be used in combination. As the olefin-based resin, an ethylene-based resin, a propylene-based resin, a butene-based resin, and an isobutylene-based resin are preferable. These olefin-based resins may be homopolymers, or copolymers such as random copolymers and block copolymers. Examples of the copolymer include a copolymer of two or more kinds of olefins and a copolymer of the olefin and a monomer other than the olefin such as unconjugated diene and styrene. Examples of preferred copolymers are ethylene-non-conjugated diene copolymers, ethylene-propylene copolymers, ethylene-propylene-non-conjugated diene copolymers, ethylene-butene copolymers, propylene-butene copolymers, propylene. Examples thereof include -butene-non-conjugated diene copolymer, styrene-isobutylene copolymer, styrene-isobutylene-styrene copolymer and the like. As the olefin resin, for example, isobutylene-modified resin, styrene-isobutylene-modified resin, modified propylene-butene resin and the like are preferably used.

The olefin resin is preferably an olefin having an acid anhydride group (that is, a carbonyloxycarbonyl group (-CO-O-CO-)) from the viewpoint of imparting excellent physical properties (for example, adhesiveness) to the adhesive layer. It contains at least one selected from a system resin and an olefin resin having an epoxy group, and more preferably contains an olefin resin having an acid anhydride group and an olefin resin having an epoxy group.

The olefin resin having an acid anhydride group is, for example, an unsaturated compound having an acid anhydride group, and is obtained by graft-modifying the olefin resin under radical reaction conditions. Further, an unsaturated compound having an acid anhydride group may be radically copolymerized together with an olefin or the like. Examples of unsaturated compounds having an acid anhydride group include succinic anhydride, maleic anhydride, glutaric anhydride and the like. As the unsaturated compound having an acid anhydride group, only one kind may be used, or two or more kinds may be used in combination.

Similarly, the olefin resin having an epoxy group is, for example, an unsaturated compound having an epoxy group, and can be obtained by graft-modifying the olefin resin under radical reaction conditions. Further, an unsaturated compound having an epoxy group may be radically copolymerized together with an olefin or the like. Examples of unsaturated compounds having an epoxy group include glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, and allyl glycidyl ether. As the unsaturated compound having an epoxy group, only one kind may be used, or two or more kinds may be used in combination.

The concentration of the acid anhydride group in the olefin resin having an acid anhydride group is preferably 0.05 to 10 mmol / g, more preferably 0.1 to 5 mmol / g. The concentration of the acid anhydride group is obtained from the value of the acid value defined as the number of mg of potassium hydroxide required to neutralize the acid present in 1 g of the resin according to the description of JIS K 2501. The amount of the olefin resin having an acid anhydride group in the olefin resin is preferably 0 to 70% by mass, more preferably 5 to 50% by mass.

The concentration of the epoxy group in the olefin resin having an epoxy group is preferably 0.05 to 10 mmol / g, more preferably 0.1 to 5 mmol / g. The epoxy group concentration is determined from the epoxy equivalent obtained based on JIS K 7236-1995. The amount of the olefin resin having an epoxy group in the olefin resin is preferably 0 to 70% by mass, more preferably 5 to 50% by mass.

The olefin resin preferably contains both an olefin resin having an acid anhydride group and an olefin resin having an epoxy group from the viewpoint of imparting excellent physical properties such as moisture resistance. In such an olefin resin, an acid anhydride group and an epoxy group are reacted by heating to form a crosslinked structure, and an adhesive layer having excellent moisture resistance and the like can be formed. It is desirable to form a crosslinked structure when the adhesive sheet is manufactured. The ratio of the olefin resin having an acid anhydride group to the olefin resin having an epoxy group is not particularly limited as long as an appropriate crosslinked structure can be formed, but the molar ratio of the epoxy group to the acid anhydride group (epoxide group: acid anhydride). The group) is preferably 100: 10 to 100: 200, more preferably 100: 50 to 100: 150, and particularly preferably 100: 90 to 100: 110.

The number average molecular weight of the olefin resin is not particularly limited, but is said to provide good coatability of the adhesive composition varnish containing an organic solvent and good compatibility with other components in the adhesive composition. From the viewpoint, 1,000,000 or less is preferable, 750,000 or less is more preferable, 500,000 or less is further preferable, 400,000 or less is further preferable, 300,000 or less is further preferable, and 200,000 or less. Is particularly preferable, and 150,000 or less is most preferable. On the other hand, from the viewpoint of preventing repelling during coating of the adhesive composition varnish, exhibiting the moisture-proof property of the formed adhesive layer, and improving the mechanical strength, the number average molecular weight is preferably 500 or more, preferably 700. The above is more preferable. The number average molecular weight in the present invention is measured by gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the number average molecular weight by the GPC method was moved by using LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K-804L / K-804L manufactured by Showa Denko Corporation as a column. It can be measured using toluene or the like as a phase at a column temperature of 40 ° C. and calculated using a standard polystyrene calibration curve.

The olefin resin is preferably amorphous from the viewpoint of suppressing a decrease in fluidity due to thickening of the adhesive composition varnish containing an organic solvent. Here, amorphous means that the olefin resin does not have a clear melting point, and for example, when the melting point is measured by DSC (differential scanning calorimetry) of the olefin resin, no clear peak is observed. You can use the one.

Next, a specific example of the olefin resin will be described. Specific examples of the isobutylene resin include BASF's "Opanol B100" (viscosity average molecular weight: 1,110,000) and BASF's "B50SF" (viscosity average molecular weight: 400,000).

Specific examples of the butene resin include "HV-1900" (polybutene, number average molecular weight: 2,900) manufactured by JXTG Energy Co., Ltd. and "HV-300M" (maleic anhydride-modified liquid polybutene) manufactured by Toho Kagaku Kogyo Co., Ltd. ("HV"). -300 ”(modified product with number average molecular weight: 1,400), number average molecular weight: 2,100, number of carboxy groups constituting the acid anhydride group: 3.2 / 1 molecule, acid value: 43. 4 mgKOH / g, acid anhydride group concentration: 0.77 mmol / g).

Specific examples of the styrene-isobutylene copolymer include "SIBSTAR T102" manufactured by Kaneka (styrene-isobutylene-styrene block copolymer, number average molecular weight: 100,000, styrene content: 30% by mass), manufactured by Seikou PMC. "T-YP757B" (maleic anhydride-modified styrene-isobutylene-styrene block copolymer, acid anhydride group concentration: 0.464 mmol / g, number average molecular weight: 100,000), "T-YP766" manufactured by Seikou PMC. (Glysidyl methacrylate-modified styrene-isobutylene-styrene block copolymer, epoxy group concentration: 0.638 mmol / g, number average molecular weight: 100,000), "T-YP8920" manufactured by Seikou PMC (maleic anhydride-modified styrene-isobutylene anhydride). -Sterite copolymer, acid anhydride group concentration: 0.464 mmol / g, number average molecular weight: 35,800), "T-YP8930" manufactured by Seikou PMC (glycidyl methacrylate-modified styrene-isobutylene-styrene copolymer, epoxy) Group concentration: 0.638 mmol / g, number average molecular weight: 48,700).

Specific examples of the ethylene-based resin or the propylene-based resin include "EPT X-3012P" manufactured by Mitsui Chemicals, Inc. (ethylene-propylene-5-ethylidene-2-norbornene copolymer, "EPT1070" manufactured by Mitsui Chemicals, Ltd. (ethylene-propylene). -Dicyclopentadiene copolymer), "Toughmer A4085" (ethylene-butene copolymer) manufactured by Mitsui Chemicals, Inc. can be mentioned.

As a specific example of the ethylene-methylmethacrylate copolymer, "T-YP429" manufactured by Seikou PMC (maleic anhydride-modified ethylene-methylmethacrylate copolymer (methylmethacrylate per 100% by mass of the total of ethylene unit and methylmethacrylate unit)). Unit amount: 32% by mass, acid anhydride group concentration: 0.46 mmol / g, number average molecular weight: 2,300) 20% by mass toluene solution), "T-YP430" (maleic anhydride modified) manufactured by Seikou PMC. Ethylene-methylmethacrylate copolymer, amount of methylmethacrylate unit per 100% by mass of ethylene unit and methylmethacrylate unit: 32% by mass, acid anhydride group concentration: 1.18 mmol / g, number average molecular weight: 4,500 ), Starlight PMC "T-YP431" (20% by mass toluene solution of glycidyl methacrylate-modified ethylene-methylmethacrylate copolymer (epoxy group concentration: 0.64 mmol / g, number average molecular weight: 2,400)), Starlight Examples thereof include "T-YP432" manufactured by PMC (glycidyl methacrylate-modified ethylene-methyl methacrylate copolymer, epoxy group concentration: 1.63 mmol / g, number average molecular weight: 3,100).

As a specific example of the propylene-butene copolymer, "T-YP341" manufactured by Seikou PMC (glycidyl methacrylate-modified propylene-butene random copolymer (amount of butene units per 100% by mass of propylene units and butene units in total:): 29% by mass, epoxy group concentration: 0.638 mmol / g, number average molecular weight: 155,000) 20% by mass swazole solution), Seikou PMC "T-YP279" (maleic anhydride-modified propylene-butene random copolymer weight) Combined, amount of butene unit per 100% by mass of propylene unit and butene unit: 36% by mass, acid anhydride group concentration: 0.464 mmol / g, number average polymer weight: 35,000), Seikou PMC "T" -YP276 "(glycidyl methacrylate-modified propylene-butene random copolymer, amount of butene units per 100% by mass of propylene units and butene units in total: 36% by mass, epoxy group concentration: 0.638 mmol / g, number average molecular weight: 57,000), "T-YP312" manufactured by Seikou PMC (maleic anhydride-modified propylene-butene random copolymer (amount of butene units per 100% by mass of propylene units and butene units in total: 29% by mass, acid anhydride) 40% by mass toluene solution of material concentration: 0.464 mmol / g, number average molecular weight: 60,900), "T-YP313" manufactured by Seikou PMC (glycidyl methacrylate-modified propylene-butene random copolymer (with propylene unit) A 20% by mass toluene solution of the amount of butene units per 100% by mass of the total butene units: 29% by mass, the epoxy group concentration: 0.638 mmol / g, and the number average molecular weight: 155,000).

When the olefin resin contains an olefin resin having an epoxy group, an olefin resin having a functional group other than the acid anhydride group that can react with the epoxy group may be used. Examples of the functional group include a hydroxyl group, a phenolic hydroxyl group, an amino group, a carboxy group and the like.

When the olefin resin contains an olefin resin having an acid anhydride group, an olefin resin having a functional group other than the epoxy group that can react with the acid anhydride group may be used. Examples of the functional group include a hydroxyl group, a primary or secondary amino group, a thiol group, an oxetane group and the like.

The content of the thermoplastic resin (particularly, the olefin resin) is not particularly limited. When a thermoplastic resin (particularly, an olefin resin) is used from the viewpoint of good coatability of the adhesive composition varnish, the content thereof is based on 100% by mass of the non-volatile content of the adhesive composition. 95% by mass or less is preferable, 85% by mass or less is more preferable, and 80% by mass or less is further preferable. The content of the olefin resin is preferably 25% by mass or more, more preferably 30% by mass or more, still more preferably 35% by mass or more, based on 100% by mass of the non-volatile content of the adhesive composition.

(Thermosetting resin)
Examples of the thermosetting resin include epoxy resin, phenolic resin, naphthol resin, benzoxazine resin, active ester resin, cyanate ester resin, carbodiimide resin, amine resin, acid anhydride resin and the like. Can be mentioned.

When a thermosetting resin is used as the organic binder, the thermosetting resin preferably contains an epoxy resin. As the epoxy resin, one having two or more epoxy groups per molecule on average can be used. However, even if the resin has an epoxy group, as described above, when the amount of the olefin unit is 50% by mass or more in the total constituent units, the resin is included in the "olefin resin" in the present invention. .. Examples of the epoxy resin include hydrogenated epoxy resins (hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, etc.), fluorine-containing epoxy resins, chain aliphatic epoxy resins, cyclic aliphatic epoxy resins, and the like. Bisphenol A type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phosphorus-containing epoxy resin, bisphenol S type epoxy resin, fragrance Group glycidylamine type epoxy resin (for example, tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, diglycidyltoluidine, diglycidylaniline, etc.), alicyclic epoxy resin, phenol novolac type epoxy resin, alkylphenol type epoxy resin, cresol Novolak type epoxy resin, bisphenol A Novolak type epoxy resin, epoxy resin having a butadiene structure, diglycidyl etherified product of bisphenol, diglycidyl etherified product of naphthalenediol, diglycidyl etherified product of phenols, and diglycidyl etherified product of alcohols , And alkyl substituents of these epoxy resins.

Only one type of epoxy resin may be used, or two or more types may be used in combination. The epoxy equivalent of the epoxy resin is preferably 50 to 5,000, more preferably 50 to 3,000, still more preferably 80 to 2,000, and particularly preferably 100 to 1,500 from the viewpoint of reactivity and the like. .. The "epoxy equivalent" is the number of grams (g / eq) of a resin containing 1 gram equivalent of an epoxy group, and is measured according to the method specified in JIS K 7236. The weight average molecular weight of the epoxy resin is preferably 5,000 or less.

The epoxy resin may be either liquid or solid, and the liquid epoxy resin and the solid epoxy resin may be used in combination. Here, "liquid" and "solid" are states of the epoxy resin at normal temperature (25 ° C.) and atmospheric pressure (1 atm). From the viewpoint of coatability, processability, and adhesiveness, it is preferable that 10% by mass or more of the total epoxy resin used is a liquid epoxy resin. From the viewpoint of kneadability 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 to 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, based on 100% by mass of the non-volatile content of the adhesive composition. 35 to 95% by mass is more preferable.

When an epoxy 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 35 to 35% by mass with respect to 100% by mass of the non-volatile content of the adhesive composition. 95% by mass is more preferable.

When an epoxy resin is used as the component (A), a phenoxy resin which is a thermoplastic resin may be further used as the component (A). When the epoxy resin and the phenoxy 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 40 to 40% by mass with respect to 100% by mass of the non-volatile content of the adhesive composition. 90% by mass is more preferable, and the content of the phenoxy resin is preferably 0.1 to 60% by mass, more preferably 3 to 60% by mass, and 5 to 50% with respect to 100% by mass of the non-volatile content of the adhesive composition. Mass% is more preferred.

When the epoxy resin and the phenoxy resin are used in combination, the weight average molecular weight of the epoxy resin is preferably 5,000 or less, and the weight average molecular weight of the phenoxy resin is preferably 10,000 to 500,000, more preferably 20, It is 000 to 300,000. These weight average molecular weights are measured by gel permeation chromatography (GPC) method (polystyrene conversion).

(Adhesive-imparting resin)
When a thermoplastic resin (particularly an olefin resin) and / or rubber is used as the component (A), it is preferable to use a tackifier resin in order to improve the tackiness of the adhesive composition. Only one type of tackifier resin may be used, or two or more types may be used in combination.

Examples of the tackifying resin include terpene-based resin, terpene phenol-based resin, rosin-based tackifier resin, hydrocarbon-based terpene-based resin, aromatic-modified terpene-based resin, kumaron resin, inden resin, and petroleum resin (aliphatic petroleum resin). , Aromatic petroleum resin, aliphatic aromatic copolymerized petroleum resin, alicyclic petroleum resin, dicyclopentadiene petroleum resin, hydrogenated dicyclopentadiene petroleum resin, etc.), saturated aliphatic hydrocarbon resin, cyclohexane ring Examples thereof include saturated hydrocarbon resins contained therein.

Examples of commercially available products of the tackifier resin include the following. Examples of the terpene resin include YS resin PX and YS resin PXN (both manufactured by Yasuhara Chemical Co., Ltd.). Examples of the aromatic-modified terpene resin include YS resin TO and TR series (both manufactured by Yasuhara Chemical Co., Ltd.). Examples of the hydrogenated terpene resin include Clearon P, Clearon M, and Clearon K series (all manufactured by Yasuhara Chemical Co., Ltd.). Examples of the terpene phenol-based resin include YS Polystar 2000, Polystar U, Polystar T, Polystar S, and Mighty Ace G (all manufactured by Yasuhara Chemical Co., Ltd.). Examples of the saturated aliphatic hydrocarbon resin include Escorez 5300 series, 5600 series (all manufactured by ExxonMobil), Archon P100, Archon P125, and Archon P140 (all manufactured by Arakawa Chemical Industries, Ltd.). Examples of the cyclohexane ring-containing saturated hydrocarbon resin include TFS13-030 (manufactured by Arakawa Chemical Industries, Ltd.). Examples of the aromatic petroleum resin include ENDEX155 (manufactured by Eastman Chemical Company) and the like. Examples of the aliphatic aromatic copolymer petroleum resin include Quintone D100 (manufactured by Zeon Corporation). Examples of the alicyclic petroleum resin include Quintone 1325 and Quintone 1345 (both manufactured by Zeon Corporation).

The softening point of the tackifier resin is preferably 50 to 200 ° C. from the viewpoint that when the adhesive composition is used in the form of a sheet, the sheet is softened in the laminating step of the adhesive sheet and has desired heat resistance. , 50-180 ° C., more preferably 50-150 ° C. The softening point is measured by the ring-and-ball method according to JIS K2207.

The content of the tackifier resin in the adhesive composition is not particularly limited. However, from the viewpoint of maintaining good moisture permeation resistance of the adhesive composition, when the tackifier resin is used, its content is 80% by mass or less with respect to 100% by mass of the non-volatile content of the adhesive composition. Is more preferable, 70% by mass or less is more preferable, 65% by mass or less is further preferable, and 60% by mass or less is particularly preferable. On the other hand, from the viewpoint of sufficient adhesiveness, when the tackifier resin is used, its content is preferably 5% by mass or more, more preferably 10% by mass or more, based on 100% by mass of the non-volatile content of the adhesive composition. It is preferable, and more preferably 15% by mass or more.

From the viewpoint of adhesiveness, moisture permeability resistance, compatibility, etc. of the composition, the tackifier resin includes saturated aliphatic hydrocarbon resin, aromatic petroleum resin, aliphatic aromatic copolymerized petroleum resin, and alicyclic petroleum. Resins are preferred, and saturated aliphatic hydrocarbon resins (eg, Archon P125) are more preferred.

The number average molecular weight of the tackifier resin is preferably 500 or more, more preferably 700 or more, preferably 2,000 or less, more preferably 1,500 or less, still more preferably 1,000 or less. The number average molecular weight is measured by a gel permeation chromatography (GPC) method (polystyrene conversion).

(Rubber)
When rubber is used as the component (A), the rubber may be either a diene-based rubber or a non-diene-based rubber. Examples of the rubber include butyl rubber (IIR), isoprene rubber (IR), butadiene rubber (BR), a rubbery copolymer of carboxylated styrene and butadiene (XSBR), and chlorinated isoprene and isoprene. Examples thereof include a rubber-like copolymer (CIIR), a rubber-like copolymer of brominated isoprene and isoprene (BIIR), and the like. Of these, butyl rubber, isoprene rubber, and butadiene rubber are preferable, and butyl rubber is more preferable.

The rubber is a rubber having an acid anhydride group (that is, a carbonyloxycarbonyl group (-CO-O-CO-)) and an epoxy group from the viewpoint of further improving the adhesiveness of the adhesive composition, the resistance to wet and heat of adhesion, and the like. It contains at least one selected from the rubbers having, more preferably a rubber having an acid anhydride group and a rubber having an epoxy group.

The rubber having an acid anhydride group is, for example, an unsaturated compound having an acid anhydride group, and is obtained by graft-modifying the rubber under radical reaction conditions. Further, an unsaturated compound having an acid anhydride group may be radically copolymerized together with an olefin or the like. Examples of unsaturated compounds having an acid anhydride group include succinic anhydride, maleic anhydride, glutaric anhydride and the like. As the unsaturated compound having an acid anhydride group, only one kind may be used, or two or more kinds may be used in combination.

Similarly, the rubber having an epoxy group is, for example, an unsaturated compound having an epoxy group, and is obtained by graft-modifying the rubber under radical reaction conditions. Further, the unsaturated compound having an epoxy group may be radically copolymerized together with the rubber having an olefinic double bond. Examples of unsaturated compounds having an epoxy group include glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, and allyl glycidyl ether. As the unsaturated compound having an epoxy group, only one kind may be used, or two or more kinds may be used in combination.

As the rubber having an acid anhydride group, butyl rubber having an acid anhydride group, isoprene rubber having an acid anhydride group, and butadiene rubber having an acid anhydride group are preferable, and butyl rubber having an acid anhydride group is particularly preferable. be. 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 the acid anhydride group is preferably 0.05 to 10 mmol / g, more preferably 0.1 to 5 mmol / g. The concentration of the acid anhydride group is obtained from the value of the acid value defined as the number of mg of potassium hydroxide required to neutralize the acid present in 1 g of rubber according to the description of JIS K 2501.

The concentration of the epoxy group in the rubber having an epoxy group is preferably 0.05 to 10 mmol / g, more preferably 0.1 to 5 mmol / g. The epoxy group concentration is determined from the epoxy equivalent obtained based on JIS K 7236-1995.

From the viewpoint of good coatability of the adhesive composition varnish and good compatibility between the rubber and other components, the number average molecular weight of the rubber is preferably 1,000,000 or less, more preferably 750,000 or less. It is preferable, more preferably 500,000 or less, and particularly preferably 400,000 or less. On the other hand, from the viewpoint of preventing repelling during coating of the sealing composition varnish, the number average molecular weight of the rubber is preferably 2,000 or more, more preferably 10,000 or more, still more preferably 30,000 or more. 50,000 or more is particularly preferable. The number average molecular weight is measured by a gel permeation chromatography (GPC) method (polystyrene conversion).

The rubber content is not particularly limited. When rubber is used, the content thereof is preferably 80% by mass or less, preferably 75% by mass, based on 100% by mass of the non-volatile content of the adhesive composition, from the viewpoint of good coatability of the adhesive composition varnish. % Or less is more preferable, 70% by mass or less is further preferable, 65% by mass or less is further preferable, and 60% by mass or less is further preferable. The rubber content is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and 7% by mass or more, based on 100% by mass of the non-volatile content of the adhesive composition. Is even more preferable, 10% by mass or more is even more preferable, 15% by mass or more is particularly preferable, and 20% by mass or more is most preferable.

(Preferable aspect)
Hereinafter, preferred embodiments of the present invention will be described in order for the component (A).
As one aspect of the present invention, the component (A) preferably contains an olefin resin, and more preferably contains an olefin resin and a tackifier resin. Further, as one aspect of the present invention, the component (A) preferably contains rubber such as butyl rubber, isoprene rubber, and butadiene rubber, and more preferably contains butyl rubber. Further, as one aspect of the present invention, the component (A) preferably contains a rubber and a tackifier resin.

When the component (A) contains an olefin resin having an acid anhydride group and / or a rubber having an acid anhydride group, the olefin resin and / or the acid anhydride having an acid anhydride group per component (A) as a whole. The amount of rubber having a physical group is preferably 1 to 70% by mass, more preferably 10 to 50% by mass. Further, when the component (A) contains an olefin resin having an epoxy group and / or a rubber having an epoxy group, the component (A) has an olefin resin having an epoxy group and / or an epoxy group per component (A). The amount of rubber is preferably 1 to 70% by mass, more preferably 10 to 50% by mass.

From the viewpoint of further improving the moisture resistance of the adhesive composition, the present invention preferably satisfies at least one of the following (a) to (d).
(A) The component (A) contains an olefin resin having an acid anhydride group and an olefin resin having an epoxy group.
(B) The component (A) includes a rubber having an acid anhydride group and a rubber having an epoxy group.
(C) The component (A) contains an olefin resin having an acid anhydride group and a rubber having an epoxy group.
(D) The component (A) contains a rubber having an acid anhydride group and an olefin resin having an epoxy group.

In the above aspects (a) to (d), the component (A) can form a crosslinked structure by reacting the acid anhydride group and the epoxy group by heating. Therefore, an adhesive layer having improved moisture permeability and the like can be formed from the adhesive composition of the present invention. Although the crosslinked structure can be formed at the time of forming the adhesive layer with the adhesive composition, it is desirable to form the crosslinked structure on the adhesive layer formed on the support at the time of manufacturing the adhesive sheet.

The ratio of the olefin resin having an acid anhydride group and / or the rubber having an acid anhydride group to the olefin resin having an epoxy group and / or the rubber having an epoxy group is particularly limited as long as an appropriate crosslinked structure can be formed. However, the molar ratio of the epoxy group to the acid anhydride group (epoxide group: acid anhydride group) is preferably 100: 10 to 100: 200, more preferably 100: 50 to 100: 150, and particularly preferably 100. : 90 to 100: 110.

In one aspect of the invention, the component (A) is preferably a mixture of (i) butyl rubber, (ii) a butyl rubber having an acid anhydride group and a butyl rubber having an epoxy group, or (iii) a butyl rubber, an acid anhydride group. It is a mixture of butyl rubber having butyl rubber and butyl rubber having an epoxy group.

In the present invention, when an olefin resin and rubber are used in combination as the component (A), the blending ratio (olefin resin / rubber) of both is preferably 1/99 to 50/50 in terms of mass ratio, and 10/90. ~ 45/55 is more preferable.

In one aspect of the present invention, the component (A) preferably contains at least one selected from 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 low moisture permeability of the adhesive composition, the suppression of outgas generation and the transparency can be further improved.

The content of the component (A) is preferably 25% by mass or more, more preferably 30% by mass or more, still more preferably 35% by mass or more, and preferably 35% by mass or more, based on 100% by mass of the non-volatile content of the adhesive composition. It is 95% by mass or less, more preferably 93% by mass or less, still more preferably 90% by mass or less.

<(B) Layered clay mineral>
One of the features of the adhesive composition of the present invention is that it contains a layered clay mineral as a component (B). By using the layered clay mineral, it is possible to improve the absorption of light in the wavelength range of 300 to 430 nm while maintaining the transparency of the adhesive layer obtained from the adhesive composition. As the component (B), only one kind may be used, or two or more kinds may be used in combination. Further, the layered clay mineral may be a processed layered clay mineral (for example, semi-calcined hydrotalcite, calcined hydrotalcite, etc.) as described later, or may be an artificial product.

Examples of the layered clay mineral include hydrotalcite and layered silicate minerals. Hereinafter, these will be described in order.

(Hydrotalcite)
Hydrotalcite can be classified into uncalcined hydrotalcite, semi-calcined hydrotalcite, and calcined hydrotalcite.

Unfired hydrotalcite is, for example, a metal hydroxide having a layered crystal structure typified by natural hydrotalcite _{(Mg 6 Al 2 (OH)} 16 CO 3 · 4H 2 O), for example, It consists of a basic skeleton layer [Mg _1-X Al _X (OH) ₂ ] ^{X +} and an intermediate layer [(CO ₃ ) _{X / 2} · mH ₂ O] ^X− . The uncalcined hydrotalcite in the present invention is a concept including hydrotalcite-like compounds such as synthetic hydrotalcite. Examples of the hydrotalcite-like compound include those represented by the following formulas (I) and (II).

^{_{[M 2+ 1-x M 3+}} x (OH) 2] x + · [(A n-) x / n · mH 2 O] x-
(I)
^{(Wherein, M 2+} is ^Mg 2+, a divalent metal ion such as ^{Zn 2+, M 3+} represents a trivalent metal ion such as ^{Al 3+, Fe} 3+, ^{A n-} is _CO ³ 2-, Cl ^-, NO ₃ ^- represents a n-valent anion, such as a 0 <x <1, a 0 ≦ m <1, n is a positive number).
Wherein ^{(I), M 2+} is preferably ^{Mg 2+, M 3+} is preferably ^{Al 3+, A n-is} preferably _CO ^{3 2-.}

^{_{M 2+ x Al 2 (OH)}} 2x + 6-nz (A n-) z · mH 2 O (II)
^{(Wherein, M 2+} is ^Mg 2+, a divalent metal ion such as ^{Zn 2+, A n-} is ^{_{CO 3 2-, Cl -, NO}} 3 - represents a n-valent anion, such as, x is 2 or more Is a positive number, z is a positive number less than or equal to 2, m is a positive number, and n is a positive number.)
Wherein ^{(II), M 2+} is preferably ^{Mg 2+, A n-is} preferably _CO ^{3 2-.}

Semi-calcined hydrotalcite refers to a metal hydroxide having a layered crystal structure in which the amount of interlayer water is reduced or eliminated, which is obtained by calcining uncalcined hydrotalcite. The term "interlayer water" refers to _{"H 2} O" described in the above-mentioned composition formulas of uncalcined natural hydrotalcite and hydrotalcite-like compounds.

On the other hand, calcined hydrotalcite is obtained by firing the unfired hydrotalcite or semi calcined hydrotalcites, not only the interlayer water (H 2 _O), hydroxyl (OH) also disappeared by condensation dehydration, amorphous structure Refers to a metal oxide having.

Uncalcined hydrotalcite, semi-calcined hydrotalcite and calcined hydrotalcite can be distinguished by the saturated water absorption rate. The saturated water absorption rate of the semi-baked hydrotalcite is 1% by mass or more and less than 20% by mass. On the other hand, the saturated water absorption rate of uncalcined hydrotalcite is less than 1% by mass, and the saturated water absorption rate of calcined hydrotalcite is 20% by mass or more.

The "saturated water absorption rate" in the present invention means that 1.5 g of unfired hydrotalcite, semi-fired hydrotalcite or fired hydrotalcite is weighed with a balance, the initial mass is measured, and then the temperature is 60 ° C. under atmospheric pressure. , The mass increase rate with respect to the initial mass when left to stand for 200 hours in a small environmental tester (SH-222 manufactured by Espec Co., Ltd.) set to 90% RH (relative humidity).
Saturated water absorption rate (mass%)
= 100 × (mass after moisture absorption-initial mass) / initial mass (i)
Can be obtained at.

The saturated water absorption of the semi-baked hydrotalcite is preferably 3% by mass or more and less than 20% by mass, and more preferably 5% by mass or more and less than 20% by mass.

Further, uncalcined hydrotalcite, semi-calcined hydrotalcite and calcined hydrotalcite can be distinguished by the thermogravimetric reduction rate measured by thermogravimetric analysis. The thermogravimetric reduction rate of the semi-baked hydrotalcite at 280 ° C. is less than 15% by mass, and the thermogravimetric reduction rate at 380 ° C. is 12% by mass or more. On the other hand, the thermogravimetric reduction rate of uncalcined hydrotalcite at 280 ° C. is 15% by mass or more, and the thermogravimetric reduction rate of calcined hydrotalcite at 380 ° C. is less than 12% by mass.

For thermogravimetric analysis, 5 mg of hydrotalcite was weighed in an aluminum sample pan using TG / DTA EXSTAR6300 manufactured by Hitachi High-Tech Science Co., Ltd., and the nitrogen flow rate was 200 mL / min in an open state without a lid. It can be carried out from 30 ° C. to 550 ° C. under the condition of a heating rate of 10 ° C./min. The thermogravimetric reduction rate is calculated by the following formula (ii):
Thermogravimetric reduction rate (mass%)
= 100 × (mass before heating-mass when a predetermined temperature is reached) / mass before heating (ii)
Can be obtained at.

Further, uncalcined hydrotalcite, semi-calcined hydrotalcite and calcined hydrotalcite can be distinguished by the peak and the relative intensity ratio measured by powder X-ray diffraction. Semi-baked hydrotalcite shows a peak in which 2θ is split into two in the vicinity of 8 to 18 ° by powder X-ray diffraction, or a peak with a shoulder due to the combination of the two peaks, and the peak or shoulder that appears on the low angle side. The relative intensity ratio (low-angle side diffraction intensity / high-angle side diffraction intensity) of the diffraction intensity (= low-angle side diffraction intensity) and the diffraction intensity of the peak or shoulder appearing on the high-angle side (= high-angle side diffraction intensity) is 0.001. ~ 1,000. On the other hand, uncalcined hydrotalcite has only one peak near 8 to 18 °, or the relative intensity ratio of the diffraction intensity of the peak or shoulder appearing on the low angle side and the peak or shoulder appearing on the high angle side is in the above range. Be outside. The calcined hydrotalcite does not have a characteristic peak in the region of 8 ° to 18 °, but has a characteristic peak in the region of 43 °. Powder X-ray diffraction measurement is performed by a powder X-ray diffractometer (PANalytical, Empyrean) with anti-cathode CuKα (1.5405 Å), voltage: 45 V, current: 40 mA, sampling width: 0.0260 °, scanning speed: 0. The measurement was performed under the conditions of .0657 ° / s and the measurement diffraction angle range (2θ): 5.0131 to 79.9711 °. The peak search uses the peak search function of the software attached to the diffractometer, and "minimum significance: 0.50, minimum peak tip: 0.01 °, maximum peak tip: 1.00 °, peak base width: 2". It can be performed under the condition of "0.00 °, method: minimum value of second derivative".

Hydrotalcite (especially semi-sintered hydrotalcite) BET specific surface area of preferably from ^{1~250m 2 / g, 5~200m 2 /} g is more preferable. The BET specific surface area of hydrotalcite can be calculated using the BET multipoint method by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM Model 1210, manufactured by Mountec) according to the BET method. can.

The average particle size of hydrotalcite (particularly semi-baked hydrotalcite) is preferably 1 to 1,000 nm, more preferably 10 to 800 nm. The average particle size of hydrotalcite is the median size of the particle size distribution when the particle size distribution is prepared on a volume basis by laser diffraction / scattering type particle size distribution measurement (JIS Z 8825).

As the hydrotalcite (particularly, semi-baked hydrotalcite), one that has been surface-treated with a surface treatment agent can be used. 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. As the surface treatment agent, one kind or two or more kinds can be used.

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 preferable. These can be used alone or in combination of two or more.

Examples of alkylsilanes include methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, dimethyldimethoxysilane, octyltrimethoxysilane, and n-octadecyl. Examples thereof include dimethyl (3- (trimethoxysilyl) propyl) ammonium chloride. One or more of these can be used.

Examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxy. Epoxy-based silane coupling agents such as silane; mercapto-based silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 11-mercaptoundecyltrimethoxysilane 3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N- (2) Amino-based silane coupling agents such as −aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane; Coupling agents, vinyl-based silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane and vinylmethyldiethoxysilane; styryl-based silane coupling agents such as p-styryltrimethoxysilane; 3-acrylicoxypropyltrimethoxy Acrylate-based silane coupling agents such as silane and 3-methacryloxypropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanvopropyltrimethoxysilane; bis (triethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) ) A sulfide-based silane coupling agent such as tetrasulfide; phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazolesilane, triazinesilane and the like can be mentioned. These can be used alone or in combination of two or more.

The surface treatment of hydrotalcite (particularly semi-baked hydrotalcite) is performed by, for example, stirring and dispersing untreated hydrotalcite at room temperature with a mixer, adding a surface treatment agent and spraying, and stirring for 5 to 60 minutes. It can be done by doing. As the mixer, a known mixer can be used, and examples thereof include blenders such as V blenders, ribbon blenders and bubble cone blenders, mixers such as Henshell mixers and concrete mixers, ball mills and cutter mills. Further, when hydrotalcite is pulverized with a ball mill or the like, the above-mentioned higher fatty acid, alkylsilanes or silane coupling agent can be added to perform surface treatment. The amount of the surface treatment agent used varies depending on the type of hydrotalcite, the type of surface treatment agent, and the like, but is preferably 1 to 10 parts by mass with respect to 100 parts by mass of hydrotalcite that has not been surface-treated. In the present invention, surface-treated hydrotalcite is also included in the "hydrotalcite" in the present invention.

When calcined hydrotalcite and / or semi-fibred hydrotalcite are used as the component (B), they are excellent in hygroscopicity, so that the moisture blocking property of the obtained adhesive layer is improved.

Examples of the semi-baked hydrotalcite include "DHT-4C" (manufactured by Kyowa Chemical Industry Co., Ltd., average particle size: 400 nm), "DHT-4A-2" (manufactured by Kyowa Chemical Industry Co., Ltd., average particle size: 400 nm) and the like. Can be mentioned. Examples of the calcined hydrotalcite include "KW-2200" (manufactured by Kyowa Chemical Industry Co., Ltd., average particle size: 400 nm) and the like. Examples of the unfired hydrotalcite include "DHT-4A" (manufactured by Kyowa Chemical Industry Co., Ltd., average particle size: 400 nm) and the like.

(Layered silicate mineral)
Layered silicate minerals are also commonly referred to as phyllosilicate minerals. The layered silicate minerals can be used alone or in combination of two or more. Further, as the layered silicate mineral, a natural product or a synthetic product may be used. As the crystal structure of the layered silicate mineral, it is preferable to use one having high purity, which is regularly stacked in the c-axis direction, but a so-called mixed layered mineral in which the crystal period is disturbed and a plurality of types of crystal structures are mixed is used. You may use it.

Examples of the layered silicate mineral include smectite, kaolinite, halloysite, talc, mica and the like. Of these, mica is preferred.

Smectite is selected from the general formula: X _{0.2 to 0.6} Y _2-3 Z ₄ O ₁₀ (OH) ₂ · nH ₂ O (where X is K, Na, 1 / 2Ca, and 1 / 2Mg. At least one, 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. H ₂ O represents a water molecule bound to an interlayer ion. N represents an integer and can vary significantly depending on the interlayer ion and relative humidity), and is naturally or synthesized. Smectite includes, for example, hectorite, montmorillonite, byderite, nontronite, saponite, iron saponite, saponite, stebunsite, bentonite, or substitutions, derivatives thereof, or mixtures thereof. Among these, hectorite and montmorillonite are preferable.

Commercially available products can be used as the layered silicate mineral. Commercially available products include, for example, "Smecton STN" and "Smekton SAN" (organized hectorite) manufactured by Kunimine Kogyo, "Orben M" (organized montmorillonite) manufactured by Shiraishi Kogyo, and "Esben" manufactured by Hojun. Examples include "NX" (organized montmorillonite) and "Benton series" (organized montmorillonite) manufactured by Toshin Kasei Co., Ltd.

The average particle size of the layered silicate mineral is preferably 1 nm to 100 μm, more preferably 5 nm to 50 μm, and even more preferably 10 nm to 10 μm. The average particle size of the layered silicate mineral is the median size of the particle size distribution when the particle size distribution is prepared on a volume basis by laser diffraction scattering type particle size distribution measurement (JIS Z 8825).

(Preferable aspect)
Hereinafter, preferred embodiments of the present invention will be described in order with respect to the component (B).
The component (B) preferably contains at least one selected from hydrotalcite and layered silicate minerals, more preferably contains hydrotalcite, more preferably contains semi-calcined hydrotalcite, and particularly preferably half. Consists of calcined hydrotalcite. The description of the hydrotalcite and the layered silicate mineral in the above embodiment is as described above.

From the viewpoint of sufficiently suppressing a decrease in the light absorption capacity of the adhesive layer in the short wavelength region, the content of the component (B) is preferably 1% by mass or more with respect to 100% by mass of the non-volatile content of the adhesive composition. More preferably, it is 3% by mass or more. On the other hand, from the viewpoint of improving the transparency of the adhesive layer, the content of the component (B) is preferably 60% by mass or less, more preferably 55, with respect to 100% by mass of the non-volatile content of the adhesive composition. It is less than mass%.

<(C) Compound having maximum absorption wavelength in the wavelength range of 300 to 430 nm>
One of the features of the adhesive composition of the present invention is that the component (C) contains a compound having a maximum absorption wavelength (λmax) in the wavelength range of 300 to 430 nm. As the component (C), only one kind may be used, or two or more kinds may be used in combination.

For the maximum absorption wavelength (λmax) of the component (C), prepare a solution of the component (C) having a concentration such that the absorbance of the maximum absorption wavelength in the light absorption spectrum is 1.0, and measure the light absorption spectrum of the solution. By doing so, it can be identified. Examples of the solvent for preparing the solution of the component (C) include chloroform, toluene and the like.

The maximum absorption wavelength (λmax) of the component (C) is preferably 320 to 430 nm, more preferably 350 to 430 nm.

The component (C) may be treated as an ultraviolet absorber. A known ultraviolet absorber having a maximum absorption wavelength in the wavelength range of 300 to 430 nm can be used as the component (C) of the present invention.

Examples of the component (C) include curcuminoid compounds, benzotriazole compounds, benzophenone compounds, triazine compounds, benzoic acid ester compounds, cyanoacrylate compounds, salicylate ester compounds, azomethine compounds, and indol compounds. Examples thereof include cinnamic acid-based compounds, pyrimidine-based compounds, porphyrin-based compounds, cyanoacrylate-based compounds, oxybenzophenone-based compounds, and polyphenol-based compounds. The component (C) is preferably at least one selected from curcuminoid compounds, benzotriazole compounds and benzophenone compounds.

Examples of the curcuminoid compound include 1,7-bis (4-hydroxy-3-methoxyphenyl) -1,6-heptadiene-3,5-dione (manufactured by Sanwa Chemical Co., Ltd., curcumin, λmax = 420 nm), 1 , 7-Bis (4-hydroxyphenyl) -1,6-heptadiene-3,5-dione (manufactured by Sanwa Chemical Co., Ltd., HPH, λmax = 416 nm) and the like.

Examples of the benzotriazole-based compound include 2- (2-hydroxy-5-methylphenyl) benzotriazole (manufactured by BASF Japan, Tinuvin P, λmax = 341 nm) and 2- [2-hydroxy-3,5-bis (manufactured by BASF Japan). α, α-dimethylbenzyl) phenyl] -2H-benzotriazole (manufactured by BASF Japan, Tinuvin234, λmax = 343 nm), 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) 5-chlorobenzotriazole (BASF Japan, Tinuvin 326, λmax = 353 nm), 2- (2-Hydroxy-5-tert-octylphenyl) benzotriazole (BASF Japan, Tinuvin 329, λmax = 343 nm), 2,2'-methylenebis [6 -(Benzotriazole-2-yl) -4-tert-octylphenol] (BASF Japan, Tinuvin 360, λmax = 349 nm), 5-chloro-2- [3- (tert-butyl) -2-hydroxy-5- Methylphenyl] -2H-benzotriazole (ADEKA, Adecastab LA-36, λmax = 355 nm), 2- (2-hydroxy-5'-methylphenyl) benzotriazole (Johoku Kagaku, JF-77, λmax = 341 nm), 2- (2'-hydroxy-3', 5'-di-tert-pentylphenyl) benzotriazole (manufactured by Johoku Chemical Co., Ltd., JF-80, λmax = 306 nm), 2- (2'-hydroxy-5) '-Tert-octylphenyl) benzotriazole (manufactured by Johoku Chemical Co., Ltd., JF-83, λmax = 343 nm), 2,2'-methylenebis [6- (2H-benzotriazole-2-yl) -4- (1, 1,3,3-Tetramethylbutyl) phenol] (JF-832, λmax = 349nm), 2- (2,4-dihydroxyphenyl) -2H-benzotriazole (Daiwa Kasei, DAINSORBT) -0, λmax = 345nm), 2- (2-hydroxy4octyloxyphenyl) -2H-benzotriazole (manufactured by Daiwa Kasei Co., Ltd., DAINSORB T-7, λmax = 345nm), 2- (2'-hydroxy-3' -Tert-Butyl-5'-methylphenyl) -5-chlorobenzotriazole (manufactured by Daiwa Kasei Co., Ltd., UV-326, λmax = 353 nm), 2- (3-tert-butyl-2-di Hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole (manufactured by Cipro Chemical Co., Ltd., SEESORB703, λmax = 354 nm) and the like can be mentioned.

Examples of the benzophenone compound include 2,2', 4,4'-tetrahydroxybenzophenone (manufactured by Daiwa Kasei Co., Ltd., DAINSORB P-6, λmax = 354 nm), 2- (3-t-butyl-2-dihydroxy-5). -Methylphenyl) -5-chloro-2H-benzotriazole (Cipro Kasei Co., Ltd., SEESORB106, λmax = 354 nm), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (Cipro Kasei Co., Ltd., SEESORB107, λmax =) 356 nm) and the like.

Examples of the triazine compound include 2- [4- (octyl-2-methylethanoate) oxy-2-hydroxyphenyl] -4,6- [bis (2,4-dimethylphenyl)] -1,3. 5-Triazine (manufactured by BASF Japan, Tinuvin 479, λmax = 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, λmax = 336 nm), 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-dibutoxyphenyl) Phenyl) -1,3,5-triazine (manufactured by BASF Japan, Tinuvin 460, λmax = 346 nm) and the like can be mentioned.

Examples of the benzoic acid ester compound include diethylaminohydroxybenzoyl benzoic acid hexyl (manufactured by BASF Japan Ltd., Uvinul A Plus, λmax = 354 nm).

Examples of the cyanoacrylate compound include ethyl-2-cyano-3,3-diphenyl acrylate (manufactured by BASF Japan, Uvinul 3035, λmax = 302 nm) and 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate (BASF). Examples thereof include Uwinul3039, λmax = 303 nm, manufactured by Japan, and 2,4-dihydroxybenzophenone (Uvinul3030, λmax = 308 nm, manufactured by BASF Japan, Ltd.).

Examples of the salicylic acid ester compound include phenyl salicylate (λmax = 310 nm) and octyl salicylate (λmax = 301 nm).
Examples of the azomethine compound include BONASORB UA-3701 (trade name, λmax = 378 nm, full width at half maximum: 60 nm, manufactured by Orient Chemical Industry Co., Ltd.).

Examples of the indole compound include BONASORB UA-3911 (trade name, λmax = 395 nm, manufactured by Orient Chemical Industry Co., Ltd.), BONASORB UA-3912 (trade name, λmax = 390 nm, manufactured by Orient Chemical Industry Co., Ltd.) and the like.

Examples of the cinnamic acid compound include ethylhexyl methoxycinnamic acid (manufactured by BASF Japan, Uvinul MC80N, λmax = 310 nm), octyl p-methoxycinnamic acid (λmax = 308 nm), and mono-2-ethylhexane citrate. Examples thereof include glyceryl acid (λmax = 312 nm), Pulsol MCX (trade name, λmax = 311 nm, manufactured by DSM Nutrition Japan), Neoheliopan AV (trade name, λmax = 311 nm, manufactured by Simrise) and the like.

Examples of the pyrimidine compound include FDB-009 (trade name, manufactured by Yamada Chemical Industry Co., Ltd., λmax = 402 nm).
Examples of the porphyrin-based compound include FDB-001 (trade name, manufactured by Yamada Chemical Industry Co., Ltd., λmax = 420 nm).

From the viewpoint of ensuring sufficient light absorption capacity in the short wavelength region of the adhesive layer formed from the adhesive composition, the content of the component (C) is based on 100% by mass of the non-volatile content of the adhesive composition. It is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more. On the other hand, in order to improve the transparency of the adhesive layer and to suppress problems such as crystallization or leakage of the component (C) and coloring of the adhesive layer, the content of the component (C) is the adhesive. It is preferably 15% by mass or less, more preferably 13% by mass or less, still more preferably 10% by mass or less, based on 100% by mass of the non-volatile content of the composition.

<Other ingredients>
The adhesive composition of the present invention may contain other components different from the components (A) to (C) as long as the effects of the present invention are not impaired. As for other components, only one kind may be used, or two or more kinds may be used in combination. Other components include, for example, curing agents; curing accelerators; organic solvents; mineral oil-based softeners, vegetable oil-based softeners, subfactis, fatty acids, fatty acid salts, softeners such as synthetic oils; rubber particles, silicone powder, nylon. Organic fillers such as powders and fluororesin powders; defoaming agents or leveling agents; adhesion imparting agents; thickeners such as Orben and Benton; antioxidants; heat stabilizers; light stabilizers and the like.

At least one selected from a thermosetting resin (for example, an epoxy resin or the like), a thermoplastic resin having an epoxy group (for example, an olefin resin having an epoxy group), and a rubber having an epoxy group as the component (A). When used, the adhesive composition of the present invention preferably contains a curing agent. Only one type of curing agent may be used, or two or more types may be used in combination.

The curing agent is not particularly limited, and known ones 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 adduct compounds, organic acid dihydrazide compounds, and organic phosphine compounds. Examples thereof include dicyandiamide compounds. The curing agent is preferably a tertiary amine compound.

The adhesive composition of the present invention may contain a curing accelerator. As the curing accelerator, only one kind may be used, or two or more kinds may be used in combination. The curing accelerator is not particularly limited, and known ones can be used. Examples of the curing accelerator include tertiary amine compounds, imidazole compounds, dimethylurea compounds, amine adduct compounds, organic phosphine compounds and the like. The curing accelerator is preferably at least one selected from tertiary amine compounds, imidazole compounds and dimethylurea compounds.

Examples of the tertiary amine compound that is a curing agent or curing accelerator include DBN (1,5-diazabicyclo [4.3.0] non-5-ene) and DBU (1,8-diazabicyclo [5.4.0] undec). -7-ene), 2-ethylhexanate of DBU, phenol salt of DBU, p-toluenesulfonate of DBU, U-CAT SA 102 (manufactured by San-Apro: octylate of DBU), formate of DBU DBU-organic acid salts such as, 2,4,6-tris (dimethylaminomethyl) phenol (TAP) and the like.

Examples of the primary or secondary amine compound that is a curing agent include diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, and 1,3-bisaminomethylcyclohexane. Aliper amines such as diproprenedamines, diethylaminopropylamines, bis (4-aminocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane; N-aminoethylpyverazine, 1,4-bis (3-aminopropyl) ) Alicyclic amines such as piperazine; aromatic amines such as diaminodiphenylmethane, m-phenylenediamine, m-xylene diamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone and diethyltoluenediamine can be mentioned. Examples of commercially available products of primary or secondary amine compounds include Kayahard A-A (manufactured by Nippon Kayaku Co., Ltd .: 4,4'-diamino-3,3'-dimethyldiphenylmethane).

Examples of the ionic liquid as a curing agent include 1-butyl-3-methylimidazolium lactate, tetrabutylphosphonium-2-pyrrolidone-5-carboxylate, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, and tetrabutylphosphonium. Trifluoroacetate, tetrabutylphosphonium α-lipoate, tetrabutylphosphonium formate salt, tetrabutylphosphonium lactate, bis (tetrabutylphosphonium) tartrate salt, tetrabutylphosphonium salt of horse urate, tetrabutylphosphonium salt of N-methyl horseurate, benzoyl- DL-alanine tetrabutylphosphonium salt, N-acetylphenylalanine tetrabutylphosphonium salt, 2,6-di-tert-butylphenol tetrabutylphosphonium salt, L-aspartate monotetrabutylphosphonium salt, glycinetetrabutylphosphonium salt, 1-ethyl -3-Methyl imidazolium lactate, 1-ethyl-3-methyl imidazolium acetate, 1-ethyl formate-3-methyl imidazolium salt, horse urate 1-ethyl-3-methyl imidazolium salt, N-methyl horse uric acid 1 -Ethyl-3-methylimidazolium salt, bis tartrate (1-ethyl-3-methylimidazolium) salt, N-acetylglycine 1-ethyl-3-methylimidazolium salt are preferable, and tetrabutylphosphonium decanoate, N. -Acetylglycine tetrabutylphosphonium salt, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium salt formicate, 1-ethyl-3-methylimidazolium salt for horse urate, N-methyl horse uric acid 1 -Ethyl-3-methylimidazolium salt and the like can be mentioned.

Examples of the acid anhydride compound as a curing agent include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, and dodecenyl succinic anhydride. Things etc. can be mentioned. Examples of commercially available acid anhydride compounds include Ricacid TH, TH-1A, HH, MH, MH-700, and MH-700G (all manufactured by Shin Nihon Rika Co., Ltd.).

Examples of the imidazole compound that is a curing agent or curing accelerator include 1H-imidazole, 2-methyl-imidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, and 1-cyanoethyl-2-ethyl. -4-Methyl-imidazole, 2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimerite, 2,4-diamino-6- (2'-un) Decylimidazolyl- (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-s-triazine isocyanuric acid adduct and the like can be mentioned. Commercially available products of the imidazole compound include, for example, Curesol 2MZ, 2P4MZ, 2E4MZ, 2E4MZ-CN, C11Z, C11Z-CN, C11Z-CNS, C11Z-A, 2PHZ, 1B2MZ, 1B2PZ, 2PZ, C17Z, 1.2DMZ, 2P4MHZ. -PW, 2MZ-A, 2MA-OK (both manufactured by Shikoku Kasei Kogyo Co., Ltd.) and the like can be mentioned.

Examples of the dimethylurea compound as a curing agent or curing accelerator include aromatic dimethylurea such as DCMU (3- (3,4-dichlorophenyl) -1,1-dimethylurea) and U-CAT3512T (manufactured by San-Apro). , U-CAT3503N (manufactured by San-Apro Co., Ltd.) and the like, aliphatic dimethylurea and the like. Of these, aromatic dimethylurea is preferable from the viewpoint of curability.

Examples of the amine adduct compound as a curing agent or curing accelerator include an epoxy adduct compound obtained by stopping the addition reaction of a tertiary amine to an epoxy resin in the middle. Commercially available products of amine adduct compounds include, for example, Amicure PN-23, Amicure MY-24, Amicure PN-D, Amicure MY-D, Amicure PN-H, Amicure MY-H, Amicure PN-31, Amicure PN- 40, Amicure PN-40J (both manufactured by Ajinomoto Fine Techno Co., Ltd.) and the like.

Examples of the organic acid dihydrazide compound as a curing agent include Amicure VDH-J, Amicure UDH, Amicure LDH (all manufactured by Ajinomoto Fine-Techno Co., Ltd.) and the like.

Examples of the organic phosphine compound which is a curing agent or curing accelerator include triphenylphosphine, tetraphenylphosphonium tetra-p-trilborate, tetraphenylphosphonium tetraphenylborate, tri-tert-butylphosphonium tetraphenylborate, (4- Methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, triphenylphosphine triphenylborane and the like can be mentioned. Examples of commercially available organic phosphine compounds include TPP, TPP-MK, TPP-K, TTBuP-K, TPP-SCN, and TPP-S (manufactured by Hokuko Chemical Industry Co., Ltd.).

Examples of the dicyandiamide compound as a curing agent include dicyandiamide. Examples of commercially available dicyandiamide products include DICY7 and DICY15 (both manufactured by Mitsubishi Chemical Corporation), which are dicyandiamide finely pulverized products.

When a thermosetting resin (particularly an epoxy resin) is used as the component (A) in the adhesive composition of the present invention, the content of the curing agent is the adhesive from the viewpoint of the balance between curability and storage stability. With respect to 100% by mass of the non-volatile content of the composition, 0.1 to 40% by mass is preferable, 0.5 to 38% by mass is more preferable, and 1 to 25% by mass is further preferable. When the adhesive composition of the present invention contains a curing accelerator, the content thereof is preferably 0.05 to 10% by mass with respect to 100% by mass of the non-volatile content of the adhesive composition from the same viewpoint. 0.1 to 8% by mass is more preferable, and 0.5 to 5% by mass is further preferable. When a thermosetting resin (particularly an epoxy resin) is used, it is preferable to use a curing agent and a curing accelerator in combination.

When a thermoplastic resin having an epoxy group (particularly, an olefin resin having an epoxy group) and / or a rubber having an epoxy group is used as the component (A) in the adhesive composition of the present invention, the adhesive material of the present invention is used. The composition 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 non-volatile content of the adhesive composition.

The adhesive composition of the present invention may contain an organic solvent. As the organic solvent, only one kind may be used, or two or more kinds may be used in combination. Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (hereinafter, also abbreviated as “MEK”) and cyclohexanone, and acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate. , Carbitols such as cellosolve and 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 ° C.) of the adhesive composition varnish is 300 to 2000 mPa · s.

<Manufacturing of adhesive composition>
The adhesive composition composition of the present invention can be produced by mixing the above-mentioned components (A) to (C) and, if necessary, other components. The mixing means is not particularly limited, and mixing can be performed using a known device (for example, a kneading roller, a rotary mixer, etc.).

<Use of adhesive composition>
The adhesive composition of the present invention is preferably used to form an adhesive layer in an optical device. The optical device in the present invention means 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 is suitably used for providing an adhesive layer for blocking light such as ultraviolet rays in an organic EL display device in which deterioration of the organic EL element due to light such as ultraviolet rays is a problem. be able to. For example, the adhesive composition varnish can be applied to the components of the optical device and dried to form an adhesive layer in the optical device.

<Adhesive sheet>
The present invention also provides an adhesive sheet containing a support and an adhesive layer formed from the adhesive composition of the present invention on the support. The adhesive sheet of the present invention, like the adhesive composition, is preferably used to form an adhesive layer in an optical device. For example, the adhesive layer in the optical device can be formed by attaching the adhesive sheet to a component of the optical device and then peeling off the support of the adhesive sheet.

The adhesive sheet of the present invention can be produced, for example, by applying an adhesive composition varnish on a support and drying the obtained coating film to form an adhesive layer on the support. The thickness of the adhesive layer in the adhesive sheet is preferably 10 to 200 μm, more preferably 20 to 180 μm, and further preferably 30 μm to 150 μm from the viewpoint of the balance between light absorption capacity and transparency in the short wavelength region.

The support used for the adhesive sheet is not particularly limited, and known ones can be used. Examples of the support include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter, may be abbreviated as "PET"), polyesters such as polyethylene naphthalate, polycarbonate, and plastics formed of polyimide. Film is mentioned. As the plastic film, a PET film is particularly preferable. Further, 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 a mat treatment and a corona treatment. Examples of the mold release treatment include a mold release treatment using a mold release agent such as a silicone resin-based mold release agent, an alkyd resin-based mold release agent, and a fluororesin-based mold release agent. When the support has a release layer in the present invention, the release layer is also regarded as a part of the support. The thickness of the support is not particularly limited, but is preferably 20 to 200 μm, more preferably 20 to 125 μm from the viewpoint of handleability and the like.

In the adhesive sheet, the adhesive layer may be protected by a protective film. By protecting with a protective film, it is possible to prevent dust and the like from adhering to the surface of the adhesive layer and scratches. As the protective film, it is preferable to use a plastic film similar to the support. Further, the protective film may also be subjected to a matte 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 μm, preferably 10 to 100 μm.

<Transparency>
The adhesive layer formed from the adhesive composition of the present invention is preferably transparent. This transparency can be evaluated by the total light transmittance of 650 nm in the visible light region of the adhesive layer having a thickness of 80 μm. The total light transmittance of the adhesive layer formed from the adhesive composition of the present invention and having a thickness of 80 μm at 650 nm is preferably 80 to 100%, more preferably 85 to 100%.

<Haze>
The adhesive layer formed from the adhesive composition of the present invention preferably has a low haze. The haze of the adhesive layer formed from the adhesive composition of the present invention and having a thickness of 80 μm is preferably 30% or less. Haze can be measured by a method according to JIS K 7136.

<Optical device>
The present invention also provides an optical device having an adhesive layer formed from the adhesive composition. Examples of the optical device include an organic EL display device, a solar cell, and the like, and an organic EL display device is preferable.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

<Evaluation of light absorption capacity and transparency in the short wavelength range>
In order to evaluate the light absorption capacity and transparency in the short wavelength region of the adhesive layer (that is, the adhesive layer formed from the adhesive composition) of the adhesive sheets produced in Examples and Comparative Examples, all light rays having wavelengths of 380 nm and 400 nm are evaluated. The transmittance and the total light transmittance at a wavelength of 650 nm were measured.

(1) Preparation of Evaluation Sample The adhesive sheet (adhesive layer thickness: 80 μm) prepared in Examples and Comparative Examples was cut into a length of 70 mm and a width of 25 mm, and the cut sheet was cut into a glass plate (length 76 mm, width 26 mm). A 1.2 mm thick microslide glass, white slide glass S1112 made by Matsunami Glass Industry Co., Ltd., and edge polishing No. 2) were laminated using a batch type vacuum laminator (Nichigo Morton Co., Ltd., V-160). The laminating conditions were a temperature of 80 ° C., a depressurization time of 30 seconds, and then a pressure of 0.3 MPa for 30 seconds. Then, the polyethylene terephthalate (PET) film of the adhesive sheet was peeled off, and the same glass plate as above was further laminated on the exposed adhesive layer to prepare an evaluation sample (laminated body).

(2) Evaluation of light absorption capacity in the short wavelength range (measurement of total light transmittance at 380 nm and 400 nm)
Fiber type spectrophotometer (MCPD-7700, type 311C, manufactured by Otsuka Electronics Co., Ltd., external light source unit: halogen lamp MC-2564 (24V, 24V,) equipped with a φ80mm integrating sphere (model name SRS-99-010, reflectance 99%) Using 150 W specification)), the distance between the integrating sphere and the evaluation sample was set to 0 mm, the distance between the light source and the evaluation sample was set to 48 mm, and the light transmittance spectrum of the obtained evaluation sample was measured. The reference was the same glass plate as above. From the obtained light transmittance spectrum, the total light transmittance of 380 nm and 400 nm was determined.

(3) Evaluation of transparency (measurement of total light transmittance at a wavelength of 650 nm)
From the light transmittance spectrum obtained by the above method, the total light transmittance at a wavelength of 650 nm was determined.

The raw materials used in Examples and Comparative Examples are as follows.
(A) Organic binder T-YP341 (manufactured by Seikou PMC): Glysidyl methacrylate-modified propylene-butene copolymer (propylene unit / butene unit: 71% by mass / 29% by mass, epoxy group concentration: 0.638 mmol / g, 20% by mass toluene solution of number average molecular weight: 155,000) ・ HV-1900 (manufactured by JXTG Energy Co., Ltd.): Polybutene (number average molecular weight: 2,900)
HV-300M (manufactured by Toho Chemical Industry Co., Ltd.): Maleic anhydride-modified liquid polybutene (acid anhydride group concentration: 0.77 mmol / g, number average molecular weight: 2,100)
-Alcon P125 (manufactured by Arakawa Chemical Co., Ltd.): Adhesive-imparting resin (saturated aliphatic hydrocarbon resin, softening point: 125 ° C., number average molecular weight: 750)
-YX8000 (manufactured by Mitsubishi Chemical Corporation): Liquid hydrogenated bisphenol A type epoxy resin (epoxy equivalent: about 205, weight average molecular weight: 410)
-YX8040 (manufactured by Mitsubishi Chemical Corporation): Solid hydrogenated bisphenol A type epoxy resin (epoxy equivalent: about 1000, weight average molecular weight: 3,000)
-YX7200B35 (manufactured by Mitsubishi Chemical Corporation): Phenoxy resin solution (solvent: MEK, non-volatile content: 35% by mass, number average molecular weight of phenoxy resin: 10,000, weight average molecular weight of phenoxy resin: 30,000)

(B) Layered clay mineral / semi-calcined hydrotalcite (saturated water absorption rate: 17% by mass, heat weight loss rate at 280 ° C.: 3.6% by mass, heat weight loss rate at 380 ° C.: 14.4% by mass, powder Low-angle side diffraction intensity / high-angle side diffraction intensity in X-ray diffraction: 0.6, average particle size: 400 nm, BET specific surface area: 15 m ² / g, magnesium oxide / aluminum oxide molar ratio: 4.16)

(C) Compound having maximum absorption wavelength in the wavelength range of 300 to 430 nm ・ SEESORB703 (benzotriazole compound manufactured by Cipro Chemical Co., Ltd.): 2- (3-tert-butyl-2-dihydroxy-5-methylphenyl) -5 -Chloro-2H-benzotriazole (λmax = 354 nm)
HPH (curcuminoid compound manufactured by Sanwa Chemical Co., Ltd.): 1,7-bis (4-hydroxyphenyl) -1,6-heptadiene-3,5-dione (λmax = 416 nm)
DAINSORB T-0 (benzotriazole compound manufactured by Daiwa Kasei Co., Ltd.): 2- (2,4-dihydroxyphenyl) -2H-benzotriazole (λmax = 345 nm)
SEESORB107 (benzophenone compound manufactured by Cipro Chemical Co., Ltd.): 2,2-dihydroxy 4,4-dimethoxybenzophenone (λmax = 356 nm)

(D) Other components ・ 2,4,6-tris (diaminomethyl) phenol (hereinafter abbreviated as “TAP”): Curing accelerator ・ Toluene ・ Ipsol # 100 (manufactured by Idemitsu Kosan Co., Ltd.): Aromatic mixture Solvent / Methyl ethyl ketone (MEK)
-Anon (manufactured by Sumitomo Chemical Co., Ltd.): Cyclohexanone-U-CAT3512T (manufactured by San-Apro Co., Ltd.): Curing accelerator-N-Acetylglycine tetrabutylphosphonium salt: Ionic liquid curing agent

<Example 1>
130 parts by mass (78 parts by mass) of 60% by mass Ipsol # 100 solution of tackifier resin ("Arcon P125" manufactured by Arakawa Chemical Industries, Ltd.), maleic anhydride-modified liquid polybutene ("HV-300M" manufactured by Toho Chemical Industry Co., Ltd.) A mixture was obtained by mixing 35 parts by mass of polybutene (“HV-1900” manufactured by JXTG Energy Co., Ltd.) and 100 parts by mass of the above semi-baked hydrotalcite as component (B) with three rolls. To the obtained mixture, 200 parts by mass of a 20% by mass toluene solution of a glycidyl methacrylate-modified propylene-butene copolymer (“T-YP341” manufactured by Seikou PMC) (40 parts by mass of a non-volatile content) and a 20% by mass toluene solution of TAP. 2.5 parts by mass (0.5 parts by mass of non-volatile content) and 14 parts by mass of toluene were blended, and 3.3 parts by mass of SEESORB703 (manufactured by Cipro Kasei Co., Ltd.) was further blended as a component (C), and the obtained mixture was prepared. The mixture was uniformly mixed with a high-speed rotary mixer to obtain an adhesive composition varnish. The obtained varnish is uniformly applied to a polyethylene terephthalate (PET) film treated with a silicone-based mold release agent with a die coater, heated at 130 ° C. for 60 minutes and dried to form an adhesive layer having a thickness of 80 μm. An adhesive sheet to have was obtained.

In Example 1, the content of the component (A) is 67.2% by mass and the content of the component (B) is 31.6% by mass with respect to 100% by mass of the non-volatile content of the adhesive composition. , The content of the component (C) was 1.0% by mass.
Table 1 below shows the results of the total light transmittance measured as described above.

<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 the component (A) is 67.9% by mass and the content of the component (B) is 31.9% by mass with respect to 100% by mass of the non-volatile content of the adhesive composition. , The content of the component (C) was 0% by mass.
Table 1 below shows the results of the total light transmittance measured as described above.

<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 component (C) SEESORB703 was changed to 2.2 parts by mass.

In Comparative Example 1b, the content of the component (A) was 98.7% by mass and the content of the component (B) was 0% by mass with respect to 100% by mass of the non-volatile content of the adhesive composition. The content of (C) was 1.0% by mass.
Table 1 below shows the results of the total light transmittance measured as described above.

From the results shown in Table 1, it can be seen that the adhesive layer of the adhesive sheet produced in Example 1 has improved light absorption capacity in the short wavelength region while maintaining transparency.

<Example 2>
As the component (C), 330 parts by mass (nonvolatile content 3.3 parts by mass) of 99 mass% anon solution of HPH (manufactured by Sanwa Chemical Co., Ltd.) was blended in place of 3.3 parts by mass of SEESORB703 (manufactured by Cipro Kasei Co., Ltd.). Obtained an adhesive sheet in the same manner as in Example 1.

In Example 2, the content of the component (A) is 67.2% by mass and the content of the component (B) is 31.6% by mass with respect to 100% by mass of the non-volatile content of the adhesive composition. , The content of the component (C) was 1.0% by mass.
Table 2 below shows the results of the total light transmittance measured as described above.

<Comparative example 2>
The same as in Example 2 except that the component (B) was not blended and the blending amount of the 99% by mass anon solution of HPH as the component (C) was changed to 220 parts by mass (nonvolatile content 2.2 parts by mass). An adhesive sheet was obtained.

In Comparative Example 2, the content of the component (A) was 98.7% by mass and the content of the component (B) was 0% by mass with respect to 100% by mass of the non-volatile content of the adhesive composition. The content of (C) was 1.0% by mass.
Table 2 below shows the results of the total light transmittance measured as described above.

From the results shown in Table 2, it can be seen that the adhesive layer of the adhesive sheet produced in Example 2 has improved light absorption capacity in the short wavelength region while maintaining transparency.

<Example 3>
As a component (C), 22 parts by mass (nonvolatile content 3.3 parts by mass) of a 15% by mass MEK solution of DAINSORB T-0 (manufactured by Daiwa Kasei Co., Ltd.) is blended in place of 3.3 parts by mass of SEESORB703 (manufactured by Sipro Kasei Co., Ltd.). An adhesive sheet was obtained in the same manner as in Example 1.

In Example 3, the content of the component (A) is 67.2% by mass and the content of the component (B) is 31.6% by mass with respect to 100% by mass of the non-volatile content of the adhesive composition. , The content of the component (C) was 1.0% by mass.
Table 3 below shows the results of the total light transmittance measured as described above.

<Comparative example 3>
Examples except that the component (B) was not blended and the blending amount of the 15 mass% MEK solution of the component (C) DAINSORB T-0 was changed to 14.7 parts by mass (nonvolatile content 2.2 parts by mass). An adhesive sheet was obtained in the same manner as in 3.

In Comparative Example 3, the content of the component (A) was 98.7% by mass and the content of the component (B) was 0% by mass with respect to 100% by mass of the non-volatile content of the adhesive composition. The content of (C) was 1.0% by mass.
Table 3 below shows the results of the total light transmittance measured as described above.

From the results shown in Table 3, it can be seen that the adhesive layer of the adhesive sheet produced in Example 3 has improved light absorption capacity in the short wavelength region while maintaining transparency.

<Example 4>
As the component (C), 16.5 parts by mass (nonvolatile content 3.3 parts by mass) of a 20% by mass toluene solution of SEESORB107 (manufactured by Sipro Kasei) was blended in place of 3.3 parts by mass of SEESORB703 (manufactured by Sipro Kasei). An adhesive sheet was obtained in the same manner as in Example 1 except for the above.

In Example 4, the content of the component (A) is 67.2% by mass and the content of the component (B) is 31.6% by mass with respect to 100% by mass of the non-volatile content of the adhesive composition. , The content of the component (C) was 1.0% by mass.
Table 4 below shows the results of the total light transmittance measured as described above.

<Comparative example 4>
Adhesive sheet in the same manner as in Example 4 except that the component (B) was not blended and the component (C) was changed to 11.0 parts by mass (nonvolatile content 2.2 parts by mass) of a 20% by mass toluene solution of SEESORB107. Got

In Comparative Example 4, the content of the component (A) was 98.7% by mass and the content of the component (B) was 0% by mass with respect to 100% by mass of the non-volatile content of the adhesive composition. The content of (C) was 1.0% by mass.
Table 4 below shows the results of the total light transmittance measured as described above.

From the results shown in Table 4, it can be seen that the adhesive layer of the adhesive sheet produced in Example 4 has improved light absorption capacity in the short wavelength region while maintaining transparency.

<Example 5>
A mixture was obtained by mixing 60 parts by mass of a liquid hydrogenated bisphenol A type epoxy resin (“YX8000” manufactured by Mitsubishi Chemical Corporation) and 40 parts by mass of the above semi-baked hydrotalcite as component (B) with three rolls. To the obtained mixture, 1.5 parts by mass of a curing accelerator (“U-CAT3512T” manufactured by San-Apro), 57.2 parts by mass of a phenoxy resin solution (“YX7200B35” manufactured by Mitsubishi Chemical Co., Ltd.) (20 parts by mass of phenoxy resin), And a mixture of 50 parts by mass (20 parts by mass of solid hydrogenated bisphenol A type epoxy resin) of a solution (solvent: MEK, non-volatile content: 40% by mass) of a solid hydrogenated bisphenol A type epoxy resin ("YX8040" manufactured by Mitsubishi Chemical Co., Ltd.). Was compounded. The obtained mixture was further blended with 3 parts by mass of an ionic liquid curing agent (N-acetylglycine tetrabutylphosphonium salt) and 1.5 parts by mass of SEESORB107 (manufactured by Cipro Kasei Co., Ltd.) as a component (C). The mixture was uniformly dispersed with a high speed rotary mixer to obtain an adhesive composition varnish. The obtained varnish was uniformly applied to a polyethylene terephthalate (PET) film treated with a silicone-based release agent with a die coater, heated at 80 ° C. for 5 minutes to dry, and then applied to the surface of the resin composition layer. A release PET film was placed as a protective film to obtain an adhesive sheet.

In Example 5, the content of the component (A) is 68.5% by mass and the content of the component (B) is 27.4% by mass with respect to 100% by mass of the non-volatile content of the adhesive composition. , The content of the component (C) was 1.0% by mass.
Table 5 below shows the results of the total light transmittance measured as described above.

<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 component (C) SEESORB107 was changed to 1.1 parts by mass.

In Comparative Example 5, the content of the component (A) was 94.7% by mass and the content of the component (B) was 0% by mass with respect to 100% by mass of the non-volatile content of the adhesive composition. The content of (C) was 1.0% by mass.
Table 5 below shows the results of the total light transmittance measured as described above.

From the results shown in Table 5, it can be seen that the adhesive layer of the adhesive sheet produced in Example 5 has improved light absorption capacity in the short wavelength region while maintaining transparency.

It is possible to form an adhesive layer having an ability to absorb light in a wavelength range of 300 to 430 nm and having good transparency from the adhesive composition of the present invention. Such an adhesive layer can prevent photodegradation of an optical device such as an organic EL element, and is particularly suitable for an organic EL display device.

This application is based on Japanese Patent Application No. 2018-219682 filed in Japan, the contents of which are incorporated herein by reference in its entirety.

Claims (15)

The following components (A) to (C):
(A) Organic binder,
An adhesive composition containing (B) a layered clay mineral and (C) a compound having a maximum absorption wavelength in the wavelength range of 300 to 430 nm. The adhesive composition according to claim 1, wherein the component (B) contains at least one selected from hydrotalcite and layered silicate minerals. The adhesive composition according to claim 1, wherein the component (B) contains hydrotalcite. The adhesive composition according to claim 1, wherein the component (B) contains semi-baked hydrotalcite. The adhesive composition according to any one of claims 1 to 4, wherein the content of the component (A) is 25 to 95% by mass with respect to 100% by mass of the non-volatile content of the adhesive composition. The adhesive composition according to any one of claims 1 to 5, wherein the content of the component (B) is 1 to 60% by mass with respect to 100% by mass of the non-volatile content of the adhesive composition. The adhesive composition according to any one of claims 1 to 6, wherein the content of the component (C) is 0.05 to 15% by mass with respect to 100% by mass of the non-volatile content of the adhesive composition. The adhesive composition according to any one of claims 1 to 7, wherein the component (A) contains at least one selected from an olefin resin and an epoxy resin. The adhesive composition according to any one of claims 1 to 8, which is used for forming an adhesive layer of an optical device. The adhesive composition according to claim 9, wherein the optical device is an organic EL display device. An adhesive sheet containing a support and an adhesive layer formed on the support from the adhesive composition according to any one of claims 1 to 8. The adhesive sheet according to claim 11, which is used to form an adhesive layer in an optical device. The adhesive sheet according to claim 12, wherein the optical device is an organic EL display device. An optical device having an adhesive layer formed from the adhesive composition according to any one of claims 1 to 8. An organic EL display device having an adhesive layer formed from the adhesive composition according to any one of claims 1 to 8.