TWI772394B - Adhesive sheet and method for producing laminate - Google Patents

Abstract

The present invention provides an adhesive sheet obtained by directly laminating a molecular adhesive layer containing a molecular adhesive on an adhesive layer containing an adhesive resin (P), and a method for producing a laminate using the adhesive sheet. The aforementioned molecular adhesive has at least one reactive group (Zα) selected from the group consisting of amino groups, azide groups, mercapto groups, isocyanate groups, urea groups, and epoxy groups, and is selected from silanol groups and borrowings. At least one reactive group (Zβ) in the group consisting of a group that forms a silanol group by a hydrolysis reaction, wherein the aforementioned adhesive resin (P) has a reactive group (Zα) capable of interacting with the aforementioned molecular adhesive. ) forms a reactive partial structure (Zγ) of a chemical bond, the shear storage elastic modulus of the adhesive layer at 23°C is 0.10-3.30 MPa, and the thickness of the adhesive layer is 0.1-100 μm. According to the present invention, there are provided an adhesive sheet which has a molecular adhesive layer and can be easily attached to an adherend even at normal temperature, and a method for producing a laminate using the adhesive sheet.

Description

Adhesive sheet and method for producing laminate

The present invention relates to having a molecular adhesive layer (meaning a layer formed using a molecular adhesive. The same applies hereinafter) and can be easily attached to an adherend even at room temperature (20 to 25°C, the same below). The adhesive sheet, and the manufacturing method of the laminated body using the adhesive sheet.

Compounds with two or more reactive groups can utilize the properties of each reactive group to form two or more chemical bonds, so they are useful as molecular adhesives. As an example of using a molecular adhesive, for example, Patent Document 1 describes a laminate in which an entropy elastic molecular adhesion layer is formed between two substrates, and the entropy elastic molecular adhesion layer is characterized in that the entropy elastic molecular adhesion layer is formed by entropy elasticity. It consists of a body layer and a molecular adhesive layer. As a method for producing a laminate, Patent Document 1 describes that a molecular adhesive layer 1 is formed on a substrate 1 , an entropy elastomer layer 1 is laminated on the molecular adhesive layer 1 , and a molecular adhesive is further laminated on the entropy elastomer layer 1 layer 2, and further lamination of the substrate 2 to form a method of lamination (lamination method). Furthermore, Patent Document 2 describes a method for producing a resin composite, which is characterized in that a solid surface is reacted with a molecular adhesive to form a reactive solid surface, and the material is covalently bonded by fusion bonding with a resin. combined with each other. [Prior Art Literature]

[Patent Document] [Patent Document 1] International Publication No. WO2009/154083 (US2011/0104505A1) [Patent Document 2] Japanese Patent Laid-Open No. 2010-254793

[Problems to be solved by the invention]

As described above, the bonding method using a molecular adhesive has attracted attention because it is less dependent on the environment such as temperature and humidity, and can firmly bond objects. However, since the thickness of the molecular adhesive layer is very thin compared to the previous adhesive layer or adhesive layer, the bonding method using the molecular adhesive is easily affected by the unevenness of the surface of the object, and there may be cases where the object cannot be sufficiently bonded situation.

In this regard, Patent Document 1 describes that by providing an entropy elastomer layer, the adhesion to a substrate having a large surface roughness can be improved. However, the example of the lamination method disclosed in the Examples of Patent Document 1 is only to form the substrate 2 by the electroplating method, and does not specifically disclose the formation of the substrate 1 , the molecular adhesive layer 1 , the entropic elastomer layer 1 and the molecular adhesive. A state in which the laminate composed of the layer 2 is used as an adhesive sheet.

Furthermore, Patent Document 2 describes that the performance of the molecular adhesive can be sufficiently exhibited by melting the resin to adhere the resin to the surface of the reactive solid. However, this method can only be used when the adherend is resin. Furthermore, in this method, the adhered surface and other parts may also be thermally deformed, so special research is necessary to prevent this. Therefore, there is a need for an adhesive sheet which has a molecular adhesive layer and can be easily attached to an adherend even at normal temperature.

The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide an adhesive sheet having a molecular adhesive layer that can be easily attached to an adherend even at room temperature, and a method for producing a laminate using the adhesive sheet . [Means for solving problems]

In order to solve the above-mentioned problems, the present inventors have intensively studied an adhesive sheet having a molecular adhesive layer. As a result, they found that by directly laminating a molecular adhesive layer on a specific adhesive layer, it is possible to obtain an adhesive sheet that can be easily attached even at room temperature. An adhesive sheet attached to an adherend completes the present invention.

Therefore, according to the present invention, the following (1) to (10) pressure-sensitive adhesive sheets and (11) to (12) laminates are provided.

(1) An adhesive sheet obtained by directly laminating a molecular adhesive layer containing a molecular adhesive on an adhesive layer containing an adhesive resin (P), wherein the molecular adhesive has a compound selected from amino group, azide At least one reactive group (Zα) selected from the group consisting of a thiol group, a mercapto group, an isocyanate group, a urea group, and an epoxy group, and a group selected from a silanol group and a group that forms a silanol group by a hydrolysis reaction At least one reactive group (Zβ) in the group consisting of the aforementioned adhesive resin (P) having a reactive partial structure (Zγ) capable of forming a chemical bond with the reactive group (Zα) of the aforementioned molecular adhesive , the shear storage elastic modulus of the adhesive layer at 23° C. is 0.10-3.30 MPa, and the thickness of the adhesive layer is 0.1-100 μm. (2) The adhesive sheet according to (1), wherein the molecular adhesive layer is formed by the reactive group (Zα) possessed by the molecular adhesive and the reactive partial structure (Zα) possessed by the adhesive resin (P). The chemical bond of Zγ) is formed by chemically fixing the molecular adhesive to the adhesive layer. (3) The adhesive sheet according to (1), wherein the reactive group (Zα) possessed by the aforementioned molecular adhesive is selected from the group consisting of amino group, mercapto group, isocyanate group, urea group and epoxy group At least one, and the reactive partial structure (Zγ) possessed by the adhesive resin (P) is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an aldehyde group, and an amino group. (4) The adhesive sheet according to (1), wherein the reactive group (Zα) possessed by the molecular adhesive is an azide group, and the reactive partial structure (Zγ) possessed by the adhesive resin (P) is a At least one selected from the group consisting of a carbon-carbon single bond, a carbon-carbon double bond, and a carbon-hydrogen single bond. (5) The adhesive sheet according to (1), wherein the adhesive layer is not applied with a treatment selected from the group consisting of corona treatment, plasma treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, ozone treatment, excimer ultraviolet treatment, acid treatment , and surface treatments in the group consisting of base treatments. (6) The adhesive sheet according to (1), wherein the molecular adhesive is a compound represented by the following chemical formula (1).

[Chemistry 1]

(R ¹ represents a reactive group (Zα) selected from the group consisting of an amino group, an azide group, a mercapto group, an isocyanate group, a urea group, and an epoxy group, or one or more of the above-mentioned reactive groups A monovalent group (but excludes amino group, azide group, mercapto group, isocyanate group, urea group and epoxy group.), A represents a divalent organic group, X represents a hydroxyl group, a carbon atom number of 1 to 10 an alkoxy group or a halogen atom, Y represents a hydrocarbon group having 1 to 20 carbon atoms, and a represents an integer of 1 to 3.) (7) The adhesive sheet according to (1), wherein the thickness of the molecular adhesive layer is 200nm or less. (8) The adhesive sheet according to (1), wherein only one side of the adhesive layer has a molecular adhesive layer. (9) The adhesive sheet according to (1), wherein both sides of the adhesive layer have molecular adhesive layers. (10) The adhesive sheet according to (1), further comprising a support. (11) A method for manufacturing a laminate, comprising laminating the molecular adhesive of the adhesive sheet described in any one of (1) to (10) on an adherend to form an adhesive layer/molecular adhesive A layered product of the layered structure of layers/adhesives. (12) The method for producing a laminated body according to (11), wherein the temperature T at the time of crimping is -20 to 140°C. [Inventive effect]

According to the present invention, there are provided an adhesive sheet which has a molecular adhesive layer and can be easily attached to an adherend even at normal temperature, and a method for producing a laminate using the adhesive sheet.

Hereinafter, the present invention will be described in detail by classifying it into 1) an adhesive sheet and 2) a method for producing a laminate.

1) Adhesive sheet The adhesive sheet of the present invention is an adhesive sheet obtained by directly laminating a molecular adhesive layer containing a molecular adhesive on an adhesive layer containing an adhesive resin (P). At least one reactive group (Zα) selected from the group consisting of a nitrogen group, a mercapto group, an isocyanate group, a urea group, and an epoxy group, and a group selected from a silanol group and a group that forms a silanol group by a hydrolysis reaction A reactive group (Zβ) of at least one of the formed groups. The aforementioned adhesive resin (P) has a reactive partial structure (Zγ) capable of forming a chemical bond with the reactive group (Zα) of the aforementioned molecular adhesive. The shear storage elastic modulus of the adhesive layer at 23° C. is 0.10 to 3.30 MPa, and the thickness of the adhesive layer is 0.1 to 100 μm. In the present invention, the so-called “molecular adhesive layer containing a molecular adhesive” "Containing a molecular adhesive" means a molecular adhesive and/or a compound derived from a molecular adhesive (eg, a compound that undergoes a reaction such that the structure of a reactive group changes). Furthermore, the phrase "the adhesive resin (P) has a reactive moiety structure (Zγ) capable of forming a chemical bond with the reactive group (Zα) of the aforementioned molecular adhesive" means that the molecular adhesive layer is formed before the adhesive layer is formed. status. In the adhesive layer after the molecular adhesive layer is formed, the adhesive resin (P) has a reactive partial structure (Zγ) and/or a structure derived from the reactive partial structure (Zγ).

[Adhesive Layer] The adhesive layer constituting the adhesive sheet of the present invention is a layer containing an adhesive resin (P). In the adhesive sheet of the present invention, the function of the adhesive layer is to fix the molecular adhesive and improve the adhesion between the molecular adhesive layer and the adherend when the adhesive sheet is used. The adhesive layer may be an adhesive layer having adhesiveness at least when it is attached to an adherend. Therefore, the adhesive layer includes not only a layer having adhesiveness at normal temperature, but also a layer that exhibits adhesiveness by heating (a so-called heat sealable adhesive layer), so as to have adhesiveness at normal temperature Sexual layers are better.

The adhesive resin (P) has a reactive partial structure (Zγ) capable of forming a chemical bond with the reactive group (Zα) of the aforementioned molecular adhesive. By giving the adhesive resin (P) a reactive partial structure (Zγ), the molecular adhesive layer can be efficiently formed.

Examples of the reactive partial structure (Zγ) of the adhesive resin (P) include a hydroxyl group, a carboxyl group, an aldehyde group, an amino group, a carbon-carbon single bond, a carbon-carbon double bond, and a carbon-hydrogen single bond. The reactive group (Zα) in the molecular adhesive can be appropriately selected from the above. For example, when the reactive group (Zα) possessed by the aforementioned molecular adhesive is at least one selected from the group consisting of an amino group, a mercapto group, an isocyanate group, a urea group, and an epoxy group, a hydroxyl group can be used. Preferably, at least one of the group consisting of , carboxyl group, aldehyde group and amino group is used as the reactive partial structure (Zγ). Furthermore, when the reactive group (Zα) possessed by the aforementioned molecular adhesive is an azide group, a group selected from the group consisting of carbon-carbon single bond, carbon-carbon double bond and carbon-hydrogen single bond is used. At least one of the group is preferably used as the reactive partial structure (Zγ).

By using an adhesive containing an adhesive resin (P), the adhesiveness between the adherend and the molecular adhesive layer at room temperature can be improved.

Examples of the adhesive include acrylic adhesives, polyurethane-based adhesives, polyester-based adhesives, rubber-based adhesives, silicone-based adhesives, and the like. Among them, acrylic adhesives are preferred from the viewpoint of easy adjustment of the shear storage elastic modulus and the ease of obtaining an adhesive sheet excellent in adhesion to the adherend even at room temperature. Furthermore, a rubber-based adhesive is preferable from the viewpoint of being able to form an adhesive layer with low water vapor permeability and to easily obtain an adhesive sheet especially used as a sealing material or the like.

Acrylic adhesives are adhesives containing an acrylic polymer as a main component. The so-called acrylic polymer is a polymer having a repeating unit derived from (meth)acrylic acid or (meth)acrylic acid ester. The so-called "(meth)acrylic acid" means acrylic acid or methacrylic acid, and the so-called "(meth)acrylate" means acrylate or methacrylate. Furthermore, the acrylic polymer may have repeating units other than those described above, as long as the effects of the present invention are not impaired.

Included in acrylic adhesives, as the adhesive resin (P) having a reactive partial structure (Zγ) such as a hydroxyl group, a carboxyl group, a carbon-carbon double bond, etc., there are exemplified those having a hydroxyl group, a carboxyl group, a carbon-carbon double bond, etc. Functional group-containing acrylic polymer (hereinafter sometimes referred to as "functional group-containing acrylic polymer"). The functional group-containing acrylic polymer can be obtained by performing a polymerization reaction using a functional group-containing acrylic monomer.

Examples of the functional group-containing acrylic monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (meth)acrylate Acrylic monomers with hydroxyl groups such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; (meth)acrylic acid, (meth)acrylic acid 2 -Acrylic monomers having carboxyl groups such as carboxyethyl esters; acrylic monomers having carbon-carbon double bonds in side chains such as vinyl (meth)acrylate and propylene (meth)acrylate, etc. The above-mentioned materials may be used alone or in combination of two or more.

When synthesizing a functional group-containing acrylic polymer, an acrylic monomer not containing a functional group or another monomer that can be copolymerized with an acrylic monomer may be used together. Examples of the functional group-free acrylic monomer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and (meth)acrylate. Amyl acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, myristyl (meth)acrylate, palm ( Acrylic monomers etc. which have a cycloalkyl group, such as cyclohexyl meth)acrylate. Among these materials, from the viewpoint that an adhesive layer with better adhesion can be formed, an acrylic monomer having no functional group is an alkane (meth)acrylate having a hydrocarbon group having 4 to 10 carbon atoms. Base ester is preferred, and butyl (meth)acrylate is preferred.

Examples of other monomers that can be copolymerized with acrylic monomers include crotonic acid, maleic acid, fumaric acid, itaconic acid, and citraconic acid. Monomers with carboxyl groups such as (meth)acrylamide, N-methyl (meth)acrylamide, N-methylol (meth)acrylamide and other monomers with amide groups; Acrylonitrile; Styrene; Vinyl Acetate; Vinylpyrrolidone, etc. The above-mentioned monomers may be used alone or in combination of two or more.

The production method of the functional group-containing acrylic polymer is not particularly limited, and conventionally known methods such as solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization can be used. Among them, the solution polymerization method is preferable because the polymerization is easy. The initiator used in the polymerization reaction is not particularly limited, and examples include benzoyl peroxide, lauroyl peroxide, and methyl ethyl ketone peroxide. Peroxide-based initiators such as azobisisobutyronitrile (azobisisobutyronitrile), azobiscyanovaleric acid, azobiscyanopentane (azobiscyano pentane), etc. starter, etc.

The solvent used in the solution polymerization reaction is not particularly limited, and examples thereof include toluene, hexane, heptane, ethyl acetate, acetone, methyl ethyl ketone, methanol, and the like. For the reaction conditions such as the temperature and reaction time of the polymerization reaction, known conditions can be employed.

The mass average molecular weight (Mw) of the functional group-containing acrylic polymer is usually 100,000 to 1,000,000, preferably 300,000 to 900,000. The mass average molecular weight (Mw) can be adjusted by adding a certain amount of polymerization initiator or chain transfer agent. The mass-average molecular weight (Mw) of the functional group-containing acrylic polymer can be obtained by performing gel permeation chromatography using tetrahydrofuran as a solvent, as a standard value in terms of polystyrene . In the functional group-containing acrylic polymer, the ratio of the repeating units derived from the functional group-containing monomer is usually 1 to 40% by mass, preferably 3 to 15% by mass, relative to all the repeating units.

The functional group-containing acrylic polymer can also be obtained by a method in which functional groups such as hydroxyl and carboxyl groups are introduced by modifying the acrylic polymer.

Acrylic adhesives may also contain crosslinking agents. A crosslinking agent is a compound which reacts with the above-mentioned functional group to form a crosslinking structure. In the case of using a crosslinking agent, the crosslinking agent to be used is not particularly limited, and examples thereof include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, and the like.

It does not specifically limit as an isocyanate type crosslinking agent, The compound which has two or more isocyanate groups in a molecule|numerator can be used. Examples of the isocyanate-based crosslinking agent include aromatic polyisocyanates such as tolylylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; Alicyclic polyisocyanates such as isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, etc.; and the above-mentioned biuret (biuret), isocyanurate (isocyanurate), and ethylene glycol, propylene glycol, new Adjective bodies of pentanediol, trimethylolpropane, castor oil, etc. and reactants of low-molecular-weight active hydrogen compounds, and the like.

As an epoxy-type crosslinking agent, the compound which has two or more epoxy groups in a molecule|numerator can be used. Examples of epoxy-based crosslinking agents include difunctional epoxy resins such as 1,6-hexanediol diglycidyl ether, N,N-diglycidyl aniline, and ethylene glycol diglycidyl ether. Compounds; trifunctional epoxy compounds such as trimethylolpropane triglycidyl ether, [4-(glycidoxy)phenyl]diglycidylamine, etc.; sorbitol tetraglycidyl ether, N, N, N Tetrafunctional epoxy compounds such as ',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(diglycidylaminomethyl)cyclohexane, and the like. A crosslinking agent may be used individually by 1 type, or may be used in combination of 2 or more types.

The amount of the crosslinking agent used also depends on the type of the crosslinking agent, but is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the functional group-containing acrylic polymer.

In addition, as described above, when the reactive group (Zα) is an azide group, a carbon-carbon single bond, a carbon-hydrogen single bond, or the like can be utilized as the reactive partial structure (Zγ). Therefore, in this case, an acrylic polymer obtained without using a functional group-containing acrylic monomer can be used as the adhesive resin (P).

Rubber-based adhesives are adhesives containing rubber-based resins. Examples of rubber-based resins include natural rubber, and one or more monomers selected from the group consisting of alkyl (meth)acrylate, styrene, and (meth)acrylonitrile. Natural rubber modified by graft polymerization on natural rubber, polybutadiene, polyisoprene, polychloroprene, ethylene-propylene copolymer, styrene-butadiene copolymer, styrene - Isoprene copolymer, acrylonitrile-butadiene copolymer, methyl methacrylate-butadiene copolymer, urethane rubber, polyisobutylene-based resin, polybutene-based resin, etc. The above-mentioned rubber compounds may be used alone or in combination of two or more. The aforementioned rubber-based compounds generally have a carbon-carbon double bond. This carbon-carbon double bond may function as a reactive moiety structure (Zγ). A commercially available product can also be used for the above-mentioned rubber compound. As such a commercially available product, a copolymer of isobutylene and isoprene (Exxon Butyl 268 (manufactured by Nippon Butyl Co., Ltd.)) can be mentioned.

Furthermore, functional groups, such as a hydroxyl group and a carboxyl group, may be introduced by modifying the above-mentioned rubber-based compound. Examples of the modified rubber compound include maleic anhydride-modified polyisobutylene, phthalic anhydride-modified polyisobutylene, maleic anhydride-modified polyisoprene, and hydroxyl-modified polyisobutylene. Pentadiene, allyl-modified polyisoprene, maleic anhydride-modified polybutadiene, hydroxyl-modified polybutadiene, etc. The modification treatment can be carried out according to known methods.

As the modified rubber compound, a commercially available product can be used. Such commercially available products include maleic anhydride-modified polyisobutylene (HV-100M, HV-300M (the above are manufactured by Nippon Oil Co., Ltd.)), maleic anhydride-modified polyisoprene (Kuraprene) LIR-403, LIR-410 (the above are manufactured by Kuraray Co., Ltd.), hydroxyl-modified polyisoprene (Kuraprene LIR-506 (manufactured by Kuraray Co., Ltd.)), allyl-modified polyisoprene ( Kuraprene UC-203, UC-102 (the above are manufactured by Kuraray Co., Ltd.), maleic anhydride-modified polybutadiene (Ricon130MA8, Ricon131MA5 (the above are manufactured by Cray Valley Corporation)), maleic anhydride-modified butadiene Ethylene-styrene copolymer polymer (Ricon 184MA6 (manufactured by Cray Valley), epoxy-modified polybutadiene (Ricon 657 (manufactured by Cray Valley)), and the like.

As the rubber-based adhesive, it is preferable to contain a polyisobutylene-based resin from the viewpoint of being able to form an adhesive layer with low water vapor permeability and to easily obtain an adhesive sheet particularly useful as a sealing material or the like.

The polyisobutylene-based resin refers to a polymer having repeating units derived from isobutylene in the main chain and/or side chain. The number of repeating units derived from isobutylene is preferably 50% by mass or more, more preferably 60% by mass or more, and more preferably 70 to 99% by mass. Examples of polyisobutylene-based resins include homopolymers of isobutylene (polyisobutylene), copolymers of isobutylene and isoprene (butyl rubber), copolymers of isobutylene and n-butylene, and copolymers of isobutylene and butadiene. , and isobutylene-based polymers such as halogenated polymers obtained by brominating or chlorinating the above-mentioned polymers. Among them, a copolymer of isobutylene and isoprene (butyl rubber) is preferred. The polyisobutylene-based resin may be used alone or in combination of two or more.

The mass average molecular weight (Mw) of the rubber-based resin is preferably 10,000 to 3,000,000, preferably 100,000 to 2,000,000, and more preferably 200,000 to 500,000. When the mass average molecular weight (Mw) is within this range, the water vapor permeability is low, and an adhesive layer having a target shear storage elastic modulus can be effectively formed. Furthermore, in the case of using two or more kinds of rubber-based resins, the content ratio of the rubber-based resins having a mass average molecular weight (Mw) of less than 10,000 is preferably 10% by mass or less of the entire rubber-based resin, and not less than 10% by mass. It is better to contain. By setting the content ratio of the rubber-based resin having a mass-average molecular weight (Mw) of less than 10,000 to 10% by mass or less of the entire rubber-based resin, it is possible to suppress a decrease in adhesive force due to bleed of low-molecular-weight components. The mass-average molecular weight (Mw) of the rubber-based resin can be obtained by performing gel permeation chromatography using tetrahydrofuran as a solvent, as a standard value in terms of polystyrene.

The rubber-based adhesive may also contain a crosslinking agent. As a crosslinking agent, an isocyanate type crosslinking agent, an epoxy type crosslinking agent, an aziridine type crosslinking agent, a metal chelate type crosslinking agent, etc. are mentioned. Among them, epoxy-based cross-linking agent is preferred as the cross-linking agent in the rubber-based adhesive.

Examples of the isocyanate-based crosslinking agent and the epoxy-based crosslinking agent include the same crosslinking agents shown as the crosslinking agent in the acrylic adhesive. Examples of the aziridine-based crosslinking agent include diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane tri-β-aziridineyl propionate , tetramethylolmethane tri-β-aziridine propionate, toluene-2,4-bis(1-aziridinecarboxamide), triethylene melamine, bisisophthalide-1-(2 - methylaziridine), tris-1-(2-methylaziridine) phosphine, trimethylolpropane tri-β-(2-methylaziridine) propionate, etc.

Examples of the metal chelate-based crosslinking agent include chelate compounds such as aluminum, zirconium, titanium, zinc, iron, and tin, and among them, aluminum chelate compounds are preferred. Examples of the aluminum chelate compound include diisopropoxyaluminum monoisoamylacetate, isopropoxyaluminum monoethoxyacetate, and monoethylacetoxymonoisopropoxymonoleate. acid ester, aluminum diisopropoxyaluminum monolauroacetate, aluminum diisopropoxyaluminum monostearylacetate, aluminum diisopropoxyaluminum monoisostearylacetate, etc. .

The above-mentioned crosslinking agents may be used alone or in combination of two or more. In the case of forming a cross-linked structure using the above-mentioned cross-linking agent, the amount of the cross-linking group used in the cross-linking agent (in the case of a metal chelate-based cross-linking agent, it is a metal chelate cross-linking agent) is relatively The hydroxyl group and carboxyl group of the rubber-based resin are preferably used in an amount of 0.1 to 5 equivalents, and preferably 0.2 to 3 equivalents.

The aforementioned acrylic adhesive or rubber-based adhesive may contain a tackifier. The tackifier is a compound that enhances the adhesiveness of the adhesive layer. By using an adhesive containing a tackifier, it is easy to obtain an adhesive sheet with better moisture barrier properties and adhesive force. Examples of the tackifier include alicyclic petroleum resins, aliphatic petroleum resins, terpene resins, ester resins, coumarone-indene indene) resins, rosin resins, epoxy resins, phenolic resins, acrylic resins, butyral resins, olefin resins, chlorinated olefin resins, vinyl acetate resins, and modified resins or hydrogenated resins mentioned above. Among them, aliphatic petroleum resins, terpene resins, rosin ester resins, and rosin resins are preferred. The tackifier may be used alone or in combination of two or more.

The mass average molecular weight (Mw) of the tackifier is preferably 100-10,000, preferably 500-7,000, and particularly preferably 1,000-5,000. The softening point of the tackifier is preferably 50 to 160°C, preferably 60 to 140°C, and more preferably 70 to 130°C.

In addition, a commercially available product can also be used as it is as a tackifier. For example, commercially available products include aliphatic petroleum resins such as Escorez 1000 series (manufactured by Exxon Chemical Co., Ltd.), Quinton A, B, R, and CX series (manufactured by Zeon Corporation); Alcon P, Alicyclic petroleum resins such as M series (manufactured by Arakawa Chemical Co., Ltd.), ESCOREZ series (manufactured by Exxon Chemical Co., Ltd.), EASTOTAC series (manufactured by Eastman Chemical Co., Ltd.), and IMARV series (manufactured by Idemitsu Kosan Co., Ltd.); YS resin P , A series (manufactured by Yasuhara Oil Co., Ltd.), Clearon P series (manufactured by Yasuhara Chemical), Piccolite A, C series (manufactured by Hercules), etc.; Foral series (manufactured by Hercules), Pensel A series, esters Ester resins such as gel (ester gum), super ester (super ester), pine crystal (made by Arakawa Chemical Industry Co., Ltd.), etc.

When the adhesive contains a tackifier, the content of the tackifier is relative to the total solid content of the adhesive, preferably 0.1 to 60 mass %, preferably 1 to 50 mass %, and 5 to 35 mass % % is excellent.

The aforementioned acrylic adhesive or rubber-based adhesive may contain various additives. Examples of additives include light stabilizers, antioxidants, plasticizers, ultraviolet absorbers, colorants, resin stabilizers, fillers, pigments, fillers, antistatic agents, silane coupling agents, and the like. These additives may be used alone or in combination of two or more.

The formation method of an adhesive bond layer is not specifically limited, A known formation method of an adhesive bond layer can be used. For example, the used binder is diluted with an appropriate organic solvent to prepare a coating liquid, which is coated on the surface of a support, a process sheet, a release sheet, etc., and a drying treatment or curing is applied to the obtained coating film processing to form an adhesive layer. As a formation method of an adhesive bond layer, a dipping method, a coating method, a spray method, etc. are mentioned, Among them, the coating method is preferable from a viewpoint of productivity. Examples of the coating method include spin coating, spray coating, bar coating, knife coating, and roll knife coating. method, roll coating method, blade coating method, dip coating method, curtain coating method, die coating method, gravure coating method ) method, etc., among which the rod coating method, the roll knife coating method and the gravure coating method are preferred.

The content of the adhesive resin (P) in the adhesive layer is preferably 20 mass % or more, preferably 30 mass % or more and 100 mass % or less, preferably 50 mass % or more, based on the entire adhesive layer. 95 mass % or less is more preferable.

The shear storage elastic modulus of the adhesive layer at 23°C is 0.10-3.30 MPa, preferably 0.13-2.00 MPa, preferably 0.16-1.00 MPa, and particularly preferably 0.19-0.40. When the shear storage elastic modulus at 23° C. is less than 0.10 MPa, the cohesive force of the adhesive layer decreases, and the problem that the shape of the adhesive layer cannot be maintained occurs. Furthermore, when it exceeds 3.30 MPa, since the adhesive layer becomes hard, the adhesiveness with respect to a to-be-adhered body falls, and as a result, it tends to become an adhesive sheet with poor adhesiveness. The shear storage elastic modulus at 23°C can be measured according to the method described in the examples.

The thickness of the adhesive layer is 0.1-100 μm, preferably 0.5-75 μm, preferably 1-50 μm, more preferably 5-25 μm, and particularly preferably 10-20 μm. If the thickness of the adhesive layer is less than 0.1 μm, it is difficult to function as an elastic body, and the adhesiveness between the adherend and the molecular adhesive layer cannot be maintained even at normal temperature. Furthermore, when it exceeds 100 micrometers, it becomes difficult to suppress the entry of water vapor|steam from a terminal when using it as a sealing material in addition to the fall of productivity.

The adhesive layer is not applied and is selected from the group consisting of corona treatment, plasma treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, ozone treatment, excimer ultraviolet treatment, acid treatment, Surface treatments in the group consisting of base treatments and base treatments are preferred. Conventionally, when a molecular adhesive is used, the above-mentioned treatment is applied to an adherend whose adhesive surface contains a resin component. By applying the above-mentioned treatment, the resin in the adherend generates hydroxyl or carboxyl groups, so that the performance of the molecular adhesive can be further improved. However, for the adhesive layer of the adhesive sheet of the present invention, the above-mentioned surface treatment may change the shear storage elastic modulus, resulting in a significant decrease in its adhesiveness. Therefore, the adhesive layer is preferably not subjected to the above-mentioned surface treatment.

[Molecular Adhesive Layer] The molecular adhesive layer constituting the adhesive sheet of the present invention has a molecular adhesive, and the molecular adhesive contains a group selected from the group consisting of amino groups, azide groups, mercapto groups, isocyanate groups, urea groups and epoxy groups At least one reactive group (Zα) in the group, and at least one reactive group (Zβ) selected from the group consisting of a silanol group and a group that forms a silanol group by a hydrolysis reaction.

The reactive group (Zα) in the molecular adhesive can form a chemical bond with the reactive partial structure (Zγ) of the adhesive resin (P) in the adhesive layer. In the adhesive sheet of the present invention, it is considered that the molecular adhesive is chemically fixed to the surface of the adhesive layer by this chemical bond. As the chemical bond in this case, a covalent bond, a hydrogen bond, an ionic bond, an intermolecular force, etc. can be mentioned, and among them, a covalent bond is preferable.

As a group which can form a silanol group by a hydrolysis reaction, the group which has ^a partial structure represented by Si-X1 is mentioned. Examples of X ¹ include alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, n-propoxy, and isopropoxy; and halogen atoms such as fluorine, chlorine, and bromine. ; and other hydrolyzable groups.

The reactive group (Zβ) in the molecular adhesive is mainly used to form a chemical bond with the adherend when the adhesive sheet of the present invention adheres to the adherend. Therefore, the adhesive sheet of the present invention is preferably used for an adherend having a group having high reactivity with these groups on the surface.

As a molecular adhesive, the compound represented by following chemical formula (1) is mentioned.

[Chemistry 2]

(R ¹ represents a reactive group (Zα) or a monovalent group having one or more reactive groups (Zα) (reactive groups (Zα) are excluded.)), and A represents a divalent group Organic group, X represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms or a halogen atom, Y represents a hydrocarbon group having 1 to 20 carbon atoms, and a represents an integer of 1 to 3.)

Examples of the monovalent group having one or more reactive groups (Zα) of R ¹ include groups represented by the following chemical formulae (2) to (4).

[Chemistry 3]

In chemical formulae (2) to (4), * represents a bond with A. R ² represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and is preferably a divalent hydrocarbon group having 2 to 6 carbon atoms. Examples of the divalent hydrocarbon group for R ² include alkylene groups such as vinyl, trimethylene, and propylene; and arylene groups such as o-phenylene, m-phenylene, and p-phenylene. .

R ³ and R ⁴ each independently represent a hydrocarbon group having 1 to 20 carbon atoms, and preferably a hydrocarbon group having 1 to 10 carbon atoms. Examples of hydrocarbon groups for R ³ and R ⁴ include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-butyl Alkyl of heptyl, n-octyl, n-nonyl, n-decyl, etc.; vinyl, 1-propenyl, 2-propenyl, isopropenyl, 3-butenyl, 4-pentenyl, 5- Alkenyl groups such as hexenyl; alkynyl groups such as ethynyl, propynyl, butynyl, etc.; aryl groups such as phenyl, 1-naphthyl, 2-naphthyl, and the like.

Z represents a single bond or a divalent group represented by -N(R ⁷ )-. R ⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. As the hydrocarbon group of R ⁷ , the same groups as those shown as the hydrocarbon group of R ³ and R ⁴ can be exemplified. R ⁵ and R ⁶ each independently represent a reactive group (Zα) or a group represented by the above-mentioned chemical formula (2).

Examples of the divalent organic group of A include an alkylene group having 1 to 20 carbon atoms with or without a substituent, and an alkenylene group with or without a substituent having 2 to 20 carbon atoms. , an alkynylene group with or without a substituent having a carbon number of 2 to 20, an arylene group with or without a substituent having a carbon number of 6 to 20, and the like.

Examples of the alkylene group having 1 to 20 carbon atoms in A include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. Examples of the alkenylene group having 2 to 20 carbon atoms in A include vinylene, propenylene, butenylene, pentenylene, and the like. Examples of the alkynylene group having 2 to 20 carbon atoms in A include an ethynylene group, a propynylene group, and the like. Examples of the arylene group having 6 to 20 carbon atoms in A include o-phenylene, m-phenylene, p-phenylene, 2,6-naphthylene, 1,5-naphthylene, and the like.

Examples of substituents for the aforementioned alkylene group, alkenylene group, and alkynylene group include halogen atoms such as fluorine atoms and chlorine atoms; alkoxy groups such as methoxy and ethoxy; methylthio and ethylthio. alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, etc., etc.

Examples of the substituent of the aforementioned arylene group include a cyano group; a nitro group; a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom; an alkyl group such as a methyl group and an ethyl group; Alkoxy; alkylthio, methylthio, ethylthio, etc., and the like. The above-mentioned substituents may be bonded to any positions of groups such as alkylene, alkenylene, alkynylene, and arylene, or a plurality of the same or different groups may be bonded.

Examples of the alkoxy group having 1 to 10 carbon atoms in X include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and the like. As a halogen atom of X, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned. Examples of the hydrocarbon group having 1 to 20 carbon atoms in Y include the same groups as those shown as the hydrocarbon groups for R ³ and R ⁴ .

Examples of molecular adhesives for R ¹ -series amino groups include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltrimethoxysilane. Propyldiethoxymethylsilane, [3-(N,N-dimethylamino)propyl]trimethoxysilane, [3-(phenylamino)propyl]trimethoxysilane, trimethyl [3-(triethoxysilyl)propyl]ammonium chloride, trimethyl[3-(trimethoxysilyl)propyl]ammonium chloride, etc.

As the molecular adhesive of the R ¹ series azide group, (11-undecyl azide)trimethoxysilane, (11-undecyl azide)triethoxysilane, and the like can be mentioned.

Examples of the molecular adhesive of the R ¹ -series mercapto group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyldimethoxymethylsilane, and the like.

As a molecular adhesive of R ¹ series isocyanate group, 3-(trimethoxysilyl)propyl isocyanate, 3-(triethoxysilyl) propyl isocyanate, etc. are mentioned.

As a molecular adhesive of R ¹ series urea group, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, etc. are mentioned.

Examples of molecular adhesives of the R ¹ -series epoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane propylpropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, etc.

Examples of molecular adhesives in which R ¹ is a monovalent group having at least one reactive group (Zα) include 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, -(2-Aminoethylamino)propyltriethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, compounds represented by the following chemical formulae (5) to (13).

[Chemistry 4]

Among the above-mentioned compounds, as the compound represented by chemical formula (1), it is preferable that R ¹ is a compound represented by a group represented by chemical formula (4), and the compound represented by chemical formula (5) to (13) is preferable, Compounds represented by chemical formulae (5) to (10) are more preferred. In the above compounds, R ¹ has a triazine ring. Molecular adhesives with triazine rings tend to be more effectively immobilized on the adhesive layer.

Most of the above-mentioned molecular adhesives are known compounds as silane coupling agents. In addition, the compound in which R ¹ is a group represented by the chemical formula (4) can be based on the compounds described in International Publication No. WO2012/046651, International Publication No. WO2012/043631, International Publication No. WO2013/186941, and the like. method synthesis.

The molecular adhesive to be used can be appropriately selected in consideration of the combination of the reactive group (Zα) of the molecular adhesive and the reactive partial structure (Zγ) of the resin (P). For example, when the reactive group (Zα) is at least one selected from the group consisting of an amino group, a mercapto group, an isocyanate group, a urea group, and an epoxy group, a hydroxyl group, a carboxyl group, an aldehyde group, and At least one of the group consisting of amino groups is preferably used as the reactive partial structure (Zγ). Among them, as a preferable combination of the reactive group (Zα) and the reactive partial structure (Zγ) [reactive group (Zα)/reactive partial structure (Zγ)], (amino/hydroxyl), (amino) /carboxy), (isocyanate/hydroxy), (isocyanate/carboxy), (hydroxy/carboxy), etc.

Furthermore, when the molecular adhesive has an azide group as a reactive group (Zα), the azide group is activated by irradiation as described later. In this case, nitrene, which is a reaction intermediate, can react with carbon-carbon single bonds, carbon-carbon double bonds, and carbon-hydrogen single bonds. Therefore, when a molecular adhesive having an azide group is used, The type of the adhesive resin (P) is not particularly limited.

The method for forming the molecular adhesive layer is not particularly limited. For example, a molecular adhesive solution containing a molecular adhesive can be prepared, and a molecular adhesive layer can be formed using this solution by a known method.

The solvent used in preparing the molecular adhesive solution is not particularly limited. Examples of the solvent include alcohol-based solvents such as methanol, ethanol, isopropanol, ethylene glycol, and diethylene glycol; ketone-based solvents such as acetone and methyl ethyl ketone; and esters such as ethyl acetate and butyl acetate. Solvents; halogen-containing compounds such as dichloromethane; aliphatic hydrocarbon solvents such as butane and hexane; ether solvents such as tetrahydrofuran and butyl ether; aromatic compounds such as benzene and toluene; N , N-dimethylformamide, N-methylpyrrolidone and other amide solvents; water, etc. The above-mentioned materials may be used alone or in combination of two or more.

The concentration of the molecular adhesive in the molecular adhesive solution is not particularly limited. Its concentration is preferably 0.005-1.000 mol/L, preferably 0.050-0.500 mol/L. By setting the concentration of the molecular adhesive to be 0.005 mol/L or more, the molecular adhesive can be efficiently formed on the object to be coated. Furthermore, by setting the concentration of the molecular adhesive to be 1.000 mol/L or less, unexpected reactions in the molecular adhesive solution can be suppressed, resulting in excellent solution stability.

Examples of the method for forming the molecular adhesive layer include a dipping method, a coating method, a spray method, and the like, and among them, the coating method is preferred from the viewpoint of productivity. Examples of the coating method include spin coating, spray coating, bar coating, blade coating, roll-knife coating, roll coating, blade coating, dip coating, curtain coating, die coating Coating method, gravure coating method, etc., among which bar coating method, dip coating method and gravure coating method are preferable.

When the coating method is selected, it is necessary to perform drying treatment by natural drying or placing in drying equipment, but from the viewpoint of improving productivity, drying treatment by placing in drying equipment is preferable. As the drying equipment, for example, batch drying equipment such as an air oven, heat roll and hot air through equipment (to be dried) can be exemplified. Continuous drying equipment, etc., such as equipment that is heated and dried by airflow while passing through the drying furnace while moving in an open drying furnace. In addition, a device that can be used as a part of the above-mentioned drying equipment, for example, a high-frequency heater, a heat medium circulating heater such as an oil heater, and a heater such as a far-infrared heater, itself Can also be used as drying equipment. Among them, from the viewpoint of improving productivity, hot air ventilation equipment is preferable. The drying temperature adjusted by the drying equipment is usually 20-250°C, preferably 50-200°C, preferably 65-150°C, and particularly preferably 80-120°C. The drying time is usually 1 second to 120 minutes, preferably 10 seconds to 10 minutes, preferably 20 seconds to 5 minutes, and particularly preferably 30 seconds to 3 minutes.

It can be considered that in the molecular adhesive layer, the molecular adhesive is fixed to the adhesive by the chemical bond between the reactive group (Zα) of the molecular adhesive and the reactive partial structure (Zγ) of the adhesive resin (P). agent layer. Therefore, when the molecular adhesive layer is formed, a process of fixing the molecular adhesive to the adhesive layer (hereinafter sometimes referred to as fixing process) is usually performed. The immobilization treatment can be appropriately selected according to the characteristics of the reactive group (Zα) of the molecular adhesive. Generally, chemical bonds are formed by coating a molecular adhesive on the adhesive layer, and the formation of chemical bonds is accelerated by heating, so from the viewpoint of improving productivity, heat treatment is preferably performed. The heating temperature is usually 40 to 250°C, preferably 60 to 200°C, and preferably 80 to 120°C. The heating time is usually 1 second to 120 minutes, preferably 1 to 60 minutes, and more preferably 1 to 30 minutes. The heating method is not particularly limited, and the same equipment and devices as the above-mentioned drying equipment can be used.

In the case where the reactive group (Zα) has photoreactivity like an azide group, irradiation treatment may be performed as an immobilization treatment. As the irradiated light, ultraviolet rays are generally used. In this case, from the viewpoint of improving the reactivity of (Zα) and (Zγ), it is preferable to perform the fixing treatment after the drying treatment. Irradiation of ultraviolet rays can be performed using an ultraviolet irradiation apparatus using a light source such as a mercury lamp, a metal halide lamp, an ultraviolet LED, an electrodeless lamp, or the like.

When forming the molecular adhesive layer, the coating, drying and fixing treatments may be repeated many times.

The molecular adhesive layer may contain components other than the molecular adhesive in a content that does not impair the following various properties. Catalysts etc. are mentioned as components other than a molecular adhesive.

The content of the molecular adhesive in the molecular adhesive layer is preferably 50% by mass or more, 70% by mass or more, 100 mass % or less is preferable, 90 mass % or more is more preferable, 100 mass % or less is more preferable, and 100 mass % is especially preferable.

The thickness of the molecular adhesive layer is preferably 200 nm or less, preferably 150 nm or less, more preferably 100 nm or less, and particularly preferably 50 nm or less. Furthermore, the thickness of the molecular adhesive layer is preferably 1 nm or more. Since the adhesive sheet of the present invention has the above-mentioned adhesive layer, even if the molecular adhesive layer is so thin, it can be easily attached to the adherend.

[Adhesive Sheet] The adhesive sheet of the present invention is obtained by directly laminating the molecular adhesive layer on the adhesive layer. In the adhesive sheet of the present invention, only one side of the adhesive layer may have a molecular adhesive layer, or both sides of the adhesive layer may have molecular adhesive layers.

The pressure-sensitive adhesive sheet of the present invention may have layers other than the pressure-sensitive adhesive layer and the molecular pressure-sensitive adhesive layer. Examples of layers other than the adhesive layer and the molecular adhesive layer include a support and a release sheet.

The support system also includes a sheet-like object that constitutes a part of the adhesive sheet at the time of storage of the adhesive sheet of the present invention. Examples of the support include paper substrates such as Daolin paper, art paper, coated paper, craft paper, glassine paper, and the like; the above-mentioned paper substrate is laminated (laminated) Laminated substrates obtained from thermoplastic resins such as polyethylene; polyethylene films, polypropylene films, polybutene films, polybutadiene films, polymethylpentene films, polyvinyl chloride films, vinyl chloride copolymer films , polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate film, ionomer (ionomer) resin film , ethylene-(meth)acrylic copolymer film, ethylene-(meth)acrylate copolymer film, polystyrene film, polycarbonate film, polyimide film, fluororesin film and other resin substrates; Metal foil, etc.

The release sheet is a sheet-like object that constitutes a part of the adhesive sheet when the adhesive sheet of the present invention is stored, and is peeled off and removed during use. As a release sheet, the release sheet etc. which provided the release layer on the surface of the said support body are mentioned.

As an adhesive sheet of this invention, the adhesive sheet which has the following layer structure is mentioned, for example. Adhesive Layer/Molecular Adhesive LayerAdhesive Layer/Molecular Adhesive Layer/Release Sheet Support/Adhesive Layer/Molecular Adhesive Layer Release Sheet/Adhesive Layer/Molecular Adhesive Layer Support/Adhesive Layer/Molecular Adhesion Adhesive Layer/Release Sheet Support/Molecular Adhesive Layer/Adhesive Layer/Molecular Adhesive Layer Support/Molecular Adhesive Layer/Adhesive Layer/Molecular Adhesive Layer/Release Sheet

The adhesive sheet of the present invention can be manufactured by forming a molecular adhesive layer on the adhesive layer according to the above method, and then disposing a release sheet on the formed molecular adhesive layer as required.

2. Manufacturing method of laminate The method of manufacturing a laminate of the present invention is a method of manufacturing a laminate having a layered structure of an adhesive layer/molecular adhesive layer/adherent, and is characterized in that the adhesive sheet of the present invention is composed of Molecular adhesive is laminated on the adherend.

The adhesion between the molecular adhesive layer and the adherend is usually performed by the reaction between the reactive group (Zβ) in the molecular adhesive and the functional group in the compound constituting the adherend to form a chemical bond. Therefore, as an adherend, a material containing a group reactive with a reactive group (Zβ) on its surface is generally used. As said adherend, glass, an inorganic oxide, a silicone resin, etc. are mentioned. Furthermore, even if the material does not contain the above-mentioned components on the surface, a layer containing a group reactive with the reactive group (Zβ) can be provided on the surface by applying surface treatment to serve as an adherend. use.

The adhesive sheet used in the method for producing the layered product of the present invention has excellent adhesion to the adherend, and can sufficiently adhere to the surface of the adherend even if the adherend has irregularities, so that the molecular adhesive layer and the Chemical bonds can be fully formed between the adherends. In this way, high temperature conditions such as melting the resin component are not required.

The temperature T at the time of crimping is usually -20 to 140°C, preferably 0 to 100°C, and more preferably 15 to 35°C. The pressure at the time of crimping is preferably 5 N/mm or less, more preferably 3 N/mm or less, and more preferably 1 N/mm or less, in the case of crimping by roll or lamination. Furthermore, the line pressure is preferably 0.1 N/mm or more, more preferably 0.2 N/mm or more, and more preferably 0.3 N/mm or more. When crimping is performed by a press machine, the crimping pressure is preferably 10 MPa or less, more preferably 5 MPa or less, more preferably 3 MPa or less, and particularly preferably 1 MPa or less. Furthermore, the crimping pressure is preferably 0.1 MPa or more, more preferably 0.2 MPa or more, more preferably 0.3 MPa or more, and particularly preferably 0.4 MPa or more.

[Examples] Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples in any way. Unless otherwise specified, the parts and % in each example are based on mass.

[Shear storage elastic modulus of the adhesive layer] Using a viscoelasticity measuring device (manufactured by Rheometric·Scientific·F·E Co., Ltd., product name "RDAII"), measured by the torsional shear method at a measurement frequency of 1 Hz. Storage elastic modulus at 23°C.

[Production Example 1] To 100 parts (solid content: 33.6 parts) of an acrylic copolymer (n-butyl acrylate, BA)/acrylic acid (AA) = 90/10 (%) A mixed solution of toluene and ethyl acetate with a solid content concentration of 33.6% and a mass average molecular weight (Mw) of 470,000 was added with 2 parts (solid content: 1.5 parts) of an isocyanate-based crosslinking agent (manufactured by Dongchu Co., Ltd., Product name "Coronate L", ethyl acetate solution with a solid content concentration of 75%), and diluted with toluene to obtain an adhesive solution (1) with a solid content concentration of 26%.

[Production Example 2] 100 parts of a copolymer of isobutylene and isoprene (Exxon Butyl 268, manufactured by Nippon Butyl Co., Ltd., mass average molecular weight: 260,000; content of isoprene: 1.7 mol%), 5 parts Polyisoprene rubber with carboxylic acid functional group (manufactured by Kuraray Co., Ltd., LIR410, mass average molecular weight: 30,000, average number of carboxyl groups per molecule: 10), 20 parts of aliphatic petroleum resin (Japan Zeon Co., Ltd. Company product, Quinton A100, softening point: 100°C) and 1 part of a crosslinking agent (epoxy compound) (Mitsubishi Chemical Corporation, TC-5) were dissolved in toluene to obtain a solid content concentration of 25%. Binder solution (2).

[Production Example 3] According to the method described in International Publication No. WO2012/046651, 6-(3-triethoxysilylpropyl)amino-1,3,5-triazine-2,4 was obtained A molecular adhesive solution of diazide (the compound represented by the aforementioned chemical formula (10)) (solvent: ethanol, concentration 0.1 g/L).

[Example 1] On the surface of a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., product name "Cosmoshine A4100", 50 μm in thickness, with an easy-adhesion layer on one surface), The adhesive solution (1) obtained in Production Example 1 was applied by a bar coater so that the thickness of the adhesive layer after drying was 20 μm, and was dried at 100° C. for 1 minute. Next, on the obtained adhesive layer, the molecular adhesive solution obtained in Production Example 3 was dip-coated for 5 seconds on the obtained adhesive layer, and dried at 110° C. for 30 seconds. Then, ultraviolet rays were irradiated from the side of the molecular adhesive layer using an ultraviolet ray irradiation device (manufactured by Heraeus Co., Ltd., product name "Light Hammer 10 MARK II", light source: mercury lamp) to obtain an adhesive sheet. The ultraviolet irradiation conditions were as follows: the illuminance was 84 mW/cm ² , and the light energy was 29 mJ/cm ² . The illuminance and light energy were measured in the UVC band using an illuminance and light energy meter (manufactured by EIT, product name "UV Power Puck II"). The illuminance and light energy of the area.

[Example 2] The same procedure as in Example 2 was carried out, except that the adhesive agent solution (2) obtained in Production Example 2 was used instead of the adhesive agent solution (1) and an adhesive agent layer with a thickness of 10 μm after drying was formed. 1 way, get the sticky sheet. [Example 3] The same procedure as in Example 2 was carried out, except that the adhesive solution (2) obtained in Production Example 2 was used instead of the adhesive solution (1) to form an adhesive layer with a thickness of 1 μm after drying. 1 way, get the sticky sheet. [Reference Example 1] The same procedure as in Examples was performed except that the adhesive solution (2) obtained in Production Example 2 was used in place of the adhesive solution (1) and an adhesive layer having a thickness of 150 μm after drying was formed. 1 way, get the sticky sheet.

[Comparative Example 1] An adhesive sheet was obtained in the same manner as in Example 1 except that the molecular adhesive layer was not formed. [Comparative Example 2] An adhesive sheet was obtained in the same manner as in Example 2 except that the molecular adhesive layer was not formed.

[Comparative Example 3] On the surface of a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., product name "Cosmoshine A4100", 50 μm in thickness, with an easy-adhesion layer on one surface), Instead of forming an adhesive layer, an ethyl acetate solution of ethylene propylene diene rubber (manufactured by Mitsui Chemicals Co., Ltd., product name "EPT") was applied with a bar coater so that the thickness after drying would be 20 μm, and the thickness after drying was 100 μm. It was dried at ℃ for 1 minute to form a molecular adhesive layer in the same manner as in Example 1 except that a layer composed of ethylene propylene diene rubber was formed to obtain an adhesive sheet.

[Comparative Example 4] On the surface of a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., product name "Cosmoshine A4100", 50 μm in thickness, with an easy-adhesion layer on one surface), An adhesive for dry lamination (manufactured by DIC Corporation, product name "LX-401A/SP-60") was applied and dried. Next, without forming an adhesive layer, an unstretched polypropylene film (manufactured by Mitsui Chemicals To Cello Co., Ltd., product name "SC", thickness 50 μm) was dry-laminated to form an unstretched polypropylene film. A molecular adhesive layer was formed in the same manner as in Example 1 except for the constituted layer, to obtain an adhesive sheet.

[Adhesive Strength] After cutting the adhesive sheets produced in the Examples and Comparative Examples into a size of 25 mm in the vertical direction and 300 mm in the horizontal direction, the use weight was 2 kg in an environment of 23° C. and 50% RH (relative humidity). The molecular adhesive layer of this pressure-sensitive adhesive sheet was attached to a glass plate (manufactured by Corning Co., Ltd., product name "Eagle XG") using a roller of 100°C, and then it was left to stand for 30 minutes in the same environment. After standing, according to the specification of JIS Z0237:2000, the adhesive force of each adhesive sheet was measured by the 180° peeling method at a drawing speed of 300 mm/min. The results are shown in Table 1.

[Blister resistance] The adhesive sheets produced in the Examples and Comparative Examples were cut into a size of 50 mm in the vertical direction x 50 mm in the horizontal direction, and then attached to 70 mm in the vertical direction x 150 mm in the horizontal direction x 2 mm in thickness The polycarbonate sheet (manufactured by Mitsubishi Gas Chemical Co., Ltd., "Iupilon sheet NF-2000VU") was strongly crimped with a squeegee to produce a test sample. This test sample was left standing at 23°C for 12 hours, then was left standing in a hot air dryer at 80°C for 1.5 hours, and was further left standing in a hot air dryer at 90°C for 1.5 hours. The state of foaming was evaluated, and the foaming resistance of each adhesive sheet was evaluated according to the following criteria. The evaluation results are shown in Table 1. A: No foaming was found. B: Partial blistering was found. C: Foaming was found on the entire surface.

[Table 1] Table 1

The following points can be learned from Table 1. The adhesive sheets of Examples 1 to 3 had excellent adhesive force and foam resistance. Furthermore, in the adhesive sheet of Reference Example 1, the thickness of the adhesive layer was 150 μm, but in the above-mentioned evaluation test, it had the same characteristics as those of Examples 1 to 3. On the other hand, the adhesive sheets of Comparative Examples 1 and 2 were inferior in foaming resistance, and the adhesive sheets of Comparative Examples 3 and 4 were inferior in adhesive force.

[Example 4] A surface with an aluminum foil on a laminated film of aluminum foil and polyethylene terephthalate (a film of a polyethylene terephthalate film with a thickness of 38 μm laminated with a 7 μm aluminum foil) Then, the adhesive solution (2) obtained in Production Example 2 was applied, and the adhesive sheet was obtained in the same manner as in Example 2 except that the polyethylene terephthalate film was used as the base material. .

[Comparative Example 5] A surface with aluminum foil of a laminated film of aluminum foil and polyethylene terephthalate (a film in which aluminum foil of 7 μm was laminated on a polyethylene terephthalate film with a thickness of 38 μm) Then, the adhesive solution (2) obtained in Production Example 2 was applied to obtain an adhesive sheet in the same manner as in Comparative Example 2, except that the polyethylene terephthalate film was used as the base material. .

[Comparative Example 6] A surface with an aluminum foil on a laminated film of aluminum foil and polyethylene terephthalate (a film in which aluminum foil of 7 μm was laminated on a polyethylene terephthalate film with a thickness of 38 μm) Then, the adhesive solution (2) obtained in Production Example 2 was applied to obtain an adhesive sheet in the same manner as in Reference Example 1, except that the polyethylene terephthalate film was used as the base material. .

[Evaluation of Moisture Barrier Property] A calcium layer having a length of 35 mm in a vertical direction x 35 mm in a horizontal direction and a film thickness of 150 nm was formed on an alkali-free glass substrate (manufactured by Corning, 45 mm×45 mm) by a vacuum deposition method. Next, the release sheets of the adhesive sheets obtained in Example 4, Comparative Examples 5 and 6 were peeled off, respectively, and the exposed molecular adhesive layer or adhesive layer and the calcium layer on the glass substrate were placed under a dry nitrogen atmosphere. , were bonded by a laminator, and subjected to autoclave treatment at 40° C. and 0.5 MPa to seal the calcium layer, thereby obtaining a test piece for the moisture barrier property test. The obtained test piece was left to stand in an environment of 60° C. and 90% RH for 500 hours, the discoloration rate of the calcium layer (the rate of water penetration) was visually observed, and the moisture barrier properties were evaluated according to the following criteria. The evaluation results are shown in Table 2. (Evaluation Criteria) A: No discoloration of the calcium layer was observed. B: Discoloration of the edge of the calcium layer was observed, but the discolored area was less than half. C: The area of more than half of the calcium layer is discolored.

[Table 2] Table 2

The following points can be learned from Table 2. The adhesive sheet of Example 4 was excellent in moisture barrier properties. On the other hand, since the pressure-sensitive adhesive sheet of Comparative Example 5 did not have a molecular pressure-sensitive adhesive layer, it was inferior in moisture barrier properties. The adhesive sheet of Comparative Example 6 had a thick adhesive layer. Such an adhesive sheet having a thick adhesive layer, as shown in the above-mentioned Reference Example 1, has excellent adhesiveness, but is poor in moisture barrier properties.

none.

none.

Claims (12)

An adhesive sheet, which is obtained by directly laminating a molecular adhesive layer containing a molecular adhesive on an adhesive layer containing an adhesive resin (P), wherein the molecular adhesive has an amino group, an azide group, a mercapto group selected from the group consisting of , at least one reactive group (Zα) selected from the group consisting of an isocyanate group, a urea group, and an epoxy group, and a group selected from the group consisting of a silanol group and a group that forms a silanol group by a hydrolysis reaction The reactive group (Zβ) of at least 1 species in the group, wherein the aforementioned adhesive resin (P) has a reactive moiety structure (Zγ) capable of forming a chemical bond with the reactive group (Zα) of the aforementioned molecular adhesive, and the aforementioned adhesive The shear storage elastic modulus of the adhesive layer at 23° C. is 0.10-3.30 MPa, and the thickness of the aforementioned adhesive layer is 0.1-100 μm. The adhesive sheet according to claim 1, wherein the molecular adhesive layer is composed of reactive groups (Zα) possessed by the molecular adhesive and reactive partial structures (Zα) possessed by the adhesive resin (P). The chemical bond of Zγ) is formed by chemically fixing the molecular adhesive to the adhesive layer. The adhesive sheet according to item 1 of the claimed scope, wherein the reactive group (Zα) possessed by the molecular adhesive is selected from the group consisting of amino group, mercapto group, isocyanate group, urea group and epoxy group At least one, and the reactive partial structure (Zγ) possessed by the adhesive resin (P) is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an aldehyde group, and an amino group. The adhesive sheet according to claim 1, wherein the reactive group (Zα) of the molecular adhesive is an azide group, and the reactive partial structure (Zγ) of the adhesive resin (P) is a At least one selected from the group consisting of a carbon-carbon single bond, a carbon-carbon double bond, and a carbon-hydrogen single bond. The adhesive sheet according to claim 1, wherein the adhesive layer is not subjected to a treatment selected from the group consisting of corona treatment, plasma treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, ozone treatment, excimer ultraviolet treatment, acid treatment , and surface treatments in the group consisting of base treatments. The adhesive sheet described in the first item of the scope of the application, wherein the aforementioned molecular adhesive is a compound represented by the following chemical formula (1):

R ¹ represents a reactive group (Zα) selected from the group consisting of an amino group, an azide group, a mercapto group, an isocyanate group, a urea group, and an epoxy group, or one or more of the above-mentioned reactive groups Monovalent group (but excludes amino group, azide group, mercapto group, isocyanate group, urea group and epoxy group), A represents a divalent organic group, X represents a hydroxyl group, an alkoxy group with 1 to 10 carbon atoms group or a halogen atom, Y represents a hydrocarbon group having 1 to 20 carbon atoms, and a represents an integer of 1 to 3. The adhesive sheet according to claim 1, wherein the molecular adhesive layer has a thickness of 200 nm or less. The adhesive sheet according to claim 1, wherein only one side of the adhesive layer has a molecular adhesive layer. The adhesive sheet according to claim 1, wherein both sides of the adhesive layer are provided with molecular adhesive layers. The adhesive sheet described in claim 1 of the scope of the application further includes a support. A method for manufacturing a laminate, comprising laminating the molecular adhesive of the adhesive sheet described in any one of the 1st to 10th patent application scope on the adherend to form an adhesive layer/molecular adhesive layer/ A laminate of the layered structure of the adherend. The manufacturing method of the laminated body according to claim 11, wherein the temperature T at the time of crimping is -20 to 140°C.