KR102314240B1 - Adhesive sheet and manufacturing method of laminated body - Google Patents

Abstract

The present invention relates to at least one reactive group (Zα) selected from the group consisting of an amino group, an azide group, a mercapto group, an isocyanate group, a ureide group and an epoxy group on the pressure-sensitive adhesive layer comprising the adhesive resin (P). An adhesive sheet in which a molecular adhesive layer comprising a molecular adhesive having at least one reactive group (Zβ) selected from the group consisting of a silanol group and a group that generates a silanol group by hydrolysis reaction is directly laminated, the adhesive sheet comprising: The adhesive resin (P) has a reactive partial structure (Zγ) capable of forming a chemical bond with the reactive group (Zα) of the molecular adhesive, and the shear storage modulus at 23°C of the pressure-sensitive adhesive layer is 0.10 to It is 3.30 Mpa, and the thickness of the said adhesive layer is the manufacturing method of the adhesive sheet which is 0.1-100 micrometers, and the laminated body using this adhesive sheet. ADVANTAGE OF THE INVENTION According to this invention, the adhesive sheet which has a molecular adhesive layer and can stick to a to-be-adhered body easily even if it is normal temperature, and the manufacturing method of the laminated body using this adhesive sheet are provided.

Description

Adhesive sheet and manufacturing method of laminated body

An adhesive sheet having a molecular adhesive layer (referring to a layer formed using a molecular adhesive; the same hereinafter) and capable of being easily adhered to an adherend even at room temperature (20 to 25° C., hereinafter the same) , and a method for producing a laminate using the adhesive sheet.

A compound having two or more reactive groups is useful as a molecular adhesive because two or more kinds of chemical bonds can be formed by utilizing the properties of each reactive group.

As an example of using a molecular adhesive, for example, Patent Document 1 discloses a laminate formed by forming an entropy elastic molecular adhesive layer between two substrates, the entropy elastic molecular adhesive layer comprising an entropy elastic body layer and a molecular adhesive layer Characterized by that is described.

In Patent Document 1, as a manufacturing method of lamination, a molecular adhesive layer (1) is formed on a substrate (1), an entropy elastic layer (1) is laminated on the molecular adhesive layer (1), and the entropy elastic layer is described above. A method (stacking system) of further laminating a molecular adhesive layer (2) on (1) and further laminating a substrate (2) to form a laminate is described.

In addition, Patent Document 2 describes a method for producing a resin composite characterized in that a molecular adhesive is reacted on a solid surface to form a reactive solid surface, and a covalent bond is formed between materials by melt adhesion with a resin. .

WO2009/154083 (US2011/0104505 A1) Japanese Patent Laid-Open No. 2010-254793

As described above, the bonding method using a molecular adhesive is attracting attention because it has low environmental dependence 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 conventional adhesive layer or pressure-sensitive adhesive layer, the bonding method using the molecular adhesive is easily affected by the unevenness of the surface of the object, and when the object cannot be sufficiently joined there was

In this regard, Patent Document 1 describes that the improvement of adhesion to a substrate having a large surface roughness is achieved by forming the entropy elastic layer.

However, an example of the stacking method disclosed in the Example of Patent Document 1 is only to form the substrate 2 by a plating method, the substrate 1, the molecular adhesive layer 1, the entropy elastic layer 1 and The aspect in which the laminated body which consists of the molecular adhesive layer 2 is used as an adhesive sheet is not specifically disclosed.

Moreover, in patent document 2, it is described that resin and a reactive solid surface are closely_contact|adhered by melting, and the performance of a molecular adhesive is fully exhibited.

However, this method can be used only when the adherend is a resin. Moreover, in this method, since there exists a possibility that not only a to-be-adhered surface but the other part may be thermally deformed, in order to prevent this, it is necessary to examine conditions specifically.

Accordingly, an adhesive sheet having a molecular adhesive layer and capable of being easily adhered to an adherend even at room temperature has been desired.

The present invention has been made in view of the above circumstances, to provide an adhesive sheet having a molecular adhesive layer and capable of being easily adhered to an adherend even at room temperature, and a method for manufacturing a laminate using the adhesive sheet The purpose.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, the present inventors earnestly studied about the adhesive sheet which has a molecular adhesive layer. As a result, by laminating|stacking a molecular adhesive layer directly on a specific adhesive layer, it discovered that the adhesive sheet which can stick easily to a to-be-adhered body even if it is normal temperature is obtained, and came to complete this invention.

In this way, according to this invention, the manufacturing method of the adhesive sheet of following (1)-(10), and the laminated body of (11), (12) is provided.

(1) at least one reactive group (Zα) selected from the group consisting of an amino group, an azide group, a mercapto group, an isocyanate group, a ureide group and an epoxy group on the pressure-sensitive adhesive layer comprising the adhesive resin (P); A molecular adhesive layer comprising a molecular adhesive having at least one reactive group (Zβ) selected from the group consisting of: The adhesive resin (P) has a reactive partial structure (Zγ) capable of forming a chemical bond with the reactive group (Zα) of the molecular adhesive, and the shear storage modulus at 23°C of the pressure-sensitive adhesive layer is 0.10 to 3.30 MPa, and the thickness of the pressure-sensitive adhesive layer is 0.1 to 100 µm.

(2) The molecular adhesive layer is formed by chemical bonding between the reactive group (Zα) of the molecular adhesive and the reactive partial structure (Zγ) of the adhesive resin (P), so that the molecular adhesive is chemically attached to the pressure-sensitive adhesive layer. The adhesive sheet according to (1), characterized in that it is fixed with

(3) the reactive group (Zα) of the 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, and the reactive moiety of the adhesive resin (P) The adhesive sheet according to (1) or (2), wherein the structure (Zγ) is at least one selected from the group consisting of a hydroxyl group, a carboxy group, an aldehyde group, and an amino group.

(4) 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 carbon-carbon single bond, a carbon-carbon double bond, and a carbon - The adhesive sheet as described in (1) or (2) which is at least 1 sort(s) selected from the group which consists of a hydrogen single bond.

(5) the pressure-sensitive adhesive layer is not subjected to a surface treatment selected from the group consisting of corona treatment, plasma treatment, ultraviolet treatment, electron beam treatment, ozone treatment, excimer ultraviolet treatment, acid treatment, and base treatment, ( 1) The adhesive sheet according to any one of (4).

(6) The adhesive sheet according to any one of (1) to (5), wherein the molecular adhesive is a compound represented by the following formula (1).

[Formula 1]

(R ¹ is a reactive group (Zα) selected from the group consisting of an amino group, an azide group, a mercapto group, an isocyanate group, a ureide group and an epoxy group, or a monovalent group having one or more of these reactive groups (however, an amino group) , azide group, mercapto group, isocyanate group, ureide group and epoxy group are excluded.), A is a divalent organic group, X is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom and Y represents a hydrocarbon group having 1 to 20 carbon atoms, a represents an integer of 1 to 3)

(7) The adhesive sheet according to any one of (1) to (6), wherein the molecular adhesive layer has a thickness of 200 nm or less.

(8) The adhesive sheet in any one of (1)-(7) which has a molecular adhesive layer only on one side of the said adhesive layer.

(9) The adhesive sheet in any one of (1)-(7) which has a molecular adhesive layer on both sides of the said adhesive layer.

(10) The adhesive sheet in any one of (1)-(9) which has a support body further.

(11) A laminate having a layer structure of an adhesive layer/molecular adhesive layer/adherent, characterized in that the molecular adhesive layer of the adhesive sheet according to any one of (1) to (10) is pressed against an adherend. manufacturing method.

(12) The manufacturing method of the laminated body as described in (11) whose temperature T at the time of crimping|compression-bonding is -20-140 degreeC.

ADVANTAGE OF THE INVENTION According to this invention, the adhesive sheet which has a molecular adhesive layer and can stick to a to-be-adhered body easily even if it is normal temperature, and the manufacturing method of the laminated body using this adhesive sheet are provided.

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 has at least one reactive group 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 on a pressure-sensitive adhesive layer comprising a pressure-sensitive adhesive resin (P). A molecular adhesive layer comprising (Zα) and a molecular adhesive having at least one reactive group (Zβ) selected from the group consisting of a silanol group and a group that generates a silanol group by hydrolysis is directly laminated. .

The adhesive resin (P) has a reactive partial structure (Zγ) capable of forming a chemical bond with the reactive group (Zα) of the molecular adhesive.

The shear storage elastic modulus in 23 degreeC of the said adhesive layer is 0.10-3.30 Mpa, and the thickness of the said adhesive layer is 0.1-100 micrometers.

In the present invention, "including molecular adhesive" in "molecular adhesive layer containing molecular adhesive" means "molecular adhesive and/or a compound derived from molecular adhesive (for example, through a reaction, the structure of a reactive group a compound in which is changed)".

In addition, "the adhesive resin (P) has a reactive partial structure (Zγ) capable of forming a chemical bond with the reactive group (Zα) of the molecular adhesive" means that the molecular adhesive layer is formed on the pressure-sensitive adhesive layer before the molecular adhesive layer is formed. state is indicated. In the pressure-sensitive adhesive layer after the molecular adhesive layer is formed, the pressure-sensitive adhesive resin (P) has a structure derived from the reactive partial structure (Zγ) and/or the reactive partial structure (Zγ).

[Adhesive layer]

The adhesive layer which comprises the adhesive sheet of this invention is a layer containing adhesive resin (P).

In the adhesive sheet of the present invention, the pressure-sensitive adhesive layer plays a role of fixing the molecular adhesive and a role of enhancing the adhesion between the molecular adhesive layer and the adherend when the adhesive sheet is used.

An adhesive layer should just have adhesiveness when sticking with a to-be-adhered body at least. Accordingly, the pressure-sensitive adhesive layer includes a pressure-sensitive adhesive layer that exhibits tackiness by heating (so-called heat-sealable pressure-sensitive adhesive layer) in addition to having tackiness at room temperature, but it is particularly preferable to have tackiness at room temperature.

The adhesive resin (P) has a reactive partial structure (Zγ) capable of forming a chemical bond with the reactive group (Zα) of the molecular adhesive.

When the adhesive resin (P) has the 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 carboxy group, an aldehyde group, an amino group, a carbon-carbon single bond, a carbon-carbon double bond, and a carbon-hydrogen single bond. These can be appropriately selected according to the reactive group (Zα) in the molecular adhesive.

For example, when the reactive group (Zα) of the 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, the reactive partial structure (Zγ) is a hydride At least one selected from the group consisting of a hydroxy group, a carboxy group, an aldehyde group, and an amino group is preferably used.

When the reactive group (Zα) of the molecular adhesive is an azide group, the reactive partial structure (Zγ) is selected from the group consisting of a carbon-carbon single bond, a carbon-carbon double bond, and a carbon-hydrogen single bond. At least one of the following is preferably used.

By using the adhesive containing adhesive resin (P), also under normal temperature, the adhesiveness of a to-be-adhered body and a molecular adhesive bond layer can be improved.

Examples of the pressure-sensitive adhesive include an acrylic pressure-sensitive adhesive, a polyurethane-based pressure-sensitive adhesive, a polyester-based pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, and a silicone pressure-sensitive adhesive.

Among these, the shear storage modulus can be easily adjusted, and an acrylic adhesive is preferable at the point that the adhesive sheet excellent in adhesiveness with a to-be-adhered body is easy to be obtained also under normal temperature. Moreover, a rubber-type adhesive is preferable at the point which can form an adhesive layer with low water vapor permeability and is especially useful as a sealing material etc. easy to be obtained.

An acrylic adhesive is an adhesive which has an acrylic polymer as a main component.

An acrylic polymer is a polymer which has a repeating unit derived from (meth)acrylic acid or (meth)acrylic acid ester.

"(meth)acrylic acid" means acrylic acid or methacrylic acid, and "(meth)acrylic acid ester" means acrylic acid ester or methacrylic acid ester.

Moreover, unless the effect of this invention is impaired, an acrylic polymer may have repeating units other than the above.

As the adhesive resin (P) having a reactive partial structure (Zγ), such as a hydroxyl group, a carboxy group, and a carbon-carbon double bond, contained in the acrylic pressure-sensitive adhesive, a hydroxyl group, a carboxy group, a carbon-carbon double bond having a functional group such as a double bond and acrylic polymers (hereinafter, may be referred to as "functional group-containing acrylic polymers").

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 2-hydroxybutyl (meth) acrylate. , 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylic monomer having a hydroxyl group, such as acrylate; having a carboxyl group such as (meth) acrylic acid, 2-carboxyethyl (meth) acrylate Acrylic monomer; Acrylic monomer which has a carbon-carbon double bond in side chains, such as vinyl (meth)acrylate and allyl (meth)acrylate; etc. are mentioned.

These can be used individually by 1 type or in combination of 2 or more type.

When synthesize|combining a functional group containing acrylic polymer, you may use together the acryl-type monomer which does not have a functional group, and the other monomer copolymerizable with an acryl-type monomer.

Examples of the acrylic monomer having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl (meth) acrylate. , octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, 2-ethyl Acrylic monomers which have alkyl groups, such as hexyl (meth)acrylate and isooctyl (meth)acrylate; Acrylic monomers which have cycloalkyl groups, such as cyclohexyl (meth)acrylate; etc. are mentioned.

Among these, as an acrylic monomer which does not have a functional group at the point which can form the adhesive layer which is more excellent in adhesiveness, (meth)acrylic acid alkylester which has a C4-C10 hydrocarbon group is preferable, and butyl (meth)acrylate is more preferable.

Examples of the other monomer copolymerizable with the acrylic monomer include a monomer having a carboxyl group such as crotonic acid, maleic acid, fumaric acid, itaconic acid, and citraconic acid; (meth)acrylamide, N-methyl (meth)acrylamide, N-methyl Monomers which have amide groups, such as all (meth)acrylamide; Acrylonitrile; Styrene; Vinyl acetate; Vinylpyrrolidone, etc. are mentioned.

These monomers can be used individually by 1 type or in combination of 2 or more type.

The method for producing 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. Especially, solution polymerization is preferable at the point which superposition|polymerization is easy.

The initiator used in the polymerization reaction is not particularly limited, and peroxide-based initiators such as benzoyl peroxide, lauroyl peroxide, and methyl ethyl ketone peroxide, azobisisobutyronitrile, azobiscyanovaleric acid, and azobiscyano Azo initiators, such as pentane, etc. are mentioned.

The solvent in particular used for the solution polymerization reaction is not restrict|limited, Toluene, hexane, heptane, ethyl acetate, acetone, methyl ethyl ketone, methanol, etc. are mentioned.

Well-known conditions can be employ|adopted for reaction conditions, such as the temperature and reaction time of a polymerization reaction.

The mass average molecular weight (Mw) of a functional group containing acrylic polymer is 100,000-1,000,000 normally, Preferably it is 300,000-900,000.

A mass average molecular weight (Mw) can be adjusted by adding the quantity of a polymerization initiator and a chain transfer agent.

The mass average molecular weight (Mw) of a functional group-containing acrylic polymer can be calculated|required as a standard polystyrene conversion value by performing gel permeation chromatography using tetrahydrofuran as a solvent.

The ratio of the repeating unit derived from the monomer which has a functional group in the functional group containing acrylic polymer is 1-40 mass % normally with respect to all the repeating units, Preferably it is 3-15 mass %.

A functional group-containing acrylic polymer can also be obtained by the method of introduce|transducing functional groups, such as a hydroxyl group and a carboxy group, by giving a modification process with respect to an acrylic polymer.

The acrylic adhesive may contain a crosslinking agent. A crosslinking agent is a compound which reacts with said functional group and forms a crosslinked structure. When using a crosslinking agent, there is no restriction|limiting in particular in the crosslinking agent to be used, An isocyanate type crosslinking agent, an epoxy type crosslinking agent, etc. are mentioned.

It does not specifically limit as an isocyanate type crosslinking agent, The compound which has two or more isocyanate groups in a molecule|numerator is used. Examples of such an isocyanate-based crosslinking agent include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate Alicyclic polyisocyanates, such as; and their biuret form, isocyanurate form, further, adduct which is a reaction product with low molecular weight active hydrogen containing compounds, such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylol propane, and castor oil. Sieve; etc. are mentioned.

As an epoxy-type crosslinking agent, the compound which has two or more epoxy groups in a molecule|numerator is used. Examples of the epoxy crosslinking agent include bifunctional epoxy compounds such as 1,6-hexanediol diglycidyl ether, N,N-diglycidyl aniline and ethylene glycol diglycidyl ether; Trifunctional epoxy compounds such as cidyl ether and [4-(glycidyloxy)phenyl]diglycidylamine; sorbitol tetraglycidyl ether, N,N,N',N'-tetraglycidyl-m - tetrafunctional epoxy compounds, such as xylylenediamine and 1, 3-bis (diglycidyl aminomethyl) cyclohexane; etc. are mentioned.

A crosslinking agent can be used individually by 1 type or in combination of 2 or more type.

Although the usage-amount of a crosslinking agent varies with the kind of crosslinking agent, it is 0.01-10 mass parts normally with respect to 100 mass parts of functional group containing acrylic polymers, Preferably it is 0.05-5 mass parts.

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 used as the reactive partial structure (Zγ). Therefore, in this case, as the adhesive resin (P), an acrylic polymer obtained without using a functional group-containing acrylic monomer can be used.

A rubber-type adhesive is an adhesive containing rubber-type resin.

Examples of the rubber-based resin include natural rubber, modified natural rubber obtained by graft polymerization of one or more monomers selected from (meth)acrylic acid alkyl ester, styrene, and (meth)acrylonitrile to 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 resins, and the like.

These rubber compounds can be used individually by 1 type or in combination of 2 or more type.

These rubber compounds usually have a carbon-carbon double bond. This carbon-carbon double bond can function as a reactive partial structure (Zγ).

A commercial item may be used for these rubber-type compounds.

As such a commercial item, the copolymer of isobutylene and isoprene (Exxon Butyl 268 (made by Nippon Butyl Co., Ltd.)) is mentioned.

Moreover, you may introduce|transduce functional groups, such as a hydroxyl group and a carboxy group, by giving a modification process to these rubber-type compounds.

Examples of the modified rubber compound include maleic anhydride-modified polyisobutylene, phthalic anhydride-modified polyisobutylene, maleic anhydride-modified polyisoprene, hydroxyl group-modified polyisoprene, allyl-modified polyisoprene, maleic anhydride-modified poly Butadiene, hydroxyl-modified polybutadiene, etc. are mentioned.

The denaturation process can be performed according to a well-known method.

You may use a commercial item as a rubber-type compound which performed the modification|denaturation process.

As such commercially available products, maleic anhydride-modified polyisobutylene (HV-100M, HV-300M (above, manufactured by New Nippon Petroleum Co., Ltd.)), maleic anhydride-modified polyisoprene (claprene LIR-403, LIR-410 (above) , Kuraray Co., Ltd.)), hydroxyl group-modified polyisoprene (Kuraprene LIR-506 (Kuraray Co., Ltd.)), allyl-modified polyisoprene (Kuraprene UC-203, UC-102 (above, Kuraray Co., Ltd.) ), maleic anhydride-modified butadiene (Ricon130MA8, Ricon131MA5 (above, Clay Valley)), maleic anhydride-modified butadiene-styrene copolymer (Ricon184MA6 (Clay Valley)), epoxy-modified polybutadiene (Ricon657 (Clay Valley)) manufacture)) and the like.

The rubber-based pressure-sensitive adhesive preferably contains a polyisobutylene-based resin from the viewpoint that an adhesive layer having low water vapor permeability can be formed and an adhesive sheet particularly useful as a sealing material or the like can be easily obtained.

Polyisobutylene-type resin says the polymer which has a repeating unit derived from isobutylene in a principal chain and/or a side chain. 50 mass % or more is preferable, as for the quantity of the repeating unit derived from isobutylene, 60 mass % or more is more preferable, and its 70-99 mass % is still more preferable.

Examples of the polyisobutylene-based resin include a homopolymer of isobutylene (polyisobutylene), a copolymer of isobutylene and isoprene (butyl rubber), a copolymer of isobutylene and n-butene, and isobutylene and butadiene. and isobutylene polymers such as halogenated polymers obtained by brominating or chlorinating these polymers. Among these, a copolymer of isobutylene and isoprene (butyl rubber) is preferable.

Polyisobutylene-type resin may be used individually by 1 type or in combination of 2 or more type.

10,000-3,000,000 are preferable, as for the mass average molecular weight (Mw) of rubber-type resin, 100,000-2,000,000 are more preferable, 200,000-500,000 are still more preferable. When a mass average molecular weight (Mw) is this range, a water vapor transmission rate is low, and the adhesive layer which has the target shear storage modulus can be formed efficiently.

Moreover, when using 2 or more types of rubber-type resin, it is preferable that the content rate of the rubber-type resin whose mass average molecular weight (Mw) is less than 10,000 is 10 mass % or less of the whole rubber-type resin, and it is more preferable not to contain it. When the mass average molecular weight (Mw) sets the content rate of the rubber-based resin of less than 10,000 to 10% by mass or less of the total rubber-based resin, it is possible to suppress a decrease in the adhesive force due to the bleed of the low molecular weight component.

The mass average molecular weight (Mw) of rubber-type resin can be calculated|required as a standard polystyrene conversion value by performing gel permeation chromatography using tetrahydrofuran as a solvent.

The rubber-based pressure-sensitive adhesive may 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 these, as a crosslinking agent in a rubber-type adhesive, an epoxy-type crosslinking agent is preferable.

As an isocyanate type crosslinking agent and an epoxy type crosslinking agent, the thing similar to what was shown as a crosslinking agent in an acrylic adhesive is mentioned.

Examples of the aziridine-based crosslinking agent include diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane tri-β-aziridinylpropionate, tetramethylolmethanetri-β-aziridinyl Propionate, toluene-2,4-bis(1-aziridinecarboxamide), triethylenemelamine, bisisophthaloyl-1-(2-methylaziridine), tris-1-(2-methylaziridine) Phosphine, trimethylol propane tri-β-(2-methylaziridine) propionate, etc. are mentioned.

As a metal chelate type crosslinking agent, the chelate compound whose metal atoms are aluminum, zirconium, titanium, zinc, iron, tin, etc. is mentioned, Especially, an aluminum chelate compound is preferable.

Examples of the aluminum chelate compound include diisopropoxyaluminum monooleylacetoacetate, monoisopropoxyaluminum bisoleylacetoacetate, monoisopropoxyaluminum monooleate monoethylacetoacetate, diisopropoxyaluminum monolaurylaceto Acetate, diisopropoxy aluminum monostearyl acetoacetate, diisopropoxy aluminum monoisostearyl acetoacetate, etc. are mentioned.

These crosslinking agents can be used individually by 1 type or in combination of 2 or more type.

In the case of forming a crosslinked structure using these crosslinking agents, the amount used is 0.1 to 5 with respect to the crosslinking group of the crosslinking agent (in the case of a metal chelate crosslinking agent, a metal chelate crosslinking agent) with respect to the hydroxyl group and carboxyl group of the rubber resin. The quantity used as an equivalent is preferable, and the quantity used as 0.2-3 equivalent is more preferable.

The said acrylic adhesive and rubber-type adhesive may contain a tackifier. A tackifier is a compound which improves the adhesiveness of an adhesive layer. By using the adhesive containing a tackifier, it becomes easy to obtain the adhesive sheet which is more excellent in moisture barrier property and adhesive force.

Examples of the tackifier include alicyclic petroleum resins, aliphatic petroleum resins, terpene resins, ester resins, coumarone-indene resins, rosin resins, epoxy resins, phenol resins, acrylic resins, butyral resins, and olefins. and resins, chlorinated olefin resins, vinyl acetate resins, and modified resins or hydrogenated resins thereof. Among these, an aliphatic petroleum resin, a terpene resin, a rosin ester type resin, a rosin type resin, etc. are preferable.

A tackifier can be used individually by 1 type or in combination of 2 or more type.

The mass average molecular weight (Mw) of a tackifier becomes like this. Preferably it is 100-10,000, More preferably, it is 500-7,000, Especially preferably, it is 1,000-5,000.

The softening point of a tackifier becomes like this. Preferably it is 50-160 degreeC, More preferably, it is 60-140 degreeC, More preferably, it is 70-130 degreeC.

Moreover, a commercial item can also be used as it is as a tackifier. For example, as a commercial item, Aliphatic petroleum resins, such as Escoletz 1000 series (made by Exxon Chemicals), Quinton A, B, R, CX series (made by Nippon Zeon); Alcon P, M series (made by Arakawa Chemicals) , alicyclic petroleum resins such as ESCOREZ series (manufactured by Exxon Chemicals), EASTOTAC series (manufactured by Eastman Chemicals), and IMARV series (manufactured by Idemitsu Kogsan); YS resin P and A series (manufactured by Yasuhara Oil Corporation); Terpene-based resins such as Clialon P series (manufactured by Yasuhara Chemicals), Picolite A and C series (manufactured by Hercules); Phoral series (manufactured by Hercules), Pencel A series, ester gum, Super Ester, Fine Crystal Ester-type resin, such as (made by Arakawa Chemical Industry Co., Ltd.); etc. are mentioned.

When an adhesive contains a tackifier, 0.1-60 mass % is preferable with respect to the whole solid content of an adhesive, as for content of a tackifier, 1-50 mass % is more preferable, 5-35 mass % is especially desirable.

The said acrylic adhesive and rubber-type adhesive may contain various additives. Examples of the additive include a light stabilizer, antioxidant, plasticizer, ultraviolet absorber, colorant, resin stabilizer, filler, pigment, extender, antistatic agent, and silane coupling agent. These additives can be used individually by 1 type or in combination of 2 or more type.

The formation method of an adhesive layer is not specifically limited, A well-known formation method of an adhesive layer can be used.

For example, by diluting the adhesive to be used with an appropriate organic solvent to prepare a coating liquid, applying this to the surface of a support, a process sheet, a release sheet, etc. layer can be formed.

Although a dipping method, a coating method, a spraying method etc. are mentioned as a formation method of an adhesive layer, Among these, a coating method is preferable from a viewpoint of productivity. As the application method, for example, a spin coat method, a spray coat method, a bar coat method, a knife coat method, a roll knife coat method, a roll coat method, a blade coat method, a dip coat method, a curtain coat method, a die coat method, Although the gravure coat method etc. are mentioned, The bar coat method, the roll knife coat method, and the gravure coat method are preferable.

It is preferable that content of the adhesive resin (P) in an adhesive layer is 20 mass % or more on the basis of the whole adhesive layer, It is more preferable that they are 30 mass % or more and 100 mass % or less, It is 50 mass % or more and 95 mass % or less more preferably.

The shear storage modulus at 23°C of the pressure-sensitive adhesive layer is 0.10 to 3.30 MPa, preferably 0.13 to 2.00 MPa, more preferably 0.16 to 1.00 MPa, and particularly preferably 0.19 to 0.40 MPa.

When the shear storage elastic modulus in 23 degreeC is less than 0.10 Mpa, the cohesive force of an adhesive layer falls, and the problem that the shape of an adhesive layer is not maintained arises. Moreover, when it exceeds 3.30 MPa, since an adhesive layer becomes hard, as a result of the followability|trackability with respect to a to-be-adhered body falling, there exists a tendency to become an adhesive sheet inferior in adhesiveness.

The shear storage modulus at 23°C can be measured according to the method described in Examples.

The thickness of the pressure-sensitive adhesive layer is 0.1 to 100 µm, preferably 0.5 to 75 µm, more preferably 1 to 50 µm, still more preferably 5 to 25 µm, and particularly preferably 10 to 20 µm.

When the thickness of the pressure-sensitive 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 room temperature. Moreover, in addition to being inferior to productivity when it exceeds 100 micrometers, when it uses as a sealing material, it is difficult to suppress penetration of the water vapor|steam from an edge part.

It is preferable that the surface treatment chosen from the group which consists of corona treatment, plasma treatment, ultraviolet treatment, electron beam treatment, ozone treatment, excimer ultraviolet treatment, acid treatment, and base treatment is not given to an adhesive layer.

Conventionally, when molecular adhesives are used, these treatments may be applied to an adherend containing a resin component on the adhesive surface. Since a hydroxyl group, a carboxy group, etc. generate|occur|produce in resin in to-be-adhered body by performing these processes, the performance of a molecular adhesive becomes higher.

However, in the adhesive layer of the adhesive sheet of this invention, there exists a possibility that these surface treatment may change a shear storage modulus, or reduce the adhesiveness greatly.

Therefore, it is preferable that said surface treatment is not performed as for an adhesive layer.

[Molecular adhesive layer]

The molecular adhesive layer constituting the adhesive sheet of the present invention comprises at least one reactive group (Zα) selected from the group consisting of an amino group, an azide group, a mercapto group, an isocyanate group, a ureide group and an epoxy group, and a silanol group and a molecular adhesive having at least one reactive group (Zβ) selected from the group consisting of a group that generates a silanol group by hydrolysis reaction.

The reactive group (Zα) in the molecular adhesive can form a chemical bond with the reactive partial structure (Zγ) of the pressure-sensitive adhesive resin (P) in the pressure-sensitive 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 pressure-sensitive adhesive layer by this chemical bonding. Although a covalent bond, a hydrogen bond, an ionic bond, intermolecular force, etc. are mentioned as a chemical bond at this time, A covalent bond is preferable.

Groups to produce a silanol group by hydrolysis reaction, there may be mentioned a group having a partial structure represented by Si-X ^1. Examples of X ¹ include an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group and an isopropoxy group; a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; have.

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

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

[Formula 2]

(R ¹ represents a reactive group (Zα) or a monovalent group having one or more reactive groups (Zα) (however, excluding the reactive group (Zα) itself.), A represents a divalent 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, a represents an integer of 1 to 3)

Examples of the monovalent group having one or more reactive groups (Zα) for R ^{1 include groups represented by the following formulas (2) to (4).}

[Formula 3]

In Formulas (2)-(4), * represents a bond with A.

R ² represents a divalent hydrocarbon group having 1 to 10 carbon atoms, 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 ethylene group, trimethylene group and propylene group; arylene groups such as o-phenylene group, m-phenylene group and p-phenylene group;

R ³ and R ⁴ each independently represent a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 10 carbon atoms.

Examples ^{of the hydrocarbon group for R 3} and R ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group Alkyl groups such as a group, n-heptyl group, n-octyl group, n-nonyl group, and n-decyl group; vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 3-butenyl group, 4-pentene group Alkenyl groups, such as a nyl group and 5-hexenyl group; Alkynyl groups, such as an ethynyl group, a propargyl group, and a butynyl group; Aryl groups, such as a phenyl group, 1-naphthyl group, 2-naphthyl group; etc. are mentioned.

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. Examples of the hydrocarbon group for ^{R 7} include the same hydrocarbon groups as those shown for the hydrocarbon group for ^{R 3} and R ^{4 .}

R ⁵ and R ⁶ each independently represent a reactive group (Zα) or a group represented by the formula (2).

As a divalent organic group of A, a C1-C20 alkylene group which may have a substituent, a C2-C20 alkenylene group which may have a substituent, a C2-C20 alkynylene group which may have a substituent, a substituent A C6-C20 arylene group which may have; etc. are mentioned.

A methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group etc. are mentioned as a C1-C20 alkylene group of A.

As a C2-C20 alkenylene group of A, a vinylene group, a propenylene group, a butenylene group, a pentenylene group, etc. are mentioned.

As a C2-C20 alkynylene group of A, an ethynylene group, a propynylene group, etc. are mentioned.

Examples of the arylene group having 6 to 20 carbon atoms for A include o-phenylene group, m-phenylene group, p-phenylene group, 2,6-naphthylene group, 1,5-naphthylene group, and the like.

Examples of the substituent of the alkylene group, the alkenylene group, and the alkynylene group include a halogen atom such as a fluorine atom and a chlorine atom; an alkoxy group such as a methoxy group and an ethoxy group; an alkylthio group such as a methylthio group and an ethylthio group; Alkoxycarbonyl groups, such as a methoxycarbonyl group and an ethoxycarbonyl group; etc. are mentioned.

Examples of the substituent of the 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; an alkoxy group such as a methoxy group and an ethoxy group; Alkylthio groups, such as Ogi; etc. are mentioned.

These substituents may be couple|bonded at arbitrary positions in groups, such as an alkylene group, an alkenylene group, an alkynylene group, and an arylene group, and may couple|bond two or more same or different.

As a C1-C10 alkoxy group of X, a methoxy group, an ethoxy group, n-propoxy group, isopropoxy group, etc. are mentioned.

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 for Y include the same hydrocarbon groups as those shown for the hydrocarbon group for ^{R 3} and R ^{4 .}

Examples of the molecular adhesive in which R ¹ is an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, [3-( N,N-dimethylamino)propyl]trimethoxysilane, [3-(phenylamino)propyl]trimethoxysilane, trimethyl[3-(triethoxysilyl)propyl]ammonium chloride, trimethyl[3-(trimethyl) oxysilyl) propyl] ammonium chloride and the like.

Examples of the molecular adhesive in which R ¹ is an azide group include (11-azidoundecyl)trimethoxysilane and (11-azidoundecyl)triethoxysilane.

Examples of the molecular adhesive in which R ¹ is a mercapto group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropyldimethoxymethylsilane.

Examples of the molecular adhesive in which R ¹ is an isocyanate group include 3-(trimethoxysilyl)propyl isocyanate, 3-(triethoxysilyl)propyl isocyanate, and the like.

Examples of the molecular adhesive in which R ¹ is a ureide group include 3-ureapropyltrimethoxysilane, 3-ureidepropyltriethoxysilane, and the like.

Examples of the molecular adhesive in which R ¹ is an epoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyl. and diethoxysilane.

Examples of the molecular adhesive in which R ¹ is a monovalent group having one or more reactive groups (Zα) include 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltri Ethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane, 2-(3,4-epoxy cyclohexyl)ethyltrimethoxysilane, and the compound represented by following formula (5)-(13) are mentioned can

[Formula 4]

Among these compounds, as the compound represented by the formula (1), a compound in which R ¹ is a group represented by the formula (4) is preferable, the compound represented by the formulas (5) to (13) is more preferable, and the compounds represented by the formulas (5) to (5) to The compound represented by (10) is more preferable.

These compounds have a triazine ring in ^R<1>. A molecular adhesive having a triazine ring tends to be more efficiently fixed on the pressure-sensitive adhesive layer.

Many of these molecular adhesives are compounds known as silane coupling agents. Moreover, the ^{compound in which R<1>} is group represented by Formula (4) can be synthesize|combined according to the method as described in WO2012/046651, WO2012/043631, WO2013/186941, etc.

The molecular adhesive to be used can be appropriately selected in consideration of the combination of the reactive group (Zα) 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 ureide group, and an epoxy group, the reactive partial structure (Zγ) includes a hydroxyl group, a carboxy group, At least one selected from the group consisting of an aldehyde group and an amino group is preferably used.

Among them, preferred combinations of the reactive group (Zα) and the reactive partial structure (Zγ) [reactive group (Zα)/reactive partial structure (Zγ)] include (amino group/hydroxy group), (amino group/carboxy group), (isocyanate group) /hydroxyl group), (isocyanate group/carboxyl group), (hydroxyl group/carboxyl group), etc. are mentioned.

In addition, when the molecular adhesive has an azide group as the reactive group (Zα), the azide group is activated by irradiation with light as will be described later. In this case, since nitrene as a reaction intermediate can react with a carbon-carbon single bond, a carbon-carbon double bond, or a carbon-hydrogen single bond, when a molecular adhesive having an azide group is used, the adhesive resin (P) The kind is not particularly limited.

The method of 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 by a well-known method using this solution.

The solvent used when preparing a molecular adhesive solution is not specifically limited. Examples of the solvent include alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol and diethylene glycol; ketone solvents such as acetone and methyl ethyl ketone; ester solvents such as ethyl acetate and butyl acetate; halogen-containing solvents such as methylene chloride Compound solvents; Aliphatic hydrocarbon solvents such as butane and hexane; Ether solvents such as tetrahydrofuran and dibutyl ether; Aromatic compound solvents such as benzene and toluene; N,N-dimethylformamide, N-methylpyrrole Amide solvents, such as money; Water; etc. are mentioned.

These can be used individually by 1 type or in combination of 2 or more type.

The concentration of the molecular adhesive in the molecular adhesive solution is not particularly limited. The concentration is preferably 0.005 to 1.000 mol/L, and more preferably 0.050 to 0.500 mol/L. When the concentration of the molecular adhesive is 0.005 mol/L or more, the molecular adhesive can be efficiently formed on the object to be coated. Moreover, by setting it as 1.000 mol/L or less, unintended reaction of a molecular adhesive solution can be suppressed and it is excellent in the stability of a solution.

Although a dipping method, a coating method, a spraying method etc. are mentioned as a formation method of a molecular adhesive bond layer, Among these, a coating method is preferable from a viewpoint of productivity. As the application method, for example, a spin coat method, a spray coat method, a bar coat method, a knife coat method, a roll knife coat method, a roll coat method, a blade coat method, a dip coat method, a curtain coat method, a die coat method, Although the gravure coat method etc. are mentioned, The bar coat method, the dip coat method, and the gravure coat method are preferable.

When the application method is selected, natural drying or drying treatment by input to a drying apparatus is required, but it is preferable from the viewpoint of productivity improvement to perform drying treatment by input to a drying apparatus. As the drying mechanism, for example, a batch-type drying mechanism such as an air oven, a heat roll, a hot air-through mechanism (a drying object is heated and dried while receiving air while moving and passing through an open drying furnace. equipment, etc.) such as continuous drying equipment and the like.

Moreover, an apparatus which can be used also as a part of these drying mechanisms, for example, heat medium circulation type heaters, such as a high frequency heating and an oil heater, and heater itself, such as a far-infrared heater, can also be used as a drying mechanism. Among these, a hot air through mechanism is preferable from a viewpoint of productivity improvement.

The drying temperature adjusted by the said drying mechanism is 20-250 degreeC normally, Preferably it is 50-200 degreeC, More preferably, it is 65-150 degreeC, Especially preferably, it is 80-120 degreeC. The drying time is usually 1 second to 120 minutes, preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, particularly preferably 30 seconds to 3 minutes.

In the molecular adhesive layer, it is considered that the molecular adhesive is fixed to the adhesive layer by chemical bonding between the reactive group (Zα) of the molecular adhesive and the reactive partial structure (Zγ) of the adhesive resin (P).

Therefore, when forming the molecular adhesive layer, a process for fixing the molecular adhesive to the pressure-sensitive adhesive layer (hereinafter, sometimes referred to as fixing process) is usually performed. The fixing treatment can be appropriately selected according to the characteristics of the reactive group (Zα) of the molecular adhesive. Usually, since a chemical bond is produced|generated by apply|coating a molecular adhesive on an adhesive layer, and the production|generation of a chemical bond is accelerated|stimulated by heating, it is preferable to heat-process from a viewpoint of productivity improvement. Heating temperature is 40-250 degreeC normally, Preferably it is 60-200 degreeC, More preferably, it is 80-120 degreeC. The heating time is usually 1 second to 120 minutes, preferably 1 to 60 minutes, and more preferably 1 to 30 minutes.

It does not specifically limit as a heating method, The mechanism and apparatus similar to the drying mechanism mentioned above can be used.

Like the azide group, when the reactive group (Zα) has photoreactivity, light irradiation treatment is performed as the fixing treatment. As light to irradiate, an ultraviolet-ray is used normally. In this case, it is preferable from the viewpoint of improving the reactivity of (Zα) and (Zγ) to perform the fixing treatment after the drying treatment.

Irradiation of an ultraviolet-ray can be performed using the ultraviolet irradiation apparatus using light sources, such as a mercury lamp, a metal halide lamp, an ultraviolet-ray LED, and an electrodeless lamp.

Formation of the molecular adhesive layer WHEREIN: You may repeat application|coating, a drying process, and a fixing process multiple times.

A molecular adhesive layer may contain components other than a molecular adhesive in the quantity of the grade which does not impair each performance mentioned later. As a component other than a molecular adhesive, a catalyst etc. are mentioned.

The content of the molecular adhesive in the molecular adhesive layer is preferably 50% by mass or more, and 70% by mass or more and 100% by mass, based on the entire molecular adhesive layer, because the adhesive force decreases when a component not involved in adhesion is included. It is more preferable that they are 90 mass % or more and 100 mass % or less, It is still more preferable, and 100 mass % is especially preferable.

200 nm or less is preferable, as for the thickness of a molecular adhesive layer, 150 nm or less is more preferable, 100 nm or less is still more preferable, and its 50 nm or less is especially preferable. Moreover, as for the thickness of a molecular adhesive layer, 1 nm or more is preferable.

Since the adhesive sheet of this invention has the said adhesive layer, even if a molecular adhesive layer is thin in this way, it can stick to a to-be-adhered body easily.

[Adhesive sheet]

In the adhesive sheet of this invention, the said molecular adhesive layer is laminated|stacked directly on the said adhesive layer.

The adhesive sheet of this invention may have a molecular adhesive layer only on one side of the said adhesive layer, and may have a molecular adhesive layer on both sides of the said adhesive layer.

The adhesive sheet of this invention may have layers other than an adhesive layer and a molecular adhesive layer.

As layers other than an adhesive layer and a molecular adhesive layer, a support body and a peeling sheet are mentioned.

The support is a sheet-like material constituting a part of the adhesive sheet of the present invention both during storage and use. Examples of the support include paper substrates such as fine paper, art paper, coated paper, kraft paper, and glassine paper; laminate substrate obtained by laminating a thermoplastic resin such as polyethylene on these paper substrates; polyethylene film, polypropylene film, polybutene film, poly Butadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, Resin base materials, such as an ethylene/(meth)acrylic acid copolymer film, an ethylene/(meth)acrylic acid ester copolymer film, a polystyrene film, a polycarbonate film, a polyimide film, and a fluororesin film; Metal foil; etc. are mentioned.

The release sheet constitutes a part of the adhesive sheet during storage of the adhesive sheet of the present invention, but is a sheet-like substance that is peeled off during use.

Examples of the release sheet include those in which a release layer is formed on the surface of the support body.

As an adhesive sheet of this invention, what has the following layer structure is mentioned, for example.

Adhesive layer/molecular adhesive layer

Adhesive layer / molecular adhesive layer / release sheet

support/adhesive layer/molecular adhesive layer

Release sheet/adhesive layer/molecular adhesive layer

Support body/adhesive layer/molecular adhesive layer/release sheet

Support/molecular adhesive layer/adhesive layer/molecular adhesive layer

Support body/molecular adhesive layer/adhesive layer/molecular adhesive layer/release sheet

The adhesive sheet of the present invention can be produced by forming a molecular adhesive layer on an adhesive layer according to the above method, and then, if necessary, forming a release sheet on the formed molecular adhesive layer.

2. Manufacturing method of laminate

The method for producing a laminate of the present invention is a method for producing a laminate having a layer structure of a pressure-sensitive adhesive layer/molecular adhesive layer/adherent, characterized in that the molecular adhesive layer of the adhesive sheet of the present invention is pressed to the adherend. .

The adhesion between the molecular adhesive layer and the adherend is usually carried out when the reactive group (Zβ) in the molecular adhesive reacts with a functional group in the compound constituting the adherend to form a chemical bond.

Therefore, usually, as an adherend, one having a group having reactivity with the reactive group (Zβ) on its surface is used.

Glass, an inorganic oxide, a silicone resin, etc. are mentioned as such an adherend.

Moreover, even if the surface does not contain these components, it can be used as a to-be-adhered body by surface-treating and forming on the surface the layer containing the group which has reactivity with the reactive group (Zβ).

The adhesive sheet used in the method for producing a laminate of the present invention has excellent followability to an adherend and sufficiently adheres to the surface of the adherend even if there are irregularities in the adherend. generation is sufficiently carried out. Therefore, a high temperature condition for melting the resin component is not required.

The temperature T at the time of crimping|compression-bonding is -20-140 degreeC normally, Preferably it is 0-100 degreeC, More preferably, it is 15-35 degreeC.

The pressure at the time of crimping is preferably 5 N/mm or less, more preferably 3 N/mm or less, still more preferably 1 N/mm or less as a linear pressure when crimping with a roller or a laminate. Moreover, as a linear pressure, Preferably it is 0.1 N/mm or more, More preferably, it is 0.2 N/mm or more, More preferably, it is 0.3 N/mm or more.

When crimping with a press machine, as a press pressure, Preferably it is 10 MPa or less, More preferably, it is 5 MPa or less, More preferably, it is 3 MPa or less, Especially preferably, it is 1 MPa or less. Moreover, as a press pressure, Preferably it is 0.1 Mpa or more, More preferably, it is 0.2 Mpa or more, More preferably, it is 0.3 Mpa or more, Especially preferably, it is 0.4 Mpa or more.

Example

Hereinafter, the present invention will be described in more detail by way of Examples. However, the present invention is not limited to the following examples at all.

Unless otherwise specified, parts and % in each example are based on mass.

[Shear storage modulus of adhesive layer]

The storage elastic modulus in 23 degreeC was measured by the measurement frequency of 1 Hz by the torsional shearing method using the viscoelasticity measuring apparatus (The Rheometric Scientific F. Co., Ltd. make, brand name "RDAII").

[Production Example 1]

A mixed solution 100 of toluene and ethyl acetate having a solid content concentration of 33.6% containing an acrylic copolymer (mass average molecular weight (Mw) 470,000) of n-butyl acrylate (BA)/acrylic acid (AA) = 90/10 (%) 100 To parts (solid content: 33.6 parts), 2 parts (solid content: 1.5 parts) of an isocyanate-based crosslinking agent (manufactured by Tosoh Corporation, product name "Colonate L", ethyl acetate solution with a solid content concentration of 75%) is added, and diluted with toluene An adhesive solution (1) having a solid content concentration of 26% was obtained.

[Production Example 2]

100 parts of a copolymer of isobutylene and isoprene (manufactured by Nippon Butyl Co., Ltd., Exxon Butyl 268, mass average molecular weight 260,000, isoprene content 1.7 mol%) 100 parts, polyisoprene rubber having a carboxylic acid-based functional group (Kuraray Co., Ltd., LIR410, Mass average molecular weight 30,000, average number of carboxyl groups per molecule: 10) 5 parts, aliphatic petroleum resin (Nippon Zeon Corporation, Quinton A100, softening point 100°C) 20 parts, crosslinking agent (epoxy compound) (Mitsubishi Chemical Corporation, TC- 5) 1 part was melt|dissolved in toluene, and the adhesive solution (2) of 25% of solid content concentration was obtained.

[Production Example 3]

6-(3-triethoxysilylpropyl)amino-1,3,5-triazine-2,4-diazide (compound represented by the above formula (10)) according to the method described in WO2012/046651 A molecular adhesive solution (solvent: ethanol, concentration 0.1 g/L) was obtained.

[Example 1]

On the side having an easily adhesive layer of a polyethylene terephthalate film (manufactured by Toyobo Corporation, product name "Cosmoshine A4100", 50 µm in thickness, and an easily adhesive layer on one surface), the adhesive solution obtained in Production Example 1 ( 1) was apply|coated with a bar coater so that the thickness of the adhesive layer after drying might be set to 20 micrometers, and it dried at 100 degreeC for 1 minute.

Next, to the obtained pressure-sensitive adhesive layer, the molecular adhesive solution obtained in Production Example 3 was immersed for 5 seconds by a dipping method, and dried at 110°C for 30 seconds. Then, the ultraviolet-ray was irradiated from the molecular adhesive layer side using the ultraviolet irradiation apparatus (The Heraeus Co., Ltd. product, product name "Light Hammer 10 MARK II", light source: Mercury lamp), and the adhesive sheet was obtained.

Ultraviolet irradiation conditions were an illuminance of 84 mW/cm 2 and a light quantity of 29 mJ/cm 2 , and the illuminance and light quantity were measured using an illuminance and light meter (manufactured by EIT, product name “UV Power Puck II”) in the UVC region. was measured.

[Example 2]

An adhesive sheet was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive solution (2) obtained in Production Example 2 was used instead of the pressure-sensitive adhesive solution (1) to form a pressure-sensitive adhesive layer having a thickness of 10 µm after drying.

[Example 3]

An adhesive sheet was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive solution (2) obtained in Production Example 2 was used instead of the pressure-sensitive adhesive solution (1) to form a pressure-sensitive adhesive layer having a thickness of 1 µm after drying.

[Reference Example 1]

An adhesive sheet was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive solution (2) obtained in Production Example 2 was used instead of the pressure-sensitive adhesive solution (1) to form a pressure-sensitive adhesive layer having a thickness of 150 µm after drying.

[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]

Instead of forming an adhesive layer on the side having an easily adhesive layer of a polyethylene terephthalate film (manufactured by Toyobo Corporation, product name "Cosmoshine A4100", 50 µm in thickness, and an easily adhesive layer on one surface), ethylene propylene diene An ethyl acetate solution of rubber (manufactured by Mitsui Chemicals Co., Ltd., product name "EPT") was coated with a bar coater so that the thickness after drying was 20 µm, dried at 100°C for 1 minute to form a layer made of ethylene propylenediene rubber Except this, it carried out similarly to Example 1, the molecular adhesive bond layer was formed, and the adhesive sheet was obtained.

[Comparative Example 4]

On the side having an easily adhesive layer of a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., product name "Cosmoshine A4100", 50 µm in thickness, and an easily adhesive layer on one surface), an adhesive for dry lamination (manufactured by DIC Corporation, product name " LX-401A/SP-60") was applied and dried. Next, instead of forming the pressure-sensitive adhesive layer, a non-stretched polypropylene film (manufactured by Mitsui Chemical Tocello Co., Ltd., product name "SC", thickness 50 µm) was dry laminated to form a layer made of unstretched polypropylene, except that It carried out similarly to Example 1, the molecular adhesive layer was formed, and the adhesive sheet was obtained.

[Adhesiveness]

After the adhesive sheets prepared in Examples and Comparative Examples were cut to a size of 25 mm in length × 300 mm in width, the molecular adhesive layer of the adhesive sheet was subjected to a weight of 2 in an environment of 23° C. and 50% RH (relative humidity). It affixed to the glass plate (the Corning Corporation make, product name "Eagle XG") using a kg roller, and then, it left still under the same environment for 30 minutes. After standing still, based on JIS Z0237:2000, the adhesive force of each adhesive sheet was measured by the 180 degree peeling method at a tensile rate of 300 mm/min. The measurement results are shown in Table 1.

[Blister resistance]

After cutting the adhesive sheets prepared in Examples and Comparative Examples to a size of 50 mm in length × 50 mm in width, a polycarbonate plate of 70 mm in length × 150 mm in width × 2 mm in thickness (manufactured by Mitsubishi Gas Chemical Co., Ltd., “Upiron”) sheet NF-2000VU") and strongly compressed using a squeegee to prepare a test sample.

After this test sample was left still at 23 degreeC for 12 hours, it left still in 80 degreeC hot-air dryer for 1.5 hours, and also left still in 90 degreeC hot-air dryer for 1.5 hours, and the generation|occurrence|production state of blister after heating promotion was observed visually. And the following criteria evaluated the blister resistance of each adhesive sheet. The evaluation result is shown in 1st table|surface.

A: No blisters were observed at all.

B: Blister was confirmed partially.

C: Blisters were confirmed on the entire surface.

From the 1st table|surface, the following can be seen.

The adhesive sheets of Examples 1-3 were excellent in adhesive force and blister resistance.

Moreover, although the thickness of an adhesive layer is 150 micrometers, the adhesive sheet of the reference example 1 has the property equivalent to Examples 1-3 in these evaluation tests.

On the other hand, the adhesive sheets of Comparative Examples 1 and 2 were inferior in blister resistance, and the adhesive sheets of Comparative Examples 3 and 4 were inferior in adhesive strength.

[Example 4]

As a base material, instead of a polyethylene terephthalate film, a bonding film of aluminum foil and polyethylene terephthalate (a film in which an aluminum foil of 7 µm is laminated on a polyethylene terephthalate film of a thickness of 38 µm) on the side having an aluminum foil, Except having applied the adhesive solution (2) obtained in manufacture example 2, it carried out similarly to Example 2, and obtained the adhesive sheet.

[Comparative Example 5]

As a base material, instead of a polyethylene terephthalate film, a bonding film of aluminum foil and polyethylene terephthalate (a film in which a 7 µm aluminum foil is laminated on a 38 µm thick polyethylene terephthalate film) on the side having an aluminum foil, Production Example 2 An adhesive sheet was obtained in the same manner as in Comparative Example 2 except that the pressure-sensitive adhesive solution (2) obtained in was applied.

[Comparative Example 6]

As a base material, instead of a polyethylene terephthalate film, a bonding film of aluminum foil and polyethylene terephthalate (a film in which a 7 µm aluminum foil is laminated on a 38 µm thick polyethylene terephthalate film) on the side having an aluminum foil, Production Example 2 An adhesive sheet was obtained in the same manner as in Reference Example 1 except that the pressure-sensitive adhesive solution (2) obtained in .

[Evaluation of moisture barrier properties]

On an alkali-free-glass substrate (the Corning company make, 45 mm x 45 mm), the calcium layer with a film thickness of 150 nm was formed by the vacuum vapor deposition method by 35 mm long and 35 mm wide.

Next, each of the release sheets of the adhesive sheets obtained in Example 4 and Comparative Examples 5 and 6 was peeled off, and the exposed molecular adhesive layer or pressure-sensitive adhesive layer and the calcium layer on the glass substrate were dried under a dry nitrogen atmosphere using a laminator. After bonding, autoclaving was carried out at 40°C and 0.5 MPa to seal the calcium layer, and a test piece for a moisture barrier test was obtained.

The obtained test piece was left to stand in an environment of 60°C and 90%RH for 500 hours, the rate of discoloration of the calcium layer (ratio of moisture intrusion) was visually confirmed, and the water barrier property was evaluated according to the following criteria. An evaluation result is shown in 2nd table|surface.

(Evaluation standard)

A: The discoloration of the calcium layer was not seen.

B: Although discoloration of the edge part of a calcium layer was seen, the discolored area was less than half.

C: More than half of the area of the calcium layer was discolored.

From the 2nd table|surface, the following can be seen.

The adhesive sheet of Example 4 was excellent in moisture barrier properties.

On the other hand, the adhesive sheet of Comparative Example 5 did not have a molecular adhesive layer and was inferior in moisture barrier properties.

The adhesive sheet of Comparative Example 6 has a thick adhesive layer. As shown in Reference Example 1 above, the adhesive sheet having such a thick adhesive layer has excellent adhesion and the like, but is poor in moisture barrier properties.

Claims (12)

On the pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive resin (P),
At least one reactive group (Zα) selected from the group consisting of an amino group, an azide group, a mercapto group, an isocyanate group, a ureide group and an epoxy group, a silanol group, and a group that generates a silanol group by hydrolysis reaction An adhesive sheet comprising a molecular adhesive layer comprising a molecular adhesive having at least one reactive group (Zβ) selected from the group consisting of:
The adhesive resin (P) has a reactive partial structure (Zγ) capable of forming a chemical bond with a reactive group (Zα) of the molecular adhesive,
The adhesive sheet whose shear storage modulus in 23 degreeC of the said adhesive layer is 0.10-3.30 Mpa, and the thickness of the said adhesive layer is 0.1-100 micrometers. The method of claim 1,
In the molecular adhesive layer, the molecular adhesive is chemically fixed to the pressure-sensitive adhesive layer by chemical bonding between the reactive group (Zα) of the molecular adhesive and the reactive partial structure (Zγ) of the adhesive resin (P). An adhesive sheet, characterized in that it is made. 2. The method of claim 1,
The reactive group (Zα) of the 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,
The adhesive sheet, wherein the reactive partial structure (Zγ) of the adhesive resin (P) is at least one selected from the group consisting of a hydroxyl group, a carboxy group, an aldehyde group, and an amino group. The method of claim 1,
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 carbon-carbon single bond, a carbon-carbon double bond, and a carbon-hydrogen group The adhesive sheet which is at least 1 type selected from the group which consists of bonding. The method of claim 1,
The adhesive sheet wherein the pressure-sensitive adhesive layer is not subjected to a surface treatment selected from the group consisting of corona treatment, plasma treatment, ultraviolet treatment, electron beam treatment, ozone treatment, excimer ultraviolet treatment, acid treatment, and base treatment. The method of claim 1,
The adhesive sheet in which the said molecular adhesive is a compound represented by following formula (1).

(R ¹ is a reactive group (Zα) selected from the group consisting of an amino group, an azide group, a mercapto group, an isocyanate group, a ureide group and an epoxy group, or a monovalent group having one or more of these reactive groups (however, an amino group) , azide group, mercapto group, isocyanate group, ureide group and epoxy group are excluded.), A is a divalent organic group, X is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom and Y represents a hydrocarbon group having 1 to 20 carbon atoms, a represents an integer of 1 to 3) The method of claim 1,
The adhesive sheet, wherein the molecular adhesive layer has a thickness of 200 nm or less. The method of claim 1,
The adhesive sheet which has a molecular adhesive layer only on one side of the said adhesive layer. The method of claim 1,
An adhesive sheet having a molecular adhesive layer on both sides of the pressure-sensitive adhesive layer. The method of claim 1,
An adhesive sheet further having a support. A method for producing a laminate having a layer structure of a pressure-sensitive adhesive layer/molecular adhesive layer/adherent, wherein the molecular adhesive layer of the adhesive sheet according to any one of claims 1 to 10 is pressed against an adherend. 12. The method of claim 11,
The manufacturing method of the laminated body whose temperature T at the time of crimping|compression-bonding is -20-140 degreeC.