CN110461975A - The manufacturing method of adhesive sheet and laminated body - Google Patents

The manufacturing method of adhesive sheet and laminated body Download PDF

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Publication number
CN110461975A
CN110461975A CN201880021870.3A CN201880021870A CN110461975A CN 110461975 A CN110461975 A CN 110461975A CN 201880021870 A CN201880021870 A CN 201880021870A CN 110461975 A CN110461975 A CN 110461975A
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China
Prior art keywords
adhesive sheet
group
layer
resin
molecular adhesion
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Granted
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CN201880021870.3A
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Chinese (zh)
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CN110461975B (en
Inventor
中山秀一
上村和惠
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Rintoku Co Ltd
Lintec Corp
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Rintoku Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/405—Adhesives in the form of films or foils characterised by release liners characterised by the substrate of the release liner
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

The present invention is: adhesive sheet, it is the resin layer that will include resin (S), obtained from molecular adhesion oxidant layer and protective film comprising molecular adhesion agent are directly laminated in order, the molecular adhesion agent, which has, is selected from amino, azido, sulfydryl, isocyanate group, at least one kind of reactive group (Z α) in urea groups and epoxy group, and it is selected from silanol group, with at least one kind of reactive group (Z β) generated by hydrolysis in the group of silanol group, aforementioned resin (S) has the reactivity part structure (Z γ) that chemical bond can be formed with the reactive group (Z α) of previous molecular bonding agent, aforementioned protective film is on the surface for contacting side with molecular adhesion oxidant layer with there are at least one with the embossed surface of upper convex portion；With the manufacturing method for the laminated body for using the adhesive sheet.According to the present invention, the manufacturing method with resin layer, molecular adhesion oxidant layer and protective film, the adhesive sheet excellent in adhesion with adherend and the laminated body using the adhesive sheet is provided.

Description

The manufacturing method of adhesive sheet and laminated body
Technical field
The present invention relates to (refer to the layer formed using molecular adhesion agent with resin layer, molecular adhesion oxidant layer；Below all Together) and the manufacturing method of protective film, laminated body with the adhesive sheet excellent in adhesion of adherend and using the adhesive sheet.
Background technique
Compound with reactive group of more than two kinds can form 2 using the characteristic of respective reactive group Kind or more chemical bond, therefore be useful as molecular adhesion agent.
As the example for using molecular adhesion agent, in patent document 1, describes and be formed with entropic elasticity between 2 substrates The laminated body of molecular adhesion layer, which is characterized in that the entropic elasticity molecular adhesion layer includes entropic elasticity body layer and molecular adhesion oxidant layer.
The application method of molecular adhesion agent when laminated body such as manufacture, it may be considered that: 2 layers will be bonded Before, on the surface of a layer coated molecular bonding agent and after forming molecular adhesion oxidant layer, by molecular adhesion oxidant layer with it is another A layer of method for being overlapped and being bonded；Molecular adhesion oxidant layer is formed on substrate after obtaining adhesive sheet, and gained adhesive sheet is bonded Method on adherend.
Existing technical literature
Patent document
Patent document 1:WO2009/154083 (US2011/0104505 A1).
Summary of the invention
Subject to be solved by the invention
In adhesive sheet, generally for long-term keeping, transfer, carry out that protective film (stripping film) is arranged on adhesive layer.
However, according to the present invention the research of people etc. it is found that in the adhesive sheet for being provided with protective film in molecular adhesion oxidant layer, Sometimes it is unable to fully show the bonding force of molecular adhesion agent inherently.
It is an object of the invention to solve the problems, such as this, it is therefore intended that, it provides with resin layer, molecular adhesion oxidant layer and protects The manufacturing method of cuticula, the adhesive sheet excellent in adhesion with adherend and the laminated body using the adhesive sheet.
The means to solve the problem
The inventors of the present invention are in order to solve the above problems and for the adhesive sheet with resin layer, molecular adhesion oxidant layer and protective film It is furtherd investigate.Itself as a result, it has been found that,
(i) for the reduction of the bonding force of molecular adhesion oxidant layer, the change that is generated due to contact of the molecular adhesion oxidant layer with protective film Learning key is reason；With
(ii) by using having on the surface for contacting side with molecular adhesion oxidant layer, there are at least one with the embossing of upper convex portion The protective film on surface is able to suppress the reduction of the bonding force of molecular adhesion oxidant layer；
So as to complete the present invention.
Therefore, according to the present invention, the manufacturer of the adhesive sheet of following [1] ~ [12] and the laminated body of [13] ~ [15] is provided Method.
[1] adhesive sheet, being will include the resin layer of resin (S), comprising the molecular adhesion oxidant layer of molecular adhesion agent and guarantor Cuticula in order directly be laminated obtained from, the molecular adhesion agent have selected from amino, azido, sulfydryl, isocyanate group, At least one kind of reactive group (Z α) in urea groups and epoxy group and silicon is generated selected from silanol group and by hydrolysis At least one kind of reactive group (Z β) in the group of alcohol radical, aforementioned resin (S) has can be anti-with previous molecular bonding agent Answering property group (Z α) forms the reactivity part structure (Z γ) of chemical bond, and aforementioned protective film is contacting one with molecular adhesion oxidant layer With there are at least one with the embossed surface of upper convex portion on the surface of side.
[2] adhesive sheet according to [1], which is characterized in that previous molecular adhesive layer passes through previous molecular bonding agent The chemical bond of reactivity part structure (Z γ) possessed by possessed reactive group (Z α) and aforementioned resin (S) and will before Molecular adhesion agent is stated chemically to be fixed on aforementioned resin layer.
[3] adhesive sheet according to [1] or [2], wherein reactive group possessed by previous molecular bonding agent (Z α) It is at least one kind of in amino, sulfydryl, isocyanate group, urea groups and epoxy group, reactivity possessed by aforementioned resin (S) Part-structure (Z γ) is at least one kind of in hydroxyl, carboxyl, aldehyde radical and amino.
[4] adhesive sheet according to [1] or [2], wherein reactive group possessed by previous molecular bonding agent (Z α) Azido, reactivity part structure possessed by aforementioned resin (S) (Z γ) be selected from carbon-to-carbon singly-bound, carbon-to-carbon double bond and It is at least one kind of in carbon-hydrogen singly-bound.
[5] adhesive sheet according to any one of [1] ~ [4], wherein previous molecular bonding agent is shown in following formula (1) Compound,
[changing 1]
(R1Indicate reactive group (Z α) in amino, azido, sulfydryl, isocyanate group, urea groups and epoxy group or With 1 the above reactive group 1 valence group (wherein, amino, azido, sulfydryl, isocyanate group, urea groups and Except epoxy group), A indicates that the organic group of divalent, X indicate that the alkoxy or halogen atom of hydroxyl, carbon atom number 1 ~ 10, Y indicate The alkyl of carbon atom number 1 ~ 20；A indicates 1 ~ 3 integer).
[6] adhesive sheet according to any one of [1] ~ [5], wherein previous molecular adhesive layer with a thickness of 200nm Below.
[7] adhesive sheet according to any one of [1] ~ [6], wherein aforementioned protective film connects with molecular adhesion oxidant layer The surface roughness (Ra) for touching the surface of side is 0.1 ~ 2.0 μm.
[8] adhesive sheet according to any one of [1] ~ [7], which is characterized in that aforementioned protective film, which does not have, is selected from silicon It alcohol radical and is generated by hydrolysis any in the reactive group (Z β) in the group of silanol group.
[9] adhesive sheet according to any one of [1] ~ [8], wherein aforementioned protective film is the film of hydrocarbon system resin.
[10] adhesive sheet according to [9], wherein aforementioned hydrocarbon system resin is selected from polyethylene, polypropylene, poly- (4- first Base -1- amylene), with carbon atom number 4 ~ 10 alicyclic structure polycyclic alkene in it is at least one kind of.
[11] adhesive sheet according to any one of [1] ~ [10], which is characterized in that at 23 DEG C of aforementioned resin (S) Young's modulus is 1 × 108~1×1010Pa。
[12] adhesive sheet according to any one of [1] ~ [11], wherein only have on the unilateral side of aforementioned resin layer Molecular adhesion oxidant layer.
[13] adhesive sheet according to any one of [1] ~ [11], wherein have on the two sides of aforementioned resin layer and divide Sub- adhesive layer.
[14] adhesive sheet according to any one of [1] ~ [13], further has supporter.
[15] adhesive sheet according to any one of [1] ~ [14], passes through the manufacture of the adhesive sheet with following step Method and obtain: previous molecular adhesive layer is formed on aforementioned resin layer, then, on being formed by molecular adhesion oxidant layer weight Prestack states protective film.
[16] there is the manufacturing method of resin layer/molecular adhesion oxidant layer/adherend layer structure laminated body, feature exists In, removing constitutes the protective film of adhesive sheet described in any one of [1] ~ [15], by exposed molecular adhesion oxidant layer be crimped on by On viscous object.
[17] manufacturing method of the laminated body according to [16], wherein temperature T when crimpingp(DEG C) meets following formula (I),
[mathematical expression 1]
Tg ≤Tp ≤ Ts+ H (I)
(TgIndicate the glass transition temperature (DEG C) of resin layer, TsIndicate the softening point (DEG C) of resin layer；40) H is.
[18] manufacturing method of the laminated body according to [16] or [17], wherein in resin layer or adherend at least Temperature T when the crimping of onepYoung's modulus under (DEG C) is 1 × 106~1×109Pa。
The effect of invention
According to the present invention, it provides and is glued with resin layer, molecular adhesion oxidant layer and protective film and the excellent in adhesion of adherend The manufacturing method of contact pin and the laminated body using the adhesive sheet.
Specific embodiment
Hereinafter, the present invention is divided into 1) adhesive sheet and 2) project of the manufacturing method of laminated body is described in detail.
1) adhesive sheet
Adhesive sheet of the invention be will comprising resin (S) resin layer, comprising the molecular adhesion oxidant layer of molecular adhesion agent and protection Obtained from film is directly laminated in order, the molecular adhesion agent, which has, is selected from amino, azido, sulfydryl, isocyanate group, urea At least one kind of reactive group (Z α) in base and epoxy group and silanol is generated selected from silanol group and by hydrolysis At least one kind of reactive group (Z β) in the group of base.
Aforementioned resin (S) has the reactivity that chemical bond can be formed with the reactive group (Z α) of previous molecular bonding agent Part-structure (Z γ).
Aforementioned protective film is on the surface for contacting side with molecular adhesion oxidant layer with there are at least one with the pressure of upper convex portion Flower surface.
In the present invention, " the including molecular adhesion agent " of " the molecular adhesion oxidant layer comprising molecular adhesion agent " refers to " comprising dividing Sub- bonding agent and/or from molecular adhesion agent compound (such as by reaction and the structure of reactive group is changed Compound) ".
In addition, " resin (S) has and can form reacting for chemical bond with the reactive group (Z α) of previous molecular bonding agent Property part-structure (Z γ) " refer to indicate on the resin layer formed molecular adhesion oxidant layer before state.Form molecular adhesion oxidant layer In resin layer afterwards, resin (S) has reactivity part structure (Z γ) and/or is originated from the knot of reactivity part structure (Z γ) Structure.
[resin layer]
The resin layer for constituting adhesive sheet of the invention is the layer containing resin (S).
In adhesive sheet of the invention, resin layer undertakes the function of fixed member bonding agent.
It should be noted that in this specification, even if in the state (states of the raw material such as resin film) that other layers are not laminated also Under, in the case wheres illustrating the manufacturing method etc. of adhesive sheet, also it is sometimes denoted as " resin layer ".
Resin (S) has the reactivity part that chemical bond can be formed with the reactive group (Z α) of previous molecular bonding agent Structure (Z γ).
By making resin (S) that there is reactivity part structure (Z γ), molecular adhesion agent can be formed with good efficiency Layer.
As reactivity part structure possessed by resin (S) (Z γ), can enumerate hydroxyl, carboxyl, aldehyde radical, amino, Carbon-to-carbon singly-bound, carbon-to-carbon double bond, carbon-hydrogen singly-bound etc..It can correspondingly be fitted with the reactive group (Z α) in molecular adhesion agent Work as selection.
For example, reactive group possessed by previous molecular bonding agent (Z α) be selected from amino, sulfydryl, isocyanate group, In the case where at least one kind of in urea groups and epoxy group, as reactivity part structure (Z γ), it is preferable to use being selected from hydroxyl, carboxylic It is at least one kind of in base, aldehyde radical and amino.
In addition, in the case that reactive group possessed by previous molecular bonding agent (Z α) is azido, as reactivity Part-structure (Z γ) is, it is preferable to use at least one kind of in carbon-to-carbon singly-bound, carbon-to-carbon double bond and carbon-hydrogen singly-bound.
It is not particularly limited as resin (S) as long as being capable of forming the resin layer of fixed member bonding agent.As tree Rouge (S) can enumerate the polyolefin resins such as polyethylene, polypropylene, polybutene, poly- 4-methyl-1-pentene；Poly terephthalic acid The polyester resin such as glycol ester, polybutylene terephthalate (PBT), polyethylene naphthalate；Polyvinyl chloride gathers inclined dichloro The vinyl resins such as ethylene, polyvinyl alcohol, vinyl-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer；Polystyrene； Acrylonitrile-butadiene-styrene (ABS) (ABS) resin；Polycarbonate；Polysulfones；Polyether-ether-ketone；Polyether sulfone；Polyphenylene sulfide；Polyetherimide Amine；Polyimides；Polyamide；Acrylic resin；Cyclic olefin resins；Fluororesin；Carbamate resins etc..
Resin (S) can be used alone, or two or more is applied in combination.
Among these, the Young's modulus at preferably 23 DEG C of resin (S) is 1 × 108~1×1010Pa.By using such Resin (S) can be readily derived the superior adhesive sheet of cementability.
Resin (S) is the resin for having the functional groups such as hydroxyl, carboxyl, aldehyde radical, amino as reactivity part structure (Z γ) (S') in the case where, these reactivity part structures (Zr') in resin (S') can be formed by well known method.
For example, there is the monomer of functional group using hydroxyl, carboxyl, aldehyde radical, amino etc. when carrying out polymerization reaction, or Implement maleic anhydride modified equal modifications to polymer obtained from polymerization reaction is carried out, thus, it is possible to form reactivity part Structure (Z γ ').
In addition, the layer (s1) to the resin containing the precursor as resin (S') implements surface treatment, it is possible thereby at this Resin (S') is generated on the surface of layer (s1).
As surface treatment, as long as generating hydroxyl, carboxyl, it is not particularly limited.As surface treatment, electricity can be enumerated Dizzy processing, corona treatment, ultraviolet treatment with irradiation, electronbeam irradiation processing, ozone treatment, excimers ultraviolet light Processing, acid processing and alkali process etc..
These surface treatments can carry out according to known methods.
Resin layer can contain the ingredient other than resin (S).As the ingredient other than resin (S), as long as The ingredient and content with the adaptation of molecular adhesion oxidant layer are not hindered, then substance appropriate can be used.As such substance, Ultraviolet absorbing agent, light stabilizer, antioxidant, antistatic agent, antiseize paste, antiblocking agent, colorant etc. can be enumerated.
The content of resin (S) in resin layer is counted on the basis of resin layer entirety, preferably 20 mass % or more, more preferably For 30 mass % or more and 100 mass % hereinafter, further preferably 50 mass % or more and 100 mass % or less.
The thickness of resin layer is not particularly limited.The thickness of resin layer is usually 2 ~ 4000 μm, preferably 5 ~ 1000 μm, more Preferably 10 ~ 600 μm, further preferably 15 ~ 400 μm.
The forming method of resin layer is not particularly limited.
The resin (S) for including in resin layer is to be used as reactivity portion with carbon-to-carbon singly-bound, carbon-to-carbon double bond, carbon-hydrogen singly-bound In the case where the resin (S'') of separation structure (Z γ), commercially available resin film usually can be directly used as resin layer.
In addition, resin (S'') is prepared coating fluid with organic solvent diluting appropriate, it is coated on supporter, work On the surfaces such as journey piece, stripping film, drying process, curing process are implemented to gained film, are thus also capable of forming resin layer.
The resin (S) for including in resin layer be above-mentioned resin (S') in the case where, such as can by (a) below ~ (d) method either in forms resin layer.
(a) layer (s1) as the resin containing the precursor as resin (S'), using commercially available resin film, resin sheet, Surface treatment above-mentioned is implemented to layer (s1), the resin layer comprising resin (S') is consequently formed.
(b) resin as the precursor of resin (S') is prepared into coating fluid with organic solvent diluting appropriate, is applied Cloth implements drying process, curing process on the surfaces such as supporter, engineering piece, stripping film, to gained film, and layer is consequently formed (s1).Then, surface treatment above-mentioned is implemented to the layer (s1), the resin layer comprising resin (S') is consequently formed.
(c) directly use the commercially available resin film comprising resin (S'), resin sheet as resin layer.
(d) resin (S') is prepared into coating fluid with organic solvent diluting appropriate, is coated on supporter, engineering On the surfaces such as piece, stripping film, drying process, curing process are implemented to gained film, resin layer is consequently formed.
[molecular adhesion oxidant layer]
The molecular adhesion oxidant layer for constituting adhesive sheet of the invention includes molecular adhesion agent, and the molecular adhesion agent, which has, is selected from ammonia At least one kind of reactive group (Z α) in base, azido, sulfydryl, isocyanate group, urea groups and epoxy group and it is selected from silicon Alcohol radical and at least one kind of reactive group (Z β) in the group of silanol group is generated by hydrolysis.
Reactive group (Z α) in molecular adhesion agent can be with the reactivity part structure (Z of the resin (S) in resin layer γ) form chemical bond.
In adhesive sheet of the invention, it is believed that by the chemical bond, molecular adhesion agent is chemically fixed on resin layer On surface.As chemical bond at this time, covalent bond, hydrogen bond, ionic bond, molecular separating force etc., preferably covalent bond can be enumerated.
As the group for generating silanol group by hydrolysis, can enumerate with Si-X1Shown in part-structure Group.As X1, the alkoxy of the carbon atom numbers such as methoxyl group, ethyoxyl, positive propoxy, isopropoxy 1 ~ 10 can be enumerated；Fluorine The halogen atoms such as atom, chlorine atom, bromine atom.
Reactive group (Z β) in molecular adhesion agent is mainly when adhesive sheet of the invention to be bonded on adherend, In It is utilized when forming chemical bond between adherend.Therefore, adhesive sheet of the invention preferably on the surface have and these groups Group with high reactivity adherend use.
As molecular adhesion agent, following formula (1) compound represented can be enumerated.
[changing 2]
(R1Indicate that 1 valence group of reactive group (Z α) or the reactive group (Z α) with 1 or more is (wherein, reactive Except group (Z α) itself), A indicates that the organic group of divalent, X indicate that hydroxyl, the alkoxy or halogen of carbon atom number 1 ~ 10 are former Son, Y indicate the alkyl of carbon atom number 1 ~ 20；A indicates 1 ~ 3 integer).
As R1The 1 valence group with 1 or more reactive group (Z α), it can be cited for example that following formula (2) ~ (4) group shown in.
[changing 3]
In formula (2) ~ (4), * expression is bonded position with A's.
R2Indicate the alkyl of the alkyl of the divalent of carbon atom number 1 ~ 10, the divalent of preferably carbon atom number 2 ~ 6.As R2Divalent Alkyl, the alkylidenes such as ethylidene, trimethylene, propylidene can be enumerated；Adjacent phenylene, metaphenylene, to Asias such as phenylenes Aryl.
R3、R4Each independently represent the alkyl of carbon atom number 1 ~ 20, the alkyl of preferably carbon atom number 1 ~ 10.
As R3、R4Alkyl, can enumerate methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, The alkyl such as tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl；Vinyl, 1- acrylic, 2- propylene The alkenyls such as base, isopropenyl, 3- cyclobutenyl, 4- pentenyl, 5- hexenyl；The alkynyls such as acetenyl, propargyl, butynyl；Phenyl, Aryl such as 1- naphthalene, 2- naphthalene etc..
Z indicates singly-bound or-N (R7)-shown in divalent group.R7Indicate the alkyl of hydrogen atom or carbon atom number 1 ~ 20.Make For R7Alkyl, can enumerate with as R3、R4Alkyl and the identical group that shows.
R5、R6Each independently represent group shown in reactive group (Z α) or previously described formula (2).
The organic group of divalent as A can enumerate the alkylidene of the carbon atom number 1 ~ 20 optionally with substituent group, appoint Select the alkenylene of the carbon atom number 2 ~ 20 the with substituent group, alkynylene of the optionally carbon atom number 2 ~ 20 with substituent group, optional The arlydene etc. of carbon atom number 6 ~ 20 with substituent group.
The alkylidene of carbon atom number 1 ~ 20 as A, can enumerate methylene, ethylidene, propylidene, trimethylene, four Methylene, pentamethylene, hexa-methylene etc..
The alkenylene of carbon atom number 2 ~ 20 as A can enumerate ethenylidene, allylidene, butenylidene, sub- amylene Base etc..
The alkynylene of carbon atom number 2 ~ 20 as A can enumerate ethynylene, sub- propinyl etc..
The arlydene of carbon atom number 6 ~ 20 as A can enumerate adjacent phenylene, metaphenylene, to phenylene, the Asia 2,6- Naphthalene, 1,5- naphthylene etc..
As the substituent group of aforementioned alkylidene, alkenylene and alkynylene, the halogens such as fluorine atom, chlorine atom original can be enumerated Son；The alkoxies such as methoxyl group, ethyoxyl；The alkylthio groups such as methyl mercapto, ethylmercapto group；The alkoxies such as methoxycarbonyl, ethoxy carbonyl Carbonyl etc..
As the substituent group of aforementioned arlydene, cyano can be enumerated；Nitro；The halogens such as fluorine atom, chlorine atom, bromine atom are former Son；The alkyl such as methyl, ethyl；The alkoxies such as methoxyl group, ethyoxyl；Alkylthio groups such as methyl mercapto, ethylmercapto group etc..
These substituent groups can be bonded to arbitrary position in the groups such as alkylidene, alkenylene, alkynylene and arlydene, It can also be bonded with identical or differently multiple.
The alkoxy of carbon atom number 1 ~ 10 as X, can enumerate methoxyl group, ethyoxyl, positive propoxy, isopropoxy Deng.
As the halogen atom of X, fluorine atom, chlorine atom, bromine atom etc. can be enumerated.
The alkyl of carbon atom number 1 ~ 20 as Y can be enumerated and as R3、R4Alkyl and the identical group that shows.
As R1For the molecular adhesion agent of amino, 3- TSL 8330,3- aminopropyl three can be enumerated Ethoxysilane, 3- aminopropyldimethoxy methyl-monosilane, 3- aminopropyl diethoxymethylsilane, [3- (N, N- diformazan Base amino) propyl] trimethoxy silane, [3- (phenyl amino) propyl] trimethoxy silane, trimethyl [3- (triethoxy first Silylation) propyl] ammonium chloride, trimethyl [3- (trimethoxysilyl) propyl] ammonium chloride etc..
As R1For the molecular adhesion agent of azido, can enumerate (11- azido undecyl) trimethoxy silane, (11- azido undecyl) triethoxysilane etc..
As R1For the molecular adhesion agent of sulfydryl, 3-mercaptopropyi trimethoxy silane, 3- mercaptopropyi three can be enumerated Ethoxysilane, 3- mercaptopropyi dimethoxymethylsilane etc..
As R1For the molecular adhesion agent of isocyanate group, 3- (trimethoxysilyl) propyl isocyanic acid can be enumerated Ester, 3- (triethoxysilyl) propylisocyanate etc..
As R1For the molecular adhesion agent of urea groups, 3- ureido-propyl trimethoxy silane, 3- ureido-propyl three can be enumerated Ethoxysilane etc..
As R1For the molecular adhesion agent of epoxy group, 3- glycidoxypropyltrime,hoxysilane, 3- ring can be enumerated Oxygen propoxypropyl triethoxysilane, 3- epoxy propoxy propyl methyl dimethoxysilane, 3- glycidoxypropyl group first Base diethoxy silane etc..
As R1For the molecular adhesion agent of 1 valence group of the reactive group (Z α) with 1 or more, it can be cited for example that 3- (2- aminoethylamino) propyl trimethoxy silicane, 3- (2- aminoethylamino) propyl-triethoxysilicane, 3- (2- ammonia Base ethylamino) dimethylamine oxygroup methyl-monosilane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, following formula (5) ~ (13) compound represented.
[changing 4]
Among these compounds, as formula (1) compound represented, preferably R1For the compound of group shown in formula (4), more Preferably formula (5) ~ (13) compound represented, further preferably formula (5) ~ (10) compound represented.
In these compounds, in R1It is upper that there is triazine ring.Molecular adhesion agent with triazine ring has on the resin layer more Expeditiously fixed tendency.
Majority in these molecular adhesion agent is well known compound as silane coupling agent.In addition, R1For formula (4) institute The compound of the group shown can be according to remembering in No. WO2012/046651, No. WO2012/043631, No. WO2013/186941 etc. The method of load and synthesize.
Used molecular adhesion agent is considered that the reactivity part structure of its reactive group (Z α) and resin (S) The combination of (Z γ) and suitably select.
For example, reactive group (Z α) is at least one kind of in amino, sulfydryl, isocyanate group, urea groups and epoxy group In the case where, as reactivity part structure (Z γ), it is preferable to use in hydroxyl, carboxyl, aldehyde radical and amino at least 1 Kind.
Wherein, the preferred combination [reactive group (Z as reactive group (Z α) and reactivity part structure (Z γ) α)/reactivity part structure (Z γ)], (amino/hydroxyl), (amino/carboxyl), (isocyanate group/hydroxyl), (different can be enumerated Cyanic acid ester group/carboxyl), (hydroxyl/carboxyl) etc..
In addition, molecular adhesion agent have azido as reactive group (Z α) in the case where, as described later, pass through irradiation Light and azido is activated.In this case, the nitrence as reaction intermediate can be with carbon-to-carbon singly-bound, carbon-to-carbon double bond, carbon- The reaction of hydrogen singly-bound, therefore using the molecular adhesion agent with azido, the type of resin (S) does not limit especially It is fixed.
The forming method of molecular adhesion oxidant layer is not particularly limited.For example, the molecule containing molecular adhesion agent can be prepared Adhesive solution forms molecular adhesion oxidant layer by well known method using the solution on the resin layer.
The solvent used when preparing molecular adhesion agent solution is not particularly limited.As solvent, methanol, second can be enumerated The alcohol series solvents such as alcohol, isopropanol, ethylene glycol, diethylene glycol；The ketone series solvents such as acetone, methyl ethyl ketone；Ethyl acetate, acetic acid butyl etc. Ester series solvent；The halide-containings series solvent such as methylene chloride；The aliphatic hydrocarbons series solvent such as butane, hexane；Tetrahydrofuran, butyl ether Etc. ether series solvents；The aromatic compounds series solvent such as benzene, toluene；The amides such as N,N-dimethylformamide, methyl pyrrolidone system is molten Agent；Water etc..
They can be used alone, or two or more is applied in combination.
The concentration of molecular adhesion agent in molecular adhesion agent solution is not particularly limited.Its concentration is preferably 0.005 ~ 1.000mol/L, more preferably 0.050 ~ 0.500mol/L.By the way that the concentration of molecular adhesion agent is set as 0.005mol/L or more, Molecular adhesion agent can be expeditiously formed in body to be coated.In addition, by being set as 1.000mol/L hereinafter, being able to suppress The undesirable reaction of molecular adhesion agent solution, the excellent in stability of solution.
As the forming method of molecular adhesion oxidant layer, infusion process, rubbing method, spray-on process etc. can be enumerated, among these, from From the perspective of productivity, preferably rubbing method.As coating method, it can be cited for example that spin-coating method, spray coating method, stick coating method, Cutter painting method, roller cutter painting method, rolling method, scraper for coating method, Dipcoat method, curtain coating processes, die coating method, gravure coating process etc., Preferably stick coating method, Dipcoat method, gravure coating process.
In the case where selecting coating method, need that place is dried using the investment into natural drying, drier Reason, but from the perspective of improving productivity, it is dried preferably by the investment into drier.It is dry as this Dry mechanism, it can be cited for example that the intermittent drier and heating roller, hot-air of air -oven etc pass through mechanism (make that dried body is mobile, passes through in open drying oven, and while receiving air-supply heat drying equipment etc.) Etc continuous drier etc..
It should be noted that the device of a part of these driers, such as high-frequency heating, oil can also will be can also act as The heaters itself such as the heating agents such as heater circulating heater and far infrared wire type heater are used as drier.Among these, From the perspective of improving productivity, preferably hot-air passes through mechanism.
Be usually 20 ~ 250 DEG C by the drying temperature that the drier adjusts, preferably 50 ~ 200 DEG C, more preferably 65 ~ 150 DEG C, particularly preferably 80 ~ 120 DEG C.Drying time is usually 1 second to 120 minutes, is preferably 5 seconds to 10 minutes, more preferable It is 10 seconds to 5 minutes, particularly preferably 20 seconds to 3 minutes.
In molecular adhesion oxidant layer, it is believed that pass through the reactive group (Z α) of molecular adhesion agent and reacting for resin (S) The chemical bond of property part-structure (Z γ), molecular adhesion agent are fixed on the resin layer.
Therefore, it when forming molecular adhesion oxidant layer, usually carries out the fixed processing on the resin layer of molecular adhesion agent is (following Sometimes referred to as fixing process).Fixing process can suitably be selected according to the characteristic of the reactive group (Z α) of molecular adhesion agent. Chemical bond usually is generated and being coated with molecular adhesion agent on the resin layer, promotes the generation of chemical bond by heating, because This is preferably heated from the perspective of improving productivity.Heating temperature is usually 40 ~ 250 DEG C, preferably 60 ~ 200 DEG C, more preferably 80 ~ 120 DEG C.Heating time is usually 1 second to 120 minutes, preferably 1 ~ 60 minute, more preferably 1 ~ 30 point Clock.
It as heating means, is not particularly limited, mechanism identical with above-mentioned drier and device can be used.
As azido, in the case that reactive group (Z α) has photoreactivity, as fixing process, illumination is carried out Penetrate processing.As the light irradiated, usually using ultraviolet light.In this case, carrying out fixing process after drying process from raising It is preferred from the perspective of (Z α) and the reactivity of (Z γ).
Ultraviolet irradiation can use using light sources such as mercury vapor lamp, metal halide lamp, ultraviolet light LED, electrodeless lamps Ultraviolet lamp carry out.
When forming molecular adhesion oxidant layer, it repeated multiple times can also be coated, be dried and fixing process.
Molecular adhesion oxidant layer can also be not damage the amount of the degree of aftermentioned each performance, containing other than molecular adhesion agent Ingredient.As the ingredient other than molecular adhesion agent, catalyst etc. can be enumerated.
If ingredient of the content of the molecular adhesion agent in molecular adhesion oxidant layer comprising being not involved in bonding, bonding force drop It is low, therefore counted on the basis of molecular adhesion oxidant layer entirety, preferably 50 mass % or more, more preferably 70 mass % or more and 100 Quality % or less, further preferably 90 mass % or more and 100 mass % or less, particularly preferably 100 mass %.
The thickness of molecular adhesion oxidant layer is preferably 200nm or less, more preferably 150nm or less, further preferably 100nm Below, it is particularly preferably 50nm or less.In addition, the thickness of molecular adhesion oxidant layer is preferably 1nm or more.
[protective film]
The protective film for constituting adhesive sheet of the invention is arranged in molecular adhesion oxidant layer.System of the protective film in adhesive sheet of the invention In time after making until use, have the function of protecting molecular adhesion oxidant layer.
Protective film used in the present invention with molecular adhesion oxidant layer contact side surface on have there are at least one with The embossed surface of upper convex portion.
Have the viscous of the smooth protective film (hereinafter sometimes referred to " smooth protective film ") without such embossed surface In contact pin, it is possible to the whole contact for causing smooth protective film with molecular adhesion oxidant layer, therefore the reactive base of molecular adhesion agent Group (Z β) is in the state for being easy to react with the compound for constituting smooth protective film, during keeping adhesive sheet, largely Reactive group (Z β) inactivation, the bonding force of molecular adhesion oxidant layer reduces sometimes.
On the other hand, as protective film, if can only make protective film using the above-mentioned substance with embossed surface It is contacted with the part of molecular adhesion oxidant layer, in most of parts, gap can be generated between protective film and molecular adhesion oxidant layer. As a result, the amount of the reactive group (Z β) inactivated in the management process of adhesive sheet can be reduced, it is viscous to be able to suppress molecule Connect the reduction of the bonding force of oxidant layer.
The protective film with embossed surface of target can be formed by well known method.
For example, become the film (hereinafter sometimes referred to " film (A) ") of the material of protective film by knurling rolls and resilient roller it Between, by being reflected in the shape of knurling rolls circumferential surface on film (A), thus, it is possible to the protections with embossed surface of manufacturing objective Film.
In addition, using printing technologies such as silk screen print methods and on film (A) setting by from film (A) same material or different materials The protrusion that matter is formed, thus, it is possible to the protective films with embossed surface of manufacturing objective.
As embossed surface present in protrusion, it can enumerate and largely form hemispherical, cylindric, triangular prism in the plane The protrusions such as shape, quadrangular shape, coniform, triangular pyramid, tetrapyamid shape, striated.
The height of protrusion is not particularly limited, and usually 10 ~ 200 μm, preferably 30 ~ 100 μm.
The total area of protrusion is not particularly limited relative to the ratio of protective film entirety, usually 3 ~ 50%, preferably 5 ~ 30%。
The thickness of protective film is not particularly limited.The thickness of protective film is preferably 1 ~ 100 μm, more preferably 5 ~ 60 μm, spy It You Xuanwei not be 10 ~ 45 μm.
[adhesive sheet]
Adhesive sheet of the invention is that aforementioned resin layer, previous molecular adhesive layer and aforementioned protective film are directly laminated in order Obtained from.
Adhesive sheet of the invention can only have molecular adhesion oxidant layer on the unilateral side of aforementioned resin layer, can also be aforementioned There is molecular adhesion oxidant layer on the two sides of resin layer.
Adhesive sheet of the invention also can have the layer other than resin layer, molecular adhesion oxidant layer, protective film.
As the layer other than resin layer, molecular adhesion oxidant layer, protective film, supporter can be enumerated.
That is, resin layer also has the function as supporter in the case where resin layer has a degree of thickness, but In the case where resin layer is excessively thin, in addition supporter is preferably set.
As supporter, the paper base materials such as good quality paper, art paper, coating paper, brown paper, glossy paper can be enumerated；At these Laminate substrate obtained from the thermoplastic resins such as laminated polyethylene on paper base material；Polyethylene film, polybutene film, gathers polypropylene screen Butadiene film, polymethylpentene film, polychloroethylene film, vinyl chloride copolymer film, polyethylene terephthalate film, poly- naphthalene two Formic acid glycol ester film, polybutylene terephthalate (PBT) film, polyurethane film, ethane-acetic acid ethyenyl ester film, ionomer resin Film, ethylene-(methyl) acrylic copolymer film, ethylene-(methyl) acrylate copolymer film, polystyrene film, polycarbonate The resin base materials such as film, polyimide film, fluororesin film；Metal foil etc..
As adhesive sheet of the invention, it can be cited for example that having following layer structures.
Resin layer/molecular adhesion oxidant layer/protective film
Supporter/resin layer/molecular adhesion oxidant layer/protective film
Supporter/molecular adhesion oxidant layer/resin layer/molecular adhesion oxidant layer/protective film
Molecular adhesion oxidant layer/resin layer/supporter/resin layer/molecular adhesion oxidant layer/protective film
The manufacturing method of adhesive sheet of the invention is not particularly limited.Wherein, preferably according to the method described above, it is formed on the resin layer Molecular adhesion oxidant layer, then, the overlapping protection film on being formed by molecular adhesion oxidant layer, so that molecular adhesion oxidant layer and protection The surface with embossed surface of film is opposite, thus manufactures.
2. the manufacturing method of laminated body
The manufacturing method of laminated body of the invention is that have resin layer/molecular adhesion oxidant layer/adherend layer structure laminated body Manufacturing method, which is characterized in that removing constitutes the protective film of adhesive sheet of the invention, and exposed molecular adhesion oxidant layer is crimped On adherend.
Between molecular adhesion oxidant layer and adherend it is Nian Jie usually by reactive group (Z β) in molecular adhesion agent with The functional group reactions in the compound of adherend are constituted, chemical bond are formed, to carry out.
Therefore, usually as adherend, using on the surface thereof with there is reactive base with reactive group (Z β) The substance of group.
As such adherend, glass, inorganic oxide, silicone resin etc. can be enumerated.
In addition, also will can include and reactive base by implementing to be surface-treated even if being free of these ingredients on the surface Group (Z β) has the layer setting of reactive group on the surface, to be used as adherend.
In the manufacturing method of laminated body of the invention, preferably make molecular adhesion oxidant layer and adherend sufficiently closely sealed.By molecule Temperature T when adhesive layer is crimped on adherendp(DEG C) is not particularly limited, and preferably satisfies following formula (I)s.
[mathematical expression 2]
Tg ≤Tp ≤ Ts+ H (I)
TgIndicate the glass transition temperature (DEG C) of resin layer, TsIndicate the softening point (DEG C) of resin layer.H is 40.
In above-mentioned formula (I), the value of H is preferably 30, more preferably 20, further preferably 0.
Pressure when crimping is usually 0.1 ~ 3.0MPa, preferably 0.5 ~ 1.5MPa.
In addition, the temperature T when crimping of at least one of resin layer or adherendpYoung's modulus under (DEG C) is preferably 1×106~1×109Pa, more preferably 1 × 107~9×108Pa, further preferably 1 × 108~8×108Pa。
By the way that molecular adhesion oxidant layer is crimped on adherend under conditions of meeting these important documents, molecular adhesion can be made Oxidant layer is sufficiently closely sealed with adherend.
Embodiment
Hereinafter, enumerating embodiment, present invention be described in more detail.But the present invention be not defined in any form it is following Embodiment.
Part and % in each example are quality criteria in case of no particular description.
[Production Example 1]
To tensionless winkler foundation polyethylene terephthalate sheet material (280 μm of Teijin Ltd's system, thickness), pass through corona treatment (letter photoelectricity gas measures Co. Ltd. system, product name " U ロ Na ス キ ャ ナ ー ASA-4 ", output voltage；9kV (surface electricity Pressure), stimulating frequency: 20kHz) carry out corona irradiation, obtain resin layer (1).
[Production Example 2]
According to the method recorded in No. WO2012/046651, obtain containing 6- (3- triethoxysilylpropyltetrasulfide) amino -1, Molecular adhesion agent solution (the 1) (solvent: ethyl alcohol, dense of 3,5- triazine -2,4- diazido (previously described formula (10) compound represented) Spend 0.1g/L).
[Production Example 3]
By 100 parts of polyisobutene system resin (BASF AG's system, product name " OppanolB50 ", matter average molecular weight 340,000), gather it is different 10 parts of butylene system resin (BASF AG's system, product name " OppanolB30 ", matter average molecular weight 200,000), hydrogenated petroleum resin are (waste River chemical industry Co., Ltd., product name " ア Le U Application P-125 ", 125 DEG C of softening point) 20 parts and toluene mixing, preparation gather different Butylene system resin solution (solvent: toluene, concentration 20%).
To polyethylene terephthalate film (eastern レ Co. Ltd. system, product name " Le ミ ラ ー ", the thickness in addition prepared 75 μm of degree), by corona treatment, (letter photoelectricity gas measures Co. Ltd. system, product name " U ロ Na ス キ ャ ナ ー ASA- 4 ", output voltage；9kV (surface voltage), stimulating frequency: 20kHz) carry out corona irradiation.
Then, multiple straight to be formed on the surface for having carried out corona irradiation of the polyethylene terephthalate film 500 μm of diameter, height 50 μm columned protrusion mode, it is molten that above-mentioned polyisobutene system resin is coated with by screen process press Liquid then dries it 2 minutes at 100 DEG C, and the gross area for obtaining protrusion is whole 10% protective film (1).
[Production Example 4]
In Production Example 3, change the density of columned protrusion, in addition to this, in a manner of identical with Production Example 3, obtains protrusion The gross area be whole 20% protective film (2).
[Production Example 5]
In the single side of polyethylene terephthalate film (eastern レ Co. Ltd. system, product name " Le ミ ラ ー ", 75 μm of thickness) On, along the direction parallel with width direction implement spacing be 200 μm, line width is 40 μm, highly be 50 μm striated pressure Flower processing.
Then, on the surface for having carried out embossing processing of the polyethylene terephthalate film, coating silicone-based stripping It is from agent, gained film is 30 seconds dry at 100 DEG C, further use ultraviolet lamp (ヘ レ ウ ス Co. Ltd. system, Product name " 10 MARK II of ラ イ ト Ha ン マ ー ", light source: mercury vapor lamp), ultraviolet light irradiation, shape are carried out under conditions of following At the peeling agent layer with a thickness of 0.1 μm, protective film (3) are obtained.In protective film (3), the gross area of protrusion is 15% on the whole.
(ultraviolet light irradiation condition)
Ultraviolet light irradiation condition is set as illumination 84mW/cm2, light quantity 100mJ/cm2, the illumination and light quantity use illumination quantometer (EIT corporation, product name " UV Power Puck II ") measures the illumination and light quantity in the region of UVC.
[Production Example 6]
In Production Example 3, polyisobutene system resin solution is coated in the whole face of polyethylene terephthalate film, except this it Outside, in a manner of identical with Production Example 3, protective film (4) are obtained.
In each embodiment and comparative example, as the forming material of each layer, product below etc. is used.
< resin layer >
Resin layer (1): surface treated resin film obtained in Production Example 1
< molecular adhesion agent solution >
Molecular adhesion agent solution (1): the solution prepared in Production Example 2
< protective film >
Protective film (1): protective film obtained in Production Example 3
Protective film (2): protective film obtained in Production Example 4
Protective film (3): protective film obtained in Production Example 5
Protective film (4): protective film obtained in Production Example 6
Protective film (5): stripping film (リ Application テ ッ Network Co. Ltd. system, product name " SP-PET381130 ", in poly- pair of 38 μm of thickness Silicone-based remover is laminated on ethylene terephthalate film).
[embodiment 1]
On resin layer (1), by infusion process by molecular adhesion agent solution (1) dip coated 5 seconds, by gained film at 100 DEG C Lower drying 30 seconds.
Then, using ultraviolet lamp (ヘ レ ウ ス Co. Ltd. system, product name " ラ イ ト Ha ン マ ー 10 MARK II ", light source: mercury vapor lamp), ultraviolet light is irradiated to the film, processing is thus fixed, obtains by resin layer (1) and divides The laminated body of sub- adhesive layer composition.
It should be noted that ultraviolet light irradiation condition is set as illumination 84mW/cm2, light quantity 29mJ/cm2, the illumination and light quantity use Illumination quantometer (EIT corporation, product name " UV Power Puck II ") and the illumination and light quantity for measuring the region of UVC.
Then, in the molecular adhesion oxidant layer of gained laminated body, overlapping protection film (1) obtains adhesive sheet.
[embodiment 2 ~ 3, comparative example 1 ~ 2]
As resin layer, molecular adhesion agent solution, protective film, using substance described in table 1, in addition to this, with 1 phase of embodiment Same mode, obtains adhesive sheet.
[evaluation of residual adhesive strength]
In the adhesive sheet made in embodiment and comparative example, apply the pressure of 0.5MPa to in-plane, stands 3 days.Then, After adhesive sheet is cut into vertical 25mm × horizontal 300mm size, the protective film is removed, makes exposed molecular adhesion oxidant layer and glass Contact, it is suppressed 10 minutes under conditions of 160 DEG C, 0.85MPa, the sample of production residual determining bonding strength.
After the sample is stood 24 hours in the environment of 23 DEG C, 50%RH (relative humidity), it is based on JIS Z0237: 2000, the bonding force of each adhesive sheet is measured under tensile speed 300mm/ minutes by 180 ° of stripping methods.
Sample obtained from not set protective film is directly suppressed with glass contact after forming molecular adhesion oxidant layer When bonding force is set as 100, the bonding force of embodiment and comparative example is calculated as residual adhesive strength.As a result shown in table 1.
[table 1]
It is as follows according to table 1.
It in the adhesive sheet obtained in embodiment 1 ~ 3, has manufactured after 24 hours, it may have sufficient bonding force.
On the other hand, using compared with not having the protective film of protrusion on the surface of molecular adhesion oxidant layer contact side In example 1,2, bonding force is significantly reduced.

Claims (18)

1. adhesive sheet is to press the resin layer comprising resin (S), molecular adhesion oxidant layer and protective film comprising molecular adhesion agent Obtained from sequence is directly laminated,
The molecular adhesion agent has at least one kind of in amino, azido, sulfydryl, isocyanate group, urea groups and epoxy group Reactive group (Z α) and at least one kind of in silanol group and the group for generating silanol group by hydrolysis Reactive group (Z β),
Aforementioned resin (S) has the reactivity part that chemical bond can be formed with the reactive group (Z α) of previous molecular bonding agent Structure (Z γ),
Young's modulus at 23 DEG C of aforementioned protective film is 1 × 107Pa or more.
2. adhesive sheet according to claim 1, which is characterized in that previous molecular adhesive layer passes through previous molecular bonding agent The chemical bond of reactivity part structure (Z γ) possessed by possessed reactive group (Z α) and aforementioned resin (S) and will before Molecular adhesion agent is stated chemically to be fixed on aforementioned resin layer.
3. adhesive sheet according to claim 1 or 2, wherein reactive group possessed by previous molecular bonding agent (Z α) Be it is at least one kind of in amino, sulfydryl, isocyanate group, urea groups and epoxy group,
Reactivity part structure possessed by aforementioned resin (S) (Z γ) be in hydroxyl, carboxyl, aldehyde radical and amino at least 1 kind.
4. adhesive sheet according to claim 1 or 2, wherein reactive group possessed by previous molecular bonding agent (Z α) It is azido,
Reactivity part structure possessed by aforementioned resin (S) (Z γ) is selected from carbon-to-carbon singly-bound, carbon-to-carbon double bond and carbon-hydrogen list It is at least one kind of in key.
5. adhesive sheet described according to claim 1 ~ any one of 4, wherein previous molecular bonding agent is shown in following formula (1) Compound,
[changing 1]
R1Indicate reactive group (Z α) or tool in amino, azido, sulfydryl, isocyanate group, urea groups and epoxy group There is 1 valence group (wherein, amino, azido, sulfydryl, isocyanate group, urea groups and the ring of 1 the above reactive group Except oxygroup), A indicates that the organic group of divalent, X indicate that the alkoxy or halogen atom of hydroxyl, carbon atom number 1 ~ 10, Y indicate carbon The alkyl of atomicity 1 ~ 20；A indicates 1 ~ 3 integer.
6. adhesive sheet described according to claim 1 ~ any one of 5, wherein previous molecular adhesive layer with a thickness of 200nm Below.
7. adhesive sheet described according to claim 1 ~ any one of 6, wherein aforementioned protective film is contacted with molecular adhesion oxidant layer The surface roughness (Ra) on the surface of side is 0.1 ~ 2.0 μm.
8. adhesive sheet described according to claim 1 ~ any one of 7, which is characterized in that aforementioned protective film, which does not have, is selected from silanol It base and is generated by hydrolysis any in the reactive group (Z β) in the group of silanol group.
9. adhesive sheet described according to claim 1 ~ any one of 8, wherein aforementioned protective film is the film of hydrocarbon system resin.
10. adhesive sheet according to claim 9, wherein aforementioned hydrocarbon system resin is selected from polyethylene, polypropylene, poly- (4- first Base -1- amylene), with carbon atom number 4 ~ 10 alicyclic structure polycyclic alkene in it is at least one kind of.
11. adhesive sheet described according to claim 1 ~ any one of 10, which is characterized in that at 23 DEG C of aforementioned resin (S) Young's modulus is 1 × 108~1×1010Pa。
12. adhesive sheet described according to claim 1 ~ any one of 11, wherein only have on the unilateral side of aforementioned resin layer and divide Sub- adhesive layer.
13. adhesive sheet described according to claim 1 ~ any one of 11, wherein have molecule on the two sides of aforementioned resin layer Adhesive layer.
14. adhesive sheet described according to claim 1 ~ any one of 13, further has supporter.
15. adhesive sheet described according to claim 1 ~ any one of 14 passes through the manufacture of the adhesive sheet with following step Method and obtain: previous molecular adhesive layer is formed on aforementioned resin layer, then, on being formed by molecular adhesion oxidant layer weight Prestack states protective film.
16. the manufacturing method with resin layer/molecular adhesion oxidant layer/adherend layer structure laminated body, which is characterized in that stripping From the protective film for constituting adhesive sheet described in any one of claim 1 ~ 15, exposed molecular adhesion oxidant layer is crimped on and is glued On object.
17. the manufacturing method of laminated body according to claim 16, wherein the temperature Tp (DEG C) when crimping meets following formula (I),
[mathematical expression 1]
Tg ≤Tp ≤ Ts+ H (I)
TgIndicate the glass transition temperature (DEG C) of resin layer, TsIndicate the softening point (DEG C) of resin layer；H is 40.
18. the manufacturing method of laminated body according to claim 16 or 17, wherein in resin layer or adherend at least The Young's modulus under temperature Tp (DEG C) when the crimping of one is 1 × 106~1×109Pa。
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WO2018181518A1 (en) 2018-10-04

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