CN105745293A - Double-sided adhesive sheet and method for producing double-sided adhesive sheet - Google Patents

Double-sided adhesive sheet and method for producing double-sided adhesive sheet Download PDF

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Publication number
CN105745293A
CN105745293A CN201480063116.8A CN201480063116A CN105745293A CN 105745293 A CN105745293 A CN 105745293A CN 201480063116 A CN201480063116 A CN 201480063116A CN 105745293 A CN105745293 A CN 105745293A
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CN
China
Prior art keywords
composition
adhesion
adhesive sheet
resin
silyl groups
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Pending
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CN201480063116.8A
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Chinese (zh)
Inventor
山口征太郎
大高翔
宫田壮
杉崎俊夫
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Lintec Corp
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Lintec Corp
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Publication of CN105745293A publication Critical patent/CN105745293A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/02—Polyalkylene oxides
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/02—Polyureas
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers
    • 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/10—Block or graft copolymers containing polysiloxane sequences
    • C09J183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
    • 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
    • C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
    • 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
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • 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
    • 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
    • C09J2475/00—Presence of polyurethane

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

Provided are: a double-sided adhesive sheet which can exhibit good peeling properties under a constant load even when an adhesive layer therein has relatively high coagulation power; and a double-sided adhesive sheet production method which enables the stable production of the double-sided adhesive sheet. A double-sided adhesive sheet which comprises a base material and adhesive agent layers each formed from a cured product of an adhesive agent composition and respectively provided on both surfaces of the base material, wherein the adhesive agent composition comprises at least a component (A) that is a silyl-terminal polymer and a component (B) that is an adhesiveness-imparting resin, the component (A), i.e., the silyl-terminal polymer, has a specific hydrolysable silyl group at each end of the main chain thereof, the component (B), i.e., the adhesiveness-imparting resin, contains a fully hydrogenated terpenephenol-type resin and is contained in an amount falling within a specified range relative to the amount of the component (A), i.e., the silyl-terminal polymer, and the maximum value of the loss tangent (tan[sigma]) which is determined by the dynamic viscoelasticity measurement (frequency: 1 Hz) of the adhesive agent layer is a value falling within a specified range.

Description

The manufacture method of two sides adhesive sheet and two sides adhesive sheet
Technical field
The present invention relates to two sides adhesive sheet and the manufacture method of two sides adhesive sheet.Even if particularly relate to adhering agent layer have relatively high cohesion when, still can obtain the two sides adhesive sheet of good constant load peel property and the manufacture method of this two sides adhesive sheet.
Background technology
In the past, adhesive sheet can be easily attached at by the advantage of adhesion by pressing owing to having, and the information widely that is therefore applied to shows with in label to many fields such as electronic material application.It addition, arrange the two sides adhesion zone of adhering agent layer on base material two sides owing to operability is good and shows the adherence of high reliability, therefore it is applied to household appliances, automobile, OA equipment etc..
Therefore, for such two sides adhesive sheet, then except requiring the adhesion strength required by usual adhesive sheet, also require on adhesive tape stationary plane through long-time load minimal stress, when namely applying so-called underload, if requiring to start to peel off, directly peeling off acceleration or producing the characteristic that the situation of skew is few, namely requiring that there is good constant load peel property.
It is therefoie, for example, in order to improve anti-resilience, it has been suggested that there is the two sides adhesion zone (such as, patent documentation 1) of the constant load peel property with regulation.
Namely, Patent Document 1 discloses a kind of two sides adhesion zone, it is the two sides adhesion zone for the display panels seized on both sides by the arms by flexible printed circuit substrate and backlight frame are fixed adhesion, and its maximum with the loss angle tangent (tan δ) under frequency of vibration 1Hz is present in the temperature province of-40～-22 DEG C and gel fraction is the adhering agent layer of 15～45%.
On the other hand, propose there is the adhesive sheet with excellent adhesion strength, although it is especially not to improve the technical scheme for the purpose of constant load peel property, but it is characterized in that the adhesion agent composition (such as, patent documentation 2) using the terminal silyl groups polymer containing regulation as host.
Namely, Patent Document 2 discloses a kind of adhesive sheet, it is characterized in that, main chain will be evenly mixed in or side chain will have amino-formate bond and/or urea key and terminal silyl groups polymer 100 mass parts containing the hydrolyzable silyl group shown in following formula (A) at end, adhesion gives resin 10～150 mass parts, select free boron trifluoride and/or its complex, after the sticker predecessor of fluoride compound 0.001～10 mass parts in the group that the alkali metal salt of fluorization agent and fluorine class mineral acid is constituted coats the surface of banding substrate or flat substrates, by making this terminal silyl groups polymer cure, so that this sticker predecessor forms adhering agent layer.
[chemical formula 1]
In formula (A), X represents hydroxyl or alkoxyl, and R represents the alkyl of carbon number 1～20, and n represents 0,1 or 2.
Prior art literature
Patent documentation
Patent documentation 1: No. 4645074 publications of Japanese Patent No. (claim of patent)
Patent documentation 2:WO2010/038715 publication (claim of patent)
Summary of the invention
The technical problem to be solved in the present invention
But, although the two sides adhesion zone disclosed in patent documentation 1 has the constant load peel property of certain degree, but owing to the gel fraction of adhering agent layer is relatively low, therefore when by two sides adhesion zone working into coil Spindle Status, then there will be the problem oozed out from the side with the time through sticker.
On the other hand, although the adhesive sheet disclosed in patent documentation 2 shows high adhesion strength, but owing to itself and non-selected suitable adhesion give resin, and do not take into account loss angle tangent, consequently found that there is the problem being difficult to obtain the constant load peel property required by two-sided tape.
Therefore, the present inventor etc. are in view of the foregoing, through meticulous effort, find the terminal silyl groups polymer relative to regulation, add the adhesion of regulation with the adding proportion of regulation and give resin, and to make the maximum of loss angle tangent be the value in prescribed limit, then can balance the adhesion strength and cohesiveness that improve adhesion agent composition, it is thus possible to obtain good constant load peel property, and then complete the present invention.
Even if that is, it is an object of the invention to provide a kind of adhering agent layer have relatively high cohesion when, still can obtain the two sides adhesive sheet of good constant load peel property and the manufacture method of this two sides adhesive sheet.
Solve the technological means of technical problem
According to the present invention, it is possible to provide a kind of two sides adhesive sheet such that it is able to solve above-mentioned technical problem；nullDescribed two sides adhesive sheet，It it is the two sides adhesive sheet possessing the adhering agent layer being made up of the solidfied material of adhesion agent composition on the two sides of base material，It is characterized in that，The adhesion agent composition of at least one adhering agent layer is including at least the terminal silyl groups polymer as (A) composition、Adhesion as (B) composition gives resin，Wherein the terminal silyl groups polymer as (A) composition is to have polyoxy alkylidene (polyoxyalkylene) structure in main chain、And there is amino-formate bond and urea key or any one in them on partial skeleton or side chain、And at two ends of main chain, there is the hydrolyzable silyl group shown in following formula (1)，(B) the adhesion imparting resin of composition comprises complete hydriding terpene phenolic resin，And relative to terminal silyl groups polymer 100 weight portion of (A) composition，Making the addition that adhesion gives resin is the value within the scope of 70～140 weight portions，And，The maximum by the loss angle tangent (tan δ) of Measurement of Dynamic Viscoelasticity (frequency: 1Hz) gained making adhering agent layer is the value within the scope of-10～15 DEG C.
[chemical formula 2]
In formula (1), X1And X2Separate and be hydroxyl or alkoxyl, R is the alkyl of carbon number 1～20.
Namely, the two sides adhesive sheet of the present invention contains the terminal silyl groups polymer of regulation as host due to the adhesion agent composition constituting adhering agent layer, and the adhesion containing regulation gives resin and gives resin as adhesion, therefore by the synergism between them, the adhesion strength of excellence can be played.
It addition, the two sides adhesive sheet of the present invention, be there is by the adhering agent layer of adhesion agent composition the maximum of the loss angle tangent of regulation, therefore, it is possible to have the constant load peel property of excellence.
Therefore, for attaching fixing component or part etc., even if apply peel stress for a long time, the skew being not likely to produce these components etc. or the characteristic peeled off can be given full play to because of two sides adhesive sheet such that it is able to obtain the adhesion reliability of excellence.
Further, since the terminal silyl groups polymer of (A) composition has poly (oxyalkylene) based structures in main chain, therefore, it is possible to the adhesion agent composition constituting adhering agent layer obtained to be given the flexibility of appropriateness.
And, owing to there is the hydrolyzable silyl group shown in formula (1) at two ends of main chain, therefore (A) composition crosslink density each other is adjusted to suitable scope such that it is able to be easier to regulate the balance between adhesion strength and the cohesiveness in the adhesion agent composition after solidifying.
nullAdditionally，Another embodiment of the present invention is a kind of two sides adhesive sheet，It is not for comprise base material，And possess the two sides adhesive sheet of the adhering agent layer being made up of the solidfied material of adhesion agent composition，It is characterized in that，Adhesion agent composition gives resin including at least the terminal silyl groups polymer as (A) composition and the adhesion as (B) composition，Wherein the terminal silyl groups polymer of (A) composition has poly (oxyalkylene) based structures in main chain，And there is amino-formate bond and urea key or any one in them in partial skeleton or side chain，And two ends at main chain have the hydrolyzable silyl group shown in following formula (1)，(B) the adhesion imparting resin of composition comprises complete hydriding terpene phenolic resin，And relative to terminal silyl groups polymer 100 weight portion of (A) composition，Making the addition that adhesion gives resin is the value within the scope of 70～140 weight portions，And，The maximum by the loss angle tangent (tan δ) of Measurement of Dynamic Viscoelasticity (frequency: 1Hz) gained making adhering agent layer is the value within the scope of-10～15 DEG C.
[chemical formula 3]
In formula (1), X1And X2Separate and be hydroxyl or alkoxyl, R is the alkyl of carbon number 1～20.
That is, two sides adhesive sheet is not by comprising base material, even if being had in irregular situation on adhesion, still can flexibly follow its jog and being fixed.
Additionally, it is possible to the surface after attaching attaches emulsion sheet etc. further.
Therefore, the two sides adhesive sheet not comprising base material of the present invention attaches owing to easily can follow jog, therefore can give the implementation of excellence.
Additionally, when constituting the two sides adhesive sheet of the present invention, the total amount (100 weight %) of resin is given, it is preferable that making the addition that the adhesion of complete hydriding terpene phenols gives resin is the value within the scope of 30～100 weight % relative to the adhesion of (B) composition.
By this composition, it is possible to regulate the maximum of the loss angle tangent of the obtained adhesion agent composition constituting adhering agent layer such that it is able to obtain excellent constant load peel property.
Additionally, when constituting the two sides adhesive sheet of the present invention, preferred adhesive compositions contains the catalyst of the solidification of the terminal silyl groups polymer of promotion (A) composition as (C) composition, and simultaneously this catalyst time at least one in the group that aluminum class catalyst, titanium class catalyst, zirconium class catalyst, bismuth class catalyst and boron trifluoride class catalyst are constituted.
By this composition, (A) composition crosslink density each other can be easily controlled, and can be easier to regulate the balance between adhesion strength and the cohesiveness in the adhesion agent composition after solidifying.
It addition, when constituting the two sides adhesive sheet of the present invention, it is preferable that adhesion agent composition contains the silane coupler in the molecule with amino as (D) composition.
By this composition, the solidification of adhesion agent composition can be effectively facilitated.
It addition, when constituting the two sides adhesive sheet of the present invention, it is preferable that the gel fraction making the adhering agent layer measured by infusion process (solvent: ethyl acetate, temperature: 23 DEG C, time: 120 hours) is the value in 30～70% scopes.
By this composition, the cohesiveness of excellence can be played.
More specifically, though adhering agent layer have relatively high cohesion when, still can obtain good constant load peel property.
Additionally, another embodiment of the present invention is the manufacture method of a kind of two sides adhesive sheet, it is the manufacture method of the two sides adhesive sheet possessing the adhering agent layer being made up of the solidfied material of adhesion agent composition on the two sides of base material, it is characterized in that, containing following step (1)～(3):
(1) step of adhesion agent composition is prepared, this adhesion agent composition at least contains the terminal silyl groups polymer as (A) composition, adhesion as (B) composition gives resin, wherein, (A) the terminal silyl groups polymer system of composition has poly (oxyalkylene) based structures in main chain, and have in partial skeleton or side chain amino-formate bond and urea key or they in any one, and two ends at main chain have the hydrolyzable silyl group shown in following formula (1), (B) the adhesion imparting resin of composition contains complete hydriding terpene phenolic resin, and relative to terminal silyl groups polymer 100 weight portion of (A) composition, making the addition that adhesion gives resin is the value within the scope of 70～140 weight portions；
(2) by adhesion agent composition lamination step at least one face of base material；
(3) make adhesion agent composition solidify, simultaneously by adhering agent layer by the step of the Maximum constraint of the loss angle tangent (tan δ) of Measurement of Dynamic Viscoelasticity (frequency: 1Hz) gained value within the scope of-10～15 DEG C.
[chemical formula 4]
In formula (1), X1And X2Separate and be hydroxyl or alkoxyl, R is the alkyl of carbon number 1～20.
By this enforcement, the two sides adhesive sheet with excellent adhesion strength and constant load peel property can be manufactured efficiently.
More specifically, by so manufacturing two sides adhesive sheet, the maximum that can make the loss angle tangent of adhering agent layer is the value in prescribed limit.
Therefore, the two sides adhesive sheet of adhesion strength and the constant load peel property with excellence can stably be obtained.
Additionally, another embodiment of the present invention is the manufacture method of a kind of two sides adhesive sheet, it is not for comprising base material and possessing the manufacture method of two sides adhesive sheet of the adhering agent layer being made up of the solidfied material of adhesion agent composition, it is characterized in that, comprise following step (1)～(3):
(1) step of adhesion agent composition is prepared；This adhesion agent composition at least contains the terminal silyl groups polymer as (A) composition, adhesion as (B) composition gives resin, wherein, (A) the terminal silyl groups polymer of composition has poly (oxyalkylene) based structures in main chain, and there is amino-formate bond and urea key or any one in them in partial skeleton or side chain, and the end at main chain has the hydrolyzable silyl group shown in following formula (1), (B) the adhesion imparting resin of composition contains complete hydriding terpene phenolic resin, and relative to terminal silyl groups polymer 100 weight portion of (A) composition, making the addition that adhesion gives resin is the value within the scope of 70～140 weight portions；
(2) by adhesion agent composition lamination step on peeling base surface；
(3) make adhesion agent composition solidify to form adhering agent layer, and make acquisition adhering agent layer by the step that maximum is the value within the scope of-10～15 DEG C of the loss angle tangent (tan δ) of Measurement of Dynamic Viscoelasticity (frequency: 1Hz) gained.
[chemical formula 5]
In formula (1), X1And X2Separate and be hydroxyl or alkoxyl, R is the alkyl of carbon number 1～20.
By this enforcement step, the two sides adhesive sheet without base material of adhesion strength and the constant load peel property with excellence can be manufactured efficiently.
More specifically, even if when being absent from base material, by this adhesion agent composition of lamination on peeling base surface, it still is able to efficient manufacture the two sides adhesive sheet with excellent adhesion strength and constant load peel property.
Therefore, by so manufacturing two sides adhesive sheet, the maximum that namely can make the loss angle tangent of adhering agent layer is the value in prescribed limit.
Namely, it is possible to stably obtain adhesion strength and the balance excellence of constant load peel property and the two sides adhesive sheet without base material.
Accompanying drawing explanation
Fig. 1 (a)～(b) is for being respectively provide for illustrating the figure of the terminal silyl groups polymer of regulation.
Fig. 2 (a)～(b) is for being respectively provide for illustrating the figure of the FT-IR spectrogram of the adhesion imparting resin of regulation.
Fig. 3 is for providing for illustrating that the adhesion of regulation gives the figure of the addition of resin and the relation of the maximum of loss angle tangent.
Fig. 4 is for providing for illustrating that the adhesion of regulation gives the figure of the addition of resin and the relation of adhesion strength.
Fig. 5 is for providing for illustrating that the adhesion of regulation gives the figure of the addition of resin and the relation of constant load peel property.
Fig. 6 (a)～(c) is for being respectively provide for illustrating the figure of the embodiment of two sides adhesive sheet.
Fig. 7 (a)～(d) is for being respectively provide for illustrating another figure of the manufacture method of two sides adhesive sheet.
Detailed description of the invention
[the first embodiment]
nullEmbodiments of the present invention are a kind of two sides adhesive sheet，It is the two sides adhesive sheet possessing the adhering agent layer being made up of the solidfied material of adhesion agent composition on the two sides of base material，It is characterized in that，The adhesion agent composition of at least one adhering agent layer is including at least the terminal silyl groups polymer as (A) composition、Adhesion as (B) composition gives resin，Wherein the terminal silyl groups polymer of (A) composition has poly (oxyalkylene) based structures in main chain，And there is amino-formate bond and urea key or any one in them in partial skeleton or side chain，And two ends at main chain have the hydrolyzable silyl group shown in following formula (1)，(B) the adhesion imparting resin of composition contains complete hydriding terpene phenolic resin，And relative to terminal silyl groups polymer 100 weight portion of (A) composition，Making the addition that adhesion gives resin is the value within the scope of 70～140 weight portions，And，The maximum by the loss angle tangent (tan δ) of Measurement of Dynamic Viscoelasticity (frequency: 1Hz) gained making adhering agent layer is the value within the scope of-10～15 DEG C.
Hereinafter, aptly with reference to accompanying drawing, first embodiment of the present invention is specifically described.
[chemical formula 6]
In formula (1), X1And X2Separate and be hydroxyl or alkoxyl, R is the alkyl of carbon number 1～20.
1. adhering agent layer
The two sides adhesive sheet of the present invention, it is characterized in that, be made up of the adhesion agent composition specified, the adhesion agent composition of this regulation contain the regulation as (A) composition terminal silyl groups polymer, as (B) composition regulation adhesion give resin.
Hereinafter, each composition in this adhesion agent composition is illustrated.
(1) (A) composition: terminal silyl groups polymer
(1)-a kind
Terminal silyl groups polymer as (A) composition, it is characterized in that, main chain or side chain have amino-formate bond and urea key or any one in them, and at two ends of main chain, there is the hydrolyzable silyl group shown in above-mentioned formula (1) simultaneously.
Its reason is in that, if such (A) composition, then because of have 2 officials shown in formula (1) can water-disintegrable terminal silyl groups, therefore can be effectively formed three-dimensional net structure by (A) composition hydrolysis dehydrating condensation each other.
Therefore, resin combination is given by the adhesion with regulation, it is possible to play excellent adhesion strength, and the high reliability as two sides adhesive sheet can be represented.
Additionally, if such (A) composition, then owing to having the water-disintegrable terminal silyl groups of 2 officials' energy shown in formula (1), therefore, it is possible to the gel fraction of the adhesion agent composition after solidification is regulated the scope in regulation, thus the cohesiveness of excellence can be played.
Therefore, by the hardness of adhesion agent composition self, when making scroll-like relation state, can suppress to ooze out from the side through sticker with the time.
Therefore, by using the terminal silyl groups polymer specified as (A) composition, then the adhesion agent composition that adhesion strength is high with the balancing good of cohesiveness and bonding reliability it is obtained in that.
It addition, from the viewpoint of hydrolysis dehydration condensation, in formula (1), the carbon number of the alkyl shown in R preferably 1～12, more preferably 1～3.
It addition, in formula (1), X1Or X2When for alkoxyl, from the viewpoint of hydrolysis dehydration condensation, the carbon number of this alkoxyl preferably 1～12, more preferably 1～3.
(i) basic comprising
Then, the basic comprising of the terminal silyl groups polymer of the regulation as (A) composition is illustrated.
That is, terminal silyl groups polymer is made up of the skeleton part of the end section specified Yu regulation.
It addition, the concrete synthetic method about terminal silyl groups polymer illustrates in the third embodiment.
(ii) end section
First, the concrete structure of the end section 32 (32a, 32b) of the terminal silyl groups polymer 30 of the regulation shown in Fig. 1 (a) is such as shown in following formula (2)～(8) (end section-A～G).
[chemical formula 7]
In formula (2), R2And R3For the alkyl of carbon number 1～20, preferred carbon number 1～8, R, X1And X2Identical with formula (1), also identical in following formula (3)～(8).
[chemical formula 8]
[chemical formula 9]
[chemical formula 10]
[chemical formula 11]
[chemical formula 12]
[chemical formula 13]
In formula (8), X3For alkylidene, X4Organic group for carbon number 1～20.
That is, terminal silyl groups polymer is by having such end section, then can be formed the compositions more strong by the attaching of adhesion.
(iii) skeleton part
It addition, the skeleton of the main chain 12 of the terminal silyl groups polymer of the regulation shown in Fig. 1 (a) or side chain (not shown), it is characterized by polyoxy alkylidene.
Reason is in that, if polyoxy alkylidene, then the adhesion agent composition obtained can give the flexibility of appropriateness, and improve by the attaching of adhesion further.
It addition, as the concrete example of this polyoxy alkylidene, can enumerate such as polyoxypropylene or polyoxyethylene etc..
(iv) position of hydrolyzable silyl group
Additionally, (A) the terminal silyl groups polymer of the regulation of composition is such as shown in Fig. 1 (a), it is characterized in that, it is not have the hydrolyzable silyl group shown in formula (1) at side chain, and only has two terminal silyl groups polymer of the hydrolyzable silyl group shown in formula (1) at two ends of main chain.
Reason is in that, if this two terminal silyl groups polymer, (A) composition crosslink density each other is adjusted in suitable scope, and the balance of the adhesion strength of the adhesion agent composition after easily dimmable solidification and cohesiveness.
Additionally, contain single terminal silyl groups polymer only at single end of main chain with the hydrolyzable silyl group shown in formula (1) preferably as (A ') composition, and make its addition be the value within the scope of 0.1～30 weight portion relative to two terminal silyl groups polymer 100 weight portions.
Reason is in that, by two terminal silyl groups polymer are mixed single terminal silyl groups polymer with the scope of regulation, (A) composition crosslink density each other is adjusted to scope preferably, is more prone to the balance of adhesion strength and the cohesiveness regulating the adhesion agent composition after solidifying.
That is, if the addition of single terminal silyl groups polymer is the value less than 0.1 weight portion, then cause having the situation that cannot fully obtain its additive effect.On the other hand, if the addition of single terminal silyl groups polymer is the value more than 30 weight portions, then can cause that (A) composition crosslink density each other excessively reduces, and be difficult to obtain the situation of the gel fraction of regulation.
It is therefore preferable that relative to two terminal silyl groups polymer 100 weight portions, the addition making single terminal silyl groups polymer is the value within the scope of 0.5～10 weight portion, more preferably the value within the scope of 1～5 weight portion.
But, even if due to it has been acknowledged that when only using two terminal silyl groups polymer, also the adhesion agent composition that adhesion strength is excellent can be obtained, therefore when without especially desirable, consider from viewpoints such as the simplifications of manufacturing step, preferably do not mix single terminal silyl groups polymer, and only use two terminal silyl groups polymer.
(1)-2 weight average molecular weight
Additionally, it is preferred that the weight average molecular weight making the terminal silyl groups polymer of the regulation of (A) composition is the value in 1000～200,000 scopes.
Its reason is in that, if this weight average molecular weight is the value less than 1000, then has molecular structure and becomes close and cannot obtain sufficient adhesion strength, and viscosity becomes too low, the situation that when being coated with, by solution, the sheet carried out, processability is deteriorated.On the other hand, if this weight average molecular weight is the value more than 200,000, then substantially having and cause fitness of process to reduce because of viscosity increase etc., crosslink density excessively reduces, and is difficult to regulate the situation of the balance between adhesion strength and cohesiveness.
It is therefore preferable that the weight average molecular weight making the terminal silyl groups polymer of the regulation of (A) composition is the value in 1000～150,000 scopes, more preferably the value in 10,000～100,000 scopes.
It addition, when adding above-mentioned (A ') composition, the weight average molecular weight of (A ') composition is also identical with (A) composition situation.
(1)-3 addition
Additionally, it is preferred that relative to the total amount 100 weight % of the adhesion agent composition before solidifying, the addition making the terminal silyl groups polymer of the regulation of (A) composition is the value within the scope of 20～90 weight %.
Its reason is in that, if this addition is the value less than 20 weight %, then the absolute magnitude having (A) composition overall relative to adhesion agent composition excessively reduces, and is difficult to obtain the situation of abundant adhesion strength.On the other hand, if this addition is the value more than 90 weight %, then there is the absolute magnitude of (A) composition to become too much relative to adhesion agent composition entirety, and be difficult to obtain the situation of abundant adhesion strength.
It is therefore preferable that relative to the total amount 100 weight % of the adhesion agent composition before solidifying, the addition making the terminal silyl groups polymer of the regulation of (A) composition is the value within the scope of 25～85 weight %, more preferably the value within the scope of 30～80 weight %.
(2) (B) composition: adhesion gives resin
(2)-1 complete hydriding terpene phenolic resins
When constituting the adhesion agent composition of two sides adhesive sheet, it is characterized by be in that, the adhesion imparting resin as (B) composition contains complete hydriding terpene phenolic resin.
Its reason is in that, the adhesion agent composition of two sides adhesive sheet is by containing complete hydriding terpene phenolic resin, the glass transition temperature of easily dimmable adhering agent layer as then aftermentioned, even if the cohesiveness of adhesion agent composition is higher value, it is possible to obtain the constant load peel property of regulation.
At this, complete hydriding terpene phenolic resin is by terpene phenolic resinoid hydrogenates the resin obtained.
More specifically, terpene phenol resin has the double bond coming from terpenes and the aromatic ring double bond coming from phenols.
Therefore, in the present invention, complete hydriding terpene phenolic resin refers to the resin that two positions at terpenes position and phenol position completely or almost completely hydrogenate.
It addition, whether belong to complete hydriding terpene phenolic resin, the FT-IR spectrum by fourier-transform infrared light splitting luminance meter (FT-IR) gained as be described hereinafter can be used to judge.
Then, to the FT-IR spectrum using the complete hydriding terpene phenolic resin shown in Fig. 2 (b), specifically illustrate.
This, by make from methyl carbon-hydrogen link stretching vibration at about 2960cm-1Crest height when being 100, if come from phenol position aromatic series carbon-to-carbon double bond stretching vibration at 1625-1575cm-1Crest height less than 20%, then be considered as phenol position and completely or almost completely hydrogenate.
On the other hand, if the crest height coming from phenol position is more than 20%, then as shown in Fig. 2 (a), it is judged that for phenol position and terpenes position almost unhydrided non-hydrogenated terpene phenolic resinoid.
It addition, the method for hydrogenation or reaction formation are without particular determination, as complete hydriding terpene phenolic resin, for instance peace former chemistry (stock) system, NH etc. can be enumerated.
(2)-2 other adhesions give resin
It addition, as the some of (B) composition, it is preferable that contain other adhesions further and give resin.At this, adhesion imparting agent kind there is no particular determination, can illustrate at least one in low-molecular weight polymer such as the rosin based resins such as newtrex, newtrex ester, rosin derivative, polyterpene resin, aromatic modified terpene resin and hydride thereof, terpene phenol resin, coumarone-indene resin, aliphatic category petroleum resinoid, fragrance same clan's Petropols and hydride, aliphatic/aromatic copolymer Petropols, partial hydrogenation terpene phenolic resinoid, styrene or substituted phenylethylene etc..
Reason is in that, if these adhesions give resin, then will not hinder the interaction of above-mentioned complete hydriding terpene phenol and the terminal silyl groups polymer of the regulation as (A) composition, and can give excellent adhesion strength to adhesion agent composition.
(2)-3 softening points
Additionally, it is preferred that making the softening point that the adhesion of (B) composition gives resin is the value within the scope of 70～160 DEG C.
Reason is in that, if the softening point as the adhesion imparting resin of (B) composition is the value less than 70 DEG C, then causes the situation having adhering agent layer that attaching and the cohesiveness of base material are reduced.On the other hand, if this softening point is the value more than 160 DEG C, then cause the situation having the intermiscibility with other sticker compositions to reduce.
It is therefore preferable that make as in the scope that softening point is 90～150 DEG C of the adhesion imparting resin of (B) composition.
It addition, in the present invention, softening point is based on the JISK2531 value measured.
(2)-4 weight average molecular weight
Additionally, it is preferred that making the weight average molecular weight giving resin as the adhesion of (B) composition is the value in 300～5000 scopes.
Reason is in that, if the weight average molecular weight that the adhesion of (B) composition gives resin is the value less than 300, then has and causes that cohesiveness excessively reduces, when making scroll-like relation state, and the situation that sticker oozes out with time process.On the other hand, if weight average molecular weight is the value more than 5000, then the situation that cohesively excessively reduces.
It is therefore preferable that making the weight average molecular weight giving resin as the adhesion of (B) composition is the value in 500～3000 scopes.
(2)-5 additions
It addition, be characterised by, relative to terminal silyl groups polymer 100 weight portion of the regulation as (A) composition, make the value giving within the scope of addition not 70～140 weight portions of resin as the adhesion of (B) composition.
Reason is in that, by making the addition of (B) composition be the value within the scope of this, can obtain the adhesion agent composition of adhesion strength and the balancing good of cohesiveness.
That is, if this addition is the value less than 70 weight portions, then the absolute magnitude of overall relative to adhesion agent composition (B) composition is very few, causes there is the situation being difficult to obtain abundant adhesion strength.On the other hand, if this addition is more than the value of 140 weight portions, then the absolute magnitude of overall relative to adhesion agent composition (B) composition is too much, then cause having cohesiveness excessively to reduce, when making scroll-like relation state, the situation that sticker oozes out with time process.
Therefore, terminal silyl groups polymer 100 weight portion preferably with respect to (A) composition, it is the value within the scope of 75～130 weight portions that the adhesion making the regulation of (B) composition gives the addition of resin, it is more preferable to the value within the scope of 85～120 weight portions.
It addition, give the total amount (100 weight %) of resin relative to the adhesion of (B) composition, it is preferable that making the addition that the adhesion of complete hydriding terpene phenols gives resin is the value within the scope of 30～100 weight %.
Its reason is in that, is the value within the scope of this by making the addition that the adhesion of complete hydriding terpene phenols gives resin, even if to make the cohesiveness of adhesion agent composition be higher value, still can give the constant load peel property of excellence.
That is, if this addition is the value less than 30 weight %, then causes there is the glass transition temperature being difficult to regulate terminal silyl groups polymer, and be difficult to obtain the situation of abundant constant load peel property.
Therefore, the total amount (100 weight %) of resin is given relative to the adhesion as (B) composition, the adhesion of complete hydriding terpene phenols is preferably made to give the value in the scope that addition is 50～100 weight % of resin, more preferably the value within the scope of 70～100 weight %.
At this, the adhesion of regulation gives the relation of the addition of resin and the maximum of loss angle tangent to use Fig. 3 to illustrate.
That is, Fig. 3 has illustrated transverse axis represent the adhesion of regulation give the addition (weight portion) of resin, the longitudinal axis represent have using the adhesion agent composition that obtains as adhering agent layer two sides adhesive sheet by characteristic curve A and B of the maximum of the loss angle tangent (Tan δ) of Measurement of Dynamic Viscoelasticity (frequency: 1Hz) gained.
It addition, characteristic curve when characteristic curve A is use complete hydriding terpene phenols adhesion imparting resin, characteristic curve B is the characteristic curve using non-hydrogenated terpenes phenols to adhere when giving resin.
If it addition, observe the characteristic curve A using complete hydriding terpene phenolic resin, can learn that, compared with using the resinoid characteristic curve B of non-hydrogenated terpene phenolic, the Tan δ of adhering agent layer is higher value.
Therefore, due to the value that Tan δ is the glass transition temperature being equivalent to adhering agent layer, it is therefore to be understood that compared with using the resinoid situation of non-hydrogenated terpene phenolic, use and be easier to when complete hydriding terpene phenolic resin the glass transition temperature of adhering agent layer is set as higher value.
It addition, the assay method of the particular make-up of adhesion agent composition or Tan δ is recorded in an embodiment.
Then, the sticker of regulation gives the addition of resin and the relation of adhesion strength to use Fig. 4 to illustrate.
That is, Fig. 4 having illustrated, transverse axis represents that the adhesion of regulation gives the addition (weight portion) of resin, the longitudinal axis and represents have characteristic curve C and D as the adhesion strength of the two sides adhesive sheet of adhering agent layer of the adhesion agent composition that obtains.
It addition, characteristic curve when characteristic curve C is to use complete hydriding terpene phenols adhesion imparting resin, characteristic curve D is the characteristic curve using non-hydrogenated terpenes phenols to adhere when giving resin.
Additionally, be understood that by characteristic curve C and characteristic curve D when using complete hydriding terpene phenolic resin with use in the resinoid situation of non-hydrogenated terpene phenolic all with the increase of imparting resin content of adhering, adhesion strength is the trend of identical increase, and its difference is little.
It addition, the assay method of the particular make-up of adhesion agent composition or adhesion strength is recorded in an embodiment.
Then, the sticker of regulation gives the addition of resin and the relation of constant load peel property to use Fig. 5 to illustrate.
That is, Fig. 5 illustrate transverse axis represent the adhesion of regulation give the addition (weight portion) of resin, the longitudinal axis represent containing will the adhesion agent composition of acquisition as the characteristic curve E of the constant load peel property of the two sides adhesive sheet of adhering agent layer.
It addition, characteristic curve when characteristic curve E is to use the adhesion of complete hydriding terpene phenols to give resin, when its addition is 0 weight portion, begins to pass through 24 hours periods from mensuration, be completely exfoliated from SUS plate because of test film and drop, therefore not shown.
Further, if observing characteristic curve E, it will be appreciated that to the increase of the addition with complete hydriding terpene phenolic resin, constant load peel property rises, if addition is more than 50 weight portions, then the constant load peel property that regulation is above can stably be obtained.
On the other hand, using in the resinoid situation of non-hydrogenated terpene phenolic, beginning to pass through 24 hours periods from mensuration, be completely exfoliated from SUS plate because of test film and drop, thus not shown.
Accordingly, it is understood that adhesion gives resin when the complete hydriding terpene phenolic resin containing ormal weight by Fig. 3～Fig. 5, easily the Tan δ of adhering agent layer, i.e. glass transition temperature are adjusted to higher, and there is good adhesion strength, and constant load peel property can be improved.
On the other hand, it will be appreciated that under only using the resinoid situation of non-hydrogenated terpene phenolic, though adhesion strength can fully be obtained, but it is not easy to regulate the glass transition temperature of adhering agent layer, and constant load peel property is poor.
Hence, it will be appreciated that in order to improve the constant load peel property required by the adhesive sheet of two sides, it is important that make adhesion give the complete hydriding terpene phenolic resin that resin contains ormal weight.
It addition, the assay method of the particular make-up of adhesion agent composition or constant load peel property is recorded in an embodiment.
(3) (C) composition: catalyst
(3)-1 kinds
Additionally, when constituting in the two sides adhesive sheet of the present invention as the adhesion agent composition of adhering agent layer, adhesion agent composition contains the catalyst being used for promoting the solidification of the terminal silyl groups polymer of the regulation of (A) composition as (C) composition, and this catalyst is at least one in the group that constitutes of the free aluminum class catalyst of choosing, titanium class catalyst, zirconium class catalyst and boron trifluoride class catalyst simultaneously.
Its reason is in that, if such catalyst, the control of (A) composition crosslink density each other can be made to become easy, and can be easier to control the adhesion strength in the adhesion agent composition after solidifying and the balance between cohesiveness.
Additionally, as aluminum class catalyst, the alkoxide (alkoxide) of aluminum, aluminium chelate compound, aluminum chloride (III) are preferably used, as titanium class catalyst, the alkoxide of titanium, titanium chelate, titanium chloride (IV) are preferably used, as zirconium class catalyst, it is preferred to use the alkoxide of zirconium, zirconium chelate, zirconium chloride (IV), as boron trifluoride class catalyst, it is preferred to use the amine complex of boron trifluoride or alcohol complex.
(3)-2 additions
Additionally, it is preferred that terminal silyl groups polymer 100 weight portion of the regulation relative to (A) composition, the addition making the catalyst of (C) composition is the value within the scope of 0.001～10 weight portion.
Reason is in that, if this addition is the value less than 0.001 weight portion, then causes having catalyst action insufficient, the situation that the cohesiveness of adhesion agent composition excessively reduces.On the other hand, if this addition is the value more than 10 weight portions, then cause having catalytic action excessive, the situation that adhesion agent composition just first solidifies before coating base material.
Therefore, terminal silyl groups polymer 100 weight portion preferably with respect to the regulation of (A) composition, the addition making the catalyst of (C) composition is the value within the scope of 0.01～8 weight portion, it is particularly preferred to be the value within the scope of 0.05～5 weight portion.
(4) (D) composition: silane coupler
It addition, when constituting in the two sides adhesive sheet of the present invention as the adhesion agent composition of adhering agent layer, relative to 1 mole of (C) composition, it is preferable that adhesion agent composition contains the silane coupler with amino of more than 1 mole as (D) composition.
Reason is in that, has the silane coupler of amino by adding within the scope of this, can play the effect of the crosslinking coagent of terminal silyl groups polymer as regulation, and can regulate the cohesiveness of adhesion agent composition to optimum range more.
Accordingly, with respect to 1 mole of (C) composition, it is preferable that the addition making the silane coupler with amino of (D) composition is the value in 1～30 molar range, more preferably the value in 2～10 molar range.
Additionally, as the silane coupler with amino, can be suitable for using such as 3-TSL 8330, APTES, N-2-(amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-2-(amino-ethyl)-3-TSL 8330, N-2-(amino-ethyl)-APTES, N-phenyl-3-TSL 8330 etc..
(5) additive
Additionally, as in the adhesion agent composition of adhering agent layer in the two sides adhesive sheet of the present invention, as the composition outside above-mentioned, can also add and mix such as age resister, the dehydrant such as vinyl silane compound or calcium oxide, filler, conductive material, thermally conductive materials, plasticiser, anhydride silica, the thixotropic agent such as amide waxe, the diluent such as isoalkane, aluminium hydroxide, halogen fire retardant, phosphorus type flame retardant, the fire retardants such as silicone based flame retardant, organosilicon alkoxyl oligomer, the functional oligomerization things such as acrylic oligomer, pigment, titanate coupling agents, aluminum coupling agent, dryness wet goods.
Additionally, when adding these additives, although it is different according to the kind of additive, but it is added under the degree of effect of the present invention preferably in not undermine, terminal silyl groups polymer 100 weight portion relative to the regulation of (A) composition, its addition is preferably the value within the scope of 0.01～100 weight portion, it is more preferable to the value within the scope of 0.01～70 weight portion, it is particularly preferred to the value within the scope of 0.01～40 weight portion.
(6) gel fraction
It addition, when constituting in the two sides adhesive sheet of the present invention as the adhesion agent composition of adhering agent layer, it is preferable that the gel fraction of adhering agent layer is the value in 30～70% scopes.
Reason is in that, if the gel fraction of adhering agent layer is the value within the scope of this, can play the cohesiveness of excellence, when making scroll-like relation state, can suppress because with time process, adhering agent layer oozes out from the side.
That is, if the gel fraction of adhering agent layer is the value less than 30%, then cohesiveness is had too small, when working into coil shaft-like, the situation that adhering agent layer oozes out from the side with time process.
On the other hand, if the gel fraction of adhering agent layer is too high, then the situation that cannot obtain sufficient adhesion strength is had.
It is therefore preferable that the gel fraction making the adhering agent layer in adhesion agent composition is the value in 35～65% scopes, more preferably the value in 40～60% scopes.
Additionally, " gel fraction of adhering agent layer " refers to after adhesion agent composition being coated on base material or peeling off material, 23 DEG C, under 50%RH environment after 14 days Ageing Treatment (seasoning), using the adhesion agent composition (adhering agent layer) after this Ageing Treatment as measuring sample and passing through the gel fraction that infusion process measures.
It addition, the concrete assay method about gel fraction is then recorded in an embodiment.
(7) thickness
Additionally, it is preferred that the thickness making adhering agent layer is the value in 1～100 μ m, more preferably the value in 5～50 μ m.
Reason is in that, if the thickness of adhering agent layer is excessively thin, then has and cannot obtain the situations such as sufficient adhesiveness, on the contrary, if blocked up, then has the situation that residual solvent throws into question.
(8) form
Additionally, in the present invention, as shown in Fig. 6 (b), when only lamination is on the one side of base material for the adhering agent layer 40 being made up of the solidfied material of the above-mentioned adhesion agent composition specified, lamination adhering agent layer 50 on base material another side is then not particularly limited, but is preferably acrylic compounds sticker, polyesters sticker, urethane class sticker etc..
2. base material
It addition, the two sides adhesive sheet of the present invention is such as shown in Fig. 6 (a)～(b), it is preferable that have adhering agent layer 40,40 ' in the one or two sides of base material 2.
As this base material, it is preferable that the resin molding being such as made up of can be enumerated resins such as polyethylene, polypropylene, polyethylene terephthalate, PEN, polybutylene terephthalate (PBT), polyimides, Polyetherimide, polyether-ketone, polyether-ether-ketone, Merlon, polymethyl methacrylate, tri acetyl cellulose, polynorbornene, ethylene-vinylacetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, vinyl chloride, urethane acrylate, polyether sulfone, polyphenylene ether sulfone.
It addition, as the thickness of base material, there is no particular restriction, it is usually preferred to the value in 1～1,000 μ m, it is more preferable to the value in 10～100 μ m.
3. peeling base (stripping film)
It addition, the two sides adhesive sheet of the present invention is preferably in the mode of peeling base (stripping film) of fitting on the two sides of adhering agent layer.
Which is because the use with this adhering agent layer that manufactures of adhering agent layer is the reason carrying out in other places waiting, and needs only to carry the situation etc. of adhering agent layer.
Additionally, as this peeling base, can enumerate such as to polyester films such as polyethylene terephthalate, polybutylene terephthalate (PBT), PENs, or the remover such as the polyolefin film such as polypropylene, polyethylene coating organic siliconresin and the peeling base of peel ply is set.
It addition, the thickness of this peeling base, it can be generally the value in 20～150 μ m.
It addition, by the difference that peeling force from adhering agent layer in 2 peeling base is arranged regulation, when peeling off the peeling base of low stripping force side, it is possible to prevent adhering agent layer from partly following.
[the second embodiment]
nullSecond embodiment is a kind of two sides adhesive sheet，It is not for comprise base material、And possess the two sides adhesive sheet of the adhering agent layer being made up of the solidfied material of adhesion agent composition，It is characterized in that，Adhesion agent composition at least contains the terminal silyl groups polymer as (A) composition、Adhesion as (B) composition gives resin，Wherein the terminal silyl groups polymer of (A) composition is to have poly (oxyalkylene) based structures in main chain，And there is amino-formate bond and urea key or any one in them at partial skeleton or side chain，And two ends at main chain have the hydrolyzable silyl group shown in following formula (1)，Adhesion imparting resin as (B) composition contains complete hydriding terpene phenolic resin，And relative to terminal silyl groups polymer 100 weight portion of (A) composition，Making the addition that adhesion gives resin is the value within the scope of 70～140 weight portions，And，The maximum by the loss angle tangent (tan δ) of Measurement of Dynamic Viscoelasticity (frequency: 1Hz) gained of adhering agent layer is the value within the scope of-10～15 DEG C.
[chemical formula 14]
In formula (1), X1And X2Separate and be hydroxyl or alkoxyl, R is the alkyl of carbon number 1～20.
That is, by such composition, even if when being had concavo-convex by adhesion, still can flexibly follow this jog and be fixed.
It addition, further emulsion sheet etc. can be attached on the surface after attaching.
It addition, the two sides adhesive sheet not comprising base material of the present invention is such as shown in Fig. 6 (c), it is preferable that mode is lamination adhering agent layer 40 on the surface of peeling base 8.
Additionally, it is possible to be made in the way of 2 pieces of peeling base above-mentioned adhering agent layers of clamping form.
It addition, the content except base material, identical with the composition of the two sides adhesive sheet comprising base material in the first embodiment, therefore omit it and specifically record.
[the 3rd embodiment]
3rd embodiment is the manufacture method of a kind of two sides adhesive sheet, it is the manufacture method of the two sides adhesive sheet possessing the adhering agent layer being made up of the solidfied material of adhesion agent composition on the two sides of base material, it is characterized in that, comprise following step (1)～(3):
(1) step of adhesion agent composition is prepared；This adhesion agent composition at least contains the terminal silyl groups polymer as (A) composition, adhesion as (B) composition gives resin, wherein the terminal silyl groups polymer of (A) composition has poly (oxyalkylene) based structures in main chain, and there is amino-formate bond and urea key or any one in them at partial skeleton or side chain, and two ends of main chain have the hydrolyzable silyl group shown in formula (1), (B) the adhesion imparting resin of composition contains complete hydriding terpene phenolic resin, and relative to terminal silyl groups polymer 100 weight portion of (A) composition, making the addition that adhesion gives resin is the value within the scope of 70～140 weight portions；
(2) by adhesion agent composition lamination step at least one face of base material；
(3) make adhesion agent composition solidify, and the same maximum by the loss angle tangent (tan δ) of Measurement of Dynamic Viscoelasticity (frequency: 1Hz) gained making adhering agent layer is the value within the scope of-10～15 DEG C.
Hereinafter, about the step manufacturing adhesive sheet, with reference to accompanying drawing, and by with the difference of content recorded in the first embodiment centered by, illustrate the manufacture method of two sides adhesive sheet.
[chemical formula 15]
In formula (1), X1And X2Separate and be hydroxyl or alkoxyl, R is the alkyl of carbon number 1～20.
(1) step (1) (preparation process of adhesion agent composition)
Step (1) is the step of the adhesion agent composition of the regulation that preparation comprises (A)～(B) composition.
Here, the synthesis example of the terminal silyl groups polymer 30 of the regulation of (A) composition has been shown in Fig. 1 (a).
First, the polymer backbone 10 at the end of molecular backbone 12 or side chain (not shown) with NCO 14 (14a, 14b) is prepared.
Then, prepare the single end at molecule and there is the active hydrogen-based 22 can reacted with NCO 14 (14a, 14b), and there is at another end of molecule the silication agent 20 of the hydrolyzable silyl group 24 shown in formula (1).
Then, after mixed polymer skeleton 10 and silication agent 20, for instance, under nitrogen environment, make it react 1 hour with 80 DEG C, the terminal silyl groups polymer 30 of regulation can be obtained.
Additionally, as shown in Fig. 1 (b), the terminal silyl groups polymer 30 of this regulation is by carrying out solidifying to form the three-dimensional net structure (polymer of 30 "), i.e. so-called moisture-curable via the cross-linking reaction of the hydrolysis (30 ') of the hydrolyzable silyl group shown in formula (1).
It addition, when synthesizing terminal silyl groups polymer, contrary with the situation of Fig. 1 (a), it is also possible to silication agent 20 has a NCO 14, and the active hydrogen-based 22 of polymer backbone 10.
It addition, the amino-formate bond being imported on the main chain of the terminal silyl groups polymer of regulation or side chain or the reactive hydrogen in urea key, illustrated in the first embodiment can be replaced by organic group.
Therefore, allophanic acid ester bond is also included within the category of amino-formate bond, and biuret linkage is also included within the category of urea key.
Secondly, it is preferable that as required (A) composition obtained is diluted with retarder thinner, under agitation add (B) composition, form uniform mixed liquor.
Then, preferably to the mixed liquor obtained, after adding (C) composition and (D) composition or other additives, it is stirred until uniformly, and add retarder thinner as required further to required viscosity, and obtain the solution of adhesion agent composition.
It addition, the details of other compositions and addition etc. are as described in above, therefore omitted.
(2) step (2) (application step of adhesion agent composition)
Step (2) for being coated on the step forming coating layer 4,4 ' on base material 2 as Suo Shi Fig. 7 (a) by adhesion agent composition.
Additionally, preferably as the method being coated with adhesion agent composition on base material 2, use such as stick coating method, scraper for coating (knifecoating) method, rolling method, scraper plate coating (bladecoating) method, die coating methods, gravure coating process etc., after coating is added with adhesion agent composition formation coating layer 4 (film) of solvent so that it is dry.
Now, it is preferable that the thickness of coating layer 4 is the value in 1～100 μ m, the more preferably value in 5～50 μ m.
Reason is in that, if the thickness of coating layer 4 is excessively thin, then has the situation that cannot obtain abundant adhesiveness etc., on the contrary, if blocked up, then has the situation that residual solvent throws into question.
It addition, as drying condition, it is usually preferred at 50～150 DEG C within the scope of 10 seconds～10 minutes.
It addition, the record that the details of base material is such as above, therefore omitted.
(3) step (3) (curing schedule of coating layer)
Step (3) is that the coating layer 4,4 ' making adhesion agent composition solidifies and makes coating layer 4,4 ' form the step of adhering agent layer 40,40 '.
That is, as shown in Fig. 7 (b)～(c), it is preferable that to being on the surface of coating layer 4,4 ' of drying regime on base material 2, to make it solidify under the state of lamination peeling base 8,8 ', thus forming adhering agent layer 40,40 '.
Or, it is possible to so that the coating layer 4,4 ' of the adhesion agent composition having been coated with on base material 2 solidifies in advance, formed after adhering agent layer 40,40 ', then lamination is to peeling base 8,8 '.
Or, it is also possible to last also not lamination peeling base 8.
It addition, the solidification of the coating layer 4 of adhesion agent composition is to be carried out by above-mentioned drying steps and Ageing Treatment step.
As the condition of this Ageing Treatment step, never the coating layer 4 of adhesion agent composition or base material 2 are caused damage, and the viewpoint making the coating layer 4 of adhesion agent composition uniform curing considers, it is preferable that making temperature is 20～50 DEG C, more preferably 23～30 DEG C.
It addition, as humidity, it is preferred to 30～75%RH, more preferably 45～65%RH.
Additionally, as the two sides finally obtained adhesive sheet 100 is fitted in by the method for adhesion 200, as shown in Fig. 7 (c)～(d), preferably first peel off lamination stripping film 8 on adhering agent layer 40, then, adhesion 200 is fitted by making the surface of the adhering agent layer 40 exposed be attached to.
(4) by adhesion
It addition, as the two sides adhesive sheet of the present invention use object by the kind of adhesion without particular determination, but preferably with resins such as polycarbonate resin, plexiglass, polystyrene resin, ABS resin etc. or glass for by adhesion.
[the 4th embodiment]
4th embodiment is the manufacture method of a kind of two sides adhesive sheet, it is not comprise base material and possess the manufacture method of two sides adhesive sheet of the adhering agent layer being made up of the solidfied material of adhesion agent composition, it is characterized in that, comprise following step (1)～(3):
(1) step of adhesion agent composition is prepared；This adhesion agent composition is including at least the terminal silyl groups polymer as (A) composition, adhesion as (B) composition gives resin, wherein the terminal silyl groups polymer of (A) composition has poly (oxyalkylene) based structures in main chain, and there is amino-formate bond and urea key or any one in them on partial skeleton or side chain, and two ends at main chain have the hydrolyzable silyl group shown in following formula (1), (B) the adhesion imparting resin of composition contains complete hydriding terpene phenolic resin, and relative to terminal silyl groups polymer 100 weight portion of (A) composition, making the addition that adhesion gives resin is the value within the scope of 70～140 weight portions；
(2) by adhesion agent composition lamination step on the surface of peeling base；
(3) make adhesion agent composition solidify to form adhering agent layer, and make the adhering agent layer obtained by the step that maximum is the value within the scope of-10～15 DEG C of the loss angle tangent (tan δ) of Measurement of Dynamic Viscoelasticity (frequency: 1Hz) gained；
[chemical formula 16]
In formula (1), X1And X2Separate and be hydroxyl or alkoxyl, R is the alkyl of carbon number 1～20.
That is, by such manufacture, even if when not comprising base material, the two sides adhesive sheet of regulation still can effectively be manufactured.
Additionally, in step (2), except adhesion agent composition being coated on the surface of peeling base 8 and form the step of coating layer 4, other are identical with the manufacture method of the two sides adhesive sheet comprising base material of the 3rd embodiment, therefore omit it and specifically record.
Embodiment
Hereinafter, by embodiment etc., the present invention is specifically described, but the scope of the present invention is not exposed to the restriction of these embodiments.
[embodiment 1]
1. the preparation of adhesion agent composition
(1) preparation of silication agent
In reaction vessel, add N-amino-ethyl-gamma-amino hydroxypropyl methyl dimethoxysilane 206 weight portion, acrylic acid methyl ester. 172 weight portion, stir 10 hours with 80 DEG C under nitrogen environment, obtain the silane compound as silication agent.
(2) preparation of carbamate prepolymer
Polyoxypropylene glycol (Asahi Glass (stock) system, PMLS4015, weight average molecular weight 15 is added in another reaction vessel, 000) 1000 weight portions, isophorone diisocyanate 24.6 weight portion (NCO/OH ratio=1.7), dibutyl tin dilaurate 0.05 weight portion, it is made to react 7 hours with 85 DEG C under nitrogen environment, it is thus achieved that carbamate prepolymer.
(3) synthesis of terminal silyl groups polymer
Then, add silane compound 42.1 weight portion as silication agent obtained relative to carbamate prepolymer 1000 weight portion obtained, make it react 1 hour with 80 DEG C under nitrogen environment, and obtain terminal silyl groups polymer.
Now, with the IR absorption (2265cm by NCO-1) disappearance situation and confirm reaction carrying out.
Additionally, obtained terminal silyl groups polymer, two ends as the polyoxypropylene (Polyoxypropylene) of main chain have the two terminal silyl groups polymer that weight average molecular weight is 40,000 of the end section shown in following formula (9).
It addition, by using N-amino-ethyl-gamma-amino hydroxypropyl methyl dimethoxysilane as the raw material of silication agent, and the terminal silyl groups polymer obtained is imported the terminal silyl groups of 2 officials' energy.
[chemical formula 17]
(4) mixing
Then, terminal silyl groups polymer 100 weight portion obtained adding ethyl acetate 100 weight portion as solvent, gives complete hydrogenated terpene phenol resin (pacifying former chemistry (stock) system, NH) 100 weight portions of resin as adhesion, stirring is until uniformly obtaining mixture.
Then, relative to terminal silyl groups polymer 100 weight portion comprised in obtained mixture, adding boron trifluoride MEA complex 0.12 weight portion as catalyst, 3-TSL 8330 (chemical company of SHIN-ETSU HANTOTAI system, KBM-903) 0.4 weight portion as silane coupler, stirring is until adhesion agent composition uniformly and before being solidified.
It addition, following, have the resin situation referred to as " NH " that above-mentioned adhesion given.
It addition, the FT-IR spectrum by the complete hydriding terpene phenol used is shown in Fig. 2 (b).
2. the coating of adhesion agent composition
Then, after adhesion agent composition before the solidification obtained is coated on the two sides of the polyester film (east beautiful (stock) system, LumilarT60#25) of thickness 25 μm by use scraper for coating method, within dry 1 minute at 100 DEG C, form the coating layer that thickness is 23 μm, and obtain two sides adhesive sheet.
Additionally, after similarly the adhesion agent composition before the solidification obtained is coated on the one side of the polyester film (east beautiful (stock) system, LumilarT50#188) of thickness 188 μm by use scraper for coating method, within dry 1 minute at 100 DEG C, form the coating layer that thickness is 23 μm, and obtain the one side adhesive sheet evaluated.
3. the Ageing Treatment of adhesion agent composition
Then, the laminate that the adhesion coating formed by the adhesion agent composition before solidifying obtained and base material (polyester film) are constituted, 23 DEG C, under the environment of 50%RH, place (Ageing Treatment) 14 days, the adhesion agent composition before solidification is made fully to solidify, and using coating layer as adhering agent layer, obtain two sides adhesive sheet and the evaluation one side adhesive sheet both of embodiment 1.
4. evaluate
(1) loss angle tangent (Tan δ)
According to following formula (10), the sticker obtained from the polyester film of the evaluation one side adhesive sheet removal thickness 188 μm obtained, namely, use dynamic spectrum analyzer RDS (II) (Rheometrics company system) the storage elastic modelling quantity measured and loss elastic modulus to calculate loss angle tangent under frequency 1Hz from through Wetted constructures step and the adhesion agent composition after solidifying, and to measure this loss angle tangent be temperature during maximum.The obtained results are shown in table 1.
Loss angle tangent (Tan δ)=loss elastic modulus/storage elastic modelling quantity (10)
(2) evaluation of adhesion strength
Measure the adhesion strength of the two sides adhesive sheet (two sides of base material is provided with adhering agent layer) obtained.
That is, from the two sides adhesive sheet obtained, cut out the test film of 25mm × 250mm, use the rubber rollers of 2kg, by the single-sided lamination of two sides adhesive sheet that cuts out on SUS#360 plate, after just laminating, be placed on 23 DEG C immediately, under the standard environment of 50%RH 24 hours.
Then, use cupping machine (Orientec (stock) system, Tensilon), in the way of peeling rate 300mm/ minute, peel angle 180 °, the two sides adhesive sheet after placing is peeled off, using the stripping loading that now measures as adhesion strength (N/25mm) from SUS#360 plate.Obtained result is shown in Table 1.
(3) evaluation of constant load peel property
Evaluate the constant load peel property of the two sides adhesive sheet (being provided with adhering agent layer on base material one side) obtained.
That is, cutting out the test film of 25mm × 100mm from the two sides adhesive sheet obtained, use the rubber rollers of 2kg, (area is 25mm × 50mm=1250mm to the 50mm started the end of the two sides adhesive sheet certainly cut out2) sticker aspect be fitted on SUS#600 plate, after just laminating, be placed on 23 DEG C immediately, under the standard environment of 50%RH 24 hours.
Then, by the test film after placement to be pasted with configuring in the way of downside of two sides adhesive sheet, the end of two sides adhesive sheet towards vertical (under) direction is plus the load of 200g, maintain this state after 24 hours, measure two sides adhesive sheet by from the distance (peel distance, mm) of SUS plate sur-face peeling.The obtained results are shown in table 1.
It addition, start to through 24 hours periods, the situation that test film is completely exfoliated from SUS plate and drops from measuring, it is recited as " dropping " in Table 1.
(4) evaluation of gel fraction
The gel fraction of the sticker that mensuration obtains from the polyester film of the one side adhesive sheet removal thickness 188 μm of the evaluation obtained, i.e. measure the gel fraction of the adhesion agent composition after solidifying through Wetted constructures step.
That is, 23 DEG C, under the environment of 50%RH, after sticker is immersed in ethyl acetate 120 hours, with 100 DEG C dry 30 minutes, the weight before and after dipping is substituted into following formula (11) and calculates gel fraction.The obtained results are shown in table 1.
Gel fraction (%)=(weight before weight/dipping after dipping) × 100 (11)
[embodiment 2]
In example 2, except when adjusting adhesion agent composition, being changed to beyond 90 weight portions by the addition that adhesion gives resin, other manufacture two sides adhesive sheet similarly to Example 1 and are evaluated.Obtained result is shown in Table 1.
[embodiment 3]
In embodiment 3, except when adjusting adhesion agent composition, being changed to beyond 80 weight portions by the addition that adhesion gives resin, other manufacture two sides adhesive sheet similarly to Example 1 and are evaluated.Obtained result is shown in Table 1.
[embodiment 4]
In example 4, except when adjusting adhesion agent composition, giving resin by adhesion and be changed to beyond complete hydriding terpene phenol (An Yuan chemical company system, NH) 50 weight portions and partial hydrogenation terpene phenolic (An Yuan chemical company system, TH130) 50 weight portions, other and embodiment 1 manufacture two sides adhesive sheet identically and are evaluated.Obtained result is shown in Table 1.
The resin situation referred to as " TH130 " that above-mentioned adhesion given is had it addition, following.
[embodiment 5]
In embodiment 5, except when adjusting adhesion agent composition, being changed to beyond 70 weight portions by the addition that adhesion gives resin, other manufacture two sides adhesive sheet similarly to Example 1 and are evaluated.Obtained result is shown in Table 1.
[comparative example 1]
In comparative example 1, except when adjusting adhesion agent composition, giving resin by adhesion and be changed to beyond partial hydrogenation terpene phenolic (An Yuan chemical company system, TH130), other manufacture two sides adhesive sheet similarly to Example 1 and are evaluated.Obtained result is shown in Table 1.
The resin situation referred to as " TH130 " that above-mentioned adhesion given is had it addition, following.
It addition, partial hydrogenation terpene phenolic is the compound that terpenes position is completely or nearly hydrogenated.
[comparative example 2]
In comparative example 2, except when adjusting adhesion agent composition, being changed to beyond 60 weight portions by the addition that adhesion gives resin, other manufacture two sides adhesive sheet similarly to Example 1 and are evaluated.Obtained result is shown in Table 1.
[comparative example 3]
In comparative example 3, except when adjusting adhesion agent composition, giving resin by adhesion and be changed to beyond non-hydrogenated terpene phenolic (An Yuan chemical company system, G125), other manufacture two sides adhesive sheet similarly to Example 1 and are evaluated.Obtained result is shown in Table 1.
The resin situation referred to as " G125 " that above-mentioned adhesion given is had it addition, following.
It addition, the FT-IR spectrum of the non-hydrogenated terpene phenolic used is shown in Fig. 2 (a).
[comparative example 4]
In comparative example 4, except being not added with adhesion imparting agent, other manufacture two sides adhesive sheet similarly to Example 1 and are evaluated.Obtained result is shown in Table 1.
[table 1]
Industrial applicibility
As previously discussed, according to the present invention, by the terminal silyl groups polymer to regulation, the adhesion adding regulation with the ratio of regulation gives resin, and, it is the value in prescribed limit by making the maximum by the loss angle tangent of Measurement of Dynamic Viscoelasticity gained of adhering agent layer, it is possible to increase the balance of the adhesion strength in adhesion agent composition and cohesiveness, and the constant load peel property of excellence can be obtained.
As a result, even if the cohesiveness of adhering agent layer is higher, owing to good constant load peel property can be played, therefore, it is possible to obtain excellent adhesion reliability.
Therefore, the two sides adhesive sheet of the present invention can be expected in household appliances, automobile, OA equipment etc. as the two sides adhesive sheet with high reliability.
Expect the laminating each other of the resin plate for the such as electronic equipment internal such as mobile phone or personal computer or the laminating of optical recording media, light magnetism record media, liquid crystal display, touch panel component especially.
Description of reference numerals
2: base material；4: coating layer；8,8 ': stripping film；10: polymer backbone；12: molecular backbone；14 (14a, 14b): NCO；20: silication agent；22: activity hydrogen-based；24: hydrolyzable silyl group；30,30 ', 30 ": terminal silyl groups polymer；32 (32a, 32b): terminal silyl groups polymer ends part；40,40 ': adhering agent layer；50: other adhering agent layers；100: two sides adhesive sheet；200: by adhesion.

Claims (8)

1. a two sides adhesive sheet, it is the two sides adhesive sheet possessing the adhering agent layer being made up of the solidfied material of adhesion agent composition on the two sides of base material, it is characterised in that
The described adhesion agent composition of at least one described adhering agent layer at least contain the terminal silyl groups polymer as (A) composition, as (B) composition adhesion give resin,
The terminal silyl groups polymer of described (A) composition has poly (oxyalkylene) based structures in main chain, and there is amino-formate bond and urea key or any one in them on partial skeleton or side chain, and two ends at main chain have the hydrolyzable silyl group shown in following formula (1)
The adhesion of described (B) composition gives resin and contains complete hydriding terpene phenolic resin, and relative to terminal silyl groups polymer 100 weight portion of described (A) composition, described adhesion is made to give the value in the scope that addition is 70～140 weight portions of resin, and
Make described adhering agent layer by the value in the scope that maximum is-10～15 DEG C of the loss angle tangent (tan σ) of Measurement of Dynamic Viscoelasticity (frequency: 1Hz) gained；
[chemical formula 1]
In formula (1), X1And X2Separate and be hydroxyl or alkoxyl, R is the alkyl of carbon number 1～20.
2. a two sides adhesive sheet, it is not for comprising base material and possessing the two sides adhesive sheet of the adhering agent layer being made up of the solidfied material of adhesion agent composition, it is characterised in that
Described adhesion agent composition at least contain the terminal silyl groups polymer as (A) composition, as (B) composition adhesion give resin,
The terminal silyl groups polymer of described (A) composition has poly (oxyalkylene) based structures in main chain, partial skeleton or side chain have amino-formate bond and urea key or any one in them, and two ends at main chain have the hydrolyzable silyl group shown in following formula (1)
The adhesion of described (B) composition gives resin and contains complete hydriding terpene phenolic resin, and relative to terminal silyl groups polymer 100 weight portion of described (A) composition, making the addition that described adhesion gives resin is the value within the scope of 70～140 weight portions, and
The maximum by the loss angle tangent (tan σ) of Measurement of Dynamic Viscoelasticity (frequency: 1Hz) gained making adhering agent layer is the value within the scope of-10～15 DEG C；
[chemical formula 2]
In formula (1), X1And X2Separate and be hydroxyl or alkoxyl, R is the alkyl of carbon number 1～20.
3. two sides as claimed in claim 1 or 2 adhesive sheet, it is characterized in that, give the total amount (100 weight %) of resin relative to the adhesion of described (B) composition, making the addition that the adhesion of described complete hydriding terpene phenols gives resin is the value within the scope of 30～100 weight %.
4. two sides adhesive sheet as described in any one in claims 1 to 3, it is characterized in that, described adhesion agent composition contains the catalyst of the solidification of terminal silyl groups polymer for promoting (A) composition as (C) composition, and this catalyst is at least one in the group that the free aluminum class catalyst of choosing, titanium class catalyst, zirconium class catalyst, bismuth class catalyst and boron trifluoride class catalyst are constituted.
5. in Claims 1 to 4 as described in any one as described in two sides adhesive sheet, it is characterised in that described adhesion agent composition contains the silane coupler in the molecule with amino as (D) composition.
6. two sides adhesive sheet as described in any one in Claims 1 to 5, it is characterized in that, make the gel fraction of the described adhering agent layer measured with infusion process (solvent: ethyl acetate, temperature: 23 DEG C, time: 120 hours) for the value in the scope of 30～70%.
7. a manufacture method for two sides adhesive sheet, it is the manufacture method of the two sides adhesive sheet possessing the adhering agent layer being made up of the solidfied material of adhesion agent composition on the two sides of base material, it is characterised in that comprise following step (1)～(3):
(1) step of adhesion agent composition is prepared, described adhesion agent composition is at least contain the terminal silyl groups polymer as (A) composition, adhesion as (B) composition gives resin, the terminal silyl groups polymer of described (A) composition has poly (oxyalkylene) based structures in main chain, and there is amino-formate bond and urea key or any one in them in partial skeleton or side chain, and two ends at main chain have the hydrolyzable silyl group shown in following formula (1), the adhesion of described (B) composition gives resin and contains complete hydriding terpene phenolic resin, and relative to terminal silyl groups polymer 100 weight portion of described (A) composition, making the addition that described adhesion gives resin is the value within the scope of 70～140 weight portions；
(2) by described adhesion agent composition lamination in the step of at least one side of base material；
(3) make described adhesion agent composition solidify, and make adhering agent layer by the step that maximum is the value within the scope of-10～15 DEG C of the loss angle tangent (tan σ) of Measurement of Dynamic Viscoelasticity (frequency: 1Hz) gained；
[chemical formula 3]
In formula (1), X1And X2Separate and be hydroxyl or alkoxyl, R is the alkyl of carbon number 1～20.
8. the manufacture method of a two sides adhesive sheet, it is not comprise base material and possess the manufacture method of two sides adhesive sheet of the adhering agent layer being made up of the solidfied material of adhesion agent composition, it is characterized in that, comprise following step (1)～(3):
(1) step of adhesion agent composition is prepared, this adhesion agent composition at least contains the terminal silyl groups polymer as (A) composition, adhesion as (B) composition gives resin, the terminal silyl groups polymer of described (A) composition has poly (oxyalkylene) based structures in main chain, and there is amino-formate bond and urea key or any one in them in partial skeleton or side chain, and two ends at main chain have the hydrolyzable silyl group shown in following formula (1), the adhesion of described (B) composition gives resin and contains complete hydriding terpene phenolic resin, and relative to terminal silyl groups polymer 100 weight portion of described (A) composition, making the addition that described adhesion gives resin is the value within the scope of 70～140 weight portions；
(2) by described adhesion agent composition lamination in the step on the surface of peeling base；
(3) make described adhesion agent composition solidify and be formed adhering agent layer, and make the adhering agent layer obtained by the step that maximum is the value within the scope of-10～15 DEG C of the loss angle tangent (tan σ) of Measurement of Dynamic Viscoelasticity (frequency: 1Hz) gained；
[chemical formula 4]
In formula (1), X1And X2Separate and be hydroxyl or alkoxyl, R is the alkyl of carbon number 1～20.
CN201480063116.8A 2013-11-26 2014-11-11 Double-sided adhesive sheet and method for producing double-sided adhesive sheet Pending CN105745293A (en)

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