CN108300342A - Bonding sheet - Google Patents

Bonding sheet Download PDF

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Publication number
CN108300342A
CN108300342A CN201710680576.0A CN201710680576A CN108300342A CN 108300342 A CN108300342 A CN 108300342A CN 201710680576 A CN201710680576 A CN 201710680576A CN 108300342 A CN108300342 A CN 108300342A
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CN
China
Prior art keywords
weight
tackifying resin
bonding sheet
adhesive
parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710680576.0A
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Chinese (zh)
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CN108300342B (en
Inventor
冈原快
大竹宏尚
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Nitto Denko Corp
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Nitto Denko Corp
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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
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • 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
    • C09J2301/122—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 only on one side of the carrier, e.g. single-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
    • C09J2301/10—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
    • C09J2301/302—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 the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • 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
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate

Abstract

The present invention relates to bonding sheets.The present invention provides the adhesive with the composition for being combined with tackifying resin in unsaturated rubber and the excellent bonding sheet of long-term quality stability.Using the present invention, a kind of bonding sheet including adhesive phase is provided.Above-mentioned adhesive phase is made of the adhesive containing unsaturated rubber and tackifying resin.At 80 DEG C in the degradation in four weeks, above-mentioned adhesive, the molecular weight that converts to polystyrene in the molecular weight distribution curve measured based on GPC be 10, the weight average molecular weight Mw that the range of 000g/mol or more calculatesHConservation rate is 70% or more.

Description

Bonding sheet
Technical field
This application claims the priority based on the Japanese patent application 2016-175607 proposed on the 8th of September in 2016, by this The full content of application is included in this specification by reference.
The present invention relates to bonding sheets.
Background technology
Usual adhesive (also referred to as pressure-sensitive adhesive；Soft solid similarly hereinafter) is presented within the temperature range of near room temperature The state of (viscoelastic body), and with by pressure simply gluing in the property of adherend.Using the property, adhesive is typical Ground reliability good as workability and gluing in the form of the bonding sheet comprising the adhesive phase being made of the adhesive is high Engagement means and be widely used in from household appliances to automobile, in the various industrial fields such as office automation (OA) equipment. For the base polymer of adhesive, it is preferred to use show the polymer of caoutchouc elasticity at normal temperatures.As such An example of polymer can enumerate the polymer with the monomeric unit containing carbon-to-carbon unsaturated bond (for example, with based on altogether The polymer of the monomeric unit of conjugate diene compound).In Japanese patent application discloses 2016-35039 bulletins, describes and contain There is part hydrogenated block copolymer (the part hydrogenation of benzene second with vinyl aromatic monomers unit and conjugated diene monomeric unit Alkene-butadiene block copolymer etc.) adhesives composition.
Invention content
As bonding sheet is using field, the expansion of occupation mode, for the long-term stay in grade of the bonding sheet after manufacture Property (hereinafter also referred to as " quality stability ") required by horizontal increase.In this respect, including having used unsaturated rubber Also there is room for improvement for the bonding sheet of adhesive (being especially the more adhesive of the content of unsaturated rubber).In particular, not When coordinating tackifying resin in saturated rubber, the deterioration such as reduction with cohesiveness (coherency) tendency easy to perform, bonding sheet Quality stability tend to reduce.
Therefore, the purpose of the present invention is to provide a kind of with the composition for being combined with tackifying resin in unsaturated rubber Adhesive composition in the case of the long-term excellent bonding sheet of quality stability.
The bonding sheet provided by this specification includes to be made of the adhesive containing unsaturated rubber and tackifying resin Adhesive phase.At 80 DEG C in the degradation in four weeks, above-mentioned adhesive, based on gel permeation chromatography (GPC) survey What the range for being 10,000g/mol or more to the molecular weight of polystyrene conversion in fixed molecular weight distribution curve calculated divides equally again Son amount MwHConservation rate be 70% or more.According to technology disclosed herein, by by above-mentioned weight average molecular weight MwHAs index, The degree of the deterioration of adhesive can accurately be grasped.Mw in above-mentioned degradationHConservation rate (hereinafter also referred to " MwHIt protects Holdup ") it can be as the excellent bonding sheet of quality stability for 70% or more bonding sheet.In addition, allowing in unsaturated rubber Therefore middle cooperation tackifying resin according to above-mentioned bonding sheet, can take into account excellent adhesion characteristic (for example, viscosity, peel strength) With long-term quality stability.
In some modes, the content of the above-mentioned unsaturated rubber in above-mentioned adhesive can be 30 weight % of the adhesive More than.More the adhesive containing unsaturated rubber is conducive to improve adhesion characteristic in this way, on the other hand, due to above-mentioned insatiable hunger With the unsaturated bond in rubber, deterioration is carried out in easy.According to technology disclosed herein, even if one kind can be provided at this Quality stability also good bonding sheet in the case of the composition of sample.
In some modes, relative to 100 parts by weight of above-mentioned unsaturated rubber, the content of above-mentioned tackifying resin can be 10 More than parts by weight and below 120 parts by weight.According to the adhesive of the composition, excellent adhesion characteristic is easy to get (for example, viscous Property, peel strength).According to technology disclosed herein, even if a kind of structure in the adhesive using such composition can be provided The quality stability also good bonding sheet in the case of.
In some modes, above-mentioned tackifying resin can contain phenols tackifying resin.Phenols tackifying resin can aid in Adhesion characteristic is improved, easily becomes the factor for the deterioration for promoting adhesive but then.It, can be with according to technology disclosed herein A kind of bonding sheet good the quality stability in the case of composition containing phenols tackifying resin is provided.Relative to upper State 100 parts by weight of unsaturated rubber, the content of phenols tackifying resin for example, it can be set to for it is more than 5 parts by weight and 60 parts by weight with Under.Such composition can suitably play the improvement effect of the adhesion characteristic because using phenols tackifying resin to bring.As phenol For class tackifying resin, such as it can preferably use terpene phenol resin.
Technology disclosed herein can preferably include phenols tackifying resin and the phenols tackifying resin with above-mentioned tackifying resin Including the mode that hydroxyl value is the terpene phenol resin of 20mgKOH/g or more is implemented.According to such composition, it can suitably take into account excellent Different adhesion characteristic and quality stability.
Above-mentioned adhesive can also contain antiaging agent in addition to unsaturated rubber and tackifying resin.By using anti-aging Agent can effectively improve the Mw of adhesive of the combination containing unsaturated rubber and tackifying resinHConservation rate can realize bonding The raising (long lifetime) of the long-term quality stability of piece.For antiaging agent, such as free radical scavenger is applied in combination It is effective with sulphur-containing antioxidant.Alternatively, it is also possible to use phosphorous antioxidant as antiaging agent.By being applied in combination certainly By base agent for capturing (for example, phenol antioxidant), sulphur-containing antioxidant and phosphorous antioxidant, higher effect can be played.
In some modes, above-mentioned adhesive viscosifies tree preferably with respect to the phenols of 100 parts by weight of above-mentioned unsaturated rubber The content of fat is 30 parts by weight or less.Or the content of phenols tackifying resin is 0 parts by weight, is free of phenols tackifying resin Adhesive.In this way, the upper limit of its content is limited by being conceived to the amount of phenols tackifying resin in tackifying resin, thus, it is possible to Effectively improve the Mw of adhesiveHConservation rate is capable of providing good (long-life) bonding sheet of quality stability.
In some modes, above-mentioned unsaturated rubber has the monomer composition containing conjugated diene compound, conjugated diene Compound ratio shared in the monomer composition can be 70 weight % or more.Conjugated diene chemical combination is used containing a large amount of in this way The adhesive of the unsaturated rubber of object can play excellent adhesion characteristic in the composition comprising tackifying resin, but then With deterioration tendency easy to perform.According to technology disclosed herein, even if can provide a kind of such composition the case where Lower quality stability also good bonding sheet.
In some modes, above-mentioned unsaturated rubber can include mono-vinyl substituted aromatic compound and conjugated diene The block copolymer of compound.Adhesive containing such block copolymer and tackifying resin, which can become, plays excellent glue Close the adhesive of characteristic.Therefore, according to the bonding sheet with the adhesive, excellent adhesion characteristic and product can suitably be taken into account Matter stability.For above-mentioned block copolymer, from the viewpoint of improving viscosity, low-temperature characteristics etc., can preferably it use Diblock object ratio is the block copolymer of 60 weight % or more.
In some modes, the thickness of above-mentioned adhesive phase can be 30 μm or more.When adhesive phase thickens, there is bonding It is (solidifying to there may come a time when that the structure for being easy to happen the inside of adhesive phase is destroyed but then for the tendency that the peel strength of piece improves It is poly- to destroy).Therefore, inhibit the reduction of coherency especially significant using technology disclosed herein.
Technology disclosed herein can preferably using with base material and by the base material it is two-sided support respectively as above-mentioned viscous The form of the bonding sheet of the first adhesive phase of mixture layer and the both-sided adhesive of second adhesive phase is implemented.Both-sided adhesive Bonding sheet, i.e. double-sided adhesive sheet are suitable for the purposes of fixing component.In the fixation of component, from preventing the position of the component inclined It moves, fall off from the viewpoint of (releasing of stationary state), preferably paste the cohesion for inhibiting adhesive after bonding sheet in a long time The reduction of property.Therefore, inhibit the reduction of the coherency of adhesive especially significant using technology disclosed herein.
Description of the drawings
Fig. 1 is the section view signal of the composition for the bonding sheet (double-sided adhesive sheet for carrying base material) for showing an embodiment Figure.
Fig. 2 is the section view signal of the composition for the bonding sheet (double-sided adhesive sheet of no base material) for showing another embodiment Figure.
Fig. 3 is the section view signal of the composition for the bonding sheet (the single side bonding sheet for carrying base material) for showing another embodiment Figure.
Reference numeral
1,2,3 bonding sheet
11 first adhesive phases
12 second adhesive phases
15 base materials
21,22 release liner
Specific implementation mode
Hereinafter, being illustrated to the preferred embodiment of the present invention.In addition to item specifically mentioned in the present specification with The outer necessary item of implementation for the present invention be those skilled in the art based on described in this specification about implementing to send out What common technical knowledge when bright introduction and application was appreciated that.The present invention can be based on content disclosed in this specification and ability The common technical knowledge in domain and implement.
It should be noted that in following attached drawings, sometimes for component/part mark the same symbol of performance phase same-action It illustrates, repeat description is omitted or simplified sometimes.In addition, embodiment described in attached drawing is in order to clearly demonstrate this hair It is bright and carry out signalization, the size or reduced scale of product actually provided is not accurately provided.
In the present specification, as described above, " adhesive " refers to that soft consolidate is presented within the temperature range of near room temperature The state of body (viscoelastic body) and with by pressure simply gluing in the material of the property of adherend.Skill disclosed herein Adhesive in art is it can be appreciated that the solid constituent of adhesive composition or the constituent of adhesive phase.
In the present specification, " unsaturated rubber " refers to the monomeric unit containing carbon-to-carbon unsaturated bond and in room temperature The polymer of caoutchouc elasticity is shown under (such as 23 DEG C).Typical unsaturated rubber contains carbon-to-carbon unsaturated bond in main chain.
In the present specification, " block copolymer of mono-vinyl substituted aromatic compound and conjugated diene compound " is Refer to that have at least one using mono-vinyl substituted aromatic compound as principal monomer (refer to being copolymerized into more than 50 mass % Point；Segment (hereinafter also referred to " A segments ") similarly hereinafter) and at least one segment using conjugated diene compound as principal monomer The polymer of (hereinafter also referred to " B segments ").The glass transition temperature of usual A segments is higher than the glass transition temperature of B segments Degree.As the representative configurations of the polymer, can enumerate：Respectively there is A segments (hard chain at the both ends of B segments (soft chain segment) Section) three block structure copolymer (the three block object of A-B-A structures), the diblock comprising an A segment and a B segment Copolymer (the diblock object of A-B structures) of structure etc..
In the present specification, " styrene block copolymers " refers to the polymer for having at least one styrene block. Above-mentioned styrene block refers to the segment using styrene as principal monomer.The segment for substantially only including styrene is in this institute The typical case for the styrene block said.In addition, " styrene-isoprene block copolymer " refers to having at least one styrene The polymer of block and at least one isoprene block (using isoprene as the segment of principal monomer).As styrene- The typical example of isoprene block copolymer can be enumerated：Respectively there is benzene second at the both ends of isoprene block (soft chain segment) The copolymer (three block object) of the three block structure of alkene block (hard segment) includes an isoprene block and a styrene Copolymer (diblock object) of the diblock structure of block etc.." styrene-butadiene block copolymer " refers to having at least one The polymer of a styrene block and at least one butadiene block (using butadiene as the segment of principal monomer).
In the present specification, " styrene-content " of styrene block copolymers refers to that styrene content is total in the block Shared weight ratio in the total weight of polymers.Above-mentioned styrene-content can be surveyed by NMR (nuclear magnetic resonance spectroscopy) It is fixed.
In addition, ratio (hereinafter sometimes referred to " the diblock object ratio that diblock object is shared in styrene block copolymers Rate " or " diblock ratio ") it can be found out by following methods.That is, styrene block copolymers is dissolved in tetrahydrofuran (THF) in, by the liquid chromatograph column of the GS5000H and G4000H of TOSOH Co., Ltd's manufacture with each 2 sections total 4 sections of series connection Connection carries out efficient liquid phase chromatographic analysis using THF as mobile phase under conditions of 40 DEG C of temperature, flow 1mL/ minutes.Root The peak area corresponding to diblock object is measured according to obtained chart.Then, the above-mentioned peak area corresponding to diblock object is calculated Relative to the percentage of total peak area, diblock object ratio is thus found out.
In the present specification, in case of no particular description, indicate that the numerical value of molecular weight or weight average molecular weight understands For carry " g/mol " unit numerical value.In addition, in case of no particular description, measuring relevant molecular weight with GPC is Refer to the molecular weight of polystyrene conversion.
<The configuration example of bonding sheet>
Bonding sheet (can be the form of band-like isometric size shape) disclosed herein for example can be with as shown in Figure 1 The form of the double-sided adhesive sheet of cross section structure.The double-sided adhesive sheet 1 has base material (such as plastic foil, non-woven fabrics) 15 and by the base The two-sided first adhesive phase 11 supported respectively and second adhesive phase 12 of material 15.More specifically, the first of base material 15 Face 15A and the second face 15B (being non-peel-away property) are respectively arranged with first adhesive phase 11 and second adhesive phase 12.Before use The double-sided adhesive sheet 1 of (before being pasted on adherend) can be with positive 21A and back side 21B be as shown in Figure 1 the stripping of release surface It is overlapped from liner 21 and is wound into spiral helicine form.For the double-sided adhesive sheet 1 of the form, respectively, the second bonding The surface (the second adhesive surface 12A) of oxidant layer 12 is by the positive 21A protections of release liner 21, the surface (the of first adhesive phase 11 One adhesive surface 11A) it is protected by the back side 21B of release liner 21.Or, or the first adhesive surface 11A and the second adhesive surface 12A is respectively by the form of the independent release liner protection of two panels.
Technology disclosed herein is preferably applied to the double-sided adhesive sheet with base material as shown in Figure 1 and also may be used in addition to this With (that is, not having base material) double-sided adhesive sheet 2 applied to no base material as shown in Figure 2.Double-sided adhesive sheet 2 before use can Think such as shown in Figure 2 the first adhesive surface 11A and the second adhesive surface 11B of the adhesive phase 11 without base material respectively by least should The surface (front) of adhesive phase side is the form that the release liner 21,22 of release surface is protected.Or, or following shape State：It omits release liner 22 and uses the two-sided release liner 21 for release surface, keep it Chong Die with adhesive phase 11 and be wound into Helical form, thus the rear-face contact of the second adhesive surface 11B and release liner 21 is to be protected.
In addition, technology disclosed herein can also be applied to have base material 15 and the first face by the base material as shown in Figure 3 The bonding sheet 3 with base material of the single side adhesion type of the adhesive phase 11 of (non-peel-away face) 15A supports.Bonding sheet 3 before use Can be for example as shown in Figure 3 its adhesive phase 11 surface (adhesive surface) 11A by at least adhesive phase side surface (just Face) it is the form that the release liner 21 of release surface is protected.Or, or following form：It omits release liner 21 and uses Second face 15B is the base material 15 of release surface, and winding carries the bonding sheet 3 of base material, as a result, the first adhesive surface 11A and base material 15 Second face 15B contacts are to be protected.
Bonding sheet disclosed herein is characterized in that including to be made of the adhesive containing unsaturated rubber and tackifying resin Adhesive phase, and the Mw of the adhesiveHConservation rate is 70% or more.The Mw of adhesiveHConservation rate is defined as four stars at 80 DEG C The weight average molecular weight Mw of adhesive after the degradation of phaseH(Mw after agingH) relative to the adhesive before the degradation Weight average molecular weight MwH(Mw before agingHThe ratio between).Above-mentioned degradation at the surface of adhesive phase (adhesive surface) by will be fitted with The bonding sheet of release liner preserved for four weeks to carry out under 80 DEG C of air atmosphere.For release liner, Ke Yiyou Choosing utilizes peeling paper (for example, having carried out the polyethylene layer platen (Port リ ラ ミ Paper) of lift-off processing).The thickness of release liner does not have Especially limitation can suitably select the stripping of the thickness of for example, about 20 μm~about 150 μm (typically about 25 μm~about 100 μm) It pads to use.More specifically, degradation can be carried out by the method described in aftermentioned embodiment.
<MwHConservation rate>
In the present specification, the weight average molecular weight Mw of adhesiveH(sometimes referred to simply as " MwH") refer to being measured by GPC To molecular weight distribution curve in polystyrene conversion molecular weight be 10,000 or more range calculate weight average molecular weight. In contrast, sometimes by the entirety of above-mentioned molecular weight distribution curve (that is, including polystyrene conversion molecular weight be less than 10, 000 range) calculate weight average molecular weight be known as weight average molecular weight MwT.For sample as GPC measurement, using passing through The adhesive acquired from bonding sheet is dissolved in tetrahydrofuran (THF) and is made the solution of 0.1 weight %, was stood Then night utilizes the filtrate after 0.45 μm of membrane filter.GPC, which is measured, in following conditions or can obtain same with it Result under conditions of carry out.Same method is also used in the later-described embodiments.
Analytical equipment：The manufacture of Tosoh company, HLC-8120GPC
Column：TSKgel SuperHZM-H/HZ 4000/HZ 3000/HZ 2000
Column dimension：6.0mmI.D.×150mm
Eluent：THF
Flow：0.6mL/ minutes
Detector：Differential refractometer (RI)
Column temperature：40℃
Sample size：20μL
Standard sample：Polystyrene
It is usually used to divide equally again for tackifying resin in the adhesive containing unsaturated rubber and tackifying resin Son amount MwTLess than the tackifying resin of unsaturated rubber.It is bent in the molecular weight distribution of such adhesive measured by GPC In line, corresponding to above-mentioned tackifying resin peak typically molecular weight be about hundreds of~about thousands of range in occur.Using The technology of the displosure, by be conceived to about in addition to the range high molecular weight range (specifically, molecular weight 10,000 with On range) molecular weight distribution curve weight average molecular weight MwH, can accurately grasp can cause the quality of bonding sheet to reduce Unsaturated rubber rotten, deterioration.According to weight average molecular weight MwHConservation rate (Mw after degradationHConservation rate) be 70% or more bonding sheet, can take into account excellent adhesion characteristic and long-term quality stability (for example, because through when caused by agglomerate Property the few property of reduction).
In some modes, MwHConservation rate can be about 75% or more or about 80% or more, may be about 85% or more.Technology disclosed herein can also be preferably with MwHMode that conservation rate is about 87% or more, about 90% or more side Formula is implemented.MwHCloser to 100%, the quality stability of bonding sheet tends to more increase conservation rate.Therefore, skill disclosed herein In art, MwHThe upper limit of conservation rate can be 100%.Alternatively, in view of balance, economy with other adhesion characteristics, from practicality From the viewpoint of upper, MwHConservation rate can be less than 100% (such as 99% or less).MwHConservation rate can for example pass through insatiable hunger Usage amount of selection, unsaturated rubber, the selection of tackifying resin, the usage amount of tackifying resin with rubber etc. are adjusted.Separately Outside, it in the composition that adhesive contains antiaging agent, can also be adjusted by the usage amount of the selection of antiaging agent, antiaging agent Save MwHConservation rate.
Although being not particularly limited, the Mw of bonding sheet disclosed hereinH(that is, Mw before agingH) be typically about 80,000 with On be appropriate, can be about 100,000 or more or about 130,000 or more or about 150,000 or more.It is viscous Close the Mw of pieceHWhen raising, coherency normally tends to improve.In addition, the Mw of bonding sheetHSuch as can be about 1,000,000 with Under or about 800,000 or less, or about 600,000 or less.The Mw of bonding sheetHWhen reduction, viscosity, stripping are strong Degree (these characteristics, the i.e. low-temperature characteristics especially under low temperature) normally tends to improve.Consider from the viewpoint, in some modes In, the Mw of bonding sheetHCan be about 400,000 or less or about 300,000 or less or about 250,000 with Under, or about 200,000 or less.Technology disclosed herein for example can be preferably with MwHIt is about 130,000 or more and about The form of 200,000 bonding sheets below is implemented.The Mw of bonding sheetHIt can be adjusted by the selection etc. of unsaturated rubber. In addition, in the composition containing crosslinking agent, can also be adjusted by the type of crosslinking agent, the usage amount of crosslinking agent.
Although being not particularly limited, the Mw after the degradation of bonding sheet disclosed hereinH(that is, Mw after agingH) it is about 70,000 or more be it is appropriate, preferably from about 90,000 or more, even more preferably about 100,000 or more (for example, about 120,000 with On).Mw after agingHWhen raising, it is intended to can also play more good adhesion characteristic (such as coherency) after long-time.
<Unsaturated rubber>
For unsaturated rubber, the various rubber with the monomeric unit containing carbon-to-carbon unsaturated bond can be used Shaped polymer.In some modes, above-mentioned unsaturated rubber can be the homopolymer or copolymer of conjugated diene compound.As For the concrete example of conjugated diene compound, 1,3-butadiene, isoprene etc. can be enumerated.Copolymer said here can be with For random copolymer, or block copolymer or graft copolymer.The non-limiting example of such unsaturated rubber Include natural rubber (NR), butadiene rubber (BR), butadiene-styrene rubber (SBR), butyl rubber (IIR), butyronitrile Rubber (NBR), neoprene (CR), styrene-isoprene block copolymer and styrene-butadiene block copolymer etc.. In some modes, the unsaturated rubber of the monomer composition containing isoprene can be preferably used.The insatiable hunger of the monomer composition Tend to be present such that Auto-oxidation reaction is easy to carry out because of isoprene structures with rubber, therefore, using being disclosed Technology meaning it is big.
In the unsaturated rubber of the monomer composition containing conjugated diene compound, conjugated diene compound is in the monomer group Shared ratio is not particularly limited in.From the viewpoint of improving adhesion characteristic, the ratio of above-mentioned conjugated diene compound For example, it can be set to being 60 weight % or more, usually 65 weight % or more are appropriate, preferably 70 weight % or more, also may be used Think 75 weight % or more, or 80 weight % more than (be typically greater than 80 weight %, for example, 82 weight % with On).According to technology disclosed herein, a kind of largely containing conjugated diene compound in this way with having used even if can provide Monomer composition unsaturated rubber adhesive in the case of, quality stability also good bonding sheet.
(block copolymer of mono-vinyl substituted aromatic compound and conjugated diene compound)
In some modes, above-mentioned unsaturated rubber can contain mono-vinyl substituted aromatic compound and conjugated diene The block copolymer of compound.Above-mentioned mono-vinyl substituted aromatic compound refers to that there are one have second for bonding on aromatic rings The compound of the functional group of alkenyl.As the typical example of above-mentioned aromatic rings, it (can be by not having vinyl that can enumerate phenyl ring Functional group's (such as alkyl) substitution after phenyl ring).For concrete example as above-mentioned mono-vinyl substituted aromatic compound, It can enumerate：Styrene, α-methylstyrene, vinyltoluene, vinyl-dimethyl benzene etc..As above-mentioned conjugated diene compound Concrete example for, 1,3-butadiene, isoprene etc. can be enumerated.Such block copolymer can individually a kind of or combination The two or more unsaturated rubbers as in technology disclosed herein and use.
A segments (hard segment) in above-mentioned block copolymer preferably above-mentioned mono-vinyl substituted aromatic compound (can be with Be used in combination two or more) copolymerization ratios be 70 weight % or more (more preferably 90 weight % or more, can be essentially 100 weights Measure %).B segments (soft chain segment) preferably above-mentioned conjugated diene compound (can be used together two or more) in above-mentioned block copolymer Copolymerization ratios be 70 weight % or more (more preferably 90 weight % or more, can be essentially 100 weight %).It is embedding according to this Section copolymer, may be implemented the bonding sheet of higher performance.
Above-mentioned block copolymer can be diblock object, three block object, radial (radial) object, their mixture etc. Form.In three block object, radial object, preferably A segments (such as styrene block) are configured in the end of polymer chain.This Be because：It configures the A segments in the end of polymer chain to be easy aggregation and form domain, pseudo- cross-linked structure is consequently formed, to viscous The coherency of mixture improves.
For the block copolymer in technology disclosed herein, from the sight of the bonding force (peel strength) to adherend Point consider it is preferable to use diblock object ratio be 30 weight % or more (more preferably 40 weight % or more, further preferably For 50 weight % or more, particularly preferably 60 weight % or more, typically 65 weight % or more) block copolymer.From stripping From the viewpoint of intensity, particularly preferred diblock object ratio is the block copolymer of 70 weight % or more.In addition, from coherency Etc. viewpoints consider it is preferable to use diblock object ratio be 90 weight % or less (more preferably 85 weight % or less, be, for example, 80 weight % or less) block copolymer.For example, it is preferable to which diblock object ratio is the block copolymerization of 60 weight of weight %~85 % Object, the block copolymerization that more preferable diblock object ratio is 70 weight of weight %~85 % (such as 70 weight % of weight %~80) Object.
(styrene block copolymers)
In one preferred embodiment of technology disclosed herein, above-mentioned unsaturated rubber is styrene block copolymers.Example As preferred above-mentioned unsaturated rubber contains in styrene-isoprene block copolymer and styrene-butadiene block copolymer The mode of at least one.In styrene block copolymers contained in adhesive, optimization styrene-isoprene block is total The ratio of polymers be 70 weight % or more or the ratio of styrene-butadiene block copolymer be 70 weight % or more or Total ratio of styrene-isoprene block copolymer and styrene-butadiene block copolymer is 70 weight % or more. In one preferred embodiment, substantially all (such as 95 weight % of weight %~100) are benzene to above-mentioned styrene block copolymers Ethylene-isoprene block copolymer.In another preferred embodiment, above-mentioned styrene block copolymers is substantially whole (such as 95 weight % of weight %~100) are styrene-butadiene block copolymer.It, can be preferably according to such composition Play effect caused by application technology disclosed herein.
Above-mentioned styrene block copolymers can be diblock object, three block object, radial (radial) object, they The forms such as mixture.In three block object and radial object, preferably styrene block is configured in the end of polymer chain.This is Because：It configures the styrene block in the end of polymer chain to be easy aggregation and form styrene domain, pseudo- crosslinking knot is consequently formed Structure improves to the coherency of adhesive.As the styrene block copolymers used in technology disclosed herein, to quilt It is (more excellent for 30 weight % or more that it is preferable to use diblock object ratios from the viewpoint of the bonding force (peel strength) of viscous object It is selected as 40 weight % or more, further preferably 50 weight % or more, particularly preferably 60 weight % or more, typically 65 weights Measure % or more) block copolymer.Can also be diblock object ratio it is 70 weight % or more (be, for example, 75 weight % or more) Styrene block copolymers.In addition, considering that it is preferable to use diblock object ratio be 90 weights from viewpoints such as coherencys Measure the styrene block copolymers of % or less (more preferably 85 weight % are hereinafter, for example, 80 weight % or less).From equilibrium From the viewpoint of adhesion characteristic and coherency are taken into account in ground, preferably diblock object ratio is the styrene of 60 weight of weight %~85 % Based block copolymer, more preferable diblock object ratio are 70 weight of weight %~85 %'s (such as 70 weight % of weight %~80) Styrene block copolymers.
The styrene-content of above-mentioned styrene block copolymers for example can be 5 weight of weight %~40 %.From cohesion Property from the viewpoint of, optimization styrene content be 10 weight % or more (more preferably higher than 10 weight %, for example, 12 weight % More than) styrene block copolymers.In addition, from the viewpoint of peel strength, styrene-content is preferably 35 weight % (typically 30 weight % or less, more preferably 25 weight % or less), particularly preferably 20 weight % or less are (typically below To be less than 20 weight %, for example, 18 weight % or less).From preferably performance using effect caused by technology disclosed herein From the viewpoint of, it can preferably use styrene-content total less than the styrenic block of 20 weight % for 12 weight % Polymers.
(content of unsaturated rubber)
In adhesive disclosed herein, unsaturated rubber as described above is (for example, styrene-isoprene block copolymerization Object) content for example can be above-mentioned adhesive entirety about 10 weight % or more, may be about 20 weight % more than.One In a little modes, the content of the unsaturated rubber in adhesive can be the about 30 weight % or more of the adhesive, may be about 40 weight % or more or about 50 weight % or more.It is easy to form the superior bonding sheet of adhesion characteristic as a result,.In addition, Content with the unsaturated rubber in adhesive increases, and the deterioration of the adhesive, therefore, can be more preferable in being easy progress Ground plays effect caused by application technology disclosed herein.Consider from the viewpoint, the content of above-mentioned unsaturated rubber can be About 55 weight % or more or about 60 weight % or more.On the other hand, from the using effect for suitably playing tackifying resin From the viewpoint of, it is appropriate, Ke Yiwei that the content of the unsaturated rubber in adhesive, which is typically set at about 95 weight % or less, About 90 weight % or less or about 80 weight % or less or about 75 weight % or less or about 70 weights Measure % or less.Technology disclosed herein can also preferably with the content of above-mentioned unsaturated rubber be about 65 weight % or less (such as About 60 weight % or less) mode implement.
<Tackifying resin>
Adhesive phase disclosed herein also contains tackifying resin in addition to unsaturated rubber.It, can for tackifying resin It is selected from phenols tackifying resin, terpene resin, modified terpene resin, rosin tackifying resin, Petropols, styrene resin to use One or more of various tackifying resins well known to fat, coumarone-indene resin, ketone resins etc..As tackifying resin For, it is not particularly limited, the tackifying resin that softening point is 40 DEG C or more can be used for example, preferably softening point is 60 DEG C or more Or 80 DEG C or more of tackifying resin.The softening point of tackifying resin for example can be 200 DEG C or less (typically 180 DEG C or less).
Phenols tackifying resin said here refers to the tackifying resin with the molecular structure comprising phenol skeleton, and it includes terpene to be The concept of alkene phenol resin, hydrogenated terpene phenol resin, phenolic resin, rosin phenol resin etc..
Terpene phenol resin refers to the polymer containing terpene residue and phenol residue, is the copolymer for including terpenes and phenols (terpenes-phenol copolymer resin) and the homopolymer of terpenes or copolymer are subjected to (the phenol modification terpene of substance obtained from phenol modification Olefine resin) both concept.The preference of terpenes as terpene phenol resin as composition can be enumerated：Australene, β- The monoterpenes such as firpene, limonene (including d forms, l forms and d/l forms (dipentene)).Hydrogenated terpene phenol resin refers to having The hydrogenated terpene phenol resin of structure obtained from such terpene phenol resin is hydrogenated.Otherwise referred to as plus hydrogen terpene phenol resin. It should be noted that for as above-mentioned phenols, can enumerate for example：Phenol, metacresol, 3,5- dimethlbenzenes, to alkyl phenol, Resorcinol etc..
Phenolic resin is typically the resin obtained with formaldehyde by various phenols as described above.Specifically, phenolic aldehyde tree Comprising such as alkyl phenol resin, xylene formaldehyde resin in fat.Include that above-mentioned phenols is made to exist with formaldehyde in the example of phenol resin First rank phenolic resin obtained from addition reaction occurs under base catalyst, above-mentioned phenols and formaldehyde is made to occur under an acid catalysis Phenolic varnish type resin obtained from condensation reaction.
Rosin phenol resin is typically that rosin or rosin derivative (are modified pine comprising rosin esters, unsaturated fatty acid Fragrant class and unsaturated fatty acid modified rosin esters) phenol modifier.Comprising by making institute as above in the example of rosin phenol resin The phenols stated and rosin or the rosin derivative rosin phenol that addition and the method etc. for carrying out thermal polymerization obtain under an acid catalysis Resin.
The example of terpene resin includes that the terpenes such as australene, nopinene, (R)-4-isopropenyl-1-methyl-1-cyclohexene, l- limonenes, dipentene are (typical Ground is monoterpenes) polymer.It can be a kind of homopolymer of terpenes, or the copolymer of two or more terpenes. For a kind of homopolymer of terpenes, australene alkene polymer, beta-pinene polymer, dipentene polymer etc. can be enumerated.
For the example of modified terpene resin, it can enumerate obtained from being modified to above-mentioned terpene resin and set Fat.Specifically, may be exemplified styrenated terpene resins, hydrogenated terpene resin etc..
The concept of rosin tackifying resin said here includes both rosin and rosin derivative resin.
The example of rosin includes the unmodified rosins such as gum rosin, wood rosin, Starex (pine gum)；By hydrogenating, Modified rosin obtained from disproportionation, polymerization etc. are modified these unmodified rosins (hydrogenated rosin, disproportionated rosin, polymerization pine Rosin etc. after fragrant, other chemical sex modifications).
Rosin derivative resin is typically the derivative of rosin as described above.Rosin resinoid said here Concept includes the derivative of the derivative and modified rosin (including hydrogenated rosin, disproportionated rosin and newtrex) of unmodified rosin Object.It can enumerate for example as the unmodified rosin ester of unmodified rosin and the ester of alcohols, as the ester of modified rosin and alcohols The rosin esters such as modified rosin ester；For example, the unsaturated lipid obtained from unsaturated fatty acid is modified rosin Fat acid modified rosin class；For example, unsaturated fatty acid changes obtained from unsaturated fatty acid is modified rosin esters Property rosin esters；For example, to rosin or above-mentioned various rosin derivatives, (including rosin esters, unsaturated fatty acid are modified pine Fragrant class and unsaturated fatty acid modified rosin esters) carboxyl carry out reduction treatment obtained from rosin alcohols；For example, rosin Or the metal salt of above-mentioned various rosin derivatives；Deng.For concrete example as rosin esters, it can enumerate：Unmodified rosin Or the methyl ester of modified rosin (hydrogenated rosin, disproportionated rosin, newtrex etc.), triglycol ester, glyceride, pentaerythritol ester Deng.
For the example of Petropols, it can enumerate：Aliphatic category (C5 classes) Petropols, aromatic (C9 classes) Petropols, aliphatic/aromatic Copolymer (C5/C9 classes) Petropols, their hydride are (for example, to aromatic stone Alicyclic ring same clan Petropols obtained from oleoresin is hydrogenated) etc..
For the example of styrene resin, it can enumerate：With the homopolymer of styrene make resin as main component, Make resin as main component with the homopolymer of α-methylstyrene, tree as main component is made with the homopolymer of vinyltoluene Fat contains two or more copolymers in styrene, α-methylstyrene and vinyltoluene using in monomer composition as master Want the resin of ingredient (for example, making α-methylstyrene as main component/benzene second with α-methylstyrene/styrol copolymer Alkene copolymer resin) etc..
For coumarone-indene resin, it can use and contain coumarone and indenes as the skeleton (main chain) for constituting resin Monomer component resin.It, can as the monomer component that coumarone and indenes can contain in addition in the skeleton of resin To illustrate styrene, α-methylstyrene, methyl indenes, vinyltoluene etc..
For ketone resins, it can enumerate for example：Methyl ethyl ketone, methyl iso-butyl ketone (MIBK), acetophenone, cyclohexanone, The condensation product etc. of the ketones such as methyl cyclohexanone and formaldehyde.
As a preferred embodiment, adhesive phase can be enumerated and contain one or more kinds of phenols tackifying resin (examples Such as terpene phenol resin) mode.Pass through the cooperation phenols thickening tree in unsaturated rubber (for example, styrene block copolymers) Fat can effectively improve adhesion characteristic.Thus, it is possible to realize that the excellent and long-term quality stability of adhesion characteristic is good (long Service life) bonding sheet.
In the case where adhesive phase contains phenols tackifying resin, content is not particularly limited.Relative to unsaturated rubber 100 parts by weight of glue, the content of phenols tackifying resin more than 5 parts by weight are usually suitable for example, it can be set to be more than 1 parts by weight When, or more than 10 parts by weight or more than 15 parts by weight.In some modes, relative to unsaturated rubber 100 parts by weight, the content of phenols tackifying resin can be 20 parts by weight or more or 30 parts by weight or more (such as 35 weights Measure part or more).In addition, from the viewpoint of the low-temperature characteristics, compatibility of adhesive, relative to 100 parts by weight of unsaturated rubber, The content of phenols tackifying resin is usually that 60 parts by weight or less are appropriate, or below 50 parts by weight.From more paying attention to product From the viewpoint of matter stability, in some modes, relative to 100 parts by weight of unsaturated rubber, the content of phenols tackifying resin Such as it can be less than 40 parts by weight, may be 35 parts by weight or less or 30 parts by weight or less or 25 weights Measure part or less.
In the case of using phenols tackifying resin, phenols tackifying resin amount shared in whole tackifying resins for example can be with For 25 weight % or more, or 30 weight % more than, or 50 weight % more than, or 80 weight % with Upper or 90 weight % or more.The substantial whole that can also be tackifying resin (is, for example, 95 weights of weight %~100 Measure %, be further the 99 weight % of weight %~100) it is phenols tackifying resin.It, can be appropriate in the case of such composition Ground is played using effect caused by phenols tackifying resin.In addition, in some modes, from raising low-temperature characteristics, stay in grade Property etc. viewpoints consider that phenols tackifying resin amount shared in whole tackifying resins can be for example 70 weight % or less, also may be used Think 60 weight % or less or 45 weight % or less.
In some modes, terpene phenol resin amount shared in used whole phenols tackifying resins can for example be set Be set to 50 weight % or more, or 70 weight % more than, or 85 weight % more than, or 90 weight % with On.Can also be substantially all (being, for example, 95 weight of weight %~100 %, be further 99 of phenols tackifying resin The weight % of weight %~100) it is terpene phenol resin.It, can be with by compatibly implementing technology disclosed herein in this way There is provided that adhesion characteristic is good and the bonding sheet of long-life.
(tackifying resin TH)
Adhesive phase disclosed herein contains the tackifying resin T that softening point is 100 DEG C or moreHAs above-mentioned tackifying resin. From the viewpoint of coherency, tackifying resin THSoftening point be preferably 120 DEG C or more, more preferably 125 DEG C or more, it is further Preferably 130 DEG C or more, particularly preferably 135 DEG C or more (being, for example, 140 DEG C or more).In addition, strong from the stripping to adherend From the viewpoint of degree etc., tackifying resin THSoftening point be 200 DEG C or less be it is appropriate, preferably 180 DEG C or less, be more preferably 170 DEG C or less (being, for example, 160 DEG C or less).
Here, the softening point of tackifying resin is defined as being based on providing in JIS K5902 and JIS K2207 in the present specification Softening point test method (ring and ball method) measure value.Specifically, sample is melted rapidly at alap temperature, it will The sample of fusing, which is full of, to be placed in the ring in flat metal sheets and pays attention to not blistering.After cooling, the pocket knife after slightly heating is utilized It will be cut off from the part for the planar projections for wrapping ring-containing upper end.Then, eyelid retractor (ring seat) is put into a diameter of 85mm or more, height Degree is in the glass container (heating bath) of 127mm or more, and injection glycerine is until depth is 90mm or more.Then, by steel ball (diameter 9.5mm, weight 3.5g) it is immersed in glycerine in a manner of mutually non-touching with the ring for being filled with sample, make the temperature of glycerine 20 DEG C ± 5 DEG C are kept for 15 minutes.Then, steel ball is placed in the center on the surface of the sample in ring, is placed it on eyelid retractor Fixed position.Then, make to remain 50mm from the upper end of ring to the distance in glycerine face, thermometer is placed, by the mercury of thermometer The position at the center of ball is adjusted to height identical with the center of ring, and is heated to container.Adjust the sheet used in heating The flame of raw burner is located at the centre at the center and edge of the bottom of container, to make homogeneous heating.It needs to illustrate It is that the increased proportion that the bath temperature after 40 DEG C is reached since heating is necessary for 5.0 DEG C ± 0.5 DEG C per minute.Sample is gradually soft Change and flowed down from ring, temperature when final contact base plate is read, as softening point.The measurement of softening point is carried out at the same time two More than secondary, using its average value.
As tackifying resin THFor, above-mentioned phenols tackifying resin, terpene resin, modified terpene resin, pine can be used One or more of fragrant class tackifying resin, Petropols, styrene resin, coumarone-indene resin, ketone resins etc.. Wherein, the preferred carboxylate of terpene phenol resin, rosin phenol resin, terpene resin, newtrex, newtrex.
As a preferred embodiment, it can enumerate and use one or more kinds of terpene phenol resins as tackifying resin TH1's Mode.For example, it is preferable to tackifying resin TH25 weight % or more (more preferably 30 weight % or more) be terpene phenol resin (thickening Resin TH1) mode.In addition, tackifying resin THIn terpene phenol resin amount can be about 70 weight % or less (be, for example, 60 weights % is measured hereinafter, typically 50 weight % or less).Alternatively, can be tackifying resin TH50 weight % or more be terpene phenolic tree Fat (tackifying resin TH1), can also be 80 weight % or more (such as 90 weight % or more) be terpene phenol resin (tackifying resin TH1), can also be tackifying resin THSubstantial whole (be, for example, 95~100 weight %, further be 99~100 weight %) For terpene phenol resin (tackifying resin TH1).It can preferably use softening point for 120 DEG C or more and 200 DEG C or less (typically 130 DEG C or more and 180 DEG C hereinafter, for example, 135 DEG C or more and 170 DEG C or less) terpene phenol resin.
Tackifying resin T in whole tackifying resins contained in adhesive phase disclosed hereinH1Shared ratio is not special Limitation.Aforementioned proportion is for example, it can be set to for 30 weight % or more (typically 40 weight % or more), in addition can for example set It is set to 70 weight % or less (typically 60 weight % or less).Alternatively, can also be the substantial whole of whole tackifying resins (be, for example, 95 weight of weight %~100 %, be further the 99 weight % of weight %~100) is tackifying resin TH1。
In addition, technology disclosed herein can preferably contain and tackifying resin TH1(typically terpene phenol resin) is different Tackifying resin TH2As tackifying resin THMode implement.Tackifying resin TH2Softening point be preferably shorter than tackifying resin TH1's Softening point, more preferably than tackifying resin TH1Low about 10 DEG C of softening point or more (such as 20 DEG C or more).According to which, such as can To realize the superior bonding sheet of peel strength.From the viewpoint of taking into account coherency and peel strength with high level, Ke Yiyou Choosing uses softening point for 100 DEG C less than 120 DEG C of tackifying resin TH2.Wherein, it is preferable to use softening point is 110 DEG C or more And the tackifying resin T less than 120 DEG CH2。
As tackifying resin TH2For, can suitably select and using above-mentioned various tackifying resins (phenols tackifying resin, Terpene resin, modified terpene resin, rosin tackifying resin, Petropols, styrene resin, coumarone-indene resin, ketone tree Fat etc.).Technology disclosed herein preferably can contain at least one of Petropols and terpene resin with above-mentioned adhesive and make For above-mentioned tackifying resin TH2Mode implement.For example, tackifying resin T can be used preferablyH2Main component (that is, tackifying resin TH2In the ingredient accounted for more than 50 weight %) be the composition of Petropols, the composition that is terpene resin, be Petropols and terpenes The composition etc. of the combination of resin.From the viewpoint of bonding force and compatibility, preferably tackifying resin TH2Main component be terpenes The mode of resin (for example, australene alkene polymer, beta-pinene polymer).Can be tackifying resin TH2Substantial whole (such as 95 weight % or more) it is terpene resin.
Adhesive phase disclosed herein contains tackifying resin TH1With tackifying resin TH2As tackifying resin THIn the case of, it Usage amount relationship preferably so that TH1:TH2Weight ratio be 25:75~70:30 (more preferably 30:70~60:40) Mode set.Technology disclosed herein can preferably be contained with above-mentioned adhesive and compare TH2More TH1As tackifying resin Mode implement.According to which, the bonding sheet of higher performance may be implemented.
Technology disclosed herein for example can preferably contain hydroxyl value be 80mgKOH/g or more (such as 90mgKOH/g with On) tackifying resin (THO1) it is used as tackifying resin THMode implement.Tackifying resin THO1Hydroxyl value be typically 200mgKOH/ G is hereinafter, preferably 180mgKOH/g or less (such as 160mgKOH/g or less).According to containing tackifying resin THO1Adhesive, can To realize the bonding sheet of higher performance.It may be implemented to take into account coherency and other characteristics (for example, the initial glue of low temperature with higher level Viscosity etc.) bonding sheet.
Here, the value of above-mentioned hydroxyl value may be used through JIS K0070：Potentiometric determination specified in 1992 Value.Specific assay method is as follows.
[assay method of hydroxyl value]
1. reagent
(1) it is used as acetylation reagent, uses the reagent obtained in the following way：Take acetic anhydride about 12.5g (about 11.8mL), it adds pyridine thereto and total amount is made to be 50mL, and be sufficiently carried out stirring.Or it uses and obtains in the following way The reagent arrived：Acetic anhydride about 25g (about 23.5mL) is taken, pyridine is added thereto and total amount is made to be 100mL, and be sufficiently carried out and stir It mixes.
(2) it is used as measure reagent, uses 0.5mol/L potassium hydroxide-ethanol solutions.
(3) in addition to this, prepare toluene, pyridine, ethyl alcohol and distilled water.
2. operation
(1) about 2g samples are accurately weighed in boiling flask, add 5mL acetylation reagents and 10mL pyridines, and sky is installed Gas condenser pipe.
(2) above-mentioned flask is heated in 100 DEG C of bath 70 minutes, then natural cooling, is added from the top of condenser pipe 35mL toluene is as solvent and is stirred, and then adds 1mL distilled water and is stirred, thus decomposes acetic anhydride.In order to Keep decomposition complete, is heated 10 minutes in bath again, and natural cooling.
(3) it utilizes 5mL ethyl alcohol to clean condenser pipe, and removes condenser pipe.Then, addition 50mL pyridines as solvent and carry out Stirring.
(4) whole pipette is utilized to add 25mL 0.5mol/L potassium hydroxide-ethanol solutions.
(5) constant-current titration is carried out using 0.5mol/L potassium hydroxide-ethanol solutions.By the inflection point of obtained titration curve As terminal.
(6) blank test is that above-mentioned (1)~(5) are carried out in the case where not being put into sample.
3. calculating
It is calculate by the following formula hydroxyl value.
Hydroxyl value (mgKOH/g)=[(B-C) × f × 28.05]/S+D
Wherein,
B：The amount (mL) of the 0.5mol/L potassium hydroxide-ethanol solutions used in blank test,
C：The amount (mL) of the 0.5mol/L potassium hydroxide-ethanol solutions used in sample,
f：The factor of 0.5mol/L potassium hydroxide-ethanol solutions,
S：The weight (g) of sample,
D：Acid value,
28.05：The 1/2 of the molecular weight 56.11 of potassium hydroxide.
As tackifying resin THO1For, it can be by the hydroxyl value in above-mentioned various tackifying resins with specified value or more Tackifying resin is independent or appropriately combined use.In a preferred embodiment, at least use terpene phenol resin as tackifying resin THO1.Terpene phenol resin can arbitrarily control hydroxyl value by the copolymerization ratios of phenol, therefore preferably.Terpene phenol resin is viscosifying Resin THO1In shared ratio to be even more preferably about 50 weight % or more (be, for example, 80 weight % or more, typically 90 weight % More than), further preferred tackifying resin THO1Substantial whole (be, for example, 95 weight of weight %~100 %, further be 99 The weight % of weight %~100) it is terpene phenol resin.
Technology disclosed herein is to use containing tackifying resin THO1Adhesive phase mode implement in the case of, thickening Resin THO1Shared ratio is not particularly limited in whole tackifying resins.Aforementioned proportion is for example, it can be set to be 10 weight % Above (typically 20 weight % or more), in addition, for example, it can be set to for 70 weight % or less (typically 60 weight % with Under).Alternatively, the substantial whole that can be whole tackifying resins (is for example, 95 weight of weight %~100 %, further 99 The weight % of weight %~100) it is tackifying resin THO1。
Adhesive phase disclosed herein can containing hydroxyl value be 0 less than 80mgKOH/g tackifying resin (THO2) make For tackifying resin TH.Tackifying resin THO2Tackifying resin T can be substitutedHO1It uses, it can also be with tackifying resin THO1It is applied in combination. As a preferred embodiment, can enumerate containing the tackifying resin T that hydroxyl value is 80mgKOH/g or moreHO1With tackifying resin THO2's Mode.
As tackifying resin THO2For, above-mentioned various tackifying resin middle hydroxyl values can be in the thickening of above range Resin is independent or appropriately combined use.It is, for example, possible to use hydroxyl value be 0 less than 80mgKOH/g phenols tackifying resin (for example, terpene phenol resin, rosin phenol resin), Petropols (for example, C5 classes Petropols), terpene resin are (for example, nopinene Polymer), rosin (such as newtrex), rosin derivative resin (for example, carboxylate of newtrex) etc..It is excellent at one It selects in mode, at least uses terpene phenol resin as tackifying resin THO2.Terpene phenol resin can be appointed by the copolymerization ratios of phenol Meaning ground control hydroxyl value, therefore preferably.Terpene phenol resin is in tackifying resin THO2In shared ratio can be about 50 weight % or more (being, for example, 80 weight % or more, typically 90 weight % or more), can also be tackifying resin THO2Substantial whole (example Such as it is 95 weight of weight %~100 %, is further the 99 weight % of weight %~100) it is terpene phenol resin.
Technology disclosed herein is to use containing tackifying resin THO2Adhesive phase mode implement in the case of, thickening Resin THO2Shared ratio is not particularly limited in whole tackifying resins.Aforementioned proportion is for example, it can be set to be 10 weight % Above (typically 20 weight % or more), in addition, for example, it can be set to for 70 weight % or less (typically 60 weight % with Under).Alternatively, the substantial whole that can be whole tackifying resins (is for example, 95 weight of weight %~100 %, further 99 The weight % of weight %~100) it is tackifying resin THO2。
Technology disclosed herein can preferably be 80mgKOH/g or more (typical containing hydroxyl value with the combination of above-mentioned adhesive phase Ground be 80mgKOH/g~160mgKOH/g, for example, 80mgKOH/g~140mgKOH/g) tackifying resin THO1It is with hydroxyl value Tackifying resin Ts of the 40mgKOH/g less than 80mgKOH/gHO2Mode implement.In this case, THO1With THO2Use The relationship of amount for example can be with so that weight ratio (THO1:THO2) it is 1:5~5:The mode of 1 range is set, so that weight Amount is than being 1:3~3:1 (such as 1:2~2:1) it is appropriate that the mode of range, which carries out setting,.It, can as a preferred embodiment To enumerate THO1、THO2It is the mode of terpene phenol resin.
In one mode of technology disclosed herein, above-mentioned tackifying resin THIt can also contain and be with aromatic rings and hydroxyl value 30mgKOH/g tackifying resin T belowHR1As with tackifying resin THO1、THO2Different tackifying resins.As with aromatic rings Tackifying resin example for, above-mentioned aromatic Petropols, aliphatic/aromatic Copolymer oil tree can be enumerated Fat, styrene resin, coumarone-indene resin, styrenated terpene resins, terpenes-phenol copolymer resin, phenol modified terpene tree Fat, rosin phenol resin etc..Among these, may be used softening point be 120 DEG C or more (be preferably 130 DEG C or more, for example, 135 DEG C or more) and tackifying resin conduct that hydroxyl value is 30mgKOH/g or less (preferably smaller than 5mgKOH/g, be, for example, less than 1mgKOH/g) Tackifying resin THR1.Wherein, as preferred tackifying resin THR1, aromatic Petropols and styrene resin can be enumerated (for example, α-methylstyrene/styrene copolymer resin).It should be noted that technology disclosed herein can also be with bonding Oxidant layer is substantially free of tackifying resin THR1Mode implement.
In another mode of adhesive disclosed herein, above-mentioned tackifying resin THCan contain has aromatic rings and essence The upper tackifying resin T without isoprene unit, terpenes skeleton and rosin skeletonHR2As with tackifying resin THO1、THO2Different Tackifying resin.Here, tackifying resin THR2It refers to these knots to be substantially free of isoprene unit, terpenes skeleton and rosin skeleton Structure part (that is, isoprene unit, terpenes skeleton and rosin skeleton) is in tackifying resin THR2In shared ratio is total is less than 10 Weight % (more preferably less than 8 weight %, is further preferably no larger than 5 weight %, be, for example, less than 3 weight %).Aforementioned proportion can be with For 0 weight %.It should be noted that isoprene unit, terpenes skeleton and rosin skeleton are in tackifying resin THR2In shared ratio Example can be for example measured by NMR (nuclear magnetic resonance spectroscopy).
As with aromatic rings and being substantially free of the tackifying resin of isoprene unit, terpenes skeleton and rosin skeleton For example, can enumerate above-mentioned aromatic Petropols, aliphatic/aromatic Copolymer Petropols, styrene resin, Coumarone-indene resin etc..Among these, may be used softening point be 120 DEG C or more (be preferably 130 DEG C or more, for example, 135 DEG C or more) tackifying resin as tackifying resin THR2.Wherein, as preferred tackifying resin THR2, aromatic can be enumerated Petropols and styrene resin (for example, α-methylstyrene/styrene copolymer resin).Although being not particularly limited, As tackifying resin THR2For, due to tackifying resin THR1Same reason, can preferably use hydroxyl value be 30mgKOH/g with Under (preferably smaller than 5mgKOH/g, be, for example, less than 1mgKOH/g) tackifying resin.Therefore, as the increasing in technology disclosed herein Viscosity resin THR2For it is preferable to use also comply with tackifying resin THR1Tackifying resin.Similarly, as skill disclosed herein Tackifying resin T in artHR1It is preferable to use also comply with tackifying resin THR2Tackifying resin.It should be noted that public herein The technology opened can also be substantially free of tackifying resin T with adhesive phaseHR2Mode implement.
In addition, from the viewpoint of improving coherency, relative to 100 parts by weight of unsaturated rubber, tackifying resin THIt is total It is appropriate, preferably 20 weights that amount (that is, the total amount for the tackifying resin that softening point is 100 DEG C or more), which is set as 10 parts by weight or more, Measure part or more (being, for example, 25 parts by weight or more).In addition, relative to 100 parts by weight of unsaturated rubber, tackifying resin THContent For example, it can be set to being 60 parts by weight.From the viewpoint of viscosity, low-temperature characteristics, relative to 100 parts by weight of unsaturated rubber, increase Viscosity resin THContent be preferably 50 parts by weight or less, more preferably (being, for example, 40 parts by weight or less) below 45 parts by weight.
From the viewpoint of balancedly taking into account coherency and low-temperature characteristics (such as the initial adhesivity of low temperature), tackifying resin TH It is appropriate, preferably 80 weight % or more that shared ratio, which is set as about 50 weight % or more, in the total amount of tackifying resin (being, for example, 90 weight % or more).Technology disclosed herein can preferably (be, for example, 95 weights with the substantial whole of tackifying resin Measure the weight of %~100 %, be further the 99 weight % of weight %~100) it is tackifying resin THMode implement.
(tackifying resin TL)
Adhesive phase disclosed herein can be less than 100 DEG C of tackifying resin T containing softening pointL.Tackifying resin TLSoftening The lower limit of point is not particularly limited.It is the tackifying resin of 40 DEG C or more (typically 60 DEG C or more) that softening point, which can be used,.Increase Viscosity resin TLHydroxyl value, structure is (for example, the presence or absence of the presence or absence of the presence or absence of aromatic rings, isoprene unit, terpenes skeleton, rosin The presence or absence of skeleton etc.) it is not particularly limited.Appropriate selection uses above-mentioned various tackifying resins (phenols tackifying resin, terpenes Resin, modified terpene resinoid, rosin tackifying resin, Petropols, styrene resin, coumarone-indene resin, ketone tree Fat etc.) in softening point be less than 100 DEG C of tackifying resin.
(content of tackifying resin)
In technology disclosed herein, the total amount (total content) of tackifying resin is not particularly limited, can be according to purpose, use Way is set in a manner of it can obtain desired performance.Relative to 100 parts by weight of unsaturated rubber, tackifying resin it is total Amount can be 5 parts by weight or more or 10 parts by weight or more for example, it can be set to be more than 1 parts by weight.From obtaining higher Bond properties (such as bonding force) from the viewpoint of, relative to 100 parts by weight of unsaturated rubber, the total amount of tackifying resin can be with For it is more than 15 parts by weight, or 20 parts by weight more than, or 25 parts by weight more than, or 30 parts by weight with On.In some modes, relative to 100 parts by weight of unsaturated rubber, the total amount of tackifying resin can be 40 parts by weight or more, Can be 55 parts by weight or more.In addition, from good viscosity, the cryogenic property easy to implement of playing (for example, the initial glue under low temperature Viscosity) adhesive from the viewpoint of, relative to 100 parts by weight of unsaturated rubber, the total amount of tackifying resin is usually 120 weight Part or less be appropriate, below preferably 100 parts by weight, more preferably below 80 parts by weight.In some modes, relative to not The total amount of 100 parts by weight of saturated rubber, tackifying resin can be 60 parts by weight or less or 50 parts by weight or less, also may be used Think 45 parts by weight or less (being, for example, 40 parts by weight or less).
<Antiaging agent>
Antiaging agent can be contained in adhesive disclosed herein as needed.By using antiaging agent, can improve Combine the Mw of the adhesive containing unsaturated rubber and tackifying resinHConservation rate can realize the long-term stay in grade of bonding sheet The raising (long lifetime) of property.Antiaging agent can be used alone, it is two or more to be applied in combination, can also combine Use three kinds or more.
(free radical scavenger)
In some modes, antiaging agent can include free radical scavenger (radical scavenger).It is caught as free radical For catching the example of agent, can enumerate phenol antioxidant, hindered amines antioxidant, aromatic amine antioxidant etc. can be with The well known free radical scavenger used in the field of unsaturated rubber.Free radical scavenger can be used alone or group It closes using two or more.
As in technology disclosed herein can it is preferable to use free radical scavenger example, phenols antioxygen can be enumerated Agent.For the non-limiting example of phenol antioxidant, it can enumerate：2,6 di tert butyl 4 methyl phenol, 2, The list phenol antioxidant such as 6- di-t-butyl -4- ethyl -phenols；2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenols), 2, It is 2 '-methylene-bis(4-ethyl-6-t-butyl phenol)s, 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol)s, 4,4 '-thio Bis-phenolic antioxidants such as bis- (3 methy 6 tert butyl phenols)；(3,5- di-t-butyls-the 4- of 1,3,5- trimethyls -2,4,6- three Hydroxybenzyl) benzene, four [methylene -3- (3 ', 5 '-di-t-butyls -4 '-hydroxy phenyl) propionic ester] methane, (the 2- first of 1,1,3- tri- Base -4- hydroxyl -5- tert-butyl-phenyls) high molecular weight such as butane phenol antioxidant；Deng.
Phenol antioxidant can be hindered phenol anti-oxidants.As the non-limiting of above-mentioned hindered phenol anti-oxidants Example for, can enumerate：Pentaerythrite four [3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester], 3- (bis- uncles of 3,5- Butyl -4- hydroxy phenyls) propionic acid stearyl, bis- (dodecylthiomethyl) o-cresols of 4,6-, the 4- [[bis- (octyls of 4,6- Sulfenyl) -1,3,5- triazine -2- bases] amino] -2,6 di t butyl phenol, the bis- [3- (3- tertiary butyl -5- methyl -4- of triethylene glycol Hydroxy phenyl) propionic ester], decanedioic acid bis- (2,2,6,6- tetramethyl -4- piperidyls) ester, dimethyl succinate and hydroxyl -2 4-, Condensation polymer (dimethyl succinate -1- (2- the hydroxyethyls) -4- hydroxyls -2,2,6,6- four of 2,6,6- tetramethyl -1- piperidine ethanols Methyl piperidine condensation polymer) etc..
Relative to 100 parts by weight of unsaturated rubber, the usage amount of free radical scavenger (such as phenol antioxidant) is for example 0.01 parts by weight or more are can be set as, it is appropriate to be typically set at 0.05 parts by weight or more, can be 0.1 parts by weight or more (such as more than 0.5 parts by weight).By the usage amount for increasing free radical scavenger, it is intended to MwHConservation rate increases, bonding sheet Quality stability improves.From the harmful effect (for example, the coherency of the adhesive before aging reduces) inhibited to bond properties Viewpoint considers that, relative to 100 parts by weight of unsaturated rubber, the usage amount of free radical scavenger is typically set at 10 parts by weight or less It is appropriate, is preferably set to 5 parts by weight or less (such as below 3 parts by weight).
(sulphur-containing antioxidant)
In some modes, antiaging agent can include sulphur-containing antioxidant.Sulphur-containing antioxidant is used as will be viscous The peroxide generated in mixture decomposes and/or is converted into the peroxide decomposer of stable compound and constantly acts as With it is possible thereby to help to improve MwHConservation rate (and then improving the quality stability of bonding sheet).Containing unsaturated rubber and It is especially effective using sulphur-containing antioxidant in the adhesive of phenols tackifying resin (such as terpene phenol resin).
For sulphur-containing antioxidant, the thioether antioxidants that intramolecular has sulfide based structural can be used for example. For the non-limiting example of sulphur-containing antioxidant, it can enumerate：Bis- ({ [3- (dodecyl sulfenyl) propionyl of 2,2- Base] oxygroup methyl) propane diyl-bis- [3- (dodecyl sulfenyl) propionic ester], bis- [2- methyl -4- (3- dodecyl sulphur For propionyloxy) -5- tert-butyl-phenyls] thioether, 3- dodecyl thiohydracrylic acid -2- tertiary butyls -4- [(5- tertiary butyl -4- hydroxyls Base -2- aminomethyl phenyls) sulfenyl] -5- methyl phenyl ester, 3,3 '-dilauryl thiodipropionates, 3,3 '-thio-2 acids two (13 Alkyl) ester, 3,3 '-thio-2 acid, two myristin, 3,3 '-distearylthiodi-propionates, (the lauryl sulphur of pentaerythrite four For propionic ester) etc..Sulphur-containing antioxidant can be used alone or be applied in combination two or more.It, can be in some modes It is preferred that using the sulphur-containing antioxidant (typically thioether antioxidants) of the structure without aromatic rings.Furthermore it is possible to it is preferred that There is one or more (for example, three or four) "-CH using an intramolecular2-OC(O)-CH2CH2-S-CH2" structure Thioether antioxidants.
The quantity of thioether sulphur atom contained in the thioether antioxidants of one molecule can be one, or two More than a.From the viewpoint of the duration of effect, more than two (typically two or more and four are contained in a preferably molecule It is a following) thioether antioxidants of thioether sulphur atom.In some modes, (correspond to one by using thioether equivalent The molecular weight of thioether sulphur atom) it is 1000 or less (preferably 700 or less, more preferably 500 hereinafter, such as 350 or less) Thioether antioxidants can effectively improve Mw while inhibiting the influence to bond propertiesHConservation rate.In addition, from effect From the viewpoint of fruit duration, thioether equivalent is preferably 150 or more, more preferably 200 or more.Thioether equivalent can by with point Son amount divided by the quantity of thioether sulphur atom are calculated.
It is appropriate, preferably 1500 or less (such as 1250 or less) that the molecular weight of sulphur-containing antioxidant, which is 2000 or less,. By using the sulphur-containing antioxidant, the influence (for example, viscosity, the initial adhesivity of low temperature) to bond properties can inhibited Simultaneously effective improve MwHConservation rate.In addition, from the viewpoint of the duration of effect, the molecular weight of sulphur-containing antioxidant is 150 or more be it is appropriate, preferably 200 or more, more preferably 350 or more.
The usage amount of the sulphur-containing antioxidant of amount relative to unsaturated rubber for example can be with so that the sulfur-bearing be anti-oxidant The molal quantity of thioether sulphur (S) contained in agent is carried out relative to the mode that above-mentioned unsaturated rubber 100g is 0.01mmol or more Setting.Hereinafter, " S molal quantitys " will be known as relative to the molal quantity of the thioether sulphur of unsaturated rubber 100g, with mmol/ sometimes The unit of 100g indicates.It is appropriate that S molal quantitys, which are typically set at 0.05mmol/100g or more, is preferably set to 0.1mmol/ 100g or more, it can be set as 0.2mmol/100g or more, 0.5mmol/100g or more (such as 0.8mmol/ can also be set as 100g or more).By increasing the S molal quantitys of sulphur-containing antioxidant, there is MwHWhat conservation rate raising, quality stability improved inclines To.Technology disclosed herein can also preferably be the side of 1mmol/100g or more (such as 2mmol/100g or more) with S molal quantitys Formula, the mode that S molal quantitys are 4mmol/100g or more (such as 5mmol/100g or more) are implemented.In addition, S molal quantitys for example can be with It is set as 100mmol/100g hereinafter, from the harmful effect inhibited to bond properties (for example, sticky, the initial adhesivity of low temperature Reduce) from the viewpoint of, it is appropriate to be typically set at 50mmol/100g or less, is preferably set to 30mmol/100g or less. Technology disclosed herein can also preferably in such a way that S molal quantitys are 20mmol/100g below, S molal quantitys is 15mmol/100g The mode of (such as 10mmol/100g or less) is implemented below.
Relative to 100 parts by weight of unsaturated rubber, the usage amount of sulphur-containing antioxidant is for example, it can be set to be 0.01 weight Part or more, more than usual 0.01 parts by weight be appropriate, can also be set as 0.05 parts by weight or more (such as 0.1 parts by weight with On).By increasing the usage amount of sulphur-containing antioxidant, there is MwHThe tendency that conservation rate improves.In addition, from inhibiting to adhesiveness From the viewpoint of the harmful effect (for example, reduction of viscosity, the initial adhesivity of low temperature) of energy, relative to 100 weight of unsaturated rubber Part is measured, it is appropriate that the usage amount of sulphur-containing antioxidant, which is usually 10 parts by weight or less, below preferably 7 parts by weight, more preferably It is set as 5 parts by weight or less (such as below 3 parts by weight).
The usage amount of sulphur-containing antioxidant based on the S molar ratio of 100 parts by weight of unsaturated rubber can for example set It is set to 0.01 or more, usually 0.05 or more is appropriate, can also be set as 0.1 or more (such as 0.5 or more).Pass through increase The S molar ratio of sulphur-containing antioxidant has MwHThe tendency that conservation rate increases, quality stability improves.In addition, from inhibiting to viscous From the viewpoint of the harmful effect (for example, reduction of viscosity, the initial adhesivity of low temperature) for closing performance, relative to unsaturated rubber The usage amount of the sulphur-containing antioxidant of 100 parts by weight in terms of S molar ratio be usually 15 or less be it is appropriate, preferably 10 or less, It is preferably set to 7 or less (such as 6 or less).It is examined from the viewpoint of the coloring (such as xanthochromia) of adhesive caused by aging is inhibited Consider, reducing S molar ratio can also become advantageous.Here, S molar ratio refers to the sulfur-bearing relative to 100 parts by weight of unsaturated rubber The parts by weight of the usage amount of antioxidant are multiplied by the quantity of thioether sulphur contained in one molecule of sulphur-containing antioxidant and obtain The value arrived.For example, anti-containing the sulphur-containing antioxidant of 1 parts by weight and the sulfur-bearing relative to 100 parts by weight of unsaturated rubber Oxidant in a molecule containing there are two in the case of thioether sulphur, S moles of above-mentioned sulphur-containing antioxidant in the composition Than being calculated as 2.
(phosphorous antioxidant)
In some modes, antiaging agent can include phosphorous antioxidant.Phosphorous antioxidant is used as will be viscous The peroxide generated in mixture decomposes or is converted into the peroxide decomposer of stable compound and works, it is possible thereby to Help to improve MwHConservation rate (and then improving the quality stability of bonding sheet).As the non-limiting of phosphorous antioxidant For example, it can enumerate：Phosphorous acid three (2,4- di-tert-butyl-phenyls) ester, phosphorous acid three (nonyl phenyl) ester, phosphorous acid three Phenyl ester, distearyl pentaerythrityl diphosphite etc..
The usage amount of phosphorous antioxidant is relative to 100 parts by weight of unsaturated rubber for example, it can be set to being 0.05 parts by weight More than, more than 0.1 parts by weight it is usually appropriate, can be set as 0.5 parts by weight or more (such as more than 1 parts by weight).It is logical The usage amount for increasing phosphorous antioxidant is crossed, there is MwHThe tendency that conservation rate improves.In addition, from inhibiting to bond properties not From the viewpoint of good influence (for example, reduction of viscosity, the initial adhesivity of low temperature), relative to 100 parts by weight of unsaturated rubber, contain The usage amount of phosphorus antioxidant is usually that 15 parts by weight or less are appropriate, below preferably 10 parts by weight, is more preferably set as 7 (such as below 5 parts by weight) below parts by weight.
In some modes, for antiaging agent, sulphur-containing antioxidant (such as thioether class antioxygen can be applied in combination Agent) and phosphorous antioxidant.According to which, the harmful effect to bond properties can be inhibited to effectively improve MwH Conservation rate.Its reason does not do limited explanation especially, such as can consider as follows.That is, compared with sulphur-containing antioxidant, it is phosphorous anti- Oxidant normally tend to quickly with peroxide reactions.On the other hand, phosphorous antioxidant passes through anti-with peroxide It answers and is irreversibly consumed, therefore, at 80 DEG C in the harsh degradation in four weeks, it is possible to which its effect continues Sexual orientation is in deficiency.By and with sulphur-containing antioxidant and phosphorous antioxidant both peroxide decomposers, can press down Good peroxide decomposition function is constantly played while making the influence to adhesion characteristic.In addition, resisting by and with sulfur-bearing Oxidant and phosphorous antioxidant, can reduce the usage amount of sulphur-containing antioxidant, this can contribute to the warp for inhibiting adhesive When property colours.By the way that sulphur-containing antioxidant, phosphorous antioxidant and phenol antioxidant is applied in combination, may be implemented preferably As a result.
Although being not particularly limited, and with phosphorous antioxidant and in the case of thioether antioxidants, relative to The usage amount A of the thioether antioxidants of 100 parts by weight of unsaturated rubberS[S molar ratio] and relative to the unsaturated rubber 100 The usage amount A of the phosphorous antioxidant of parts by weightPThe ratio between [parts by weight], i.e. AS/APFor example, it can be set to for 0.1~10 range. By being set as the range, it is intended to can suitably play and be imitated caused by sulphur-containing antioxidant and phosphorous antioxidant Fruit.From the viewpoint of obtaining more good effect, in some modes, AS/APCan be 0.2 or more, or 0.5 with On.In addition, AS/APCan be 5 or less or 3 or less.It should be noted that APAnd ASIt each refers to parts by weight and S Molar ratio indicates the numerical part when usage amount relative to 100 parts by weight of unsaturated rubber, APAnd ASValue itself be dimensionless Number.
Free radical scavenger disclosed herein can be with one of phosphorous antioxidant and thioether antioxidants or two Person combines or can include that the other antioxidants that can be worked as peroxide decomposer replace these anti-oxidant Agent.As the example of such other antioxidants, can enumerate：Amine antioxidants (phenyl-α-naphthylamine, diphenylamines etc.), Benzimidazole antioxidant etc..Above-mentioned other antioxidants can be used alone, but generally preferably with free radical scavenger (example Such as phenol antioxidant) it is applied in combination.
(content of antiaging agent)
Although being not particularly limited, the total amount of antiaging agent is relative to unsaturation contained in adhesive disclosed herein 100 parts by weight of rubber for example, it can be set to be about 20 parts by weight hereinafter, be typically set at 15 parts by weight or less be it is appropriate, can be with It is set as 10 parts by weight or less.Technology disclosed herein can be preferably with relative to used in 100 parts by weight of unsaturated rubber The total amount of antiaging agent is that the mode of 7 parts by weight or less (such as below 5 parts by weight or below 4 parts by weight) is implemented.In addition, phase For 100 parts by weight of unsaturated rubber, the total amount of above-mentioned antiaging agent for example, it can be set to for it is more than 0.5 parts by weight, can also It is set as 1 parts by weight or more, 1.5 parts by weight or more can also be set as, 2 parts by weight or more can also be set as.
<Isocyanate compound>
Adhesive phase disclosed herein can be by also containing isocyanates in addition to unsaturated rubber and tackifying resin The adhesive phase that the adhesive composition of compound is formed.According to the adhesive composition, long-term quality stability may be implemented Superior (such as, it is suppressed that the reduction of coherency) bonding sheet.As for isocyanate compound it is preferable to use Polyfunctional isocyanate (refers to the compound that each molecule has average more than two isocyanate group, including having isocyanide urea The substance of acrylate structure).For the polyfunctional isocyanate, can use has more than two isocyanides in a molecule One or more of various isocyanate compounds (polyisocyanates) of perester radical.As the polyfunctional isocyanate Example, can enumerate：Aliphatic polyisocyante class, alicyclic polyisocyanates class, aromatic polyisocyanate class etc..
For concrete example as aliphatic polyisocyante class, it can enumerate：1,2- ethylidene diisocyanates；1,2- The tetramethylene diisocyanates such as tetramethylene diisocyanate, 1,3- tetramethylene diisocyanates, 1,4- tetramethylene diisocyanates； 1,2- hexylidene diisocyanates, 1,3- hexylidene diisocyanates, 1,4- hexylidene diisocyanates, 1,5- hexylidenes two are different The hexylidene diisocyanates such as cyanate, 1,6- hexylidene diisocyanates, 2,5- hexylidene diisocyanates；2- methyl-1s, Penta diisocyanate of 5-, 3- methyl-1s, penta diisocyanate of 5-, lysine diisocyanate etc..
For concrete example as alicyclic polyisocyanates class, it can enumerate：Isophorone diisocyanate；1,2- rings The cyclohexyl diisocyanates such as hexyl diisocyanate, 1,3- cyclohexyl diisocyanates, 1,4- cyclohexyl diisocyanates；1, The cyclopenta diisocyanate such as 2- cyclopenta diisocyanate, 1,3- cyclopenta diisocyanate；It is different to hydrogenate phenylenedimethylidyne two Cyanate, hydrogenated toluene diisocyanate, hydrogenated diphenyl methane diisocyanate, hydrogenation tetramethyl xylene diisocyanate Ester, 4,4 '-dicyclohexyl methyl hydride diisocyanates etc..
As the concrete example of aromatic polyisocyanate class, can enumerate：2,4 toluene diisocyanate, 2,6- toluene two Isocyanates, 4,4 '-methyl diphenylene diisocyanates, 2,4 '-methyl diphenylene diisocyanates, 2,2 '-diphenyl methanes Diisocyanate, 4,4 '-diphenyl ether diisocyanates, 2 nitro biphenyl -4,4 '-diisocyanate, 2,2 '-diphenylprops Alkane -4,4 '-diisocyanate, 3,3 '-dimethyl diphenylmethanes -4,4 '-diisocyanate, 4,4 '-diphenyl propanes two are different Cyanate, m-benzene diisocyanate, paraphenylene diisocyanate, 1,4- naphthalene diisocyanates, 1,5- naphthalene diisocyanates, 3,3 '- Dimethoxy-biphenyl -4,4 '-diisocyanate, 1,4- benzene dimethylene diisocyanate, 1,3- phenylenedimethylidyne diisocyanates Ester etc..
As preferred isocyanate compound, may be exemplified each molecule has average three or more isocyanate group Polyfunctional isocyanate.The isocyanates more than trifunctional can be the more of the isocyanates of two functions or trifunctional or more Polymers (being typically dimer or trimer), derivative are (for example, polyfunctional isocyanates more than polyalcohol and two molecules Addition reaction product), polymer etc..Can enumerate for example, the dimer or trimer of methyl diphenylene diisocyanate, it is sub- oneself Isocyanuric acid ester-formin (the trimer addition product of isocyanurate structure), trimethylolpropane and the toluene of group diisocyanate The reaction product of diisocyanate, the reaction product of trimethylolpropane and hexylidene diisocyanate, polymethylene polyphenyl The polyfunctional isocyanates such as isocyanates, polyethers polyisocyanates, polyester polyisocyanates.As the polyfunctional isocyanate's Commercially available product can be enumerated：The trade name " DURANATE TPA-100 " of chemical company of Asahi Chemical Industry manufacture, the quotient of Tosoh company manufacture The name of an article " CORONATE L ", " CORONATE HL ", " CORONATE HK ", " CORONATE HX ", " CORONATE 2096 " etc..
In the case of using isocyanate compound, usage amount is not particularly limited, such as relative to unsaturated rubber 100 parts by weight can be set as being more than 0 parts by weight and 10 parts by weight or less (typically 0.01 parts by weight~10 parts by weight).It is excellent It is (typical that choosing will be set as 0.1 parts by weight or more relative to the usage amount of the isocyanate compound of 100 parts by weight of unsaturated rubber Ground is 0.3 parts by weight or more, is, for example, 0.5 parts by weight or more), in addition, it is appropriate to be set as 10 parts by weight or less, preferably set It is set to 5 parts by weight or less (typically 3 parts by weight are hereinafter, below for example, 1 parts by weight).It is different by being used in the range The excellent bonding sheet of especially performance balance may be implemented in cyanate esters.
<Other ingredients>
In the limit for not damaging effect of the present invention, adhesive phase disclosed herein can contain one kind or two as needed Kind or more rubber-like polymer in addition to unsaturated rubber.The rubber-like polymer can be well known in the field of adhesive The various polymerizations such as rubber, acrylic compounds, polyesters, polyurethanes, polyethers, polysiloxane-based, polyamide-based, fluorine-containing type Object.It is poly- that technology disclosed herein preferably can contain substantially no the rubber-like in addition to unsaturated rubber with above-mentioned adhesive phase The mode (for example, the content relative to 100 parts by weight of unsaturated rubber is the mode of 0~1 parts by weight) for closing object is implemented.
Adhesive composition (or adhesive phase) disclosed herein can contain levelling agent, crosslinking as needed Agent, crosslinking coagent, plasticizer, softening agent, filler, colorant (pigment, dyestuff etc.), antistatic agent, ultra-violet absorber, light Common various additives in the adhesive fields such as stabilizer.About such various additives, can make by conventional method With conventionally known additive.
Adhesive disclosed herein can preferably contain substantially no the liquid rubbers such as polybutene (for example, relative to not The content of 100 parts by weight of saturated rubber be 1 parts by weight below, or 0 parts by weight) mode implement.It is strong from stripping is improved From the viewpoint of degree, coherency, which can become advantageous.
In some modes, above-mentioned adhesive composition can be the composition for being substantially free of chelate.Here, above-mentioned chela It refers to such as the oxide of alkaline-earth metal and with the functional group that can be coordinated with the oxide to close object (hydroxyl, methylol) The chelate of resin (alkyl phenolic resin etc.).Technology disclosed herein can be preferably entirely free of with above-mentioned adhesive composition It is that 1 weight % modes below are implemented to have the content ratio of such chelate or the chelate.According to which, Ke Yishi The superior bonding sheet of existing bonding force.
In some modes, above-mentioned adhesive can account for the adhesive for the total amount of unsaturated rubber and tackifying resin The 75 weight %'s or more of total weight (that is, the weight for the adhesive phase being made of the adhesive) forms.For example, can preferably adopt With 80 weight % or more (such as the 85 weight % for the total weight that the total amount of unsaturated rubber and tackifying resin is above-mentioned adhesive Above or 90 weight % or more) and be the mode of 99.8 weight % or less (typically such as 99.5 weight % or less).
<Adhesive composition>
Adhesive phase disclosed herein can be by the adhesive composition containing ingredient corresponding with the adhesive phase The layer of formation.The form of adhesive composition is not particularly limited, such as can be to contain in organic solvent as described above Adhesive composition, the adhesive of the form (solvent type) of the adhesive (adhesive composition) of composition are dispersed in the shape in aqueous solvent The adhesive composition of state (water-dispersion type, typically water-based emulsion type), the adhesive composition etc. of heat molten type.From coating Consider with viewpoints such as the selection degree of freedom of base material, can preferably use the adhesive composition of solvent type or water-dispersion type.From reality From the viewpoint of existing higher bond properties, particularly preferred solvent type adhesive composition.
Solvent type adhesive composition is typically prepared as containing the solution morphology of above-mentioned each ingredient in organic solvent.On Stating organic solvent can be from known or there are commonly suitably selected in solvent.It can be used for example selected from toluene, dimethylbenzene etc. Aromatic compound species (typically aromatic hydrocarbon)；The acetate esters such as ethyl acetate, butyl acetate；Hexane, hexamethylene, first The aliphatic such as butylcyclohexane or ester ring type hydro carbons；The alkyl halides hydro carbons such as 1,2- dichloroethanes；The ketone such as methyl ethyl ketone, acetylacetone,2,4-pentanedione Class；Any one solvent in or two or more mixed solvents.Although being not particularly limited, above-mentioned solvent type is bonded It is appropriate that it is 30 weight % or more (such as 40 weight % or more) that agent composition, which is prepared into nonvolatile component (NV), and is prepared At NV be 65 weight % or less (such as 55 weight % or less) be appropriate.When NV is too low, manufacturing cost is tended to increase, NV mistakes Gao Shi, the sometimes operability such as coating reduction.
For obtaining the method for bonding sheet by adhesive composition, conventionally known various methods can be applied.Example Such as, it can preferably use and be formed by directly applying and (being typically coated with) adhesive composition on base material and make it dry The method (direct method) of adhesive phase.Furthermore it is possible to using by the good surface of fissility (for example, the table of release liner Face, the supporting base material back side etc. through demoulding processing) on apply above-mentioned adhesive composition and make it dry and shape on a surface Composite adhesives layer and the method (transfer printing) that the adhesive phase is transferred to base material.
The coating of adhesive composition can be used for example gravure roll coating machine, reverse roll coater, roller and lick coating Machine, dipping roll coater, bar coater, knife type coater, known in flush coater etc. or common coating machine carries out.From Promote cross-linking reaction, improve the consideration of the viewpoints such as manufacture efficiency, the drying of adhesive composition preferably carries out under heating.For example, About 40 DEG C or more (being, for example, about 50 DEG C or more, be further about 70 DEG C or more) and about 150 DEG C or less can preferably be used The drying temperature of (be typically about 120 DEG C or less, be further about 100 DEG C or less).Drying time is not particularly limited, setting (within for example, about 5 minutes, to be preferably from about 30 seconds~about 2 minutes) from about tens seconds to about a few minutes.It is then possible to root According to needing that additional drying process is arranged.Adhesive phase typically be continuously formed, but can also according to purpose and purposes and Be formed as the regular or irregular pattern such as dotted, striated.
(thickness of adhesive phase)
Although being not particularly limited, the thickness of adhesive phase be about 4 μm or more (typically about 20 μm or more, for example Be about 30 μm or more) be appropriate, and be about 150 μm or less (typically about 120 μm or less, for example, about 100 μm with Under) it is appropriate.In some modes, the thickness of adhesive phase can be preferably 30 μm or more, more preferably 40 μm or more, into One step is preferably 50 μm or more (being, for example, 60 μm or more).The bonding sheet of adhesive phase with the thickness can be in the bonding Oxidant layer be the composition containing unsaturated rubber and tackifying resin in the case of play excellent bond properties (such as peel strength). It is, therefore, possible to provide highly taking into account the bonding sheet of bond properties and quality stability (long-life).Double-sided adhesive with base material In the case of closing piece, the composition of the two-sided adhesive phase for being respectively arranged with above-mentioned thickness of base material can be formed in.Each adhesive The thickness of layer can be the same or different.
<Bonding sheet>
(base material)
Technology disclosed herein is applied to the feelings of the double-sided adhesive sheet with base material or the single side bonding sheet with base material Under condition, for base material, it can suitably select to use for example following base material according to the purposes of bonding sheet：Polypropylene screen, ethylene- The plastic foils such as propylene copolymer film, polyester film, polychloroethylene film；Including polyurethane foam, polyethylene, polychloroprene foam The foaming body piece of equal foaming bodies；(can be the natural fibers such as fiber crops, cotton by various fibrous materials；The synthesis such as polyester, vinylon is fine Dimension；Semisynthetic fibres such as acetate fiber etc.) the obtained woven fabric such as independent or blended and non-woven fabrics be (for comprising Japan paper, glazed printing paper The Shang Quality Paper of () etc. stationeries meaning)；The metal foils such as aluminium foil, copper foil；Deng.(typically refer to non-porous plastics as above-mentioned plastic foil Film is the concept different from woven fabric or non-woven fabrics) for, unstretching film can be used and stretch (being stretched uniaxially or biaxially) Any one in film.Furthermore it is possible to implement the coating of silane coupling agent, corona discharge to the face that adhesive phase will be arranged in base material The surface treatments such as processing.
In a preferred embodiment, using non-woven fabrics (non-woven fabrics base material) as base material.By using non-woven fabrics base material, incline It is improved in the initial adhesivity of low temperature, coherency (for example, the performance being resistant in retentivity experiment without falling).As For the non-woven fabrics of base material, the nonwoven constituted such as natural fibers such as the pulp type by wood pulp, cotton, fiber crops can be used Cloth；By polyester fibers, artificial silk, vinylon, acetate fiber, polyvinyl alcohol such as polyethylene terephthalate (PET) fibers (PVA) non-woven fabrics that the chemical fibres such as fiber, Fypro, polyolefine fiber, polyurethane fiber (synthetic fibers) are constituted；And The non-woven fabrics constituted with the different two or more fibers of material；Deng.Wherein, from the infiltration of adhesive, resistance to resilience (curved surface Tracing ability) from the viewpoint of, preferably by paper pulp, the non-woven fabrics that fiber crops (such as jute pulp) are constituted, the non-woven fabrics being made of PET fiber Deng.Also contribute to improve flexibility, the tearing property of bonding sheet using non-woven fabrics base material.
For non-woven fabrics (non-woven fabrics base material), it can preferably use base weight (level ground amount) for about 30g/m2Below (such as It is about 25g/m2Below, it is typically about 20g/m2Non-woven fabrics below).The non-woven fabrics of the base weight be suitable for make light weight and The excellent bonding sheet of bond properties.From the viewpoint of resistance to resilience, preferred basis weights are less than 18g/m2(it is, for example, 16g/m2Below, Typically 15g/m2Non-woven fabrics below).From the viewpoint of the intensity for improving base material itself, above-mentioned base weight is preferably 10g/ m2(it is, for example, above 12g/m2Above, it is typically 13g/m2More than).
The bulk density (can be calculated with base weight divided by thickness) of non-woven fabrics base material is about 0.20g/cm3It is suitable above When, preferably 0.25g/cm3(it is, for example, above 0.30g/cm3More than), and be about 0.50g/cm3Be below it is appropriate, it is excellent It is selected as 0.40g/cm3(it is, for example, below 0.35g/cm3Below).Within the above range by bulk density, base material itself has suitable When intensity, good adhesive infiltration property can be obtained.From the viewpoint of resistance to resilience, bulk density is particularly preferably used It is about 0.25g/cm3~about 0.40g/cm3(it is, for example, about 0.30g/cm3~about 0.35g/cm3) non-woven fabrics base material.
It can also contain starch (for example, cation forms sediment other than constituting fiber as described above in non-woven fabrics base material Powder), polyacrylamide, viscose glue, polyvinyl alcohol, urea formaldehyde resin, melamine resin, the trees such as polyamide polyamines epichlorohydrin Fat ingredient.Above-mentioned resin component can work as the paper power reinforcing agent of the non-woven fabrics base material.By using institute as needed Resin component is stated, the intensity of non-woven fabrics base material can be adjusted.Non-woven fabrics base material in technology disclosed herein in addition to this can be with As needed containing yield rate enhancer, drainage agent, viscosity modifier, dispersant etc. in field related with the manufacture of non-woven fabrics In common additive.
The thickness of base material can suitably be selected according to purpose, be typically set at about 2 μm or more (typically about 10 μm with On) it is appropriate, additionally, it is preferred that being set as 500 μm or less (typically 200 μm or less).Use non-woven fabrics as base material In the case of, it is appropriate that the thickness of non-woven fabrics base material, which is about 150 μm or less,.Entire base material is fully infiltrated from adhesive is made Viewpoint considers that above-mentioned thickness is preferably 100 μm or less (being, for example, 70 μm or less).Additionally, it is contemplated that operation when bonding sheet makes Property when, above-mentioned thickness be preferably 10 μm or more (being, for example, 25 μm or more).From the viewpoint of resistance to resilience, above-mentioned thickness is preferred For 30 μm or more (are, for example, 35 μm or more, typically 40 μm or more) and preferably 60 μm or less (for example, 50 μm with Under, typically 45 μm or less).Non-woven fabrics base material disclosed herein preferably satisfies base weight, thickness and the heap of above-mentioned preferred scope Two or more (such as base weight and thickness, more preferably base weight, thickness and bulk density are whole) in product density.Thus, it is possible to Realize the bonding sheet of a variety of adhesion characteristics (such as resistance to resilience, coherency, peel strength etc.) high balance.
(release liner)
For release liner, common peeling paper etc. can be used, is not particularly limited.It can be used for example and moulding Expect that the surface of the base materials such as film, paper has the release liner of lift-off processing layer, comprising fluoropolymer (polytetrafluoroethylene (PTFE) etc.), polyene The release liner etc. of the low adhesive materials such as hydrocarbon resins (polyethylene, polypropylene etc.).Above-mentioned lift-off processing layer for example can profit Above-mentioned base material is surface-treated and shape with stripping treatment agents such as polysiloxane-based, chain alkyl class, fluorine-containing type, molybdenum sulfides At.
(thickness of bonding sheet)
The overall thickness of bonding sheet disclosed herein is not particularly limited, and is examined from viewpoints such as filming, lightweight, resource-savings Consider, is preferably set to about 1000 μm or less (being, for example, 500 μm or less, typically 300 μm or less).In addition, good from ensuring The viewpoints such as adhesion characteristic consider that it is appropriate to be set as 50 μm or more (they are, for example, 70 μm or more, are typically 100 μm or more) 's.
(characteristic)
For bonding sheet disclosed herein, the retentivity of the bonding sheet preferably after above-mentioned degradation tests pilot scale Piece is tested not fall.That is, it is preferred that keeping showing the horizontal coherency of above-mentioned retentivity in adhesive phase after degradation. The long-term quality stability for meeting the bonding sheet of above-mentioned characteristic is excellent.Bonding sheet disclosed herein is more preferably in above-mentioned degradation Offset distance in retentivity experiment afterwards from initial position is 1mm or less, further preferably 0.5mm or less.
In addition, bonding sheet disclosed herein is preferably shown in being tested for the retentivity of the bonding sheet before above-mentioned degradation The horizontal coherency that test film is not fallen is shown.Offset distance more preferably in the experiment of above-mentioned retentivity from initial position For 1mm or less, further preferably 0.5mm or less.
After above-mentioned degradation and degradation before retentivity experiment by the method described in aftermentioned embodiment into Row.It should be noted that in the case where implementing retentivity experiment using single side bonding sheet as test film, without in test film The first adhesive surface be bonded PET film.
<Purposes>
Bonding sheet disclosed herein is for various office automations (OA) equipment (such as PC (PC)), household appliances The engagement between component in (such as electric cooker, refrigerator), automobile, construction material (such as building construction material) etc. is (for example, described The fixed-purpose of various parts or label in product etc.) it is useful.Bonding sheet disclosed herein utilizes long-term stay in grade The excellent feature of property can be preferred for for example will be in order to be fixed on the dress to building the cosmetic sheet that object inner wall is decorated and used The use of the paste position (inner wall) of spike is on the way.
Include following the description by the item of this disclosure.
(1) a kind of bonding sheet, it includes adhesive phases, wherein
Above-mentioned adhesive phase is made of the adhesive containing unsaturated rubber and tackifying resin, and
It is above-mentioned adhesive, bent in the molecular weight distribution measured based on GPC at 80 DEG C in the degradation in four weeks The weight average molecular weight Mw that the range that molecular weight is 10,000g/mol or more is calculated in lineHConservation rate be 70% or more (example Such as, 70%~100%).
(2) bonding sheet as described in above-mentioned (1), wherein the content of above-mentioned unsaturated rubber is about the 30 of above-mentioned adhesive Weight % or more.
(3) bonding sheet as described in above-mentioned (1) or (2), wherein the content of above-mentioned tackifying resin is relative to above-mentioned unsaturation 100 parts by weight of rubber are about 10 parts by weight or more and about 120 parts by weight or less.
(4) bonding sheet as described in any one of above-mentioned (1)~(3), wherein above-mentioned tackifying resin includes selected from by phenols Tackifying resin, terpene resin, modified terpene resin, rosin tackifying resin, Petropols, styrene resin, coumarone-indenes tree At least one of the group that fat and ketone resins are constituted.
(5) bonding sheet as described in any one of above-mentioned (1)~(4), wherein above-mentioned tackifying resin includes phenols thickening tree Fat, the content of the phenols tackifying resin are about 5 parts by weight or more and about 60 weight relative to 100 parts by weight of above-mentioned unsaturated rubber Part or less.
(6) bonding sheet as described in any one of above-mentioned (1)~(5), wherein above-mentioned tackifying resin includes phenols thickening tree Fat, the phenols tackifying resin include the terpene phenol resin that hydroxyl value is 20mgKOH/g or more.
(7) bonding sheet as described in any one of above-mentioned (1)~(6), wherein above-mentioned tackifying resin includes phenols thickening tree Fat, the phenols tackifying resin include the terpene phenol resin that hydroxyl value is 80mgKOH/g or more.
(8) bonding sheet as described in any one of above-mentioned (1)~(7), wherein the softening point of above-mentioned tackifying resin is 40 DEG C (being, for example, 60 DEG C or more) above.
(9) bonding sheet as described in any one of above-mentioned (1)~(8), wherein above-mentioned adhesive contains antiaging agent, should Antiaging agent includes free radical scavenger and sulphur-containing antioxidant.
(10) bonding sheet as described in any one of above-mentioned (1)~(9), wherein above-mentioned adhesive contains antiaging agent, should Antiaging agent includes phosphorous antioxidant.
(11) bonding sheet as described in any one of above-mentioned (1)~(10), wherein above-mentioned adhesive contains antiaging agent, The antiaging agent includes the thioether antioxidants and phosphorous antioxidant as sulphur-containing antioxidant,
The usage amount A of thioether antioxidants relative to 100 parts by weight of above-mentioned unsaturated rubberS[S molar ratio] and phase For the usage amount A of the phosphorous antioxidant relative to 100 parts by weight of unsaturated rubberPThe ratio between [parts by weight] (AS/AP) be 0.1~10.
(12) bonding sheet as described in any one of above-mentioned (8)~(11), wherein the total amount of above-mentioned antiaging agent relative to 100 parts by weight of above-mentioned unsaturated rubber are 1.5 parts by weight or more and 10 parts by weight or less.
(13) bonding sheet as described in any one of above-mentioned (1)~(12), wherein in above-mentioned adhesive, relative to above-mentioned The content of the phenols tackifying resin of 100 parts by weight of unsaturated rubber is 30 parts by weight or less.
(14) bonding sheet as described in any one of above-mentioned (1)~(13), wherein be used to form the viscous of above-mentioned adhesive phase Mixture composite contains isocyanate compound.
(15) bonding sheet as described in any one of above-mentioned (1)~(14), wherein in above-mentioned adhesive, above-mentioned unsaturation The total amount of rubber and above-mentioned tackifying resin be the about 85 weight % or more and about 99.8 weight % of the total weight of the adhesive with Under.
(16) bonding sheet as described in any one of above-mentioned (1)~(15), wherein above-mentioned unsaturated rubber is conjugated diene The homopolymer or copolymer of compound.
(17) bonding sheet as described in any one of above-mentioned (1)~(16), wherein above-mentioned unsaturated rubber is isoprene Homopolymer or copolymer.
(18) bonding sheet as described in any one of above-mentioned (1)~(17), wherein above-mentioned unsaturated rubber has containing altogether The monomer composition of conjugate diene compound, conjugated diene compound ratio shared in the monomer composition be about 70 weight % with On.
(19) bonding sheet as described in any one of above-mentioned (1)~(18), wherein above-mentioned unsaturated rubber contains single ethylene The block copolymer of base substituted aromatic compound and conjugated diene compound.
(20) bonding sheet as described in above-mentioned (19), wherein the diblock object ratio of above-mentioned block copolymer is about 60 weights Measure % or more.
(21) bonding sheet as described in any one of above-mentioned (1)~(20), wherein the thickness of above-mentioned adhesive phase is about 30 μm or more.
(22) bonding sheet as described in any one of above-mentioned (1)~(21), wherein the bonding sheet with base material and by The base material it is two-sided support respectively as the first adhesive phase of above-mentioned adhesive phase and the both-sided adhesive of second adhesive phase Property bonding sheet form constitute.
(23) a kind of bonding sheet, it includes adhesive phases, wherein
The adhesive for constituting above-mentioned adhesive phase contains the tackifying resin that unsaturated rubber and softening point are 60 DEG C or more,
Above-mentioned unsaturated rubber contains the block copolymerization of mono-vinyl substituted aromatic compound and conjugated diene compound Object, in above-mentioned block copolymer, conjugated diene compound ratio shared in monomer composition is 70 weight % or more and two is embedding Section object ratio is about 60 weight % or more,
The content of above-mentioned unsaturated rubber is the about 30 weight % or more of above-mentioned adhesive,
Above-mentioned tackifying resin includes selected from by phenols tackifying resin, terpene resin, modified terpene resin, rosin thickening tree At least one of the group that fat, Petropols and coumarone-indene resin are constituted,
The total amount of above-mentioned tackifying resin is about 10 parts by weight or more and about relative to 100 parts by weight of above-mentioned unsaturated rubber 120 parts by weight hereinafter,
It is above-mentioned adhesive, bent in the molecular weight distribution measured based on GPC at 80 DEG C in the degradation in four weeks The weight average molecular weight Mw that the range that molecular weight is 10,000g/mol or more is calculated in lineHConservation rate be 70% or more (example Such as, 70%~100%).
(24) bonding sheet as described in above-mentioned (23), wherein above-mentioned adhesive contains antiaging agent, which includes Free radical scavenger and sulphur-containing antioxidant.
Embodiment
Hereinafter, being illustrated to some embodiments related to the present invention, but it is not intended to limit the invention to the embodiment Shown in content.It should be noted that in the following description, " part " and " % " is then weight base if not otherwise specified It is accurate.In addition, as long as no special declaration, the record of usage amount of each material etc. is not if not otherwise specified then to consider solvent Amount on the basis of.
<The making of double-sided adhesive sheet>
(example 1)
By 100 parts of styrene-isoprene block copolymers (Nippon Zeon Co., Ltd.'s manufacture, ProductName " Quintac 3520 ", styrene-content 15%, diblock object ratio 78%), 40 parts of terpene phenol resins, 30 parts of terpene resins, 0.75 part of isocyanide Ester compound (Tosoh Products, ProductName " CORONATE L "), 1 part of Hinered phenols antioxygen as free radical scavenger Agent (ProductName " EUNOX AO-565 ", 4- [[bis- (the octylthio) -1,3,5- of 4,6- of Eutec Chemical companies manufacture Triazine -2- bases] amino] -2,6 di t butyl phenol), 2 parts of phosphorous antioxidant (products of BASF (BASF) company manufacture Name " IRGAFOS 168 ", phosphorous acid three (2,4- di-tert-butyl-phenyls) ester), 2 parts of thioether antioxidants (Ai Dike (ADEKA) ProductName " ADK STAB AO-503 ", 3,3 '-thio-2 acid two (tridecyl) esters of company's manufacture) and as solvent Toluene is stirred, and is prepared for the adhesive composition of NV50%.
Here, for as terpene phenol resin, so that the quotient of former chemical (Yasuhara Chemical) company manufacture of peace Trade name " the YS of the name of an article " YS Polyster S145 " (145 DEG C of softening point, hydroxyl value 100mgKOH/g) and the said firm's manufacture Polyster T145 " (145 DEG C of softening point, hydroxyl value 60mgKOH/g) are 1:1 weight ratio and their side for adding up to 40 parts Formula uses two kinds of terpene phenol resins.For terpene resin, the ProductName " YS that is manufactured using An Yuan chemical companies Resin PX1150N " (115 DEG C of softening point, hydroxyl value are less than 1mgKOH/g).
Adhesive composition obtained above is coated on release liner, carries out being dried for 3 minutes at 120 DEG C, patch Together in 12 μm of PET film (Toray manufactures, trade name " Lumirror S10 ") of thickness, so as to form 64 μm glue of thickness Mixture layer (first adhesive phase).Then, on the second face of above-mentioned PET film (face with the first face opposite side) with the first face Identical mode forms the adhesive phase (second adhesive phase) of 64 μm of thickness.In this way, having made the double-sided adhesive sheet of this example. It should be noted that for as release liner, the first surface side, the second surface side have used single side (face of adhesive phase side) sharp Peeling paper that thickness after carrying out lift-off processing with polysiloxane-based remover is about 89 μm (prince F-TEX Co., Ltd. manufactures, " Separator 75EPS (M) Cream of polyethylene layer platen, ProductName obtained from the single sided lamination polyethylene of glazed printing paper (Modified)”)。
(example 2)
Thioether antioxidants are changed to the ProductName " ADK STAB AO-412S " that Chinese mugwort Dicon A/S manufactures, and (2,2- is bis- ({ [3- (dodecyl sulfenyl) propiono] oxygroup } methyl) 2 parts of propane diyl-bis- [3- (dodecyl sulfenyl) propionic ester], is removed The double-sided adhesive sheet of this example has been made other than this in a manner of same as Example 1.
(example 3)
The usage amount of each terpene phenol resin and terpene resin is changed to content shown in table 1, in addition to this with 1 phase of example Same mode has made the double-sided adhesive sheet of example 3.
(example 4)
Without using thioether antioxidants, the double-sided adhesive sheet of example 4 has been made in a manner of same as Example 1 in addition to this.
<Degradation>
By the bonding sheet of each example together with the release liner cut growth 30cm of two adhesive surfaces of covering, the rectangle of width 20cm Shape, to make the sample of degradation.By above-mentioned Sample storage in being held in 80 DEG C of the drier of air atmosphere Four weeks.Sample is preserved in the state of suspension in above-mentioned drier in a manner of not overlapping each other.
<MwHConservation rate>
For the adhesive of the second adhesive phase of the bonding sheet before composition degradation and after degradation, by above-mentioned Method carries out GPC measurement, and Mw before aging is calculated using the incidental analysis software of GPC measurement devicesHWith Mw after agingH.Into one Step ground, passes through following formula：(Mw after agingHMw before/agingH)×100；Find out MwHConservation rate (%).It shows the result in table 1.
<Retentivity is tested>
For each bonding sheet before degradation and after degradation, in the first adhesive surface (the first bonding of the bonding sheet The adhesive surface of oxidant layer) on 25 μm of coating thickness PET film (Toray manufacture, trade name " Lumirror S10 "), by gained Object cuts into the band-like of width 10mm, has thus made test film.Make the second adhesive surface (second adhesive of above-mentioned test film The adhesive surface of layer) expose, in the environment of 23 DEG C, 50%RH, with width 10mm, length by making the roller round trip of 2kg Above-mentioned test film is crimped on the bakelite plate (phenolic resin plate) as adherend by the bonding area of 20mm.It will be with such side The test film that formula is pasted on adherend is placed 30 minutes under identical environment, then so that the length direction of test film is vertical The mode in direction hangs down adherend, applies the load of 500g in the free end of the test film, according to JIS Z0237, to apply There is the state of the load to placed in the environment of 40 DEG C 30 minutes.For the test film after the placement, measures and glued from initial Paste the distance (offset distance) of position offset.It measures and carries out (i.e. n=3) using three test films for each bonding sheet, by these In the arithmetic mean of instantaneous value of the offset distance of test film " retentivity " column shown in table 1.It should be noted that even if there are one examinations It tests in the case that piece is fallen and is also expressed as " falling ".
As shown in table 1, even if at 80 DEG C after the harsh degradation in four weeks, MwHConservation rate be 70% with On the bonding sheet of example 1~3 also maintain the horizontal good coherency not fallen in the experiment of above-mentioned retentivity.With this phase It is right, MwHInitially the coherency of (before degradation) and example 1,2 are same for the bonding sheet of example 4 of the conservation rate less than 70%, but by upper Degradation is stated, coherency significantly reduces, and is not resistant to the experiment of the retentivity after degradation.Specifically, three test films All fallen before by 30 minutes.It should be noted that for the bonding sheet of example 1, after degradation in adhesive It observes and slightly colours.
More than, the concrete example of the present invention is illustrated in detail, but these examples are only to illustrate, and are not wanted to right Book is asked to be limited.Technology described in claim includes carrying out various modifications and changes to the concrete example illustrated above Obtained from technology.

Claims (13)

1. a kind of bonding sheet, it includes adhesive phases, wherein
Described adhesive layer is made of the adhesive containing unsaturated rubber and tackifying resin, and
At 80 DEG C in the degradation in four weeks, described adhesive, in the molecular weight measured based on gel permeation chromatography The weight average molecular weight Mw that the range for being 10,000g/mol or more to the molecular weight of polystyrene conversion in distribution curve calculatesH's Conservation rate is 70% or more.
2. bonding sheet as described in claim 1, wherein the content of the unsaturated rubber is 30 weight % of described adhesive More than.
3. bonding sheet as claimed in claim 1 or 2, wherein the content of the tackifying resin is relative to the unsaturated rubber 100 parts by weight are 10 parts by weight or more and 120 parts by weight or less.
4. bonding sheet according to any one of claims 1 to 3, wherein the softening point of the tackifying resin is 40 DEG C or more.
5. bonding sheet as described in any one of claims 1 to 4, wherein
The tackifying resin includes phenols tackifying resin,
The content of the phenols tackifying resin is 5 parts by weight or more and 60 weight relative to 100 parts by weight of the unsaturated rubber Part or less.
6. such as bonding sheet according to any one of claims 1 to 5, wherein
The tackifying resin includes phenols tackifying resin,
The phenols tackifying resin includes the terpene phenol resin that hydroxyl value is 20mgKOH/g or more.
7. such as bonding sheet according to any one of claims 1 to 6, wherein
Described adhesive contains antiaging agent,
The antiaging agent includes free radical scavenger and sulphur-containing antioxidant.
8. such as bonding sheet according to any one of claims 1 to 7, wherein
Described adhesive contains antiaging agent,
The antiaging agent includes phosphorous antioxidant.
9. such as bonding sheet according to any one of claims 1 to 8, wherein in described adhesive, relative to the unsaturated rubber The content of 100 parts by weight of glue, phenols tackifying resin is 30 parts by weight or less.
10. such as bonding sheet according to any one of claims 1 to 9, wherein the unsaturated rubber, which has, contains conjugated diene The monomer composition of compound, conjugated diene compound ratio shared in the monomer composition are 70 weight % or more.
11. such as bonding sheet according to any one of claims 1 to 10, wherein the unsaturated rubber contains mono-vinyl and takes For the block copolymer of aromatic compound and conjugated diene compound, the ratio of the diblock object of the block copolymer is 60 weights Measure % or more.
12. the bonding sheet as described in any one of claim 1~11, wherein the thickness of described adhesive layer is 30 μm or more.
13. the bonding sheet as described in any one of claim 1~12, wherein the bonding sheet is with base material and by the base The both-sided adhesive of the two-sided first adhesive phase and second adhesive phase as described adhesive layer supported respectively of material The form of bonding sheet is constituted.
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