CN107429131A - Adhesive tape, wirning harness are tied up with sheet material and article - Google Patents

Adhesive tape, wirning harness are tied up with sheet material and article Download PDF

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Publication number
CN107429131A
CN107429131A CN201680019512.XA CN201680019512A CN107429131A CN 107429131 A CN107429131 A CN 107429131A CN 201680019512 A CN201680019512 A CN 201680019512A CN 107429131 A CN107429131 A CN 107429131A
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CN
China
Prior art keywords
mentioned
adhesive
adhesive phase
adhesive tape
plasticizer
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Granted
Application number
CN201680019512.XA
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Chinese (zh)
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CN107429131B (en
Inventor
下冈澄生
森野彰规
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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Priority to CN202110124130.6A priority Critical patent/CN112960274B/en
Publication of CN107429131A publication Critical patent/CN107429131A/en
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Publication of CN107429131B publication Critical patent/CN107429131B/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D63/00—Flexible elongated elements, e.g. straps, for bundling or supporting articles
    • B65D63/10—Non-metallic straps, tapes, or bands; Filamentary elements, e.g. strings, threads or wires; Joints between ends thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D63/00—Flexible elongated elements, e.g. straps, for bundling or supporting articles
    • B65D63/10—Non-metallic straps, tapes, or bands; Filamentary elements, e.g. strings, threads or wires; Joints between ends thereof
    • B65D63/1009—Adhesive tapes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • 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
    • C09J2203/302—Applications of adhesives in processes or use of adhesives in the form of films or foils for bundling cables
    • 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
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/20—Presence of organic materials
    • C09J2400/24—Presence of a foam
    • C09J2400/243—Presence of a foam in the substrate
    • 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
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/20—Presence of organic materials
    • C09J2400/26—Presence of textile or fabric
    • C09J2400/263—Presence of textile or fabric in the substrate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Insulated Conductors (AREA)
  • Package Frames And Binding Bands (AREA)
  • Laminated Bodies (AREA)

Abstract

Problem to be solved by this invention is to provide a kind of adhesive tape, and it will not also cause peeling, and can keep above-mentioned attaching for a long time in the case of the attaching for the adherend containing plasticizer at the interface of above-mentioned adherend and adhesive phase.The present invention relates to a kind of adhesive tape, it is characterized in that, it is the adhesive tape for the attaching of the adherend (a1) containing plasticizer, there is adhesive phase (b1) in a surface side of gas permeability base material, there is adhesive phase (b2) in another surface side of gas permeability base material, and the weight per unit area of the total of above-mentioned adhesive phase (b1) and adhesive phase (b2) is 125g/m2~175g/m2Scope, and the gel fraction of the total of above-mentioned adhesive phase (b1) and adhesive phase (b2) is the mass % of 2 mass %~35.

Description

Adhesive tape, wirning harness are tied up with sheet material and article
Technical field
The present invention relates to the adhesive tape for the fixation that can be used in the component containing plasticizer.
Background technology
Multiple wires (distribution) on automobile or electronic equipment etc. are installed in generally by comprising polyvinyl chloride film-making material And adhesive tape is tied up with sheet material and is tied.
Tied up as above-mentioned with sheet material, it is known that have be laminated with the one side of polyvinyl chloride film-making material by containing The tying up for adhesive phase for having rubber series latex and bonding the aqueous adhesive composition formation of imparting agent resin emulsion uses sheet material (referring for example to patent document 1.).
But above-mentioned polyvinyl chloride film-making material is due to usually containing more plasticizer, if thus above-mentioned plasticizer through when It is transferred in adhesive phase, then causes peeling at the interface of above-mentioned polyvinyl chloride film-making material and adhesive phase sometimes.Especially for By by thickness for 0.2mm~1mm or so polyvinyl chloride film-making material doubling or in the form of being involved in into web-like several distributions are entered Row bundle, and in the case that above-mentioned polyvinyl chloride film-making material is bonded with adhesive tape, because plasticizer is from polyvinyl chloride film-making material To splicing tape through when transfer and polyvinyl chloride film-making material attempt slowly to revert to the repulsive force president of flat sheet material state Temporally act on adhesive tape, thus worry to be possible to produce and above-mentioned tie up the problems such as untiing.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2007-211231 publications
The content of the invention
Invent problem to be solved
Problem to be solved by this invention is to provide a kind of adhesive tape, and it is even in for the adherend containing plasticizer In the case of attaching, peeling will not be also caused in the interface of above-mentioned adherend and adhesive phase, and can keep for a long time Above-mentioned attaching.
For solving the scheme of problem
The present inventor etc. think it is above-mentioned through when peel off and be likely to be adhesive phase and adhesive phase are transferred to by plasticizer Carry out softness caused by, and have studied in advance by above-mentioned plasticizer shift before adhesive phase hardness be set as compared with It is high.
But in above-mentioned adhesive phase, can not still more efficiently prevent from sometimes it is above-mentioned through when peel off.Especially for Several distributions are tied by by thickness for 0.2mm~1mm or so polychlorovinyl sheet material doubling or in the form of being involved in into tubular Beam, and in the case that above-mentioned polyvinyl chloride film-making material is bonded with adhesive tape, exist easily cause through when the tendency peeled off.This Outside, due to inhibiting above-mentioned plasticizer to be shifted into above-mentioned harder adhesive phase, thus it concentrates on polyvinyl chloride film-making material With the interface of adhesive phase, easily peeled off at their interface on the contrary sometimes.
Therefore, the present inventor etc. have studied the further softness of adhesive phase before making above-mentioned plasticizer transfer, as a result It is surprised to find that：In the case of the scope of gel fraction as defined in be set as, can more efficiently prevent from it is above-mentioned through when peel off.
That is, the present invention relates to a kind of adhesive tape, it is characterised in that it is the patch for the adherend (a1) containing plasticizer Attached adhesive tape, there is adhesive phase (b1) in a surface side of gas permeability base material, have in another surface side of gas permeability base material Adhesive phase (b2), and the weight per unit area of the total of above-mentioned adhesive phase (b1) and adhesive phase (b2) is 125g/m2~ 175g/m2Scope, and the gel fraction of the total of above-mentioned adhesive phase (b1) and adhesive phase (b2) is the matter of 2 mass %~35 Measure %.
Invention effect
The adhesive tape of the present invention, also will not be above-mentioned in the case of the attaching for the adherend containing plasticizer The interface of adherend and adhesive phase causes peeling, can keep above-mentioned attaching for a long time.
Embodiment
The adhesive tape that the adhesive tape of the present invention is discussed further below, it has adhesive phase in a surface side of gas permeability base material (b1), there is adhesive phase (b2), and above-mentioned adhesive phase (b1) and adhesive phase (b2) in another surface side of gas permeability base material The weight per unit area of total be 125g/m2~175g/m2Scope, and above-mentioned adhesive phase (b1) and adhesive phase (b2) The gel fraction of total be the mass % of 2 mass %~35, the adhesive tape is dedicated for the adherend (a1) containing plasticizer Attaching.
Above-mentioned adhesive tape can be used for the engagement of the adherend (a1) of more than 2 or with above-mentioned adherend (a1) and except upper State the engagement of the adherend beyond adherend (a1).
As above-mentioned adhesive phase (b1) and adhesive phase (b2), the gel fraction using its total is 2 mass %~35 The adhesive phase of quality % scope.Thus, even in the case that above-mentioned plasticizer is transferred to adhesive phase (b1) etc., also can It is enough effectively prevent through when the generation peeled off.It is preferred that use the viscous of the scope that above-mentioned gel fraction is the mass % of 2 mass %~25 Mixture layer, for the adhesive phase using the scope for the mass % of 2 mass %~15, even being transferred in above-mentioned plasticizer In the case of adhesive phase (b1) etc., also effectively prevent through when the caused aspect peeled off more preferably.
In addition, the adhesive phase of the gel fraction with above range is just used as above-mentioned adhesive phase (b1) and bonding For oxidant layer (b2), above-mentioned plasticizer is by above-mentioned gas permeability base material so as to which above-mentioned plasticizer is set than being relatively uniformly dispersed throughout Above-mentioned adhesive phase (b1) and adhesive phase (b2) in the two sides of above-mentioned gas permeability base material is interior, thus can suppress plasticizer not Uniformly be present in the interface of adherend (a1) and adhesive phase, as a result, can effectively suppress above-mentioned adherend (a1) with The interface peel of adhesive phase.
In addition, above-mentioned gel fraction refers to value as described below, i.e. is being adjusted to 23 DEG C of the mass parts of toluene 70 and first The adhesive tape of the in the mixed solvents of the mass parts of alcohol 30 quality of adhesive phase by measured in advance impregnates 72 hours, then, uses Ultrasonic unit, after being vibrated 15 minutes with 40kHz frequency under 23 DEG C of atmosphere, based on remaining in above-mentioned in the mixed solvent The dried quality and following formula of adhesive phase and calculate value.
Gel fraction (quality %)=(quality for remaining in the adhesive phase of in the mixed solvent)/it is (viscous before above-mentioned dipping The quality of mixture layer) } × 100
The quality for forming the adhesive phase of the adhesive tape before above-mentioned dipping refers to be subtracted in its manufacture by the quality of above-mentioned adhesive tape Value obtained from the quality of the gas permeability base material used.In addition, the quality of the adhesive phase of above-mentioned residual refers to by above-mentioned residual The dried quality of thing subtracts value obtained from the quality of above-mentioned gas permeability base material.
For by using above-mentioned mixed solvent and the above-mentioned gel fraction giving ultrasonic activation and calculate, it is simultaneously It is not the value related to the gel fraction relative to the single solvent of toluene, and refers to by the intermolecular and molecule of adhesive phase Apparent bonding is blocked caused by interior hydrogen bond etc., due to the gel fraction of the cross-linking reaction of crosslinking agent etc..
As above-mentioned adhesive tape, the unit area of the total with above-mentioned adhesive phase (b1) and adhesive phase (b2) is used Weight is 125g/m2~175g/m2Adhesive phase adhesive tape.Thus, the plasticizer in above-mentioned adherend (a1) passes through above-mentioned When gas permeability base material to the above-mentioned adhesive phase on the two sides for being arranged at above-mentioned gas permeability base material so as to shift, above-mentioned adherend (a1) In plasticizer by than being relatively uniformly dispersed throughout in above-mentioned adhesive phase (b1) and adhesive phase (b2), thus can suppress to be plasticized The uneven interface for being present in adherend (a1) and adhesive phase of agent, as a result, can effectively suppress above-mentioned adherend (a1) with the interface peel of adhesive phase.In addition, by using the adhesive phase of the weight per unit area with above range, When taking care of the adhesive tape before being attached to adherend (a1), adhesive phase can be suppressed and overflowed from the end of adhesive tape.As above-mentioned Weight per unit area, preferably 135g/m2~155g/m2Scope, more preferably 138g/m2~145g/m2Scope.
The weight per unit area of the total of above-mentioned adhesive phase (b1) and adhesive phase (b2) represents per unit area (1m2) Adhesive tape present in the quality of above-mentioned adhesive phase (b1) and adhesive phase (b2) total, represent based on following formula calculate The value gone out.
Weight per unit area (the g/m of the total of above-mentioned adhesive phase (b1) and adhesive phase (b2)2)={ (adhesive phase (b1) quality)+(quality of adhesive phase (b2)) }/(area of a surface side of adhesive tape)
As the adhesive tape of the present invention, preferably using the adhesive tape that gross thickness is 130 μm~180 μm, just 140 μm~150 μ are used For m adhesive tape, effectively suppress above-mentioned adherend (a1) and adhesive phase interface peel, suppress adhesive tape guarantor In pipe adhesive phase from the end of adhesive tape overflow in terms of more preferably.
As above-mentioned adhesive phase (b1) and adhesive phase (b2), preferably glued using utilization with the dynamic of frequency 1Hz measure The adhesive phase that storage modulus at elastic spectrum determined 23 DEG C is 0.08MPa~0.12MPa, just using 0.08MPa~ For 0.09MPa adhesive phase, the excellent bonding force at the attaching initial stage attached to adherend (a1) can assigned and can Suppress the bonding force of the transfer due to plasticizer through when the aspect that declines more preferably.
In addition, as above-mentioned adhesive phase (b1) and adhesive phase (b2), preferably using utilization with the dynamic of frequency 1Hz measure The bonding that loss modulus at state Viscoelastic Spectral determined 60 DEG C is 0.40~0.60 relative to the ratio (tan δ) of storage modulus Oxidant layer, for using the above-mentioned adhesive phase for being 0.45~0.50 than (tan δ), the upper of adherend (a1) will be adhered to When stating in the environment of adhesive tape is placed on 60 DEG C, can through when from adherend (a1) transfer plasticizer uneven will not be present in With the bonding interface of adherend (a1), kept the aspect of the adhesive tape of excellent bonding force and cohesiveness more excellent for a long time Choosing.
In addition, as above-mentioned adhesive phase (b1) and adhesive phase (b2), preferably using utilization with the dynamic of frequency 1Hz measure The bonding that loss modulus at state Viscoelastic Spectral determined 100 DEG C is 0.55~0.80 relative to the ratio (tan δ) of storage modulus Oxidant layer, for using the above-mentioned adhesive phase for being 0.60~0.70 than (tan δ), the upper of adherend (a1) will be adhered to When stating in the environment of adhesive tape is placed on 100 DEG C, can through when from adherend (a1) transfer plasticizer uneven will not exist In the bonding interface with adherend (a1), the aspect of adhesive tape of excellent bonding force and cohesiveness is kept for a long time more It is preferred that.
In addition, above-mentioned refer to what the formula based on tan δ=loss modulus (Pa)/storage modulus (Pa) calculated than (tan δ) Value.
Tan δ at storage modulus at above-mentioned 23 DEG C, 60 DEG C and 100 DEG C refer to use test for viscoelastic machine (TA Instruments Japan, Inc. system, trade name：ARES-G2), it is to sandwich between parallel disk in the determination part of the testing machine Test film, with the storage modulus of frequency 1Hz measure and based on above-mentioned under the temperature conditionss of 23 DEG C, 60 DEG C or 100 DEG C of temperature The value that storage modulus and loss modulus calculate.In addition, as above-mentioned test film, included using the adhesive tape of the present invention is cut into Thickness is the test film of the round shape of 2mm and a diameter of 8mm size.
Just comprising the adhesive with the storage modulus at 23 DEG C in above range and 60 DEG C and 100 DEG C of tan δ For the adhesive tape of layer (b1) and adhesive phase (b2), it is not easy to cause the peeling due to the repulsive force of adherend (a1) etc., i.e., Make to be in the case of being placed under less than 100 DEG C of environment, also can effectively suppress to be glued from above-mentioned due to plasticizer The adherend (a1) of transfer of the thing (a1) to adhesive phase and the interface peel of adhesive phase.
Above-mentioned adhesive phase (b1) and adhesive phase (b2) can for example be formed by using adhesive.As above-mentioned viscous Mixture, such as acrylic adhesive, urethane adhesive, synthetic rubber system adhesive, natural rubber system can be used Adhesive, silicon-type adhesive etc., preferably using acrylic adhesive.
As aforesaid propylene acid system adhesive, it can use containing acrylate copolymer and crosslinking agent as needed, glue The acrylic adhesive for assigning resin etc. is closed, just assigns resin etc. using containing acrylate copolymer, crosslinking agent and bonding It is preferred in terms of obtaining possessing the adhesive tape of adhesive phase of weatherability and excellent heat resistance for acrylic adhesive.
As acrylate copolymer, it can use the polymerizing monomer components comprising (methyl) acrylic monomers etc. and obtain Acrylate copolymer.
As above-mentioned (methyl) acrylic monomers, such as (methyl) methyl acrylate, (methyl) acrylic acid second can be used Ester, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid just oneself Ester, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, the different nonyl ester of (methyl) acrylic acid, (methyl) acrylate Ester, (methyl) 2-EHA etc. have (methyl) acrylate for the alkyl that carbon number is 1~14, preferably use (methyl) acrylate with the alkyl that carbon number is 4~9, further preferably by n-butyl acrylate or acrylic acid 2- second The own ester of base is used alone or in combination.Excellent bonding force is being embodied suitable for the surface of adherend (a1) from attaching initial stage, And even in plasticizer through when from adherend (a1) to adhesive phase shift after, plasticizer, which uneven will not also be present in, to be glued Thing (a1) and bonding interface, the aspect of the adhesive tape of excellent bonding force and cohesiveness is kept for a long time, is most preferably made The n-butyl acrylate for being 4 with the few carbon number of the influence of the steric hindrance of more than 60 mass % abovementioned alkyl.
Above-mentioned (methyl) acrylic monomers with the alkyl that carbon number is 1~14 is relative to aforesaid propylene acid polymer Manufacture in the total amount of monomer component that uses preferably used in the range of the mass % of 80 mass %~98.5, more preferably 90 Used in the range of the mass % of quality %~98.5.
In addition to as the above-mentioned substance of above-mentioned (methyl) acrylic monomers, further preferably using highly polar vinyl monomer Contour polar monomer.
As above-mentioned highly polar vinyl monomer, can by (methyl) acrylic monomers with carboxyl, with amino or Nitrogenous vinyl monomer of amide groups etc. is used alone or two or more is applied in combination.
Wherein, as above-mentioned highly polar vinyl monomer, preferably and with nitrogenous vinyl monomer.
In the case that above-mentioned adherend (a1) is for example highly polar polyvinyl chloride, in order to further effectively be gathered The plasticized of vinyl chloride, mostly using the intermolecular plasticizer for easily immersing above-mentioned polyvinyl chloride., can as above-mentioned plasticizer Including intramolecular has the plasticizer of aromatic rings and ester group.Just have what is easily polarized between above-mentioned aromatic rings and ester group etc. For the plasticizer of structure, the intermolecular of above-mentioned polyvinyl chloride is easily immersed.
Wherein, the aforesaid propylene acid polymer in above-mentioned adhesive phase (b1) and (b2) is the acroleic acid polymerization with carboxyl In the case of thing, because above-mentioned carboxyl has high polarity in the same manner as above-mentioned polyvinyl chloride, thus above-mentioned plasticizer becomes Easily immerse in adhesive phase the intramolecular of acrylate copolymer included, as a result, in the presence of by adhesive phase plasticized and Make the tendency of some declines of its bonding force.
Therefore, if using adhesive phase as described below, above-mentioned adhesive phase (b1) etc. as caused by above-mentioned plasticizer Plasticized more effectively suppressed, as a result, excellent bonding force, wherein described adhesive can be kept for a long time Layer include the vinyl monomer nitrogenous as above-mentioned highly polar vinyl monomer exclusive use or with the above-mentioned (first with carboxyl Base) acrylate copolymer that is applied in combination of acrylic monomers.
As above-mentioned nitrogenous vinyl monomer, NVP, N- vinyl acyl in oneself can be included Amine, acryloyl morpholine, dimethyl amino ethyl acrylate, N, N- DMAAs, NIPA etc..On It is preferably 0.5 matter that nitrogenous vinyl monomer, which is stated, relative to the total amount of the monomer component used in the manufacture of acrylate copolymer Measure the mass % of %~20 mass %, more preferably 0.8 mass %~10 mass %, more preferably 1.0 mass %~2.5. The mass % of most preferably 1.0 mass %~1.9.
By the way that the structure proportion for forming the above-mentioned nitrogenous vinyl monomer source of aforesaid propylene acid polymer is adjusted to Above range, acrylic adhesive layer moderately softness, embodied from attaching initial stage suitable for the surface of adherend (a1) Go out excellent bonding force, and even in plasticizer through when shifted from adherend (a1) to adhesive phase after, plasticizer is not yet Can it is uneven be present in the bonding interface of adherend (a1), excellent bonding force and cohesiveness can be kept for a long time Adhesive tape.
The above-mentioned vinyl monomer with carboxyl is relative to the total amount of above-mentioned monomer component preferably in the matter of 0.2 mass %~5 Use in the range of amount %, more preferably used in the range of the mass % of 0.4 mass %~3.Most preferably 1.5 mass %~ Used in the range of 2.5 mass %.If the usage amount of the above-mentioned vinyl monomer with carboxyl is within the above range, relative to The highly polar adherend such as Corvic (a1), excellent bonding force can be embodied from attaching initial stage.
Because above-mentioned carboxyl is as described above to be highly polar, if thus its more exist in adhesive phase (b1) etc., Sometimes formed by the plasticizer in adherend (a1) source and the adhesive phase of easily being plasticized.Therefore, it is just above-mentioned that there is carboxylic The vinyl monomer of base for use, is suppressing above-mentioned plasticizer entering to adhesive phase (b1) etc. in above-mentioned shown scope Enter, the bonding force as caused by the influence of above-mentioned plasticizer declines less, is kept excellent bonding force and cohesiveness for a long time Adhesive tape aspect it is preferred.
As above-mentioned highly polar vinyl monomer, in addition to above-mentioned highly polar vinyl monomer, acetic acid can also be used Vinyl acetate, ethylene-oxide-modified butanedioic acid acrylate, 2- acrylamide-2-methyl propane sulfonics etc. have sulfonic monomer, The end alkoxy groups such as (methyl) acrylic acid 2- methoxy acrylates, (methyl) acrylic acid 2- phenoxy ethyls are modified (methyl) acrylic acid Other highly polar vinyl monomers such as ester.
Other above-mentioned highly polar vinyl monomers are relative to the total amount of above-mentioned monomer component preferably in the matter of 0.2 mass %~5 Use in the range of amount %, more preferably used in the range of the mass % of 0.4 mass %~3.Most preferably 2.0 mass %~ Used in the range of 3.0 mass %.If due to other above-mentioned highly polar vinyl monomers usage amount within the above range, from Bonding force from from attaching initial stage to the highly polar adherend such as Corvic (a1) surface uprises, and does not have above-mentioned tool Polarity as having the vinyl monomer of carboxyl, thus plasticizer is difficult to the intermolecular immersion to above-mentioned acrylate copolymer, i.e., Make plasticizer through when from adherend (a1) to adhesive phase shift after, also kept excellent bonding force for a long time With the adhesive tape of cohesiveness.
As the monomer that can be used in the manufacture of aforesaid propylene acid polymer, it can use that have can be with crosslinking described later The monomer of the functional group of agent reaction, (methyl) acrylic monomers for example with hydroxyl can be used.
As above-mentioned (methyl) acrylic monomers with hydroxyl, can use such as (methyl) acrylic acid 2- hydroxyl ethyl esters, (methyl) acrylic acid 2- hydroxypropyl acrylates, (methyl) acrylic acid 4- hydroxy butyl esters, the own ester of (methyl) acrylic acid 6- hydroxyls etc..
Above-mentioned (methyl) acrylic monomers with hydroxyl is relative to the total amount of above-mentioned monomer component preferably in 0.05 matter Use, more preferably used in the range of the mass % of 0.1 mass %~0.5, with regard to 0.1 matter in the range of amount %~2.0 mass % For measuring the mass % of %~0.2, the gel fraction of above-mentioned adhesive phase (b1) and adhesive phase (b2) is easily adjusted to above-mentioned Scope, as a result, due to embodying excellent bonding force suitable for the surface of adherend (a1) from attaching initial stage, and i.e. Make plasticizer through when shifted from adherend (a1) to adhesive phase when, the cross-linked structure between acrylate copolymer will not also hinder Hinder the mobility of plasticizer, can suppress plasticizer it is uneven be present in the bonding interface of adherend (a1), it is thus possible to To the adhesive tape for keeping excellent bonding force and cohesiveness for a long time.
Aforesaid propylene acid polymer can be by making above-mentioned monomer component with such as solution polymerization process, mass polymerization, hanging Method known to floating polymerization, emulsion polymerization etc. polymerize to manufacture, and makes the life of adhesive tape by solution polymerization process to manufacture Production efficiency improve and reduce its production cost aspect it is preferred.
As aforesaid propylene acid polymer, preferably using the propylene of the weight average molecular weight with 300,000~1,500,000 scope Acid polymer, preferably using the acrylate copolymer of the weight average molecular weight with 500,000~1,000,000 scope.
In addition, above-mentioned weight average molecular weight can be determined by gel permeation chromatography (GPC).More specifically, as GPC determines device,, can be following by polystyrene scaled value using TOSOH CORPORATION systems " SC8020 " Determine and obtain under GPC condition determinations.
(GPC condition determination)
Sample concentration：0.5 mass % (tetrahydrofuran solution)
Sample injection rate：100μL
Eluent：Tetrahydrofuran (THF)
Flow velocity：1.0mL/min
Column temperature (measurement temperature)：40℃
Post：TOSOH CORPORATION systems " TSKgel GMHHR-H "
Detector：Differential refraction
The adhesive that can be used in formation as above-mentioned adhesive phase (b1) and adhesive phase (b2), preferably using removing The also adhesive containing crosslinking agent beyond aforesaid propylene acid polymer.By using the above-mentioned adhesive containing crosslinking agent, from patch It is excellent to the adhesive strength on adherend (a1) surface from attached initial stage, and even in plasticizer through when from adherend (a1) to bonding After oxidant layer transfer, the adhesive tape of excellent bonding force and cohesiveness can be also kept for a long time.
As above-mentioned crosslinking agent, can according to possessed by aforesaid propylene acid polymer the species of cross-linking functional group and select Select and use such as isocyanates system crosslinking agent, epoxy crosslinking agent, chelate system crosslinking agent, aziridine system crosslinking agent, oxazoline It is crosslinking agent etc..The content of above-mentioned crosslinking agent is relative to the mass parts of aforesaid propylene acid polymer 100 preferably 0.3 mass parts~1.8 The mass parts of mass parts, more preferably 0.6 mass parts~1.3, the mass parts of most preferably 0.6 mass parts~0.9.
Above-mentioned adhesive phase (b1) that the content of above-mentioned crosslinking agent can possess above-mentioned gel fraction according to that can be formed and The mode of adhesive phase (b2) suitably selects to use.
In order that the bonding force of adhesive tape further improves, above-mentioned adhesive can use and assign resin containing bonding Adhesive.
Resin is assigned as above-mentioned bonding, rosin series resin, terpenic series resin, aliphatic (C5 systems) or fragrance can be used The Petropols such as race (C9 systems), phenylethylene resin series, phenol resin, diformazan benzene series resin, metha crylic resin etc..Its In, resin is assigned as above-mentioned bonding, preferably using rosin series resin, preferably using newtrex system resin.
Above-mentioned bonding assigns resin relative to the mass parts of aforesaid propylene acid polymer 100 preferably using the matter of 5 mass parts~50 Measure part, just assign resin using the above-mentioned bonding of the mass parts of 10 mass parts~30 for, due to that can assign to adherend (a1) patch The excellent bonding force at attached attaching initial stage, and can suppress the bonding force of the transfer due to plasticizer through when decline, because And more preferably.
As the embodiment of the adhesive tape of the present invention, it can include and have respectively in two surface sides of gas permeability base material (SMIS) There is the adhesive tape of above-mentioned adhesive phase (b1) and adhesive phase (b2).
The adhesive tape of the present invention can be by manufacturing via following process：Such as pass through the external coating in release liner Above-mentioned adhesive and drying etc. and the process for forming above-mentioned adhesive phase (b1) and adhesive phase (b2) respectively；And will be above-mentioned viscous The process that mixture layer is transferred to two surface sides of gas permeability base material respectively.
(gas permeability base material)
As above-mentioned gas permeability base material, base material as described below is used, i.e. plasticizer turns from adherend (a1) to adhesive phase Move, afterwards, above-mentioned plasticizer can effectively suppress to be glued by the base material of gas permeability base material (SMIS) using above-mentioned base material Thing (a1) with and its adhesive phase to connect interface peel aspect it is preferred.
As above-mentioned gas permeability base material, preferably use using material obtained from 10 gas permeability base materials are laminated and be used as experiment Piece, Ge Lai (Gurley) the formulas air permeability that the foundation JIS P 8117 of above-mentioned test film are determined are 0.35 second/below 100ml base Material, more preferably using 0.05 second/100ml~0.3 second/100ml scope base material, just using 0.1 second/100ml~0.2 second/ For the base material of 100ml scope, plasticizer compares in the entirety for being formed at the adhesive phase on two sides of above-mentioned gas permeability base material Relatively evenly disperse, as a result, can effectively suppress adherend (a1) with and its adhesive phase to connect interface peel.
In addition, above-mentioned Ge Laishi air permeabilities are air permeability as described below, i.e. are laminated 10 gas permeability base materials, with 10 The overlapping base material of piece determines air permeability as test film, and according to JIS P 8117.It is determined as follows described：In 23 DEG C of 50%RH 10 SMIS base materials are overlapping and fix, and measurement internal diameter is 28.6mm, weight falls the sky for determining 100ml for 567g inner cylinder Passage time in the case of the time that gas passes through.
As above-mentioned gas permeability base material, the gas permeability base material that thickness is 10 μm~50 μm, preferably 20 μm~45 μm is used. By using the gas permeability base material of above-mentioned thickness, because above-mentioned adhesive phase (b1) and adhesive phase (b2) are above-mentioned ventilative containing being dipped into Property base material cavity portion in, make from adherend (a1) transfer come above-mentioned plasticizer pass through, it is thus possible to suppress above-mentioned bonding The uneven presence of oxidant layer (b1) and the above-mentioned plasticizer in adhesive phase (b2), it can be kept excellent for a long time and be glued Relay and the adhesive tape of cohesiveness.And then by using the gas permeability base material of above-mentioned thickness, above-mentioned adhesive phase (b1) and bonding Containing being dipped into the cavity portion of above-mentioned gas permeability base material, the tensile strength of above-mentioned gas permeability base material improves oxidant layer (b2), can obtain The adhesive tape excellent to the processing operability in cut off operation or attaching process.
As above-mentioned gas permeability base material, using non-woven fabrics base material or porous membrane substrate, this is due to it is easy to ensure that above range Air permeability, thus preferably.As above-mentioned gas permeability base material, specifically, can include non-woven fabrics base material, base material of weaving cotton cloth, by Fabric (Network substrates) that monofilament is formed etc., even being preferably also readily obtained high tensile elasticity mould using thin thickness The non-woven fabrics base material of amount or the Network substrates for being readily obtained high Ge Laishi air permeabilities.
As the material of non-woven fabrics base material, the known usual nonwoven used as the non-woven fabrics of adhesive tape can be used Cloth.As representational example, it is cellulose-based that the fiber crops such as abaca, artificial silk, regenerated cellulose, wood pulp etc. can be included The chemical fibres such as fiber, acetic ester fiber, polyester fiber, polyvinyl alcohol fibers, Fypro and their mixture etc.. And then viscose glue impregnation can also be implemented as needed or handled using thermoplastic resin as the impregnation of adhesive.
In addition, for the purpose for improving the intensity of non-woven fabrics, it is usual known in addition preferably in non-woven fabrics manufacturing process Hardening agent.Hardening agent can freshen hardening agent or the outer hardening agent that freshens is used alone or is used in combination by interior.Freshen hardening agent as interior, can be with Use Polyacrylamide resin, urea-formaldehyde system resin, carbamide system resin, epoxy-polyamide system resin etc.. Particularly epoxy-polyamide system resin is interlaminar strength of the daiamid epichlorohydrin resins due to significantly improving non-woven fabrics, because And it is preferred that.It is 0.2~1 mass % preferably with respect to non-woven fabrics as the interior addition for freshening hardening agent, more preferably 0.3 ~0.5 mass %.On the other hand, as hardening agent is freshened outside, starch can be used；Viscose glue, carboxymethyl cellulose, polyvinyl The thermoplastic resins such as alcohol, polyacrylamide.Wherein, in order to improve the interlaminar strength of non-woven fabrics base material, preferably using above-mentioned interior Freshen hardening agent.
The weight per unit area of above-mentioned non-woven fabrics base material is preferably 5~15g/m2, more preferably 7~12g/m2.On in addition, The density for stating non-woven fabrics base material is preferably 0.15~0.35g/m3, more preferably 0.2~0.3g/m3.If above-mentioned non-woven fabrics base material Weight per unit area scope, then because above-mentioned adhesive phase (b1) and adhesive phase (b2) are containing being dipped into above-mentioned non-woven fabrics base material Cavity portion, make from adherend (a1) transfer come above-mentioned plasticizer pass through, it is thus possible to suppress above-mentioned adhesive phase (b1) and The uneven presence of above-mentioned plasticizer in adhesive phase (b2), excellent bonding force and cohesion can be kept for a long time The adhesive tape of power.And then by using the non-woven fabrics base material of above-mentioned weight per unit area, above-mentioned adhesive phase (b1) and adhesive Layer (b2) contains the cavity portion for being dipped into above-mentioned base material, and the tensile strength of above-mentioned non-woven fabrics base material improves, it is possible to increase cut off operation Or the processing attached in process is operational.
As the copy paper method of non-woven fabrics base material, it is not particularly limited, can be obtained by known damp process, using makes With cylinder paper machine, short net paper machine, fourdrinier paper machine, the various copy paper methods for tilting short net paper machine etc..
As porous membrane substrate, can use monofilament known to polyester resin, amide resin, polyacrylate resin etc. Fiber is made into Network substrates of mesh-like etc..Wherein, as monofilament, preferably gather using tensile modulus of elasticity or tensile strength are high Ester resin.As the form of Network substrates, using the monofilament that fibre diameter is 5~25 μm every 1 inch 80~300 on MD and TD The thickness that root is alternately woven into is 10~50 μm of Network substrates.Preferably fibre diameter is 5~25 μm of monofilament in MD And every 1 inch of 100~200 thickness being alternately woven into are 10~50 μm of Network substrates on TD.If above-mentioned netted The fiber diameter range of base material, then because above-mentioned adhesive phase (b1) and adhesive phase (b2) are containing the hole portion for being dipped into above-mentioned base material Point, make to pass through from the above-mentioned plasticizer that adherend (a1) transfer comes, it is thus possible to suppress above-mentioned adhesive phase (b1) and adhesive The uneven presence of above-mentioned plasticizer in layer (b2), the viscous of excellent bonding force and cohesiveness can be kept for a long time Crossed belt.It is and then above-mentioned containing being dipped into by using the Network substrates of above-mentioned thickness, above-mentioned adhesive phase (b1) and adhesive phase (b2) The cavity portion of base material, the tensile strength of above-mentioned Network substrates improve, it is possible to increase the processing in cut off operation or attaching process Operability.
The adhesive tape of the invention obtained by the above method can also be in above-mentioned adhesive phase (b1) and adhesive phase (b2) release liner is laminated with.As above-mentioned release liner, the paper such as by brown paper, glassine paper or good quality paper can be used Class, polyethylene, polypropylene (oriented polypropylene (OPP), Oriented polypropylene (OPP), cast polypropylene (CPP)), poly- pair The resin films such as PET, by laminated paper obtained from above-mentioned stationery and resin film stacking, to above-mentioned stationery with viscous Soil or polyvinyl alcohol etc. implement being peeled off one or both sides with silicon-type resin etc. of the paper of filling processing etc. Paper of processing etc..
(adherend (a1))
As above-mentioned adherend (a1), such as being glued containing plasticizer and polyvinyl chloride or plasticizer and rubber can be used Thing.
As above-mentioned plasticizer, the 2- ethylhexyls of phthalic acid two, diisononyl phthalate, adjacent benzene can be exemplified The phosphates such as phthalic acid ester, the trioctyl phosphates such as the isodecyl ester of dioctyl phthalate two, dioctyl adipate, diisononyl adipate, Trimellitate, the epoxystearic acid fourths such as the fatty group dibasic acids such as diisodecyl adipate (DIDA), tri trimellitate 2- ethylhexyls Epoxy plasticizer such as ester etc..Above-mentioned plasticizer can also combine two or more.The adhesive tape of the present invention is preferably for containing adjacent benzene Dicarboxylic acid esters use as the adherend of above-mentioned plasticizer, just for containing diisononyl phthalate adherend use and Speech, due to can effectively carry out the plasticized of polychlorovinyl sheet material, it is thus possible to make polychlorovinyl sheet material with a small amount of addition Plasticized, the decline of the bonding force due to above-mentioned plasticizer can be effectively prevented, therefore more preferably.
As the content of above-mentioned plasticizer, contain the matter of 15 mass %~30 preferably with respect to the quality of above-mentioned adherend (a1) The plasticizer of % scope is measured, the mass % of 20 mass %~26 model is more preferably contained relative to the quality of above-mentioned adherend (a1) The plasticizer enclosed.The content of plasticizer is low temperature environment of the above-mentioned adherend (a1) of above range even in less than about 5 DEG C Under also have for tying up the sufficient flexibility of distribution, and transfer amount of the plasticizer from adherend to adhesive tape also obtains more effectively Ground suppresses, therefore preferably.
As the above-mentioned adherend (a1) containing plasticizer, in order to assign the appropriate impact resistance according to purposes, also may be used With containing calcium carbonate, talcum, burn till the inorganic fillers such as clay, kaolin, aluminium hydroxide, titanium oxide or having for coloring Machine pigment.The usage amount of above-mentioned inorganic additive is preferably the matter of 10 mass %~60 relative to the quality of polyvinyl chloride or rubber Measure %, just above-mentioned inorganic additive usage amount be the mass % of 20 mass %~40 for, excellent impact resistance can be taken into account With the flexibility sufficiently horizontal for tying up distribution.As above-mentioned organic pigment, carbon black etc. can be used.Above-mentioned organic pigment Usage amount relative to the scope that the quality of polyvinyl chloride or rubber is the mass % of 2 mass %~10, it can keep good Impact resistance and flexibility.
The thickness of the above-mentioned adherend (a1) containing plasticizer is preferably 0.2mm~1mm, just the above-mentioned quilt containing plasticizer For the thickness of viscous thing (a1) is 0.3mm~0.5mm, due to possessing the flexibility and easy sticker sufficiently level for tying up distribution Property, and adherend (a1) is not easy to extend when distribution is bent, tying up for distribution is not easy to relax, therefore more preferably.It is in addition, above-mentioned The surface of adherend (a1) containing plasticizer can also be the surface as needed with embossing pattern etc..Above-mentioned embossing pattern Can be by the way that adherend (a1) be arranged at into the adherend (a1) by being heated between more than 80 DEG C of metal niproll Surface.
The above-mentioned adherend (a1) containing plasticizer can make above-mentioned resin complex be in the shape melted at high temperature State is simultaneously configured to sheet by the arbitrary film-forming method such as T moulds extrusion molding, calendaring molding, blow molding.
(matching somebody with somebody line tying sheet material)
By the adhesive tape of the invention that the above method obtains such as can in order to be adhesively fixed vehicle in use 2 with On the sheet material with line tying and use.Above-mentioned sheet material is the adherend of the strip of the volume for example to the width for cutting into 50mm (a1) one end continuously attaches the adhesive tape for the volume for equally cutting into 15mm width along flow direction and ties up use as distribution Sheet material.
In order to evaluate the spalling resistance as caused by the plasticizer transfer in stock's keeping, above-mentioned sheet material for example can also be 60 DEG C and 80%RH wet heat condition under place a couple of days.As wet heat condition, preferably in the softening temperature of adherend (a1) to transfer Put.Specifically, placed 3 days~10 days preferably at 40 DEG C~70 DEG C of temperature and 70%~90%RH humidity.If upper In the range of stating wet heat condition, then the thermal deformation of adherend (a1) is few, can suppress the transfer drastically of plasticizer, and plasticizer is easy It is dispersed into above-mentioned adhesive phase (b1) and adhesive phase (b2).
Above-mentioned adherend (a1) is wrapped up the distribution of more than 2 by one side with being pasted with the above-mentioned sheet material of above-mentioned adhesive tape In center, while above-mentioned adhesive tape is fitted in one end without the above-mentioned adhesive tape of attaching of same sheet surface, or it is above-mentioned The distribution of more than 2 is wrapped in center by adherend (a1) with being pasted with the above-mentioned sheet material of above-mentioned adhesive tape by one side, on one side Above-mentioned adhesive tape one end overleaf attached into web-like, thus, it is possible to match somebody with somebody line tying by more than 2.
In addition, as dispersed method is confirmed after plasticizer shifts into adhesive phase, with for example using adjacent benzene Dioctyl phthalate dinonyl is used as above-mentioned adhesive phase (b1) and adhesive phase (b2) as plasticizer, using acrylic adhesive Formation in case of the adhesive that uses, refer to the value determined by the method for following (1)~(3).
(1) standard curve making
By the plasticizer that the mass parts of solid constituent 100 relative to acrylic adhesive equably with the addition of to 10 mass parts Obtained from adhesive be coated on the surface of release liner and make its dry and form adhesive phase, by being transferred to nonwoven On the two sides of cloth base material, adhesive tape (C1) is made.
Then, by the way that the acrylic adhesive of no addition plasticizer is coated on the surface of release liner and makes it Dry and form adhesive phase, adhesive tape (C0) is made by being transferred on the two sides of non-woven fabrics base material.
Then, the infrared absorption spectroscopy of the adhesive layer surface of adhesive tape (C1) is determined by ATR methods, obtains infrared absorption Spectrum (D1).
Then, the infrared absorption spectroscopy of the adhesive layer surface of adhesive tape (C0) is determined by ATR methods, obtains infrared absorption Spectrum (D0).
Then, by subtracting infrared absorption spectroscopy (D0) (difference spectra) by above-mentioned infrared absorption spectroscopy (D1), plasticising is extracted out The infrared absorption spectroscopy (E1) of agent.
1285cm by above-mentioned infrared absorption spectroscopy (E1) measure from plasticizer-1Absworption peak height (F1).
Then, infrared suction is obtained by the infrared absorption spectroscopy of the adhesive layer surface of ATR methods measure adhesive tape (C1) Receive spectrum (D1).Then, the 1160cm by above-mentioned infrared absorption spectroscopy (D1) measure from acrylate copolymer-1Absworption peak Height (G1).
Then, prepare to the addition of the increasing of 20 mass parts relative to the mass parts of solid constituent 100 of acrylic adhesive respectively The acrylic adhesive of agent is moulded, with the addition of the acrylic adhesive of 30 mass parts plasticizer and with the addition of the increasing of 40 mass parts The acrylic adhesive of agent is moulded, by the way that each adhesive to be coated on to the surface of release liner and it is dried to form adhesive Layer, by being transferred on the two sides of non-woven fabrics base material, make 4 kinds of adhesive tapes.
Then, the infrared absorption spectroscopy of the adhesive layer surface of above-mentioned 4 kinds of adhesive tapes is determined by ATR methods.By above-mentioned 4 kinds Infrared absorption spectroscopy determines the 1285cm from plasticizer respectively-1Absworption peak height and from acrylate copolymer 1160cm-1Absworption peak height.
It is the plasticizer addition [matter added relative to the mass parts of solid constituent 100 of acrylic adhesive to make the longitudinal axis Measure part], and make transverse axis be the 1285cm from plasticizer-1Absworption peak height (F1) relative to from acroleic acid polymerization The 1160cm of thing-1Absworption peak height (G1) ratio (F1/G1), by the addition of the plasticizer included in above-mentioned 4 kinds of adhesive tapes Measure and marked and drawed equivalent to the above-mentioned value than (F1/G1) and make standard curve.
In addition, above-mentioned infrared absorption spectroscopy uses Fourier transform infrared spectrophotometer (Japan light splitting society FT/IR- 4100) determine.
(2) measure of the plasticising dosage of adhesive layer surface
After release liner is removed from adhesive phase (b1) surface of arbitrary adhesive tape, the adherend containing plasticizer is attached at (a1) on, placed 9 days under the wet heat condition such as 60 DEG C and 80%RH, obtain adhesive tape (C2).
Then, release liner is removed from above-mentioned adhesive tape (C2) adhesive phase (b2) surface, should using ATR methods measure The infrared absorption spectroscopy (D2) on adhesive phase (b2) surface, based on infrared absorption spectroscopy (D2), is obtained from plasticizer 1285cm-1Absworption peak height (F2) with from acrylate copolymer 1160cm-1Absworption peak height (G2) ratio (F2/G2)。
Then, above-mentioned F2/G2 is applied to the transverse axis of above-mentioned standard curve, calculates above-mentioned adhesive tape (C2) adhesive phase (b2) content (H2) [mass parts] of the plasticizer included in.In addition, the content of above-mentioned plasticizer will remove the viscous of plasticizer In the case that mixture layer (b2) is set to 100 mass parts, the transfer of plasticizer come from the transfer of above-mentioned polyvinyl chloride film-making material is represented Measure [mass parts].
Then, the adhesive phase (b1) that will connect with above-mentioned adherend (a1) is peeled off, and is calculated by method similar to the above Go out in adhesive phase (b1) surface the content (J2) [mass parts] of the plasticizer included.
(3) the uniformly dispersed evaluation of plasticizer
The uniformly dispersed content (H2) that can be based on the plasticizer obtained by the above method of above-mentioned plasticizer and above-mentioned increasing The difference for moulding the content (J2) of agent is evaluated, can if the difference of above-mentioned content (H2) and content (J2) is the scope of ± 2 mass parts To be evaluated as the uniformly dispersed excellent adhesive tape of above-mentioned plasticizer.
Plasticizer is from above-mentioned adherend (a1) to the above-mentioned adhesive phase (b1) and adhesive phase for forming above-mentioned adhesive tape (b2) transfer amount is preferably the mass parts of 0 mass parts~35, the mass parts of more preferably 0 mass parts~20.If above-mentioned plasticizer Transfer amount is within 35 mass parts, then is uniformly dispersed due to that can compare in adhesive phase (A) reactive plasticizer, thus above-mentioned increasing Modeling agent will not hinder above-mentioned adherend (a1) bonding with adhesive phase (A), be able to maintain that good spalling resistance.
(T words peeling adhesion force)
The adhesive tape that release liner is eliminated from adhesive phase (b1) is attached at adherend (a1-1), be cut into 15mm width and 100mm length and be used as test film.Above-mentioned test film is placed 9 days under the wet heat condition such as 60 DEG C and 80%RH.In addition, will not have Have attach adhesive tape adherend (a1-2) be cut into 15mm width and 100mm length, with above-mentioned test film identical condition Lower placement.
After above-mentioned placement, above-mentioned test film and above-mentioned adherend (a1-2) are fetched under 23 DEG C and 50%RH atmosphere, The above-mentioned adherend (a1-2) of face attaching for eliminating release liner is peeled off in the adhesive phase (b2) from above-mentioned test film, and is made 2kg rollers come and go 1 time, are bonded them by placing 30 minutes under the atmosphere.
One end of adherend (a1-2) is fixed on the downside chuck in the stretching device portion of Tensilon cupping machines, Adherend (a1-1) is fixed on the upside chuck in the stretching device portion of Tensilon cupping machines, by with 3mm/ minutes Speed tensile on the upside of chuck, determine its bonding force (T words peeling adhesion force).
The numerical value of above-mentioned bonding force is higher, then judges that the spalling resistance tied up in holding etc. of distribution is better.It is above-mentioned viscous Relay ranges preferably from more than 1.5N/15mm, more preferably more than 2.0N/15mm.In addition, in the measure of above-mentioned bonding force When, preferably cohesion destruction occurs for adhesive phase.Situation about being peeled off in the interface of above-mentioned adherend (a1-1) and adhesive tape Under, the plasticizer that represents to come from adherend (a1-1) transfer is uneven be present in adherend (a1) and above-mentioned adhesive phase (b1) and The interface of adhesive phase (b2), but above-mentioned cohesion is destroyed it may be said that representing that plasticizer is homogeneously dispersed in above-mentioned adhesive phase (b1) And adhesive phase (b2).
More specifically illustrate by the following examples.
(embodiment 1)
The preparation of (1-1) acrylic adhesive composition (S)
In the reaction vessel for possessing mixer, reflux condensing tube, nitrogen ingress pipe, thermometer, by the matter of butyl acrylate 93.4 Measure part, the mass parts of vinylacetate 3, the mass parts of acrylic acid 2.5, the mass parts of NVP 1, acrylic acid 2- hydroxyls The mass parts of ethyl ester 0.1 and 2 as polymerization initiator, the mass parts of 2 '-azobis isobutyronitrile 0.2 are dissolved into the matter of ethyl acetate 100 Measure in part, carry out polymerizeing for 8 hours at 80 DEG C, obtain the acrylic acid polymer solution that weight average molecular weight is 700,000.Relative to upper The mass parts of acrylate copolymer (solid constituent) 100 are stated, add (the famine of rosin ester system Resin A -100 that resin is assigned as bonding River chemical industry Co. Ltd. system) 15 mass parts, newtrex ester system resin D-135 (Arakawa Chemical Industries, Ltd.'s system) 15 Mass parts, mixed with dilution with toluene, obtain the acrylic adhesive composition (S) that nonvolatile component is 40 mass %.
(1-2) double-faced adhesive tape S-1
Relative to aforesaid propylene acid system adhesive composition (S) 100 mass parts, addition isocyanates system crosslinking agent (TOSOH CORPORATION systems, CORONATE L-45E, solid constituent are 45 mass %) 0.52 mass parts, are stirred with dissolving mechanical stirrer After 15 minutes, turn into 69g/m according to dried weight per unit area2Mode be coated on release liner with roll coater, 85 Dried 3 minutes in DEG C drying machine and obtain adhesive phase.Crosslinking agent (solid constituent) is relative to aforesaid propylene acid polymer (solid Composition) contents of 100 mass parts is 0.76 mass parts.
By the above method, 2 adhesive phases are made, are laminated to the non-woven fabrics A (NIPPON that thickness is 43 μm PAPER PAPYLIA CO., LTD. system, No.1215) both sides, while to being heated to 100 DEG C of roller (TESTER SANGYO CO .LTD. SA-1010, small desk test laminating machine) apply 0.4MPa pressurization side with the speed of 1m/ minutes by rear, By being cultivated 48 hours in 40 DEG C of drying machine, the total unit area of the adhesive phase on the two sides for being arranged on non-woven fabrics is made Weight is 138g/m2, adhesive phase gel fraction be 10 mass %, the double-faced adhesive tape that thickness is 145 μm.Above-mentioned non-woven fabrics No.1215 Ge Laishi air permeabilities are 0.2 second/100ml.
(embodiment 2)
(2-1) double-faced adhesive tape S-2
Except by isocyanates system crosslinking agent (TOSOH CORPORATION systems, CORONATE L-45E, the matter of solid constituent 45 Amount %) usage amount be changed to by 0.52 mass parts beyond 0.39 mass parts, operate similarly to Example 1 and obtain double-sided adhesive Crossed belt S-2.The gel fraction of adhesive phase is 2 mass %.Crosslinking agent (solid constituent) relative to aforesaid propylene acid polymer (Gu Body composition) contents of 100 mass parts is 0.57 mass parts.
(embodiment 3)
(3-1) double-faced adhesive tape S-3
Except by isocyanates system crosslinking agent (TOSOH CORPORATION systems, CORONATE L-45E, the matter of solid constituent 45 Amount %) usage amount be changed to by 0.52 mass parts beyond 0.71 mass parts, operate similarly to Example 1 and obtain double-sided adhesive Crossed belt S-3.The gel fraction of adhesive phase is 30 mass %.Crosslinking agent (solid constituent) is relative to aforesaid propylene acid polymer The content of (solid constituent) 100 mass parts is 1.04 mass parts.
(embodiment 4)
The preparation of (4-1) acrylic adhesive composition (T)
Deionized water 75g, Aqualon KH-1025 [the first industrial pharmaceuticals (strain) as surfactant are added in a reservoir System；Active ingredient is 25 mass %] 20 mass parts and as surfactant LATEMUL PD-104 [flower king (strain) system；Have Effect composition is 20 mass %] 37.5 mass parts, equably dissolve.The mass parts of n-butyl acrylate 227.5, propylene are added wherein The sour mass parts of 2- ethylhexyls 227.5, the mass parts of methyl methacrylate 25, the mass parts of NVP 6, third The mass parts of olefin(e) acid 4, the mass parts of methacrylic acid 10, the mass parts of lauryl mercaptan 0.2 as chain-transferring agent are emulsified, and are obtained The mass parts of emulsion (1) 632.7.
Add and go in the reaction vessel for possessing mixer, reflux condensing tube, nitrogen ingress pipe, thermometer, dropping funel The mass parts of ionized water 333.35,60 DEG C are warming up to when being blown into nitrogen.Under agitation, a part 7.59 for emulsion (1) is added Mass parts, the mass parts of ammonium persulfate aqueous solution 2.5 [active ingredient is 6 mass %], the mass parts of aqueous solution of sodium bisulfite 2.5 [active ingredient is 2 mass %], made its polymerization when being kept for 60 DEG C with 1 hour.
Then, by the remaining mass parts of emulsion (1) 625.11 and the mass parts [active ingredient of the aqueous solution 50 of ammonium persulfate For 1 mass %] different funnels is used, carried out dropwise addition polymerization with 6 hours when reaction vessel is maintained at into 60 DEG C.
Then, by the mass parts of ammonium persulfate aqueous solution 2.5 [active ingredient is 6 mass %], aqueous solution of sodium bisulfite 2.5 Mass parts [active ingredient is 2 mass %] use different funnels, are dripped when reaction vessel is maintained at into 60 DEG C with 1 hour Add.
After completion of dropwise addition, after stirring 1 hour when reaction vessel to be maintained to 60 DEG C, content is cooled down, according to pH into Adjusted for 7.2 mode ammoniacal liquor [active ingredient is 10 mass %].By it with 200 mesh metal mesh filters, obtain acrylic acid and gather Compound emulsion (1).Wherein, the solid component concentration of resulting acrylate polymer emulsion (1) is 50 mass %, average grain diameter For 333nm, weight average molecular weight is 800,000.
In the above-mentioned mass parts of acrylate polymer emulsion (1) 1000, the EPOCROS of Zuo Wei oxazoline crosslinking agents is added [Nippon Shokubai Co., Ltd's system, water-soluble type, nonvolatile component are 25 mass % to WS-700, oxazoline base unit weight is 4.5mmol/g (solid, solid)] 25 mass parts, as bonding assign resin emulsion-type polymerization rosin ester system bonding assign resin be SUPER ESTER E-865NT [Arakawa Chemical Industries, Ltd.'s systems；Softening point is 160 DEG C, solid constituent rate is 50 mass %] 200 matter Amount part, Surfynol PSA-336 [Air Products Japan Inc. systems] 2.5 mass parts as levelling agent, as disappearing Surfynol DF-110D [Air Products Japan Inc. systems] 2.5 mass parts of infusion.After equably stirring, with 200 Mesh metal mesh filter.Cultivated 30 days under 23 DEG C of environment, obtain acrylic adhesive composition (T).Crosslinking agent (solid into Point) relative to the content of the mass parts of aforesaid propylene acid polymer (solid constituent) 100 it is 1.28 mass parts.
(4-2) double-faced adhesive tape T-1
Except turning into 65g/m according to dried weight per unit area2Mode be applied to release liner with roll coater beyond, with The total weight per unit area that embodiment 1 similarly operated and obtained being arranged on the adhesive phase on the two sides of non-woven fabrics is 130g/ m2, thickness be 140 μm of double-faced adhesive tape T-1.The gel fraction of adhesive phase is 28 mass %.
(embodiment 5)
The preparation of (5-1) acrylic adhesive composition (U)
Without using 2-EHA, methyl methacrylate, NVP, methacrylic acid, and make With the mass parts of n-butyl acrylate 492.5 and the mass parts of acrylic acid 7.5, the emulsion-type polymerization rosin of resin will be assigned as bonding It is SUPER ESTER E-865NT [Arakawa Chemical Industries, Ltd.'s systems that the bonding of ester system, which assigns resin,；Softening point is 160 DEG C, admittedly Body composition rate is 50 mass %] it is reduced by 200 mass parts to 50 mass parts, in addition, operate and obtain similarly to Example 4 To acrylic adhesive composition (U).Except replacing aforesaid propylene sour using aforesaid propylene acid system adhesive composition (U) It is beyond adhesive composition (T), it is 130g/m to obtain weight per unit area by method similarly to Example 42, thickness be 140 μm of double-faced adhesive tape U-1.The gel fraction of adhesive phase is 26 mass %.Crosslinking agent (solid constituent) is relative to above-mentioned The content of the mass parts of acrylate copolymer (solid constituent) 100 is 1.28 mass parts.
(embodiment 6)
As base material, using by polyester monofilament that fibre diameter is 25 μm to MD and TD according to the every 1 inch side for turning into 132 The thickness that formula is alternately woven into is 50 μm of Network substrates B, in addition, is obtained by method similarly to Example 1 Double-faced adhesive tape S-5.The Ge Laishi air permeabilities of above-mentioned Network substrates are 0.1 second/100ml.
(embodiment 7)
The preparation of (7-1) acrylic adhesive composition (V)
In the reaction vessel for possessing mixer, reflux condensing tube, nitrogen ingress pipe, thermometer, by the matter of butyl acrylate 93.4 Measure part, the mass parts of methyl acrylate 3, the mass parts of acrylic acid 2.3, the mass parts of NIPA 1.2, acrylic acid 2- hydroxyl second The mass parts of ester 0.1 and 2 as polymerization initiator, the mass parts of 2 '-azobis isobutyronitrile 0.2 are dissolved into the mass of ethyl acetate 100 In part, it polymerize 8 hours at 80 DEG C, obtains the acrylic acid copolymer soln that weight average molecular weight is 800,000.Relative to aforesaid propylene The mass parts of acid copolymer solid constituent 100, (society of Arakawa Chemical Industries, Ltd. system) 15 matter of addition rosin ester system Resin A -100 Part, newtrex ester system resin D-135 (Arakawa Chemical Industries, Ltd.'s system) 15 mass parts are measured, is diluted and mixed with MEK, Obtain the acrylic adhesive composition (V) that nonvolatile component is 45 mass %.
(7-2) double-faced adhesive tape V-1
Except by isocyanates system crosslinking agent, (TOSOH CORPORATION systems, CORONATE L-45E, solid constituent are 45 matter Amount %) usage amount be set as beyond 1.24 mass parts, operate similarly to Example 1 and obtain double-faced adhesive tape V-1.Bonding The gel fraction of oxidant layer is 2 mass %.Crosslinking agent (solid constituent) is relative to the matter of aforesaid propylene acid polymer (solid constituent) 100 The content for measuring part is 1.61 mass parts.
(embodiment 8)
The preparation of (8-1) acrylic adhesive composition (W)
In the reaction vessel for possessing mixer, reflux condensing tube, nitrogen ingress pipe, thermometer, n-butyl acrylate is put into 76.4 mass parts, the mass parts of 2-EHA 18.6, the mass parts of acrylic acid 1.2, the mass parts of vinylacetate 3.9, third The mass parts of olefin(e) acid 2- hydroxyl ethyl esters 0.1, the mass parts of ethyl acetate 98, under agitation, 80 DEG C are warming up to when being blown into nitrogen.Afterwards, Addition advances with the mass parts of azobis isobutyronitrile solution 2 of ethyl acetate dissolving (solid constituent is 5 mass %).Afterwards, exist Stir after being kept for 8 hours at lower 80 DEG C, content is cooled down, obtain the acrylic acid copolymer soln that weight average molecular weight is 520,000. Relative to the aforesaid propylene acid copolymerization mass parts of solid constituent 100, mixed polymerization rosin series ester resin PCJ (Harima Chemicals Group, Inc. system) 25 mass parts, obtain the acrylic adhesive that nonvolatile component is 47 mass % and combine Thing (W).Crosslinking agent (solid constituent) is 1.08 matter relative to the content of the mass parts of aforesaid propylene acid polymer (solid constituent) 100 Measure part.
(8-2) double-faced adhesive tape W-1
Except by isocyanates system crosslinking agent, (TOSOH CORPORATION systems, CORONATE L-45E, solid constituent are 45 matter Amount %) usage amount be set as beyond 0.90 mass parts, operate similarly to Example 1 and obtain double-faced adhesive tape W-1.Bonding The gel fraction of oxidant layer is 2 mass %.
(comparative example 1)
Except by isocyanates system crosslinking agent, (TOSOH CORPORATION systems, CORONATE L-45E, solid constituent are 45 matter Amount %) usage amount be changed to by 0.52 mass parts beyond 1.1 mass parts, operate similarly to Example 1 and obtain double-sided adhesive Crossed belt S-6.The gel fraction of adhesive phase is 42 mass %.Crosslinking agent (solid constituent) is relative to aforesaid propylene acid polymer The content of (solid constituent) 100 mass parts is 1.61 mass parts.
(comparative example 2)
In embodiment 1, except dried weight per unit area is set as into 50g/m for release liner2In addition, with implementation The total weight per unit area that example 1 similarly operated and made the adhesive phase on the two sides for being arranged at non-woven fabrics is 100g/m2, it is viscous The thickness of mixture layer is 110 μm of double-faced adhesive tape S-7.
(comparative example 3)
Except by isocyanates system crosslinking agent, (TOSOH CORPORATION systems, CORONATE L-45E, solid constituent are 45 matter Amount %) usage amount be changed to by 0.52 mass parts beyond 1.9 mass parts, operate similarly to Example 1 and obtain double-sided adhesive Crossed belt S-8.The gel fraction of adhesive phase is 52 mass %.Crosslinking agent (solid constituent) is relative to aforesaid propylene acid polymer The content of (solid constituent) 100 mass parts is 2.78 mass parts.
[making of adherend]
Use the mass parts of polyvinyl chloride (degree of polymerization 1400) 100, the mass parts of diisononyl phthalate 34, the matter of calcium carbonate 25 Part, the mass parts of carbon black 3, the mass parts of barium-zinc system stabilizer 3 are measured, prepare Corvic mixture.By resulting polychlorostyrene second Olefine resin mixture obtains the polyvinyl chloride film-making material that thickness is 0.4mm by calendaring molding (processing temperature is 170 DEG C).
[evaluation method of gel fraction]
After the double-faced adhesive tape obtained in above-described embodiment and comparative example is cut into 40mm × 50mm size, by release liner Test film is used as after peeling.After the quality for determining above-mentioned test film, 23 DEG C of the mass parts of toluene 70 and methanol 30 are being adjusted to The in the mixed solvent of mass parts impregnates above-mentioned test film 72 hours, then, uses ultrasonic unit (AS ONE Corporation systems, trade name：US CLEANER US-5R), it is vibrated 15 minutes with 40kHz frequency at 23 DEG C.
After above-mentioned vibration, determine (105 DEG C) dryings 1 of substance migration drying machine for remaining in above-mentioned in the mixed solvent are small When after quality.
Gel fraction is calculated based on above-mentioned quality and following formula.
Gel fraction (quality %)=(quality for remaining in the adhesive phase of in the mixed solvent)/it is (viscous before above-mentioned dipping The quality of mixture layer) } × 100
The quality for forming the adhesive phase of the adhesive tape before above-mentioned dipping refers to subtract its system by the quality of above-mentioned double-faced adhesive tape Value obtained from making the quality of the gas permeability base material used.In addition, the quality of the adhesive phase of above-mentioned residual refers to by above-mentioned The dried quality of residue subtracts value obtained from the quality of above-mentioned gas permeability base material.
[evaluation method of dynamic viscoelastic]
By the way that the adhesive phase multi-disc used when manufacturing double-faced adhesive tape in above-described embodiment and comparative example is laminated 2mm is made Thickness, cut into the cylindric of a diameter of 8mm and be used as test film.Use test for viscoelastic machine (TA Instruments Japan, Inc. system, trade name：ARES-G2), it is clamp assay piece between parallel disk in the determination part of the testing machine, in temperature At 23 DEG C, 60 DEG C, 100 DEG C of degree, storage modulus and loss modulus under frequency 1Hz are determined.Loss modulus is relative to storage modulus Ratio (tan δ) calculated by following formula.Tan δ=loss modulus (Pa)/storage modulus (Pa)
[evaluation method (T words peeling adhesion force) of initial bond power]
Above-mentioned initial bond power determines according to JIS Z 0237.Specifically, it is measured by the following method.
The double-faced adhesive tape for eliminating a release liner is attached at adherend (a1-1), be cut into 15mm width and 100mm length and be used as test film.Above-mentioned test film is placed 1 day under 23 DEG C and 50%RH of atmosphere.In addition, will it not paste The adherend (a1-2) of attached double-faced adhesive tape is cut into 15mm width and 100mm length, with above-mentioned test film identical condition Lower placement.
After above-mentioned placement, by above-mentioned test film and above-mentioned adherend (a1-2) under 23 DEG C and 50%RH atmosphere, upper The stripping for stating test film eliminates the above-mentioned adherend (a1-2) of face attaching of another release liner and 2kg rollers is come and gone 1 time, leads to Cross and placed 30 minutes under the atmosphere and be bonded them.
One end of adherend (a1-2) is fixed to the downside chuck in the stretching device portion of Tensilon cupping machines, will Adherend (a1-1) is fixed to the upside chuck in the stretching device portion of Tensilon cupping machines, by with the speed of 3mm/ minutes Degree stretching upside chuck, determines the bonding force (T words peeling adhesion force).
[evaluation method (T words peeling adhesion force) of the bonding force after long-term keeping]
Operated in the same manner as the evaluation method of above-mentioned initial bond power, the double-faced adhesive tape for eliminating a release liner is pasted Invest adherend (a1-1) and be cut into the test film of 15mm width and 100mm length and be cut into 15mm width and 100mm length After the adherend (a1-2) of degree is placed 9 days under the wet heat condition such as 60 DEG C and 80%RH, it is fetched under 23 DEG C and 50%RH atmosphere, The face that another release liner is eliminated in the stripping of above-mentioned test film attaches above-mentioned adherend (a1-2), and 2kg rollers is come and gone 1 It is secondary, it is bonded them by placing 30 minutes under the atmosphere.
One end of adherend (a1-2) is fixed to the downside chuck in the stretching device portion of Tensilon cupping machines, will Adherend (a1-1) is fixed to the upside chuck in the stretching device portion of Tensilon cupping machines, by with the speed of 3mm/ minutes Degree stretching upside chuck, determines the bonding force (T words peeling adhesion force).
In addition, in the measure of above-mentioned bonding force, according to following benchmark evaluation adhesive tape from adherend (a1-1) or by The peeling mode of viscous thing (a1-2).
[metewand]
Cohesion destroys：Cohesion occurs by adhesive phase to destroy and adherend stripping
Interface peel：In the test film being placed before damp and hot placement, at the interface of polyvinyl chloride film-making material and double-faced adhesive tape Peel off
(1) standard curve making
It is used as polyvinyl chloride by the way that the mass parts of solid constituent 100 relative to acrylic adhesive composition (S) with the addition of The adhesive for the mass parts of diisononyl phthalate 10 that the plasticizer of film-making material uses is coated on the surface of release liner simultaneously It is set to dry and form adhesive phase, by being transferred to non-woven fabrics A (the NIPPON PAPER PAPYLIA that thickness is 43 μm CO., LTD. systems, No.1215) two sides on, make double-faced adhesive tape (C1).
Then, by the way that the acrylic adhesive composition (S) for not containing plasticizer to be coated on to the surface of release liner Go up and it is dried and is formed adhesive phase, it is two-sided to make on above-mentioned non-woven fabrics A two sides by the way that adhesive phase is transferred to Adhesive tape (C0).
Then, the infrared absorption spectroscopy of the adhesive layer surface of double-faced adhesive tape (C1) is determined by ATR methods, is obtained infrared Absorption spectrum (D1).
Then, the infrared absorption spectroscopy of the adhesive layer surface of double-faced adhesive tape (C0) is determined by ATR methods, is obtained infrared Absorption spectrum (D0).
Then, by subtracting infrared absorption spectroscopy (D0) (difference spectra) by above-mentioned infrared absorption spectroscopy (D1), plasticising is extracted out The infrared absorption spectroscopy (E1) of agent.
1285cm by above-mentioned infrared absorption spectroscopy (E1) measure from diisononyl phthalate-1Absworption peak Highly (F1).
Then, the infrared absorption spectroscopy that the adhesive layer surface of double-faced adhesive tape (C1) is determined by ATR methods is red to obtain Outer absorption spectrum (D1).Then, the 1160cm by above-mentioned infrared absorption spectroscopy (D1) measure from acrylate copolymer-1Suction Receive the height (G1) at peak.
Then, prepare to the addition of work relative to the mass parts of solid constituent 100 of acrylic adhesive composition (S) respectively The acrylic adhesive of the mass parts of diisononyl phthalate 20 used for the plasticizer of polyvinyl chloride film-making material, addition The acrylic adhesive for diisononyl phthalate 30 mass parts that plasticizer as polyvinyl chloride film-making material uses, And it with the addition of the acrylic acid series of the mass parts of diisononyl phthalate 40 used as the plasticizer of polyvinyl chloride film-making material Adhesive, adhesive phase is formed by the way that each adhesive to be coated on to the surface of release liner and dries it, by by its turn Print on above-mentioned non-woven fabrics A two sides, make 4 kinds of double-faced adhesive tapes.
Then, the release liner of any one of above-mentioned 4 kinds of double-faced adhesive tapes is removed, adhesive is determined by ATR methods The infrared absorption spectroscopy of layer surface.Determined respectively from diisononyl phthalate by above-mentioned 4 kinds of infrared absorption spectroscopies 1285cm-1Absworption peak height and the 1160cm from acrylate copolymer-1Absworption peak height.
It is the diisononyl phthalate addition [quality added in the mass parts of acrylic copolymer 100 to make the longitudinal axis Part], and make transverse axis be the 1285cm from diisononyl phthalate-1Absworption peak height (F1) relative to from The 1160cm of acrylate copolymer-1Absworption peak height (G1) ratio (F1/G1), will be included in above-mentioned 4 kinds of double-faced adhesive tapes Diisononyl phthalate addition and marked and drawed equivalent to above-mentioned value than (F1/G1) and make standard curve.
In addition, above-mentioned infrared absorption spectroscopy uses Fourier transform infrared spectrophotometer (Japan light splitting society FT/IR- 4100) determine.
In addition, respectively using acrylic adhesive composition (T), acrylic adhesive composition (U), acrylic acid series Adhesive composition (V), acrylic adhesive composition (W) replace aforesaid propylene acid system adhesive composition (S), except this In addition, standard curve is made by method similar to the above respectively.
(2) measure of the plasticising dosage of adhesive layer surface
The adhesive equivalent to adhesive phase (b1) for the double-faced adhesive tape that release liner is obtained from embodiment and comparative example After the surface of layer removes, the polyvinyl chloride film-making material obtained above containing plasticizer is attached to, it is wet in 60 DEG C and 80%RH etc. Placed 9 days under heat condition, obtain double-faced adhesive tape (C2).
Then, the bonding equivalent to adhesive phase (b2) by release liner from the double-faced adhesive tape (C2) after above-mentioned placement The surface of oxidant layer removes, and the infrared absorption spectroscopy (D2) on adhesive phase (b2) surface is determined by ATR methods, based on infrared absorption Spectrum (D2), obtains the 1285cm from diisononyl phthalate-1Absworption peak height (F2) and derive from propylene The 1160cm of acid polymer-1Absworption peak height (G2) ratio (F2/G2).
Then, above-mentioned F2/G2 is applied to the transverse axis of above-mentioned standard curve, calculate above-mentioned adhesive tape (C2) equivalent to viscous The content (H2) [mass parts] of the plasticizer included in the adhesive phase of mixture layer (b2).In addition, the phase of plasticizer will removed In the case of 100 mass parts are set in the adhesive phase of adhesive phase (b2), the content of above-mentioned plasticizer is represented by above-mentioned poly- The transfer amount [mass parts] for the plasticizer that the transfer of vinyl chloride film-making material comes.
Then, by the adhesive phase (b1) to connect with above-mentioned polyvinyl chloride film-making material from polychlorovinyl sheet material sur-face peeling, The content (J2) [mass parts] for the plasticizer that the surface of adhesive phase (b1) is included is calculated by method similar to the above.
(3) the uniformly dispersed evaluation of plasticizer
The uniformly dispersed content (H2) based on the diisononyl phthalate obtained by the above method of above-mentioned plasticizer With the difference of the content (J2) of above-mentioned diisononyl phthalate, evaluated according to following metewands.
〇：In the range of the difference of above-mentioned content (H2) and content (J2) is ± 2 mass parts, plasticizer it is uniformly dispersed excellent It is different.
×：The difference of above-mentioned content (H2) and content (J2) for the scope of ± 2 mass parts outside, plasticizer it is uniformly dispersed Difference.
[evaluation method of spalling resistance]
Under 23 DEG C and 50%RH environment, the one end for the above-mentioned polyvinyl chloride film-making material that width is 50mm is being cut into, attaching will The double-faced adhesive tape obtained in embodiment and comparative example cuts into the adhesive surface that width is the side of band obtained from 15mm, makes 2kg rollers come and go 1 time and pressurizeed.Then, the test film for the polyvinyl chloride film-making material for being pasted with above-mentioned double-faced adhesive tape is cut into 100mm length, the test film that length is 100mm and width is 50mm is made, is placed 9 days under 60 DEG C and 80%RH atmosphere.
Then, under 23 DEG C and 50%RH environment, by above-mentioned polyvinyl chloride film-making material in middle bending and in its end Attach the adhesive phase (central bend attaching) of opposite side.
Similarly operate, the test film of polyvinyl chloride film-making material of above-mentioned adhesive tape will be pasted with 60 DEG C and 80%RH gas After being placed 9 days under atmosphere, under 23 DEG C and 50%RH environment, above-mentioned polyvinyl chloride film-making material is bent into cylindrical shape, at its back side One end attach opposite side adhesive phase (screw winding attaching).
Using test film obtained from carrying out above-mentioned central bend attaching and screw winding attaching at 23 DEG C and 50%RH Test film obtained from 24 hours is placed under environment, their spalling resistance is evaluated according to following benchmark.
◎：Any test film of central bend attaching and screw winding attaching has been carried out without the generation peeled off.
○：It is the peeling length less than 3mm to have carried out any test film that central bend attaches and screw winding attaches.
△：One of test film that central bend attaches and screw winding attaches has been carried out to grow for more than 3mm peeling Degree.
×：The peeling length that any test film that central bend attaches and screw winding attaches is more than 3mm is carried out.
[the Ge Laishi air permeabilities of base material]
The base material used in above-described embodiment and comparative example is overlapping and fix by 10 plate substrates in 23 DEG C of 50%RH, determines diameter The inner cylinder for being 567g for 28.6mm, weight is fallen and time that 100ml air passes through.As sensing equipment, using according to JIS P8117 Toyo Seiki makes made Ge Laishi air permeabilities.
[table 1]
[table 2]
[table 3]

Claims (8)

1. a kind of adhesive tape, it is characterised in that it is the adhesive tape for the attaching of the adherend (a1) containing plasticizer, saturating One surface side of gas base material has adhesive phase (b1), has adhesive phase (b2) in another surface side of gas permeability base material, and The weight per unit area of the total of described adhesive layer (b1) and adhesive phase (b2) is 125g/m2~175g/m2Scope, and The gel fraction of the total of described adhesive layer (b1) and adhesive phase (b2) is the mass % of 2 mass %~35.
2. adhesive tape according to claim 1, wherein,
The gas permeability base material is the non-woven fabrics base material or porous membrane substrate that thickness is 10 μm~50 μm.
3. adhesive tape according to claim 1 or 2, wherein,
The material using obtained from by 10 gas permeability base material stackings is used as test film, the foundation JIS P of the test film The Ge Laishi air permeabilities of 8117 measure are 0.35 second/below 100ml.
4. according to adhesive tape according to any one of claims 1 to 3, wherein,
At 23 DEG C based on the dynamic viscoelastic spectrum determined with frequency 1Hz of described adhesive layer (b1) and adhesive phase (b2) Storage modulus is 0.08MPa~0.12MPa scope, at 60 DEG C based on the dynamic viscoelastic spectrum determined with frequency 1Hz The scope that loss modulus is 0.40~0.60 relative to the ratio (tan δ) of storage modulus, and based on the dynamic determined with frequency 1Hz The scope that loss modulus at 100 DEG C of Viscoelastic Spectral is 0.55~0.80 relative to the ratio (tan δ) of storage modulus.
5. according to adhesive tape according to any one of claims 1 to 4, wherein,
The adherend (a1) is the scope for containing the mass % of 15 mass %~30 relative to the quality of the adherend (a1) The film or sheet object for the scope that plasticizer and thickness are 0.2mm~1mm.
6. according to adhesive tape according to any one of claims 1 to 5, wherein,
The plasticizer is phthalic acid ester system plasticizer.
7. one kind matches somebody with somebody line tying sheet material, it has is pasted with any one of claim 1~6 institute on the adherend (a1) The structure for the adhesive tape stated.
8. it is a kind of by described in claim 7 with line tying with sheet material and the article tying up the distribution of more than 2 and formed.
CN201680019512.XA 2015-06-29 2016-06-16 Adhesive tape, sheet for bundling wire harness, and article Active CN107429131B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112105701A (en) * 2018-06-15 2020-12-18 Dic株式会社 Adhesive composition
TWI779199B (en) * 2018-06-15 2022-10-01 日商Ｄｉｃ股份有限公司 Adhesive composition

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JPWO2017002634A1 (en) 2017-07-06
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CN112960274B (en) 2023-04-25
CN112960274A (en) 2021-06-15

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