CN102702988B - Method for manufacturing adhesive composition, adhesive composition and adhesive tape - Google Patents

Method for manufacturing adhesive composition, adhesive composition and adhesive tape Download PDF

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Publication number
CN102702988B
CN102702988B CN201210082689.8A CN201210082689A CN102702988B CN 102702988 B CN102702988 B CN 102702988B CN 201210082689 A CN201210082689 A CN 201210082689A CN 102702988 B CN102702988 B CN 102702988B
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Prior art keywords
adhesive composition
film
composition
contact adhesive
methyl
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CN102702988A (en
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藤田志郎
铃木淳史
五十岚智美
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Fujimori Kogyo Co Ltd
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Fujimori Kogyo Co Ltd
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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
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/28—Metal sheet
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • 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
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Non-Insulated Conductors (AREA)

Abstract

The present invention discloses a method for manufacturing adhesive composition, the adhesive composition is used in an adhesive tape, and the adhesive tape is glued on the surface of indium tin oxide of a transparent conductive film formed by indium tin oxide. The adhesive composition is formed at least through the following (1) to (2) procedures: (1) mixing raw material composition for the adhesive formed by at least one (methyl) acrylate monomer with hydroxyl and a light polymerization initiator in a pressure-sensitive adhesive composition formed by crylic acid resin; (2) using the raw material composition for the adhesive to realize polymerization reaction through light exposure, and obtaining the adhesive composition.

Description

The manufacture method of binder composition, binder composition and self adhesive tape
Technical field
The present invention relates to be formed with on the surface of transparent substrate the self adhesive tape that fits in this ITO surface in transparent conductive laminated of the nesa coating that formed by ITO (abbreviation of indium tin oxide) (following, to be sometimes referred to as ITO).More specifically, relate to providing after the variation of the surface impedance rate that suppresses nesa coating and the envrionment test under hot and humid at binder layer manufacture method, the binder composition of binder composition of self adhesive tape of gonorrhoea phenomenon and the self adhesive tape that uses this binder composition do not occur.The application advocates the right of priority No. 2011-067884, the application for a patent for invention of Japanese publication on March 25th, 2011, and by its content quotation in the application.
Background technology
In recent years, transparent conductive laminated that on the face of transparent substrate one side being formed by transparent resin film or sheet glass, is formed with as the ito thin film of nesa coating is used to various uses.
As the purposes of transparent conductive laminated, such as enumerating transparency electrode for touch-screen, liquid-crystal display and OLED display, solar cell etc. etc.
The present invention is about transparent conductive laminated.Therefore, take that to use the touch-screen of transparent conductive laminated be example below, illustrate until complete the present invention's technical background.
In the touch-screen that transparent conductive laminated is integrated into as parts, in order to improve operability and the weather resistance of touch-screen, from starting in the past just to carry out various improvement.For example, take prevent touch screen surface damage and deteriorated be object, the surface protective film (for example,, referring to patent documentation 1,2) using in touch screen surface laminating has been proposed.
In the past, as being used in transparent conductive laminated of general touch-screen, known have a kind of so transparent conductive laminated (so-called fit type transparent conductive laminated): by forming on the one side of the base material being formed by transparent resin film, be firmly coated with the hardcoat film of (Hard Coating) layer and on the one side of transparent substrate, form transparent conductive laminated of nesa coating, with the face that does not form hard coat of hardcoat film and the opposed facing state of the face that does not form nesa coating of transparent conductive laminated, by tackiness agent, fit and form.
But, in recent years, be accompanied by the purposes expanding day of transparent conductive laminated, there is reducing the requirement of manufacturing cost.And, require to improve the conductivity of transparent conductive laminated and use simplification.And, require by reducing number of components etc. by transparent conductive laminated monolithic film membrane.As a kind of method that solves these problems, from the parts formation of transparent conductive laminated of aforesaid fit type, dispense a transparent substrate and binder layer.Its result, above forms conductive membrane by being formed on some of transparent substrate, and on another face, forms transparent conductive laminated of hard coat, seeks the reduction of transparent conductive laminated whole filming and manufacturing cost.
About transparent conductive laminated, also propose to have to fit on transparent conductive film layer and for the protection of the protective film (for example,, referring to patent documentation 3) of nesa coating.
And, in recent years, in using the touch-screen of transparent conductive laminated, required further to improve and completed outward appearance and dimensional precision while making.And, in manufacturing the optics of transparent conductive laminated of integration and the technique of Optical devices, the binder layer that requires inhibition to fit in the self adhesive tape on nesa coating changes the surface impedance rate of the nesa coating that forms transparent conductive laminated, and then at binder layer, gonorrhoea phenomenon does not occur yet after the envrionment test under hot and humid.
Therefore, about the adhesive sheet for the optics of fitting, self adhesive tape and for these binder composition, also improving, to reduce that gonorrhoea phenomenon (for example,, referring to patent documentation 4～7) does not occur in corrodibility and the envrionment test under hot and humid yet.
In manufacture, integrated in the technique of the optics of transparent conductive laminated and Optical devices; when use as patent documentation 3 disclosed transparent conductive film layers protective film time; even if there is not the damage causing because being heated in more than 120 ℃ heating processes yet; there is not the damage of nesa coating yet; therefore can be by processing according to the manufacturing process of roll-to-roll (roll to roll), therefore transparent conductive laminated of use and comparatively effective in the technique of processing optical device and Optical devices.
Yet the protective film that the disclosed transparent conductive film layer of patent documentation 3 is used, owing to having used heat-resistant resin film, therefore can prevent that in more than 120 ℃ heating processes nesa coating from sustaining damage, and can be used in this.But, as the change solution of this problem of the surface impedance rate of nesa coating in the process for using transparent conductive laminated processing optical device and Optical devices, be but no-good.
And, gas generated few (this gas is to cause that electronic unit moves bad reason) disclosed in patent documentation 4, can not corrode precise electronic parts and cause the good bond property of having of bad order, especially to the tackiness of metal and the good resin combination of viscosity, disclose especially resin composition for adhesive and used binder composition and the adhesive sheet of said composition.The disclosed adhesive sheet of patent documentation 4 is used acrylic acid acrylic pressure-sensitive adhesive compositions, at corrosion test, with fitting adhesive sheet be when placing 7 days and whether judging corrosion condition according to the variable color of copper coin under 60 ℃, the relative humidity envrionment conditions that is 90% in temperature on copper coin, do not find corrosion phenomenon yet.
Yet, in patent documentation 4, not about not causing the record in binder layer generation gonorrhoea phenomenon after the envrionment test under hot and humid, as the solution in this problem of binder layer generation gonorrhoea phenomenon, be useless.
And, in patent documentation 5, disclose the binder composition of using as the colour filter above that fits in the front face side of PDP (plasma display) and also can easily peel off while using and under hot and humid environment, also be difficult to cause the optical polymerism binder composition of gonorrhoea phenomenon and the adhesive sheet that uses said composition.But, in patent documentation 5, the not record about not having a negative impact to the variation of the surface impedance rate of nesa coating when fitting in ITO surface.And, in the embodiment of patent documentation 5, the vinylformic acid that contains 4% (weight) in effective acrylic pressure-sensitive adhesive compositions aspect preventing gonorrhoea phenomenon, but because described binder composition exerts an influence to corrosion ITO surface, therefore there is the secret worry of the surface impedance rate increase that causes ITO film.
And, the optical resin composition that can not corrode the constituent materials such as device used for image display panel transparent and necessary impact absorbency while having suitable bounding force and protection image display device etc. and the optical resin composition that uses said composition are disclosed in patent documentation 6.Specifically, be the optical resin composition that contains acrylate derivative, acrylate derivative polymkeric substance and high molecular weight crosslinked dose.But, in patent documentation 6, not about not causing the record in binder layer generation gonorrhoea phenomenon after the envrionment test under hot and humid, as the solution in this problem of binder layer generation gonorrhoea phenomenon, be useless.
And, in patent documentation 7, disclose the binder layer that the electronic console of gonorrhoea phenomenon is used, the multipolymer of monomer and/or the binder composition of mixture of this binder layer for comprising (methyl) alkyl acrylate monomer and containing carboxyl also can not occur under the environment under hot and humid.But, in patent documentation 7, the not record about not having a negative impact to the variation of the surface impedance rate of nesa coating when fitting in ITO surface, whether therefore unclear described binder composition can fit in ITO surface and use.
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 8-329767 communique
Patent documentation 2: Japanese kokai publication hei 2-066809 communique
Patent documentation 3: Japanese kokai publication hei 7-068691 communique
Patent documentation 4: TOHKEMY 2007-246882 communique
Patent documentation 5: TOHKEMY 2007-161908 communique
Patent documentation 6: TOHKEMY 2008-248221 communique
Patent documentation 7: TOHKEMY 2008-001739 communique
Summary of the invention
As mentioned above, in the prior art, just be used in the transparent conductive film layer of transparent conductive laminated with regard to self adhesive tape, also openly do not prevent from not occurring after the variation of surface impedance rate of nesa coating and the envrionment test under hot and humid the self adhesive tape of gonorrhoea phenomenon.
That is to say, the object of the invention is to, for the self adhesive tape that is fitted in the ITO surface of transparent conductive laminated that is formed with nesa coating, provide manufacture method, the binder composition of binder composition of the self adhesive tape that gonorrhoea phenomenon does not occur after a kind of variation of the surface impedance rate that suppresses nesa coating and the envrionment test under hot and humid and the self adhesive tape that uses this binder composition.
In order to prevent that outside atmosphere sharply from changing the cohesion of the water molecules causing and preventing binder layer generation gonorrhoea phenomenon, the present invention adopts following technological thought: when fit in ITO when surface also can be directly as the monomer of crosslinked hydroxyl in can suppressing the contact adhesive composition of polymer formation of acrylic acid or the like tackiness agent, that be 0～33 by acid value of variation of surface impedance rate of nesa coating, thereby give the new function that water molecules is existed to be separated into the state of the degree being invisible to the naked eye, the binder composition of the function that is improved thus.
That is to say, in the contact adhesive composition in the present invention, (methyl) acrylate monomer of at least one hydroxyl being formed by the crosslinked acrylic polymers that to import to by acid value be 0～33, play thus the effect that prevents that water molecules from condensing.Accordingly, can provide after the variation of the surface impedance rate that also can suppress nesa coating when the ITO fitting in as bonded object and the envrionment test under hot and humid at binder layer the binder composition of self adhesive tape of gonorrhoea phenomenon and the self adhesive tape that uses said composition do not occur.
Therefore, in the first embodiment of the present invention, in order to address the above problem, a kind of manufacture method of binder composition is provided, this binder composition is for self adhesive tape, this self adhesive tape fits in the described ITO surface of the nesa coating being formed by ITO (indium tin oxide), wherein at least by following (1)～(2) operation, obtains having the binder composition (polymkeric substance C) of physical property K.; a kind of manufacture method of contact adhesive composition; this contact adhesive composition is for pressure-sensitive adhesive tape; this pressure-sensitive adhesive tape fits in the described indium tin oxide surface of the nesa coating being formed by indium tin oxide, wherein at least by following (1)～(2) operation, obtains having the contact adhesive composition (polymkeric substance C) of physical property K:
(1) in the contact adhesive composition (polymer A) that the acrylic resin that to be formulated in by acid value be 0～33 forms, mix (methyl) acrylate monomer (monomers B) of at least one hydroxyl and the used in pressure sensitive adhesive feedstock composition that Photoepolymerizationinitiater initiater forms;
(2) use described used in pressure sensitive adhesive feedstock composition to carry out polyreaction by rayed, obtain having the contact adhesive composition (polymkeric substance C) of physical property K;
Wherein, physical property K is defined as follows.
Physical property K is defined as: at indium tin oxide surface coated contact adhesive composition (polymkeric substance C) and after forming the film that dried thickness is 200 μ m, from being that the hot and humid envrionment test of 500 hours implemented 85, the relative humidity environment that is 85% is with after taking out in baking oven in temperature, the variation multiplying power of the resistance value of indium tin oxide film is compared with initial value below 1.7 times, and while just taking out, at contact adhesive composition (polymkeric substance C) layer, there is not gonorrhoea phenomenon from described baking oven.
And, in the second embodiment of the present invention, a kind of manufacture method of binder composition is provided, this binder composition is for self adhesive tape, this self adhesive tape fits in the described ITO surface of the nesa coating being formed by ITO, at least by following (1)～(3) operation, obtains having the binder composition (polymkeric substance C) of physical property K.
A kind of manufacture method of contact adhesive composition, this contact adhesive composition is for pressure-sensitive adhesive tape, this pressure-sensitive adhesive tape fits in the described indium tin oxide surface of the nesa coating being formed by indium tin oxide, at least by following (1)～(3) operation, obtains having the contact adhesive composition (polymkeric substance C) of physical property K:
(1) in the contact adhesive composition (polymer A) that the acrylic resin that to be formulated in by acid value be 0～33 forms, mix (methyl) acrylate monomer (monomers B) of at least one hydroxyl and the used in pressure sensitive adhesive feedstock composition that Photoepolymerizationinitiater initiater forms;
(2) on the base material film being formed by thermoplastic resin of long size, be coated with and be dried described used in pressure sensitive adhesive feedstock composition, so that dried thickness reaches 20～500 μ m, obtain thus the coating film of long size;
(3) use the coating film of described long size to carry out polyreaction by rayed, on described base material film, obtain having thus the contact adhesive composition (polymkeric substance C) of physical property K;
Wherein, physical property K is defined as follows.
Physical property K is defined as: at indium tin oxide surface coated contact adhesive composition (polymkeric substance C) and after forming the film that dried thickness is 200 μ m, from being that the hot and humid envrionment test of 500 hours implemented 85, the relative humidity environment that is 85% is with after taking out in baking oven in temperature, the variation multiplying power of the resistance value of indium tin oxide film is compared with initial value below 1.7 times, and while just taking out, at contact adhesive composition (polymkeric substance C) layer, there is not gonorrhoea phenomenon from described baking oven.
In the 3rd embodiment of the present invention, a kind of contact adhesive composition (polymkeric substance C) is provided, contain following material, and there is physical property K:
In solid substance, the contact adhesive composition (polymer A) that the acrylic resin that is 0～33 by acid value of 100 weight parts forms;
(methyl) 5～15 weight parts, at least one hydroxyl acrylate monomer (monomers B);
The Photoepolymerizationinitiater initiater of 0.01～0.5 weight part;
Wherein, physical property K is defined as follows.
Physical property K is defined as: at indium tin oxide surface coated contact adhesive composition (polymkeric substance C) and after forming the film that dried thickness is 200 μ m, from being that the hot and humid envrionment test of 500 hours implemented 85 ℃, the relative humidity environment that is 85% is with after taking out in baking oven in temperature, the variation multiplying power of the resistance value of indium tin oxide film is compared with initial value below 1.7 times, and while just taking out, at contact adhesive composition (polymkeric substance C) layer, there is not gonorrhoea phenomenon from described baking oven.
And, in the 4th embodiment of the present invention, the pressure-sensitive adhesive tape that the contact adhesive composition (polymkeric substance C) that provides on base material film lamination to manufacture by the method described in the above-mentioned first or second embodiment forms.
And, in the 5th embodiment of the present invention, the pressure-sensitive adhesive tape that the contact adhesive composition (polymkeric substance C) that provides on base material film lamination to manufacture by the method described in above-mentioned the 3rd embodiment forms.
And, in the 6th embodiment of the present invention, provide by the method manufacture described in the above-mentioned the 4th or the 5th embodiment, its purposes is the pressure-sensitive adhesive tape of adhesive parts on indicating meter.
According to above-mentioned the present invention, the contact adhesive composition that is 0～33 to existing acid value carries out modification, thereby provide, is the binder composition being dispersed with for the state of the hydroxyl of adsorbed water molecule.Thus, can be by the moisture under the Polymer adsorption hot and humid environment condition of hydroxyl, therefore can bring into play following new function: even if thicken binder layer in order to improve shock-absorbing capacity, also can prevent the generation of the caused gonorrhoea phenomenon of cohesion of absorbed water molecules.
And, by adjusting rightly the mobility of adhesive coated liquid, can thicken the coating thickness on base material, form and there is certain thickness self adhesive tape, thereby can improve shock-absorbing capacity.
Accompanying drawing explanation
Figure 1A be model utility represent to use the sectional view of an example of binder composition of the present invention one side self adhesive tape that form, that there is binder layer;
Figure 1B be model utility represent to use the sectional view of a binder composition of the present invention example without base material adhesive tape (transfer tape) that form, that there is binder layer;
Fig. 2 be model utility represent the explanatory view of an example of the manufacture method of adhesive film of the present invention;
Fig. 3 A is about embodiment 1 and comparative example 2, the envrionment test graphic representation that takes out the variation of mist degree (Haze) value afterwards in baking oven from hot and humid is shown, after being shown, the envrionment test under hot and humid telling on as the present invention there is not this fact of gonorrhoea phenomenon, with for referencial use;
Fig. 3 B is by the graphic representation shown in the scope amplification of 0～40 minute of Fig. 3 A.
Nomenclature:
1-base material, 2-binder layer, 3-separate sheet, 5-one side self adhesive tape, 6-is without base material adhesive tape, the base material that 11-is transmitted or separate sheet, 12-coated film, 13-separate sheet, 21-die slot dispense tip (die coater), 22-support roll, 23-kiln, 24-separate sheet feeding unit, 25-clip wheel, 26-UV irradiation equipment.
Embodiment
Below, the preferred embodiment of the present invention is described.
Below, the manufacture method of binder composition involved in the present invention (polymkeric substance C) is described.Be formulated in and in the contact adhesive composition (polymer A) being formed by acrylic resin, mix (methyl) acrylate monomer (monomers B) of at least one hydroxyl and the tackiness agent feedstock composition that Photoepolymerizationinitiater initiater forms.Then, use described tackiness agent by rayed, to carry out polyreaction with feedstock composition, can obtain having the binder composition (polymkeric substance C) of physical property K.
Wherein, physical property K is: after ITO surface coated binder composition (polymkeric substance C) forms the film that dried thickness is 200 μ m, from being that the hot and humid envrionment test of 500 hours implemented 85 ℃, the relative humidity environment that is 85% is with after taking out in baking oven in temperature, the variation multiplying power of the resistance value of ITO (indium tin oxide) film is compared with initial value below 1.7 times, and while just taking out, at binder composition (polymkeric substance C) layer, there is not gonorrhoea phenomenon from described baking oven.
When manufacturing binder composition of the present invention, at first the monomer of at least one hydroxyl (monomers B) is mixed into for making the polymerization starter of this monomers B polymerization and the contact adhesive composition being formed by acrylic resin (polymer A), prepares thus tackiness agent feedstock composition.This tackiness agent comprises conduct according to (methyl) the optical polymerism compound of energy-ray generation polymerization, at least one hydroxyl acrylate (monomers B) with feedstock composition.(methyl) acrylate monomer B has as carrying out the polymerizable compound of (methyl) acrylic of the vinyl of radical polymerization with Photoepolymerizationinitiater initiater, is for example the ultraviolet ray within the scope of 300nm～400nm to be had the ultraviolet curable resin material of solidified nature.
At this, in this specification sheets, (methyl) acrylate refers to the general name of acrylate and methacrylic ester.
Polymer A is the matrix resin of binder composition of the present invention, and its acid value is 0～33, so long as easily disperse the material of the acrylic monomer (monomers B) of hydroxyl.
Polymer A is for monomers B is easily disperseed, preferred acrylic polymers, and more preferably copolymerization has hydrophilic monomer.This is because monomers B is acrylic acid or the like and hydroxyl.And binder composition of the present invention, owing to being to be used in optical applications, therefore must having the transparency, and consider the power that can simply control clinging power, so the preferred acrylic polymers of polymer A.
Acid value is derived from carboxyl and other acidic groups (sulfonic group, phosphate etc.) that (methyl) acrylic acid esters co-polymer has.The mg number of the required potassium hydroxide of contained free fatty acids, resinous acid, measures acid value by potential difference titration during described acid value refers to and in 1g sample.
Specifically, according to JIS-K-2501:2003 (Japanese Industrial Standards number), tackiness agent is dissolved in to the titration solvent of mixed toluene and methyl alcohol (1+1) (volume ratio), with the titration of 0.1mol/L potassium hydroxide-methanol solution, using the flex point of titration curve as terminal.From potassium hydroxide-methanol solution to terminal till titer calculate acid value.
Use binder composition of the present invention, after the upper coating of base material (or can be also separate sheet, interleaving paper), being dried, irradiate light and make its polymerization can obtain self adhesive tape.
At this, in this specification sheets, self adhesive tape does not need to be distinguished according to width, all comprises self adhesive tape and the adhesive sheet of JIS-Z-0109 (Japanese Industrial Standards number) defined.As its concrete example, can enumerate the single mask of base material have the one side self adhesive tape (or one side adhesive sheet) of binder layer, the binder layer that has the double-faced adhesive tape (or double-sided adhesive sheet) of binder layer or do not there is base material at two masks of base material form film like without base material adhesive tape (transfer belt).Adhesive sheet can form big area shape, both can keep its wider lateral dimension directly to use, and also can be cut into compared with thin band shape and as self adhesive tape.Especially, the adhesive sheet or the self adhesive tape that are rolled into roller shape are well suited for the purposes for adhesive parts on indicating meter.
In Figure 1A, model utility ground represents to use an example of binder composition of the present invention one side self adhesive tape 5 that form, that have binder layer 2.One side self adhesive tape 5 forms binder layer 2 on single of the base material 1 of the supporter as binder layer 2, and separated 3 protection of the adhesive face of binder layer 2.During use, peel separation sheet 3 and expose adhesive face, makes to fit in bonded object at the binder layer 2 of its back side laminate substrate 1.
About having the structure of the double-faced adhesive tape of base material, although do not illustrate especially in the drawings, its two faces that have at base material form binder layer, and by separate sheet, protect the structure of the adhesive face of each binder layer.
Figure 1B model utility ground represents to use a binder composition of the present invention example without base material adhesive tape (transfer tape) 6 that form, that have binder layer 2.This arranges separate sheet 3,3 without base material adhesive tape 6 on two faces of binder layer 2.During use, peel off the separate sheet 3 of one of them, expose the adhesive face of a side and fit to bonded object.And then, then peel off another separate sheet 3, thus can be only by the binder layer of film like 2 transfer printings (transfer) to bonded object.After peeling off another separate sheet 3, other bonded object of can also fitting on new adhesive face.
The effect of improving about the generation that can prevent gonorrhoea phenomenon under hot and humid environment condition of the present invention, when take without the bonded object of the form laminating of base material adhesive tape when glass (unorganic glass) and acrylic resin (acrylic glass) etc. is difficult to the material through moisture, its effect is especially remarkable.Its reason is as follows:
When laminating can see through the resin film of water molecules well, the water molecules that is distributed to bonding belt can easily see through resin film and overflow.Therefore, reducing the probability of water molecules cohesion, even and water molecules cohesion, also can by resin film, overflow at once.So the time that gonorrhoea phenomenon occurs is very short.But if the material that laminating water molecules is difficult to see through, while there is gonorrhoea phenomenon in water molecules cohesion, water diffusion just can be overflowed after the periphery end of self adhesive tape, therefore gonorrhoea phenomenon can continue to occur in a long time.
(contact adhesive composition (polymer A))
In the present invention, preferably, the contact adhesive composition (polymer A) that the acrylic monomer manufacture of using at least one to have ester group (COO-) is formed by acrylic resin.As the acrylic monomer with ester group (COO-), for example, can enumerate and use general formula CH 2=CR 1-COOR 2(in formula, R 1represent hydrogen atom or methyl, R 2the alkyl that expression carbonatoms is 1～14) (methyl) alkyl acrylate representing and (methyl) acrylate such as (methyl) acrylate of hydroxyl.
As using general formula CH 2=CR 1-COOR 2(in formula, R 1represent hydrogen atom or methyl, R 2the alkyl that expression carbonatoms is 1～14) (methyl) alkyl acrylate representing, specifically can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid n-pentyl ester, (methyl) vinylformic acid isopentyl ester, the just own ester of (methyl) vinylformic acid, (methyl) 2-ethylhexyl acrylate, (methyl) vinylformic acid n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) decyl acrylate, or (methyl) vinylformic acid dodecane ester etc., can use separately wherein a kind of or use two or more materials wherein simultaneously.Wherein, preferably use (methyl) 2-ethylhexyl acrylate or (methyl) n-butyl acrylate.
From the angle of bounding force, consider the alkyl R of (methyl) alkyl acrylate 2carbonatoms be taken as 1～14.If the possibility that the carbonatoms of alkyl more than 15, exists bounding force to reduce, therefore should not choose.This alkyl R 2carbonatoms be preferably 1～12, more preferably carbonatoms is 4～12, further preferably carbonatoms is 4～8.
And, at alkyl R 2carbonatoms (methyl) alkyl acrylate that is 1～14 in, also can be by alkyl R 2carbonatoms be that (methyl) alkyl acrylate of 1～3 or 13～14 is used as a part for monomer.Preferably, by alkyl R 2carbonatoms (methyl) alkyl acrylate that is 4～12 for example, as the material (50～100 % by mole) that must use.
At this, these alkyl R 2can be straight chain, also can be side chain.
(monomers B)
And, as (methyl) acrylate of hydroxyl, such as enumerating (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-4-hydroxy butyl ester, (methyl) vinylformic acid list macrogol ester, (methyl) vinylformic acid list polypropylene glycol ester or (methyl) vinylformic acid list cyclohexanedimethanoester ester etc.
And, as carboxylic acrylic monomer, such as enumerating vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid or 2-acryloyl ethyl succsinic acid etc.
Just there is the acrylic monomer of ester group and have with regard to the ratio of mixture of acrylic monomer of carboxyl, be preferably that at least one of acrylic monomer with ester group accounts for 85～95 weight parts, at least one of acrylic monomer with carboxyl accounts for the ratio of mixture of 5～15 weight parts, to can give thermotolerance according to the degree cross-linked binder of the distortion of bonded object, and prevent from floating and peeling off from bonded object.
In the starting monomer of the contact adhesive composition for the manufacture of being formed by acrylic resin (polymer A), can also add other monomer.The monomer for example, can choice for use with hydrophilic groups such as carboxyl, alkoxysilyl group (Alkoxy silyl), amino, hydroxyl or sulfonic groups.
Form in the monomer of polymer A, (methyl) alkyl acrylate and the proportioning with the monomer of hydrophilic group require the shared weight ratio of hydrophilic group in the kind, 1 molecule of the characteristic that has and monomer etc. and difference according to tackiness agent.Above-mentioned proportioning, being for example preferably 5～50 % by weight is that monomer, 95～50 % by weight with hydrophilic group are (methyl) alkyl acrylate.
And, as the acrylic monomer that contains alkoxysilyl group, such as enumerating (methyl) vinylformic acid-γ propyltrimethoxy silane, (methyl) vinylformic acid-γ-methyl dimethoxy oxygen base silicon propyl ester or (methyl) vinylformic acid-γ-propyl group silicon etc.
And, as the non-acrylic monomer containing alkoxysilyl group, such as enumerating methoxy-ethylene base glue or vinyltrimethoxy silane etc.
And, as containing amino acrylic monomer, for example can enumerate (methyl) vinylformic acid dimethylamino ethyl ester, (methyl) vinylformic acid diformazan ammonia ester, (methyl) vinylformic acid tertiary butyl urethanum, (methyl) vinylformic acid methylamino ethyl methyl esters etc. are containing amino (methyl) acrylate, can enumerate in addition (methyl) acrylic acid amides, methylene-succinic acid acid amides, dimethylamino (methyl) acrylamide, dimethyl aminoethyl (methyl) acrylamide, N-(methoxymethyl)-2-acrylamide, N-ethoxy (methyl) acrylamide, N-methoxymethyl (methyl) acrylamide, or N-butoxymethyl (methyl) acrylamide etc.
Polymer A is preferably its major portion (for example, more than 50 % by weight, more preferably more than 80 % by weight) by acrylic monomer ((methyl) alkyl acrylate and the acrylic monomer with hydrophilic group), formed, in the situation that not affecting effect of the present invention, can use acrylic monomer monomer (non-acrylic monomer) in addition simultaneously.
For polymerization forms the acrylic monomer of polymer A and the non-acrylic monomer of arranging in pairs or groups arbitrarily, can be undertaken by known methods such as solution polymerization, block polymerization, suspension polymerization or emulsion polymerizations.In these methods, the solution polymerization that applicable employing is easy to reduce phlegm and internal heat.As the organic solvent using in solution polymerization, specifically can enumerate the aliphatic hydrocarbon classes such as the alicyclic hydrocarbons such as aliphatic ester, hexanaphthene such as the class such as the aromatic hydrocarbons such as toluene, dimethylbenzene, ethyl acetate, N-BUTYL ACETATE or normal hexane, pentane etc., but as long as do not hinder above-mentioned polyreaction, be not particularly limited.These solvents can only be used a kind of, also can mix two or more uses.The usage quantity of solvent can suitably be determined.
Generally speaking, in solution polymerization, along with polymerization temperature rises, the molecular weight of the polymkeric substance generating reduces.While carrying out polyreaction under the reflux temperature of solvent, by use, there is the solvent of the boiling temperature of the polyreaction of being adapted to, can when eliminating polymerization reaction heat, obtain polymer A.
And, the contact adhesive composition being formed by acrylic resin of the present invention (polymer A) is even if the binder composition of using as the self adhesive tape that fits in the ITO surface of transparent conductive laminated that is formed with nesa coating also can suppress the variation of the surface impedance rate of nesa coating.Described binder composition is so-called free acid binder composition, therefore comparatively desirable.
Now, as the index of variation that can suppress the surface impedance rate of nesa coating, it is 0～33 even more ideal that the acid value of polymer A is got.
The polymer A of the contact adhesive composition that conduct of the present invention is formed by acrylic resin also can be used the pressure sensitive adhesive of selling on general commercially available market.As the pressure sensitive adhesive of selling on this market, can use so-called free acid binder compositions such as not thering is carboxyl and acrylic acid acrylic adhesives.As the free acid binder composition of selling on market, for example can enumerate SK ダ イ Application 2147 (Soken Chemical & Engineering Co., Ltd.'s manufacture), as the less self adhesive tape of variation of the ITO surface impedance rate of selling on market, such as enumerating CS9621 (manufacture of electricity Dong work Co., Ltd.), MHM-F25, MHM-F50, MHM-F125 (manufacture of Rong Chemical Co., Ltd) or ZB7032W (Dainippon Ink Chemicals's manufacture) etc.
With regard to the molecular weight distribution of polymer A, be preferably number-average molecular weight (Mn) more than 70,000, and weight-average molecular weight (Mw) is more than 1,000,000.And then more preferably weight-average molecular weight (Mw) is more than 1,200 ten thousand.
So, the molecular weight of polymer A is larger, and its thermotolerance and weathering resistance are better.
If molecular weight is excessive, the viscosity of binder composition becomes too high, and the process velocity on base material film during laminating adhesive composition reduces.Although can consider improve the technological process for coating such as temperature of coating (adhesive coated liquid) and further expand the upper limit of molecular weight by research, while being at room temperature coated with, or the preference material that is less than 5,000,000 as Mw.
And, (methyl) acrylate monomer (monomers B) that binder composition of the present invention comprises at least one hydroxyl.
At tackiness agent of the present invention, with in a kind of preferred implementation of feedstock composition, polymerization is (methyl) alkyl acrylate of hydroxyl and Acrylic Acid Monomer and the acrylic polymers that obtains and (methyl) acrylate monomer of hydroxyl copolymerization do not occur and exist with the admixture of disperseing respectively not.And, in other preferred implementation, at tackiness agent with comprising the monomer that contains (methyl) acrylate of polymer A that the monomer of hydrophilic monomer obtains and hydroxyl by aggregate packet in feedstock composition.
Preferably, with respect to polymeric matrix (polymer A) 100 weight parts, the content of monomers B (being its total amount when monomers B has when two or more) is 5～20 weight parts, and in the situation that the requirement such as test under the environment that temperature is 85 ℃, relative humidity is 85%, there is high-durability, more preferably 5～15 weight parts.
At this, in the known binder composition being formed by the acrylic polymers of hydroxyl, as unreacted monomer, can comprise on a small quantity (methyl) acrylate monomer of hydroxyl.But its containing ratio is the containing ratio with (methyl) acrylate of the hydroxyl in feedstock composition lower than tackiness agent of the present invention significantly.
Below, the manufacture method of the binder composition that the present invention is relevant (polymkeric substance C) is described.Be formulated in and in the contact adhesive composition (polymer A) being formed by acrylic resin, mix (methyl) acrylate monomer (monomers B) of at least one hydroxyl and the tackiness agent feedstock composition that Photoepolymerizationinitiater initiater forms.Then, use described tackiness agent by rayed, to carry out polyreaction with feedstock composition, can obtain binder composition (polymkeric substance C).
Consider (methyl) acrylate monomer (monomers B) of comprising the contact adhesive composition (polymer A) that formed by acrylic resin and hydroxyl and Photoepolymerizationinitiater initiater, the state of acrylic syrup (Acrylic Syrup) or the monomer (monomers B) of coating and hydroxyl dispersed, be formulated as described acrylic syrup and be dissolved in the resin solution in organic solvent.
In (methyl) acrylate monomer (monomers B) of hydroxyl is dissolved in to the contact adhesive composition (polymer A) being formed by described acrylic resin and obtain in the operation of acrylic syrup, before monomers B is dissolved in to polymer A, preferably with organic solvent etc., clean as required.Thus, can remove unreacted acrylic monomer from polymer A.And, the weight of quantifying polymers A more exactly, thus the acrylic syrup of the content of having prepared more rightly the monomers B used and Photoepolymerizationinitiater initiater in ensuing operation can be manufactured.When making acrylic syrup, also can after being dissolved in to polymer A, monomers B utilize above-mentioned organic solvent etc. to clean.
And, add Photoepolymerizationinitiater initiater in acrylic syrup after, if the action of ultraviolet light comprising in room light and sunlight in acrylic syrup, may polymerization reaction take place.Therefore thus, will be difficult to manage acrylic syrup, and preferably carry out adding Photoepolymerizationinitiater initiater before the painting process as rear operation being about to as far as possible.For acrylic syrup, be dissolved in the resin solution of organic solvent, adopt too aforesaid method.What should be noted that is exactly, and should prevent that light trigger from starting reaction because of external cause before coating, film forming.
In order to make binder composition of the present invention (polymkeric substance C) there is the mobility that is applicable to being coated on base material, preferably make the adhesive coated liquid coordinating with appropriate organic solvent.As the organic solvent using in adhesive coated liquid, specifically, such as enumerating the aliphatic hydrocarbon classes such as the alicyclic hydrocarbons such as the aliphatic esters such as aromatic hydrocarbons class, ethyl acetate, N-BUTYL ACETATE, hexanaphthene such as toluene, dimethylbenzene or normal hexane, pentane etc., as long as but can reach the object of above-mentioned coating and dispersion, be not particularly limited.
When preparation adhesive coated liquid, as long as can access these three kinds of materials of polymer A, monomers B and Photoepolymerizationinitiater initiater, mutually with appropriate proportioning, be dissolved in the organic solution of organic solvent, for its dissolving, be sequentially not particularly limited.For example, monomers B, Photoepolymerizationinitiater initiater can be in the acrylic syrup that has dissolved polymer A, directly put into, also the liquid that monomers B, Photoepolymerizationinitiater initiater is dissolved in to appropriate organic solvent can be in polymer A, put into.
In the present invention, (methyl) acrylate monomer of the hydroxyl using as monomers B can be from (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-3-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid 5-hydroxyl DOPCP, the own ester of (methyl) vinylformic acid-6-hydroxyl, (methyl) vinylformic acid 7-hydroxyl heptyl ester, (methyl) vinylformic acid 8-hydroxyl monooctyl ester, (methyl) vinylformic acid 7-methyl-8-hydroxyl monooctyl ester, (methyl) vinylformic acid 2-methyl-8-hydroxyl monooctyl ester, (methyl) vinylformic acid 9-hydroxyl ester in the ninth of the ten Heavenly Stems, in (methyl) vinylformic acid-10-hydroxyl ester in the last of the ten Heavenly stems or (methyl) vinylformic acid 12-hydroxyl dodecane ester etc., select.These materials can only be used a kind of, also can use two or more simultaneously.Especially, be applicable to using (methyl) 2-Hydroxy ethyl acrylate, (methyl) vinylformic acid hydroxy propyl ester or (methyl) vinylformic acid 4-hydroxyl butyl ester.
As (methyl) acrylate of hydroxyl, be applicable to using hydroxyalkyl (methyl) acrylate.A hydroxyl in these two hydroxyls that dibasic alcohol (diol compound) is had obtains with acrylic or methacrylic acid esters, has respectively 1 hydroxyl and 1 vinyl in 1 molecule.
The kind of the monomers B of using in the present invention, changes according to the bounding force of needed self adhesive tape, storage Young's modulus.If as the self adhesive tape with reprocessing (rework) performance, also can be made as the high and binder composition (polymkeric substance C) firmly of storage Young's modulus, therefore as the scheme of selecting monomers B, preferably select the monomers B of Tg more than room temperature.When requiring to there is strong adhesive power or want to reduce storage Young's modulus, need on the contrary Tg lower than room temperature, preferably the monomers B of Tg below zero degrees celsius.
(Photoepolymerizationinitiater initiater)
For the Photoepolymerizationinitiater initiater using in the present invention (polymerizing catalyst), be not particularly limited, such as enumerating acetophenones Photoepolymerizationinitiater initiater, st-yrax class Photoepolymerizationinitiater initiater, benzophenone Photoepolymerizationinitiater initiater or thioxanthones Photoepolymerizationinitiater initiater etc.
As acetophenones Photoepolymerizationinitiater initiater, can enumerate methyl phenyl ketone, P-(tertiary butyl) 1 ', 1 ', 1 '-Trichloroacetophenon, chloro-acetophenone, 2 ', 2 '-diethoxy acetophenone, hydroxyl ethyl ketone, 2,2-methoxyl group-2 '-phenyl methyl phenyl ketone, 2-aminoacetophenone or dialkyl amino benzoylformaldoxime etc.
As st-yrax class Photoepolymerizationinitiater initiater, can enumerate benzyl, st-yrax, st-yrax methyl ether, Benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl butyl ether, 1-hydroxyphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-2-methyl isophthalic acid-acetone, 1-(4-cumyl)-2-hydroxy-2-methyl-1-acetone or benzyl dimethyl ketal etc.
As benzophenone Photoepolymerizationinitiater initiater; can enumerate benzophenone, benzoylacrylic acid, benzoylbenzoic acid methyl esters, methyl-O-benzoyl phenylformic acid, 4-phenyl benzophenone, dihydroxy benaophenonel, hydroxypropyl benzophenone, vinylformic acid benzophenone or 4,4 '-bis-(dimethylamino) benzophenone etc.
As thioxanthones Photoepolymerizationinitiater initiater, can enumerate thioxanthone, CTX, 2-methyl thioxanthone or diethyl thioxanthone, dimethyl thia anthrone etc.
As other Photoepolymerizationinitiater initiater, can enumerate α-acyl group oxime ester, benzyl-(O-ethoxy)-α-di-acetyl, acylphosphine oxide, glyoxylic ester (グ リ オ キ シ エ ス テ Le), 3-coumarin ketone compounds, 2-ethyl-anthraquinone, camphorquinone, tetra methylthiuram sulfide, Diisopropyl azodicarboxylate, benzoyl peroxide, dialkyl superoxide or tert-butyl hydroperoxide trimethylacetic acid etc.
These Photoepolymerizationinitiater initiaters can only be used a kind of, and also can use two or more simultaneously.Using the full dose of polymerizable compound (being (methyl) acrylate of hydroxyl in the present invention) in the weight percent of 100 % by weight, the content of Photoepolymerizationinitiater initiater is preferably 0.005～5 % by weight, is especially preferably 0.01～2 % by weight.When the content of Photoepolymerizationinitiater initiater is in 0.005 % by weight when above, polymerization compound at short notice, when the content of Photoepolymerizationinitiater initiater is in 5 % by weight when following, the residue of Photoepolymerizationinitiater initiater is difficult to remain in cured article.
And, as mentioned above, for polymer A 100 weight parts, (methyl) acrylate monomer B of hydroxyl (is used when two or more, get total amount) be preferably 3～20 weight parts, such as thering is the high-durability under hot and humid condition in the situation that the requirement such as test under the environment that temperature is 85 ℃, relative humidity is 85%, 5～15 weight parts more preferably.Therefore, usining the polymer A of 100 weight parts is preferably 0.01～0.5 weight part as the content of the Photoepolymerizationinitiater initiater of benchmark.
In the present invention, preferably, in the binder composition after photopolymerization, monomer is with the scope generation polymerization of 40～80 % by weight, more preferably with the scope generation polymerization of 50～75 % by weight.That is to say, preferably with the scope residual unreacted monomers of 60～20 % by weight, more preferably with the scope residual unreacted monomers of 50～25 % by weight.When percent polymerization is less than 40 % by weight, resulting polymkeric substance cannot obtain enough binding propertys, and surpassing the decline that there will be cohesive force under the percent polymerization of 80 % by weight, causes occurring cull phenomenon when divesting binder layer.
The material of the base material using while forming self adhesive tape tackiness agent is coated to base material with feedstock composition preferably has the transparency, thermotolerance, and hinder ultra-violet solidified resin composition solidify, for the little material of scattering, the receptivity of near ultra-violet region 350nm～400nm.For example, can enumerate polyethylene terephthalate (PET), the polyester such as PEN (PEN), polysulfones, polyethersulfone, polystyrene, polyacrylic ester, polyether-ether-ketone, polycarbonate, the polyolefine such as polyethylene and polypropylene, polymeric amide, nylon, polyimide, triacetyl cellulose (cellulosetri-acetate), Cellulose diacetate, poly-(methyl) alkyl acrylate, poly-(methyl) acrylate copolymer, polymethylmethacrylate, the fluorine-type resin such as tetrafluoroethylene and poly-trifluoro, polyvinyl chloride, polyvinylidene chloride copolymer, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol, glassine paper or cellulose family film etc.These materials can be used separately a kind of, also can use two or more simultaneously.
Especially, from thermotolerance, ultraviolet (uv) transmission and consideration in price, preferably use the polyethylene terephthalate in described base material.
At this, the thickness of base material is preferably 16 μ m～200 μ m, more preferably 50 μ m～188 μ m.If the thickness of base material is excessively thin, treatability variation, and if the thickness of base material blocked up, the disadvantage that exists manufacturing cost to improve, and also have the disadvantage of treatability variation.
(transparent resin film)
As the base material 1 that is used in self adhesive tape of the present invention, preferably transparent resin film.Consider with laminating self adhesive tape, transparent conductive laminated of being protected comes in the operation of processing optical device and Optical devices; carry out 150 ℃ of heat treated under the high temperature of left and right, so this transparent resin film need to have the thermotolerance that at least can bear 150 ℃ of temperature.
As the material of this heat-resistant resin film, any one that select in the resin film group preferably forming from the polyethylene terephthalate by as heat-resistant resin (PET), PEN (PEN), cyclic polyolefin (COP).The heat resisting temperature of any one in these heat stable resins is all more than 200 ℃, when the lower use of the common heat treated temperature (150 ℃) of transparent conductive laminated, without any problem.
And, as the transparent resin film of the base material of self adhesive tape of the present invention, from workability angle, consider, preferably in the manufacturing process of transparent conductive laminated, be rolled into roller shape.Therefore, transparent resin film need to have pliability.In order to have pliability, the thickness of transparent resin film is preferably below 500 μ m, and preferred thickness is 10～150 μ m.If thickness is below 10 μ m, flexibility is excessive and be difficult to process, and if thickness surpass 500 μ m, rigidity is excessive and cannot be rolled into roller shape, therefore inadvisable.
And, for the transparent resin film of the base material as self adhesive tape of the present invention, percent thermal shrinkage while maintaining 30 minutes at 150 ℃, no matter be preferably MD direction when film shaped (flow direction), or TD direction when film shaped (width), all below 0.5%.
By make as the transparent resin film of the base material of self adhesive tape of the present invention so the percent thermal shrinkage in any direction in MD direction and TD direction all below 0.5%, can reduce the caused fold of thermal strain of generation in heating treatment step etc.
Therefore, be used as the transparent resin film of the base material of self adhesive tape of the present invention, in order to reduce percent thermal shrinkage, preferably implement anneal.By implementing anneal, can obtain percent thermal shrinkage below 1%, more preferably at the vibrin below 0.5%.
In the anneal that the transparent resin film of the base material as self adhesive tape of the present invention is implemented, can utilize known method in the past.
With regard to the transparent resin film as the base material of self adhesive tape of the present invention, the preferred polyethylene terephthalate (PET) of two-way stretch for example, to have good physical strength.Two-way stretch PET film is generally to carry out heat treated and make its crystalline orientation after the PET film of extension state is not extended respectively to 2～6 times of left and right with width along its length.And then, when using two-way stretch PET film, more preferably by anneal etc., adjust, the percent thermal shrinkage that makes the PET film to heat the PET film dimensions after 30 minutes at 150 ℃ the length direction of PET film and therewith vertical direction be all less than 0.5%.Less with the distortion of PET film substrate in the step of high-temperature heating treatment, therefore with this PET film, can easily manufacture fine panel.
And, as the transparent resin film of the base material of self adhesive tape of the present invention, can use the not extension clear PET film that becomes the filmings such as embrane method by melt extruding into embrane method with solution-cast, and then implement anneal and percent thermal shrinkage is controlled at below 0.5%.
At this, when making by solution-cast film forming legal system, can reduce the MD direction of film and the residual stress in TD direction, therefore very good.
And the transparent resin film as the base material as self adhesive tape of the present invention, can also be used cyclic polyolefin.Cyclic polyolefin is at main chain, to have the polyolefine of alicyclic structure.As the alicyclic structure of main chain, can enumerate structure, the cyclenes structure of naphthenic hydrocarbon.As the object lesson of cyclic polyolefin, can enumerate the preferences such as addition polymer of norbornylene based polyalcohol, monocycle cyclic olefin polymer, cyclic conjugated diene polymer and hydrogenation thing thereof, alicyclic vinyl cyclic hydrocarbon polymer and hydrogenation thing, cycloolefin monomers and ethene.As the cyclic polyolefin resin of selling on market, for example, can enumerate the ZEONOR 1060R (ProductName) that Japanese zeon Co., Ltd. manufactures.
(stripping film)
In self adhesive tape of the present invention, for example, by binder layer 2 laminations, there is the stripping film 3 that has carried out lift-off processing the face of a side of transparent resin film (, Fig. 1 above) is upper.Base material as the stripping film using in the present invention, can enumerate the paper such as good quality paper, glassine paper, coat paper, the synthetic resins such as polyolefin resin, polyvinyl chloride, polyurethane resin, acrylic resin, fluorine-type resin such as polyethylene terephthalate (PET), PEN (PEN), polyimide (PI), polyphenylene sulfide (PPS), polyethylene and polypropylene etc., but from angle easy to use, be applicable to using synthetic resins.
Thickness to the base material of stripping film is not particularly limited, and can use foamed substrate, also can use a plurality of flat substrates of lamination and have the base material of multi-ply construction.And then flat substrates carries out painted also harmless, or lamination coating is also harmless in order to give certain function.
Some the upper lift-off processing of implementing of the base material of the stripping film using in the present invention.As the method for lift-off processing, can use some the first-class known method that silicon rubber gross rubber, fluoride compound, long-chain alkyl compound etc. is coated on to flat substrates.
(transparent conductive laminated)
Self adhesive tape of the present invention fits in and on a face of transparent substrate, forms on the nesa coating of transparent conductive laminated that is preferably formed with hard coat on transparent conductive film layer, another face at transparent substrate and use.Or, fit in and on two faces of transparent substrate, form the nesa coating of transparent conductive laminated of transparent conductive film layer and use.Be used in the transparent substrate of transparent conductive laminated, a kind of or transparency glass plate of preferably selecting from the heat-resistant resin group being formed by polyethylene terephthalate (PET) resin, PEN (PEN) resin, cyclic polyolefin (COP) resinoid.
With regard to being used in the thickness of transparent substrate of transparent conductive laminated, when transparent substrate is transparent resin base material, be preferably 10～250 μ m, more preferably 30～200 μ m.If the thickness of transparent resin base material is less than 10 μ m, be difficult to operate, therefore inadvisable.If the thickness of transparent resin base material is greater than 250 μ m, the transparency reduces, and manufacturing cost also rises, and can reduce the process velocity in the manufacturing process of transparent conductive laminated, therefore inadvisable.Based on above-mentioned factor, the thickness of transparent resin base material is preferably 10～250 μ m, more preferably 30～200 μ m.And, can also be for the adhesive object improving between transparent resin base material and nesa coating, on the surface of transparent resin base material, lamination is suitable is easy to bonding resin layer, or implements the surface treatments such as flame treating, corona treatment, the processing of electricity slurry.And, also can between transparent resin base material and nesa coating, basal layer be set.
With regard to being formed on the hard coat of transparent substrate of transparent conductive laminated, can be as the hard painting performance of touch screen surface material as long as have, the measured value conventionally needing only in pencil hardness test is just no problem in practicality more than 2H.Use is not particularly limited at the resin of hard coat, can use the thermohardening types such as silicone resin class, melamine class firmly to resinize or the ultraviolet hardening such as silicone resin class, acrylic acid or the like is resinized etc. firmly.
And the thickness of hard coat is 1～10 μ m preferably, 2～8 μ m more preferably.If the thickness of hard coat is less than 1 μ m, cannot obtain being firmly coated with performance, reduce scuff resistance, and when using ultraviolet hardening firmly to resinize, easily occur to solidify bad.
And, if the thickness of hard coat is greater than 10 μ m, on hard coat, easily there is crackle, easily there is fold in hard-coated film itself, therefore inadvisable.
And, in hard coat, also can add as required charged preventor, UV light absorber etc. for giving the additive of various functions.The method that forms hard coat on the surface of transparent substrate can be used the contrary known method in the past such as (reverse coating) method, pressing mold coating (die coating) method or concave surface coating method that is coated with.
And any one method of selecting in method group by forming of the nesa coating from consisting of sputtering, vacuum deposition method and ion plating on the face of a side of the transparent substrate of transparent conductive laminated that the present invention was correlated with forms transparent conductive film layer.
Preferably, in the formation operation of this nesa coating, or after the formation operation of described nesa coating, comprise the operation forming by the film formed wiring pattern of described electrically conducting transparent.As the method that forms the wiring pattern of transparency electrode, can use known gimmick.As representational method, can enumerate the method that forms pattern by photolithography.And what form transparent conductive film layer on glass substrate also can be used as transparent conductive substrate.
With regard to tackiness agent is coated to the apparatus for coating of base material with feedstock composition with regard to, so long as have on base material, supply equably the mechanism that tackiness agent is coated with feedstock composition, any device all can.As apparatus for coating, preferably employing can be continuously fed to tackiness agent the device (not shown) of the structure that having of being coated with on base material consist of with container, liquid delivery pump, pipe arrangement, foreign matter removal strainer and the dispense tip of feedstock composition storage tackiness agent with feedstock composition.Dispense tip is such as being applicable to adopting die slot dispense tip (die coater) etc.
By apparatus for coating, on single of base material, form the thin film layer (coated film) of feedstock composition for tackiness agent.
The tackiness agent feedstock composition being just coated with by apparatus for coating is uncured fraction, has the mobility that is suitable for coating.
When tackiness agent feedstock composition is syrup type (Syrup-type), the thickness of coated film is preferably between 0.05～3mm, more preferably 0.1～2mm.The thickness of coated film with by photopolymerization getable binder layer thickness about equally.Therefore, the thickness of the binder layer in self adhesive tape of the present invention is also preferably between 0.05～3mm, more preferably 0.1～2mm.
When tackiness agent feedstock composition is solution-type, the Thickness Ratio syrup type of dry front coated film is thick, is equivalent to the numeral divided by concentration by the thickness of above-mentioned coated film.The concentration of dried coated film is identical with syrup type.
If be coated with lepthymenia, also attenuation of the thickness of binder layer, so shock absorbing capability variation.And if coated film is blocked up, manufacturing cost rises, this point is very unfavorable.
In Fig. 2, model utility ground represents an example of the manufacture method of self adhesive tape of the present invention.In device shown in Fig. 2, tackiness agent is fed on base material 11 by die slot dispense tip 21 with feedstock composition, forms coated film 12.Symbol 22 represents and the face-to-face support roll 22 that arrange, support base material 11 of die slot dispense tip 21.The base material 11 that is formed with coated film 12 is longitudinally transmitted along it, and in kiln 23, it is dried, to remove the solvent in coated film 12.In dried coated film 12, by separate sheet feeding unit 24, in coated film 12, supply separate sheet 13, by clip wheel 25, fit.
As long as the temperature in kiln 23 reaches the temperature that the solvent in coated film 12 can fully volatilize, preferably remain on the temperature that thermopolymerization does not occur polymerizable compound.
Separate sheet feeding unit 24 forms by batching the roller shape body of separate sheet 13 and the axle of this roller shape body of maintenance etc.
Clip wheel 25 is formed with the base material 11 of coated film 12 by clamping and a pair of running roller of separate sheet 13 forms, and is for fitting, to be formed with the base material 11 of coated film 12 and the device of separate sheet 13.Preferably, possess the presser unit for fitting, and preferably at least one running roller is made by rubber, to be easy to applying uniform pressure to film.
As separate sheet, such as can enumerate to by polycarbonate film, polyarylester film, polyethersulfone film, polysulphone film, polyester film, polyamide layer, Kapton, polystyrene bag Oh, the single or multiple lift plastics film that forms of polyolefin film, norbornylene class film, phenoxy group ether type polymeric film or organic resistance to gas permeable film implements at least to make one side have the stripping film of separability according to the lift-off processing of silicone resin class separating agent etc.; On paper, implement at least to make one side there is the interleaving paper of separability according to the lift-off processing of silicone resin class separating agent etc.; The films self such as fluorine-type resin film and certain polyolefins film have the film of separability; In inside, add separating agent and the film of film forming etc.Thickness for separate sheet does not limit, and is conventionally made as 5～500 μ m more, is preferably made as 10～100 μ m.Separate sheet is corresponding to used tackiness agent and use (stripping strength) and the article of selecting.
UV irradiation equipment 26 has the refrigerating unit that produces ultraviolet light source portion and remove the heat that light source produces.For light source portion, as long as can access the fully curing ultraviolet irradiation amount of polymerizable compound making in coated film 12, can freely select the lamp source such as high pressure mercury vapour lamp, metal halide lamp and there is the photodiode etc. of the luminescence peak of ultra-violet region.
Polymerizable compound by appropriate rayed polymerization coated film 12, improves thus the cohesive force of coated film 12, and makes it show binding property.
And, while manufacturing as self adhesive tape of the present invention the double-faced adhesive tape that there is no supporter as without base material adhesive tape, be not only now separate sheet 13, the base material 11 that transmits use is also served as by separate sheet, thereby forms binder layer in separate sheet.
And, during the two-sided double-faced adhesive tape with binder layer that is manufactured on supporter as self adhesive tape of the present invention, can be on each face simultaneously or successively carry out the coating of coating fluid, the photopolymerization of dry and coated film.
Take after the rayed that photopolymerization reaction is object, the maintenance (curing) that to carry out take crosslinking reaction be object.Method for maintenance, is not particularly limited, for example, the self adhesive tape being wound on running roller is placed under predetermined temperature and time condition.For example, although the temperature of maintenance also depends on the kind of linking agent etc., preferably heat as required (40～80 ℃).
After resulting binder layer is preferably after its adhesive face is fitted in to bonded object and places 1 hour under 23 ℃, the environment of relative humidity 50%, reach 10N/25mm with respect to the bounding force of glass and acrylic resin when peeling off with the peeling rate of 300mm/ minute more than.In order to obtain high like this bounding force, storage Young's modulus (the storage elastic modulus) G ' of the tackiness agent that forms binder layer under 23 ℃, 1Hz is preferably 1 * 10 4pa is above and be less than 1 * 10 6pa, and when having while the high-durability such as testing under 85 ℃, the environment of relative humidity 85%, be preferably 5 * 10 4more than Pa and 5 * 10 5below Pa.When storage Young's modulus is lower, binder layer is soft easily to deform, and is therefore easy to laminating.If storage Young's modulus in above-mentioned scope, can have stickiness, the weather resistance after laminating and bounding force etc. while fitting two parts (such as the harder parts such as sheet glass, acrylic board) simultaneously.
Self adhesive tape of the present invention can be well suited for the purposes for adhesive parts on the ito surface of transparent conductive laminated in uses such as touch-screens.
[embodiment]
Below, according to embodiment, illustrate the present invention.
Use the tackiness agent feedstock composition shown in lower list 1, by following manufacture method, made the self adhesive tape of embodiment 1～3 and comparative example 1～6.
Table 1
Figure BDA0000147040880000221
At this, in table 1,2094,2147 represent respectively " SK ダ イ Application " (registered trademark) 2094, " SK ダ イ Application " (registered trademark) 2147, " AA/2EHA " represents the multipolymer of vinylformic acid and 2-ethylhexyl acrylate, " 4HBA " represents vinylformic acid-4-hydroxyl butyl ester, and Irg184, Irg651 represent respectively Irgacure (registered trademark) 184, Irgacure (registered trademark) 651.At this, the Photoepolymerizationinitiater initiater of ProductName: Irgacure (registered trademark) 184 is usingd 1-hydroxy-cyclohexyl phenyl ketone as effective constituent.The Photoepolymerizationinitiater initiater of ProductName: Irgacure (registered trademark) 651 is usingd benzil dimethyl ketal as effective constituent.
(embodiment 1)
Use is by " SK ダ イ Application " 2094 (Soken Chemical & Engineering Co., Ltd.'s manufacture of the material as contact adhesive composition (polymer A), acid value: 33) 1000g and the solution for preparing as E-AX (Soken Chemical & Engineering Co., Ltd.'s manufacture) 2.7g of solidifying agent, the contact adhesive composition that obtains being formed by acrylic resin polymer (polymer A).
In resulting contact adhesive composition (polymer A), add further vinylformic acid-4-hydroxyl butyl ester (Osaka organic materials Industrial Co., Ltd manufacture as (methyl) acrylate monomer (monomers B) of hydroxyl, 4HBA) (Ciba Japan Co., Ltd. manufactures the Photoepolymerizationinitiater initiater of 100.0g and alkylbenzene ketone, ProductName: Irgacure184) 0.10g and prepare tackiness agent feedstock composition.
Use spreadometer (applicator) (Mitsubishi Plastics Inc manufactures by polyethylene terephthalate, ProductName: T100, thickness 38 μ m) above the base material film forming, be coated with this tackiness agent feedstock composition, make the thickness of dried binder layer reach 200 μ m.Then, be dried and making layer is pressed with the laminate of binder layer.
Then, the separate sheet of fitting on the binder layer of resulting laminate (Mitsubishi Plastics Inc manufacture, ProductName: MRF, thickness 38 μ m), thereby the laminated film of tackiness agent of having made lamination.
Then, continuous UV irradiating unit by employing high pressure mercury vapour lamp when transmitting resulting laminated film carries out UV irradiation with the irradiation dose (wavelength 300nm～400nm) of about 200mJ, when irradiating, adjust transfer rate as the laminated film of the tackiness agent of base material, the light quantity that UV irradiates etc., utilize thus Photoepolymerizationinitiater initiater to carry out polyreaction, thus the self adhesive tape of embodiment 1 of binder composition (polymkeric substance C) that finally obtained lamination.
(embodiment 2)
Use is by " SK ダ イ Application " 2147 (Soken Chemical & Engineering Co., Ltd.'s manufacture of the material as contact adhesive composition (polymer A), acid value: 0) 1000g and as TD-75 (Soken Chemical & Engineering Co., Ltd.'s manufacture) 0.4g of solidifying agent, the solution for preparing as A-50 (Soken Chemical & Engineering Co., Ltd.'s manufacture) 0.6g of additive, the contact adhesive composition that obtains being formed by acrylic resin polymer (polymer A).In resulting contact adhesive composition (polymer A), add further vinylformic acid-4-hydroxyl butyl ester (Osaka organic materials Industrial Co., Ltd manufacture as (methyl) acrylate monomer (monomers B) of hydroxyl, 4HBA) (Ciba Japan Co., Ltd. manufactures the Photoepolymerizationinitiater initiater of 50.0g and alkylbenzene ketone, ProductName: Irgacure184) 0.10g and prepare tackiness agent feedstock composition.In addition, identical with embodiment 1, thus obtain the self adhesive tape of embodiment 2.
(embodiment 3)
Use is by " SK ダ イ Application " 2147 (Soken Chemical & Engineering Co., Ltd.'s manufacture of the material as contact adhesive composition (polymer A), acid value: 0) 1000g and as TD-75 (Soken Chemical & Engineering Co., Ltd.'s manufacture) 0.4g of solidifying agent, the solution for preparing as A-50 (Soken Chemical & Engineering Co., Ltd.'s manufacture) 0.6g of additive, the contact adhesive composition that obtains being formed by acrylic resin polymer (polymer A).In resulting contact adhesive composition (polymer A), add further vinylformic acid-4-hydroxyl butyl ester (Osaka organic materials Industrial Co., Ltd manufacture as (methyl) acrylate monomer (monomers B) of hydroxyl, 4HBA) (Ciba Japan Co., Ltd. manufactures the Photoepolymerizationinitiater initiater of 100.0g and alkylbenzene ketone, ProductName: Irgacure184) 0.10g and prepare tackiness agent feedstock composition.In addition, identical with embodiment 1, thus obtain the self adhesive tape of embodiment 3.
(comparative example 1)
As the surface impedance rate of the ito surface when self adhesive tape of the present invention is fitted to ito surface change compare contrast benchmark (blank), will be less than in ito thin film (Zhong Jing Industrial Co., Ltd, ProductName: メ タ Off オ mono-ス 125R2 * A, surface impedance rate 250 Ω/m 2) ito thin film of upper laminating self adhesive tape of the present invention directly puts into baking oven.
(comparative example 2)
" SK ダ イ Application " 2094 (Soken Chemical & Engineering Co., Ltd.'s manufacture by the material as feedstock composition for tackiness agent (polymkeric substance C), acid value: 33) 1000g and coordinate preparation composition (polymkeric substance C) for tackiness agent as E-AX (Soken Chemical & Engineering Co., Ltd.'s manufacture) 2.7g of solidifying agent.In addition, identical with embodiment 1, thus obtain the self adhesive tape of comparative example 2.
(comparative example 3)
" SK ダ イ Application " 2147 (Soken Chemical & Engineering Co., Ltd.'s manufacture by the material as feedstock composition for tackiness agent (polymkeric substance C), acid value: 0) 1000g and as TD-75 (Soken Chemical & Engineering Co., Ltd.'s manufacture) 0.4g of solidifying agent, as A-50 (Soken Chemical & Engineering Co., Ltd.'s manufacture) 0.6g of additive, coordinate preparation composition (polymkeric substance C) for tackiness agent.In addition, identical with embodiment 1, thus obtain the self adhesive tape of comparative example 3.
(comparative example 4)
Use is by " SK ダ イ Application " 2147 (Soken Chemical & Engineering Co., Ltd.'s manufacture of the material as contact adhesive composition (polymer A), acid value: 0) 1000g and as TD-75 (Soken Chemical & Engineering Co., Ltd.'s manufacture) 0.4g of solidifying agent, the solution for preparing as A-50 (Soken Chemical & Engineering Co., Ltd.'s manufacture) 0.6g of additive, the contact adhesive composition that obtains being formed by acrylic resin polymer (polymer A).In resulting contact adhesive composition (polymer A), add further vinylformic acid-4-hydroxyl butyl ester (Osaka organic materials Industrial Co., Ltd manufacture as (methyl) acrylate monomer (monomers B) of hydroxyl, 4HBA) (CibaJapan Co., Ltd. manufactures the Photoepolymerizationinitiater initiater of 150.0g and alkylbenzene ketone, ProductName: Irgacure184) 0.10g and prepare feedstock composition for tackiness agent (polymkeric substance C).In addition, identical with embodiment 1, thus obtain the self adhesive tape of comparative example 4.
(comparative example 5)
Use by the material as contact adhesive composition (polymer A) using vinylformic acid/2-ethylhexyl acrylate=87: 13 (acid values: 101.25) the polymkeric substance 1000g of furnishing 40% concentration and the solution for preparing as EX-830 (manufacture of the Nagase ChemteX Co., Ltd.) 8.0g of solidifying agent in ethyl acetate, the contact adhesive composition that obtains being formed by acrylic resin polymer (polymer A).In resulting contact adhesive composition (polymer A), add further vinylformic acid-4-hydroxyl butyl ester (Osaka organic materials Industrial Co., Ltd manufacture as (methyl) acrylate monomer (monomers B) of hydroxyl, 4HBA) (Ciba Japan Co., Ltd. manufactures the Photoepolymerizationinitiater initiater of 60.0g and alkylbenzene ketone, ProductName: Irgacure651) 0.40g and prepare feedstock composition for tackiness agent (polymkeric substance C).In addition, identical with embodiment 1, thus obtain the self adhesive tape of comparative example 5.
(comparative example 6)
Use by the material as contact adhesive composition (polymer A) using vinylformic acid/2-ethylhexyl acrylate=95: 5 (acid values: 38.2) the polymkeric substance 1000g of furnishing 34% concentration and the solution for preparing as EX-830 (manufacture of the Nagase ChemteX Co., Ltd.) 6.0g of solidifying agent in ethyl acetate, the contact adhesive composition that obtains being formed by acrylic resin polymer (polymer A).In resulting contact adhesive composition (polymer A), add further vinylformic acid-4-hydroxyl butyl ester (Osaka organic materials Industrial Co., Ltd manufacture as (methyl) acrylate monomer (monomers B) of hydroxyl, 4HBA) (Ciba Japan Co., Ltd. manufactures the Photoepolymerizationinitiater initiater of 40.0g and alkylbenzene ketone, ProductName: Irgacure651) 0.60g and prepare feedstock composition for tackiness agent (polymkeric substance C).In addition, identical with embodiment 1, thus obtain the self adhesive tape of comparative example 6.
(test method of self adhesive tape)
Utilize the self adhesive tape of the above embodiments 1～3 and comparative example 2,3,5,6, be produced on the test sample sheet of the self adhesive tape of fitting on ito thin film, measured ITO film resistance value variation multiplying power and carried out confirming the test of the generation of gonorrhoea phenomenon.And, as blank (blank), in comparative example 1, the ito thin film of the self adhesive tape of not fitting is directly put into baking oven on ito thin film, measured the variation multiplying power of the resistance value of ITO film.
(measuring method of the variation multiplying power of the resistance value of nesa coating)
(Zhong Jing Industrial Co., Ltd manufactures, ProductName: メ タ Off オ mono-ス 125R2 * A, surface impedance rate 250 Ω/m to prepare ito thin film 2), be cut to the short strip shape of wide 25mm * long 120mm size.On the ito surface of the small pieces of the ito thin film of the short strip shape of cutting, take central position as starting point, by the fit self adhesive tape of wide 25mm * long 100mm size of binder layer, made the test sample sheet at ito thin film upper strata pressure viscosity crossed belt.In order to improve the bond strength of the self adhesive tape of the ito surface that fits in test sample sheet, test sample sheet is put into autoclave under the condition of pressure 0.5MPa, temperature 40, implemented the heating operation of 15 minutes.
Position at the self adhesive tape of not fitting of the ito thin film two end portions of test sample sheet, (Fujikura Kasei Co., Ltd manufactures coating silver paste, ProductName: dotite, model: FA-301CA) form and measure terminal, after the enforcement temperature heat of 80 ℃ * 1 hour is burnt till, Contact test device on the mensuration terminal at test sample sheet two ends and measure the resistance value between ito thin film two ends, as the initial impedance value of nesa coating.
Then, it is the baking oven that 85 ℃, relative humidity are 85% that test sample sheet is put into temperature, after through 500 hours, take out, again Contact test device and measure the resistance value between ito thin film two ends on the mensuration terminal at ito thin film two ends, as the resistance value after the envrionment test under hot and humid condition.
By following calculation formula, calculate the variation multiplying power of resistance value of the ITO film of test sample sheet.
The variation multiplying power of the resistance value of nesa coating=(resistance value after hot and humid envrionment test)/(initial impedance value)
(confirming the test of the generation of gonorrhoea phenomenon)
It is in 85 ℃, the relative humidity hot and humid environment that is 85% that the test sample sheet of making when measuring the variation multiplying power of resistance value of nesa coating is put into temperature, after 12 hours, takes out.Then, under the environment that to be placed on temperature and to be 23 ℃, relative humidity be 50%, the appearance change of range estimation validation test sample strip.To there is be evaluated as (*) of gonorrhoea phenomenon, will not confirm being evaluated as of generation (zero) of gonorrhoea phenomenon.
(test-results)
The result of above-mentioned test shown in table 2.
Table 2
Change in impedance value multiplying power The outward appearance of binder layer Gonorrhoea is evaluated
Embodiment 1 1.61 Transparent Without gonorrhoea phenomenon
Embodiment
2 1.40 Transparent Without gonorrhoea phenomenon
Embodiment
3 1.38 Transparent Without gonorrhoea phenomenon
Comparative example 1 1.45 - -
Comparative example 2 1.99 Transparent There is gonorrhoea phenomenon
Comparative example 3 1.46 Transparent There is gonorrhoea phenomenon
Comparative example 4 - Gonorrhoea -
Comparative example 5 140 Transparent Without gonorrhoea phenomenon
Comparative example 6 More than 1000 Transparent Without gonorrhoea phenomenon
(measurement result of the variation multiplying power of the resistance value of nesa coating)
From the test-results shown in table 2, with the comparative example 2 that only uses the contact adhesive composition being formed by acrylic resin (polymer A) that the acid value of selling is 0～33 on market, 3 compare, in the contact adhesive composition being formed by acrylic resin (polymer A) that is 0～33 as the acid value selling on market equally, add in the embodiment 1～3 of (methyl) acrylate monomer (monomers B) of at least one hydroxyl and the binder composition (polymkeric substance C) that Photoepolymerizationinitiater initiater photopolymerization is made, make the variation multiplying power step-down of the resistance value of ITO film.
Inventors of the present invention think: minimally, (methyl) acrylate monomer (monomers B) of at least one hydroxyl not only can not increase the variation multiplying power of the resistance value of ITO film, in the time of in the contact adhesive composition (polymer A) forming at its acrylic resin that to be added to by the acid value of selling on market be 0～33 on the contrary, polymer A is diluted by monomers B, increase the hydroxyl in resin, there is thus the effect of the variation multiplying power of the resistance value that further forces down ITO film.For acid value, be greater than the comparative example 5,6 of embodiment 1～3, although imported monomers B and Photoepolymerizationinitiater initiater, the variation multiplying power of the resistance value of ITO film enlarges markedly.Can confirm thus, further force down the effect of variation multiplying power of the resistance value of ITO film, not only depend on the existence of the polymkeric substance of monomers B, and very important influence factor be the acid value of contact adhesive composition (polymer A).
(test-results of the generation of the gonorrhoea phenomenon of confirmation self adhesive tape)
In embodiment 1～3, comparative example 5 and 6, do not confirm the generation of gonorrhoea phenomenon.In comparative example 2 and 3, confirmed the generation of gonorrhoea phenomenon.In comparative example 2 and 3, do not import monomers B and Photoepolymerizationinitiater initiater, even if therefore carry out UV irradiation, do not have monomers B polymerization yet.Owing to not becoming the improvement effect tackiness agent with the generation that prevents gonorrhoea phenomenon in comparative example 2, therefore can confirm to make monomers B generation polymerization is effective to obtaining the improvement of the generation that prevents gonorrhoea phenomenon.And, in comparative example 4, owing to having monomers B and Photoepolymerizationinitiater initiater, therefore by UV, irradiate light trigger reacted.But, compare with embodiment 3, because the content of monomers B in comparative example 4 is more, so in comparative example 4, there is gonorrhoea phenomenon.Can confirm thus, gonorrhoea phenomenon not occur under usual conditions, prevent the effect that gonorrhoea phenomenon occurs while taking out from hot and humid environment, not only depend on the existence of the polymkeric substance of monomers B, and very important influence factor be ratio of components.
And, the graphic representation that the variation of mist degree (Haze) value after taking-up in the envrionment test use baking oven from hot and humid is shown of Fig. 3 A and Fig. 3 B, after being shown, the envrionment test under hot and humid telling on as the present invention there is not this fact of gonorrhoea phenomenon, with for referencial use.In the embodiment 1 relevant to self adhesive tape of the present invention, in the just envrionment test from hot and humid when taking out in baking oven and when from baking oven, taking-up is afterwards through 60 minutes, haze value does not have to change substantially, can learn that it has the performance of the good generation that prevents gonorrhoea phenomenon.
On the other hand, demonstrate a kind of like this tendency in comparative example 2: just the envrionment test from hot and humid has only been crossed afterwards several minutes with taking-up in baking oven, haze value rises and approximately 11% reaches maximum value, and along with the prolongation of storage period, haze value slowly declines afterwards.But, the state continuance of known generation gonorrhoea phenomenon more than 120 minutes.
This evaluation is between separate sheet or the resin film such as polyethylene terephthalate (PET) between the variation that occurs while implementing.But between the poor glass of gas-premeable or although that opportunity of gonorrhoea phenomenon occurs in the sample such as acrylic board and glass is identical, the situation that gonorrhoea phenomenon disappears also continues several days sometimes.At this, any gonorrhoea phenomenon occurring in the envrionment test under hot and humid, is all eliminated and becomes vitreous state by room temperature placing a few hours.
By above result, the contact adhesive composition (polymer A) that the acrylic resin by being 0～33 by acid value by the principal constituent to as binder composition of the present invention forms and (methyl) acrylate monomer (monomers B) of at least one hydroxyl and the tackiness agent that Photoepolymerizationinitiater initiater mixes carry out rayed with feedstock composition makes its polymerization reaction take place obtain binder composition (polymkeric substance C), even if can provide thus, fit in the variation that ito surface also suppresses the surface impedance rate of nesa coating, and after the envrionment test under hot and humid, at binder layer, there is not the manufacture method of binder composition of the self adhesive tape of gonorrhoea phenomenon, binder composition and the self adhesive tape that uses this binder composition.

Claims (7)

1. the manufacture method of a contact adhesive composition, this contact adhesive composition is for pressure-sensitive adhesive tape, this pressure-sensitive adhesive tape fits in the described indium tin oxide surface of the nesa coating being formed by indium tin oxide, wherein at least by following (1)～(2) operation, obtains having the contact adhesive composition (polymkeric substance C) of physical property K:
(1) the used in pressure sensitive adhesive feedstock composition that preparation contact adhesive composition (polymer A) that the acrylic resin that is 0～33 by acid value is formed mixes in (methyl) acrylate monomer (monomers B) 5～15 weight parts and Photoepolymerizationinitiater initiater 0.01～0.5 weight part of solid substance 100 weight parts, at least one hydroxyl;
(2) use described used in pressure sensitive adhesive feedstock composition to carry out polyreaction by rayed, obtain having the contact adhesive composition (polymkeric substance C) of physical property K;
Wherein, physical property K is defined as: at indium tin oxide surface coated contact adhesive composition (polymkeric substance C) and after forming the film that dried thickness is 200 μ m, from being that the hot and humid envrionment test of 500 hours implemented 85 ℃, the relative humidity environment that is 85% is with after taking out in baking oven in temperature, the variation multiplying power of the resistance value of indium tin oxide film is compared with initial value below 1.7 times, and while just taking out, at contact adhesive composition (polymkeric substance C) layer, there is not gonorrhoea phenomenon from described baking oven.
2. the manufacture method of a contact adhesive composition, this contact adhesive composition is for pressure-sensitive adhesive tape, this pressure-sensitive adhesive tape fits in the described indium tin oxide surface of the nesa coating being formed by indium tin oxide, at least by following (1)～(3) operation, obtains having the contact adhesive composition (polymkeric substance C) of physical property K:
(1) the used in pressure sensitive adhesive feedstock composition that preparation contact adhesive composition (polymer A) that the acrylic resin that is 0～33 by acid value is formed mixes in (methyl) acrylate monomer (monomers B) 5～15 weight parts and Photoepolymerizationinitiater initiater 0.01～0.5 weight part of solid substance 100 weight parts, at least one hydroxyl;
(2) on the base material film being formed by thermoplastic resin of long size, be coated with and be dried described used in pressure sensitive adhesive feedstock composition, so that dried thickness reaches 20～500 μ m, obtain thus the coating film of long size;
(3) use the coating film of described long size to carry out polyreaction by rayed, on described base material film, obtain having thus the contact adhesive composition (polymkeric substance C) of physical property K;
Wherein, physical property K is defined as: at indium tin oxide surface coated contact adhesive composition (polymkeric substance C) and after forming the film that dried thickness is 200 μ m, from being that the hot and humid envrionment test of 500 hours implemented 85 ℃, the relative humidity environment that is 85% is with after taking out in baking oven in temperature, the variation multiplying power of the resistance value of indium tin oxide film is compared with initial value below 1.7 times, and while just taking out, at contact adhesive composition (polymkeric substance C) layer, there is not gonorrhoea phenomenon from described baking oven.
3. a contact adhesive composition (polymkeric substance C), contains following material, and has physical property K:
In solid substance, the contact adhesive composition (polymer A) that the acrylic resin that is 0～33 by acid value of 100 weight parts forms;
(methyl) 5～15 weight parts, at least one hydroxyl acrylate monomer (monomers B);
The Photoepolymerizationinitiater initiater of 0.01～0.5 weight part;
Wherein, physical property K is defined as: at indium tin oxide surface coated contact adhesive composition (polymkeric substance C) and after forming the film that dried thickness is 200 μ m, from being that the hot and humid envrionment test of 500 hours implemented 85 ℃, the relative humidity environment that is 85% is with after taking out in baking oven in temperature, the variation multiplying power of the resistance value of indium tin oxide film is compared with initial value below 1.7 times, and while just taking out, at contact adhesive composition (polymkeric substance C) layer, there is not gonorrhoea phenomenon from described baking oven.
4. a pressure-sensitive adhesive tape, the contact adhesive composition (polymkeric substance C) that lamination is manufactured by the method described in claim 1 or 2 on base material film forms.
5. a pressure-sensitive adhesive tape, lamination contact adhesive composition claimed in claim 3 (polymkeric substance C) on base material film and forming.
6. pressure-sensitive adhesive tape as claimed in claim 4, its purposes is adhesive parts on indicating meter.
7. pressure-sensitive adhesive tape as claimed in claim 5, its purposes is adhesive parts on indicating meter.
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TWI479000B (en) * 2013-02-07 2015-04-01 Sumika Technology Co Ltd Adhesive polymer composition and application thereof
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CN103320037B (en) * 2013-06-20 2015-05-20 明尼苏达矿业制造特殊材料（上海）有限公司 Ultrathin foam conductive adhesive tape
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CN111363484B (en) * 2020-05-09 2022-02-11 永大（中山）有限公司 Double-sided adhesive tape for fixing low-polarity high-rebound material and preparation method
CN112301799A (en) * 2020-11-07 2021-02-02 中国制浆造纸研究院衢州分院 Preparation method of bright release paper

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1196370A (en) * 1997-04-02 1998-10-21 三星电管株式会社 Coating composition for cathode ray tube and method of coating same
WO2009044732A1 (en) * 2007-10-05 2009-04-09 Hitachi Chemical Company, Ltd. Adhesive composition, circuit connecting material using the same, method for connecting circuit members, and circuit connection structure
CN101809106A (en) * 2007-09-28 2010-08-18 3M创新有限公司 Indium-tin-oxide compatible optically clear adhesive

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1632541A4 (en) * 2003-06-04 2006-06-14 Mitsubishi Plastics Inc Transparent gel self-adhesive agent, transparent gel self-adhesive sheet, optical filter for display
JP2010155974A (en) * 2008-12-01 2010-07-15 Nitto Denko Corp Acrylic pressure sensitive adhesive sheet, method of manufacturing the same, and laminated constitution
JP2011038021A (en) * 2009-08-14 2011-02-24 Fujimori Kogyo Co Ltd Method for manufacturing adhesive composition, method for manufacturing adhesive film, raw material composition for adhesive agent, and adhesive film

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1196370A (en) * 1997-04-02 1998-10-21 三星电管株式会社 Coating composition for cathode ray tube and method of coating same
CN101809106A (en) * 2007-09-28 2010-08-18 3M创新有限公司 Indium-tin-oxide compatible optically clear adhesive
WO2009044732A1 (en) * 2007-10-05 2009-04-09 Hitachi Chemical Company, Ltd. Adhesive composition, circuit connecting material using the same, method for connecting circuit members, and circuit connection structure

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TW201241131A (en) 2012-10-16
KR101386936B1 (en) 2014-04-18

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