CN104946148B - Bonding sheet - Google Patents

Abstract

The present invention provides a kind of bonding sheet, even across heating process, can also reduce the unfavorable condition as caused by the leakage of oligomer.Bonding sheet (1) of the invention has mold release film (10), the mold release film (10) has the 1st base material film (11) formed by polyester film, resin layer (12) on a surface of the 1st base material film (11) is set, and the release layer (13) being arranged on another surface of the base material film (11), the bonding sheet (1) is also equipped with the adhesive phase (14) being arranged on the surface of the release layer (13), the resin layer (12) is solidified by resin combination, the resin combination includes: (A) 50 mass % or more and 80 mass % bisphenol A type epoxy compounds below, (B) 5 mass % or more and 30 mass % petchems below, and (C) 10 mass % or more and 40 mass % multifunctional amino-compound below.

Description

Bonding sheet

Technical field

The present invention relates to the bonding sheets with adhesive phase, in particular to the bonding using polyester film as base material film Piece.

Background technique

In the past, it in the manufacturing process of touch panel, has used and has had the transparent electricity such as ITO (Indium Tin Oxide) film The transparent conductive film of pole layer.The transparent conductive film manufactures as follows: hard conating is respectively equipped on a pair of of interarea of supporter, one Transparent electrode layer is set on a hard conating, while strippingly bonding of the fitting as surface protection film on another hard conating Piece.The bonding sheet used when manufacture as transparent conductive film, proposes in the substrate formed by the polyester film with heat resistance Film is equipped with the bonding sheet of adhesive phase (for example, referring to patent document 1).

In addition, in the manufacturing process of touch panel, by optics with bonding film (Optical Clear Adhesive, Hereinafter sometimes referred to " OCA ") transparent conductive film is pasted on glass substrate etc..Usually in the two sides lamination of OCA by polyester film The stripping film of formation.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2003-205567 bulletin

Summary of the invention

Subject to be solved by the invention

However, having used in the manufacturing process of the transparent conductive film used in touch panel using polyester film as substrate The screening glass of film.But using polyester film manufacture transparent conductive film, if in the annealing of transparent electrode layer When etc. screening glass is heated, then there is the case where oligomer such as monomer, dimer and trimer escape to screening glass surface. When being rolled into a roll transparent conductive film together with screening glass in the state that oligomer precipitation is to screening glass surface, there are oligomer It is attached to the surface of transparent electrode layer and makes transparent electrode layer pollution or damaged situation.

The present invention is completed in view of above-mentioned actual conditions, and its purpose is to provide a kind of bondings for having mold release film Piece, the mold release film can also reduce unfavorable condition caused by being leaked out by oligomer even across heating process.

The method to solve the problem

The adhesive phase that bonding sheet of the invention has mold release film and is arranged in the demoulding film surface, the mold release film Include the 1st base material film formed by polyester film, the resin layer being arranged on a surface of the 1st base material film and setting Release layer on another surface of the 1st base material film, wherein the resin layer is solidified by resin combination, described Resin combination contains: (A) 50 mass % or more and 80 mass % bisphenol A type epoxy compound below, (B) 5 mass % with Upper and 30 mass % petchem below and (C) 10 mass % or more and 40 mass % multifunctional amination below Close object.

According to this constitution, since bisphenol A type epoxy resin compound, petchem and multifunctional amino chemical combination will be contained The resin combination of object solidifies and resin layer is arranged on a surface of the 1st base material film, therefore, makes the crosslink density of resin layer In the range of appropriateness.Bonding sheet can not only prevent oligomer from precipitateing into the surface side of bonding sheet from polyester film as a result, and Even if bonding sheet application pressure, impact are also possible to prevent resin layer and are produced fracture, it can prevent oligomer from leaking out from breaking part. Moreover, because mold release film also has the screening glass in the face as the outer surface opposite side with the functional layer etc. being set on adhesive phase Function, therefore the manufacturing cost of functional membrane can be reduced.

In bonding sheet of the invention, it is preferably also equipped with the 2nd base material film being arranged on described adhesive layer.

In bonding sheet of the invention, it is preferably also equipped with the functional layer being arranged on the 2nd base material film.

In bonding sheet of the invention, the preferably described functional layer is transparency conducting layer.

In bonding sheet of the invention, preferably described adhesive layer include core layer, the core layer is set with it is de- Mold layer connect side surface on the 1st adhesive phase and the 2nd adhesive phase that is arranged on another surface of the core layer.

In bonding sheet of the invention, it is preferably also equipped with the 2nd base material film being arranged on the 2nd adhesive phase.

In bonding sheet of the invention, it is preferably also equipped with the functional layer being arranged on the 2nd base material film.

In bonding sheet of the invention, the preferably described functional layer is transparency conducting layer.

In bonding sheet of the invention, the preferably described release layer is solidified by addition reaction-type polysiloxanes.

In bonding sheet of the invention, the weight average molecular weight of the preferably described bisphenol A type epoxy compound be 10000 or more and 50000 or less.

In bonding sheet of the invention, the glass transition temperature (Tg) of the preferably described petchem be 0 DEG C or more and 50 DEG C or less.

In bonding sheet of the invention, the preferably described resin layer is by the solution coating of the resin combination described The cured film for foring coating layer on 1 base material film, the coating layer being heated again and is formed.

In bonding sheet of the invention, the film thickness of the preferably described resin layer is 50nm or more and 500nm or less.

The effect of invention

A kind of bonding sheet for having mold release film is provided in accordance with the invention it is possible to realize, the mold release film is even across heating Technique can also reduce unfavorable condition caused by being leaked out by oligomer.

Detailed description of the invention

Fig. 1 is the diagrammatic cross-section of the bonding sheet of the 1st embodiment of the invention.

Fig. 2 is the diagrammatic cross-section of the bonding sheet of the 2nd embodiment of the invention.

Fig. 3 is the diagrammatic cross-section of the bonding sheet of the 3rd embodiment of the invention.

Fig. 4 is the diagrammatic cross-section of the bonding sheet of the 4th embodiment of the invention.

Fig. 5 is the explanatory diagram for having used the transparent conductive film of bonding sheet of embodiments of the present invention.

Symbol description

1,2,3,4 bonding sheet

5 transparent conductive films

10 the 1st mold release films

11 base material films (the 1st base material film)

12 resin layers

13 release layers

14 adhesive phases

21 the 2nd mold release films

22 base material films (the 2nd base material film)

23 functional layers

51 supporters

52a, 52b hard conating

53 transparency conducting layers

141 core materials

142 the 1st adhesive phases

143 the 2nd adhesive phases

Specific embodiment

Hereinafter, an embodiment of the invention is described in detail referring to attached drawing.It should be noted that the present invention is simultaneously Embodiment not limited to the following can be changed suitably and be implemented.Alternatively, it is also possible to which following implementation is appropriately combined rear real It applies.In addition, assigning identical symbol to element is commonly constructed in the following embodiments and the accompanying drawings to avoid repeated explanation.

Fig. 1 is the diagrammatic cross-section of the bonding sheet of the 1st embodiment of the invention.As shown in Figure 1, present embodiment is viscous It closes piece 1 and has the 1st mold release film 10 and adhesive phase 14, the 1st mold release film 10 includes the base material film the (the 1st formed by polyester film Base material film) 11, resin layer made of being solidified on a surface of the base material film 11 as resin layer formation composition is set 12 and be arranged on another surface of base material film 11 by the solidification of release layer formation composition into release layer 13, it is described Adhesive phase 14 is arranged on the surface of release layer 13.That is, successively lamination has resin layer 12, base material film in the bonding sheet 1 11, release layer 13 and adhesive phase 14.

The 2nd mold release film 21 has strippingly been pasted on the face with 10 opposite side of the 1st mold release film of adhesive phase 14.Bonding Piece 1 is taken care of after being rolled into a roll on core material in the form of the laminated body that the 2nd mold release film 21 is stacked on adhesive phase 14.Then, By the laminated body uncoiling of the bonding sheet 1 of web-like and the 2nd mold release film 21, the 2nd mold release film 21 is removed from bonding sheet 1, the 1st is glued Addendum is pasted in the exposed surface of adhesive phase 14.Then, the 1st mold release film 10 is removed, the exposed surface of adhesive phase 14 is pasted In in the 2nd adherend.In the process, across adhesive phase 14 by the shape of the 1st adherend and 10 lamination of the 1st mold release film The stage of state implements given heat treatment, can manufacture desired product.It should be noted that as the 1st adherend, Transparent conductive film (or its raw material film), which can be enumerated, as the 2nd adherend can enumerate glass substrate, as given Heat treatment, can enumerate the annealing of the crystallization for transparent conductive material, but not limited to this.By making to bond Piece 1 becomes such composition, and polyester film can prevent the 1st adherend from meeting with as the 1st base material film 11 whether or not using Pollution caused by by oligomer damages.

In the bonding sheet 1 of present embodiment, the resin layer 12 on a surface of base material film 11 is set by resin group It closes object to solidify, the resin combination contains: (A) 50 mass % or more and 80 mass % bisphenol type epoxies below Close object, (B) 5 mass % or more and 30 mass % petchem below and (C) 10 mass % or more and 40 mass % with Under multifunctional amino-compound.Resin layer 12 forms remaining in the polyester film that can prevent constituting base material film 11 as a result, Therefore the crosslink density that the oligomer such as monomer, dimer and trimer penetrate can prevent oligomer to be exuded to bonding sheet 1 One surface.As a result, bonding sheet 1 can make Δ haze value 0.15% hereinafter, the Δ haze value be initial haze value with The bonding sheet 1 heated 2 hours at 150 DEG C after heating after haze value absolute value of the difference.In addition, resin layer 12 have can The crosslink density of appropriate flexibility is obtained, it therefore, will bonding in the state of to secure the 2nd mold release film 21 on adhesive phase 14 When piece 1 is on core material, it can prevent resin layer 12 from producing fracture applying pressure, impact.Moreover, the 1st mold release film 10 can also play the protection on the face for the outer surface opposite side for being pasted on and being arranged in the 1st adherend on adhesive phase 14 The effect of piece, therefore the manufacturing cost of product can be reduced.

Fig. 2 is the diagrammatic cross-section of the bonding sheet 2 of the 2nd embodiment of the invention.As shown in Fig. 2, the bonding sheet 2 includes Core material 141, the side that connects with release layer that the core material 141 is set surface on the 1st adhesive phase 142 and be arranged in core material The 2nd adhesive phase 143 on 141 another surface is as the adhesive phase 14 in the bonding sheet 1 of the 1st embodiment.That is, at this In bonding sheet 2, there are the 1st adhesive phase 142, core material 141 and the 2nd adhesive phase 143 in the surface superimposed layer of release layer 13, The 2nd mold release film 21 of 2 adhesive phase 143 superimposed layer.As core material 141, polyester for example same as base material film 11 can be used The various films such as film, paper and non-woven fabrics etc..Adhesive phase 14, the 1st adhesive phase 142 and the 2nd adhesive phase 143 can be by identical Material is constituted.Moreover, the 1st mold release film 10, which can play, is pasted on and is set to the outer of the 1st adherend on adhesive phase 14 The effect of screening glass on the face of surface opposite side, therefore the manufacturing cost of product can be reduced.

Fig. 3 is the diagrammatic cross-section of the bonding sheet 3 of the 3rd embodiment of the invention.As shown in figure 3, the bonding sheet 3 with On adhesive phase 14 strippingly in lamination bonding sheet 1 of base material film (the 2nd base material film) 22 to replace the 1st embodiment 2 mold release films 21.The bonding sheet 3 can be used as the substrate use that the functional layers such as transparent conductive film are arranged on base material film 22.At this In bonding sheet 3, under the action of resin layer 12, oligomer precipitation can be prevented to the surface of bonding sheet 3, therefore, even After heating to bonding sheet 3, in the case where being rolled into a roll on core material, be also possible to prevent oligomeric inside base material film 11 The pollution and damage of the outer surface of base material film 22 caused by object exudation.Moreover, the 1st mold release film 10 can also play be pasted on The effect of screening glass on the face of the outer surface opposite side of base material film 22, therefore the manufacturing cost of product can be reduced.

Fig. 4 is the diagrammatic cross-section of the bonding sheet 4 of the 4th embodiment of the invention.As shown in figure 4, the bonding sheet 4 be Made of the 3 superimposed layer functional layer 23 of bonding sheet of 3rd embodiment.As functional layer 23, it can enumerate and for example constitute transparent lead The transparent conductive film of electric layer, but it is not limited to this.What the bonding sheet 4 can be used for used in such as touch panel transparent leads The manufacture of electrolemma.The bonding sheet 4 can form a film functional layer 23 on the base material film 22 of the bonding sheet 3 of above-mentioned 3rd embodiment And manufacture, by the way that the bonding sheet 4 for being formed with functional layer 23 is heated and made annealing treatment, transparent conductive film can be manufactured.And And it is provided with resin layer 12 in the back side of functional layer 23 (surface side of bonding sheet 4), oligomer precipitation can be prevented to bonding One surface side of piece 4.Therefore, even in the state to be formed with functional layer 23 in the case where wound into rolls on core material, It can prevent the pollution and damage on 23 surface of functional layer.Moreover, the 1st mold release film 10 can also play and be pasted on the saturating of the prior art The effect of screening glass on the back side of bright conductive film, therefore the manufacturing cost of transparent conductive film can be reduced.Below to this implementation The various constituent elements of the bonding sheet 1~4 of mode are illustrated.

(base material film 11)

As base material film (the 1st base material film) 11, various polyester films can be used in the range of can play effect of the present invention. Even if the excellent heat resistance of polyester film will not make annealing treatment at high temperature to transparent electrode layers such as transparent conductive films A problem that shrinking and melting.As polyester film, preferably such as polyethylene terephthalate, poly terephthalic acid The polyester films such as butanediol ester and polyethylene naphthalate.In addition, as polyester film, the more preferable poly- terephthaldehyde of biaxial tension Sour glycol ester film.

The thickness of base material film 11 can suitably change depending on the application.From the viewpoint for keeping bonding sheet intensity and passing through From the viewpoint of roll-to-roll (roll to roll) mode ensures flexibility whens manufacturing transparent conductive film etc., the thickness of base material film 11 Preferably 10 μm or more, more preferably 20 μm or more, be more preferably 30 μm or more, and preferably 250 μm or less, it is more excellent It is selected as 225 μm or less, further preferably 200 μm or less.If it is considered that above situation, then the thickness of base material film 11 is preferably 10 μm or more and 250 μm hereinafter, more preferably 20 μm or more and 225 μm hereinafter, further preferably 30 μm or more 200 μm or less.

(base material film 22)

It, can suitably film use of the selection with heat resistance from plastic foil as the 2nd base material film 22.As such modeling Expect film, can be used for example: polyethylene terephthalate (PET), polybutylene terephthalate (PBT), poly- naphthalenedicarboxylic acid second The polyester films such as diol ester (PEN), polyethylene film, polypropylene screen, glassine paper, cellulose diacetate film, tri cellulose acetate membrane, second Sour cellulose butyrate film, polyvinylidene chlorida film, polyvinyl alcohol film, vinyl-vinyl acetate copolymer film, gathers polychloroethylene film Styrene film, polycarbonate membrane, polymethylpentene film, PS membrane, polyether-ether-ketone film, poly (ether sulfone) film, polyetherimde films, polyamides The plastics such as imines film, fluororesin film, PA membrane, acrylic resin film, norbornene resin film and cycloolefin resin film Film.In these, from be suitable as viewpoint that optical substrate uses and the transparency it is excellent from the viewpoint of, preferably polyester film, Polycarbonate membrane, polyimide film, norbornene resin film and cycloolefin resin film etc., more preferable polyester film.

As the 2nd base material film 22, the layer that attached various functions can also be set on the surface of above-mentioned plastic foil.Example Such as, can have on the face for the side that connects with adhesive phase 14 for the secured closely sealed adhesive layer of adhesive phase 14, can also With with hard conating is set on the face of 14 opposite side of adhesive phase.

The thickness of 2nd base material film 22 is preferably 25 μm or more, more preferably 30 μm or more, be more preferably 35 μm with On, and preferably 250 μm or less, more preferably 225 μm or less, further preferably 200 μm or less.More than if it is considered that Situation, then the thickness of the 2nd base material film 22 be preferably 25 μm or more and 250 μm hereinafter, more preferably 30 μm or more and 225 μm with Under, further preferably 35 μm or more and 200 μm or less.

(resin layer 12)

Resin layer 12 is cured film made of solidifying resin layer formation resin combination, and the resin layer is formed with tree Oil/fat composition includes: (A) 50 mass % or more, preferably 60 mass % or more, and is 80 mass % or less, preferably 70 matter Measure % bisphenol A type epoxy compound below (hereinafter, also referred to as " (A) ingredient ")；(B) 5 mass % or more, preferably 10 matter % or more is measured, and is 30 mass % or less, preferably 20 mass % petchems below (hereinafter, also referred to as " (B) Ingredient ")；And (C) 10 mass % or more, preferably 20 mass % or more, and be 40 mass % or less, preferably 30 matter Measure % multifunctional amino-compound below (hereinafter, also referred to as " (C) ingredient ").Below to constitute resin combination it is each at Divide and is described in detail.

< (A) bisphenol A type epoxy compound >

It as (A) bisphenol A type epoxy compound, can enumerate such as bisphenol A type epoxy resin, the bisphenol-A type ring Oxygen resin is the copolymer that bisphenol-A and epoxychloropropane are formed.

From the viewpoint of the cured film that can obtain appropriately crosslinked density, the preferred weight average molecular weight (Mw) of (A) ingredient It is 10000 or more and 50000 or less.If the weight average molecular weight (Mw) of (A) ingredient is 10000 or more, can as cured film Enough crosslink densities are obtained, the precipitation of oligomer can be substantially prevented from.In addition, if the weight average molecular weight (Mw) of (A) ingredient For 50000 hereinafter, can then assign the flexibility of appropriateness to cured film, the resin layer 12 when bonding sheet 1 deforms can be prevented Fracture.

< (B) petchem >

As (B) petchem, well known various polyesterifications can be used in the range of can play effect of the present invention Close object.As petchem, can enumerate for example as polyalcohol and polyacid resin as obtained from condensation reaction.As Such resin can be enumerated: the condensation product of binary acid and dihydric alcohol changes condensation product by non-drying oil fatty acid etc. Property obtained from nonconvertible petchem and the condensation product formed as alcohol more than binary acid and ternary transformant Petchem etc..Petchem can be used alone, and can also be applied in combination two or more.

As polyalcohol, can enumerate for example: ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-PD, 1, The dihydric alcohols such as 4- butanediol and neopentyl glycol, the trihydroxylic alcohols such as glycerol, trimethylolethane and trimethylolpropane, a contracting two are sweet The polyalcohols more than quaternarys such as oil, two triglycerols, pentaerythrite, dipentaerythritol, mannitol and D-sorbite.These are polynary Alcohol can be used alone, and can also be applied in combination two or more.

As polyacid, can enumerate for example: phthalic anhydride, terephthalic acid (TPA), M-phthalic acid and trimellitic acid The aromatic polyvalents such as acid anhydride acid, the aliphatic saturated polybasic acid such as succinic acid, adipic acid and decanedioic acid, maleic acid, maleic anhydride, rich horse The aliphatic unsaturation polyacids such as acid, itaconic acid and citraconic anhydride, cyclopentadiene-maleic anhydride adduct, terpenes-maleic anhydride Addition product and rosin-maleic acid anhydride addition product etc. are obtained by Diels-Alder reaction (Diels-Alder reaction) The polyacid etc. arrived.These polyacids can be used alone, and can also be applied in combination two or more.

As (B) petchem, preferably there is hydroxyl, carboxyl and amino of reaction site as cross-linking reaction etc. The compound of active hydrogen more preferably has hydroxyl.It is preferred that the hydroxyl value of (B) petchem is 5mgKOH/g or more, is more preferably 10mgKOH/g or more, and preferably 500mgKOH/g or less, more preferably 300mgKOH/g or less.

From the viewpoint of it can assign appropriate flexibility to resin layer 12, the preferred equal molecule of number of (B) petchem Measuring (Mn) is 500 or more, more preferably 1000 or more, and preferably 10000 or less, more preferably 5000 or less.From can From the viewpoint of assigning appropriate flexibility to resin layer 12, preferably the glass transition temperature Tg of petchem (B) be 0 DEG C with Above, more preferably 10 DEG C or more, and preferably 50 DEG C or less, more preferably 40 DEG C or less.By using such polyesterification It closes object (B), the flexibility that can assign appropriateness to the cured film of resin layer 12 also can even if bonding sheet 1 is under pressure, impacts The fracture of resin layer 12 is prevented, enough so as to prevent the oligomer caused by being broken from leaking out.

Relative to 100 mass parts of (A) ingredient, in resin combination the use level of (B) ingredient be preferably 5 mass parts or more, More than more preferably 10 mass parts, and preferably 50 below the mass, more preferably 45 below the mass.

The multifunctional amino-compound > of < (C)

It as (C) multifunctional amino-compound, can enumerate for example: hexamethoxymethyl melamine, methylation trimerization The melamine compounds such as cyanamide compound and butylated melamines compound, methyl urea compounds and butyl carbamide compound etc. Carbamide compound, methylate the benzene birds droppings amine compounds such as benzene birds droppings polyimide resin and butylation benzene birds droppings amine compounds, ethylenediamine, Isosorbide-5-Nitrae- Butanediamine, 1,6- hexamethylene diamine, N, Diamines such as N '-diphenyl ethylene diamine and p dimethylamine etc..Wherein, from the viewpoint of curability Consider, preferably hexamethoxymethyl melamine.

Relative to 100 mass parts of (A) ingredient, in resin combination the use level of (C) ingredient be preferably 20 mass parts or more, More than more preferably 25 mass parts, and preferably 60 below the mass, more preferably 55 below the mass.

< (D) acidic catalyst >

In order to promote curing reaction, as resin combination, can according to need using containing hydrochloric acid, p-methyl benzenesulfonic acid etc. The resin combination of well known (D) acidic catalyst (hreinafter referred to as " (D) ingredient ").When cooperation (D) ingredient, relative to The gross mass of resin combination, the preferably content of (D) ingredient are 1 mass % or more and 5 mass % or less.

Resin layer 12 can obtain as follows: the dissolution of above-mentioned resin combination organic solvent is obtained into solution, this is molten Liquid is coated on base material film 11 and forms coating layer, then makes to be formed by coating layer in 100 DEG C or more and 170 DEG C of temperature below Under be heating and curing 5 seconds or more and 5 minutes or less.

As organic solvent, as long as capableing of the solvent of dissolving resin composition, it is not particularly limited.As organic Solvent can be enumerated for example: the aromatics solvent such as benzene, toluene and dimethylbenzene, the aliphatic solvents such as n-hexane and normal heptane, second The esters solvents such as acetoacetic ester and butyl acetate, the ketones solvents such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone and cyclopentanone, isopropyl Alcohols solvents such as alcohol and methanol etc..

From the viewpoint of effective inhibition oligomer precipitation, the film thickness of resin layer 12 is preferably 50nm or more, is more preferably 80nm or more, further preferably 100nm or more, and preferably 500nm or less, more preferably 300nm or less, further it is excellent It is selected as 250nm or less.When the film thickness of resin layer 12 is 50nm or more, it can sufficiently inhibit oligomer precipitation, the film of resin layer 12 When thickness is 500nm or less, and it can prevent when coating forms resin layer 12 on base material film 11 as the crosslinking of resin layer 12 is consolidated Change and shrinks caused curling.In view of above situation, the film thickness of resin layer 12 is preferably 50nm or more and 500nm hereinafter, more Preferably 80nm or more and 300nm are hereinafter, further preferably 100nm or more and 250nm or less.

(release layer 13)

Release layer 13 can for example be formed by the solidfied material of the release layer formation composition comprising release agent.As de- Mould agent removes the adhesive phase 14 being stacked on release layer 13 as long as can assign to release layer 13 from the 1st mold release film 10 Function, be not particularly limited.As release agent, can enumerate for example: polyorganosiloxane resin, chain alkyl resin, with And alkyd resin etc..

As polysiloxane-based release agent, addition reaction-type polysiloxanes, condensation reaction type polysiloxanes, energy can be enumerated Measure line curing type polysiloxanes.In addition, dimethyl silicone polymer, the benzene of no functional group also can be used in order to adjust peeling force Base modified polyorganosiloxane, polyorganosiloxane resin, silica, cellulose compound are as additive.

The thickness of release layer 13 is preferably 30nm or more, more preferably 50nm or more, is more preferably 70nm or more, and And preferably 500nm or less, more preferably 400nm or less, further preferably 300nm or less.If the thickness of release layer 13 It in such range, then is easy to obtain uniform demolding performace between the 1st mold release film 10 and adhesive phase 14, and can be to prevent The face for the 1st mold release film 10 being only in contact when the 1st mold release film 10 to be rolled into a roll sticks to each other.

Release layer 13 for example can be formed: using conventionally known coating method by release layer formation resin combination Then object heats at a given temperature coated on a face of base material film 11, drying simultaneously makes its solidification.Here, can also be with Solution after being diluted release layer formation with composition with organic solvent is coated on base material film 11.It, can be with as organic solvent It enumerates: the aromatic hydrocarbon such as toluene and dimethylbenzene, the aliphatic esters such as ethyl acetate and butyl acetate, methyl ethyl ketone and methyl iso-butyl ketone (MIBK) etc. Aliphatic hydrocarbons such as ketone, hexane and heptane etc..

As the coating method of release layer formation resin combination, can enumerate for example: gravure coating process, stick coating method, Spray coating method, spin-coating method, air knife coating method, rolling method, scraper coating method, door roller coating method and die coating method etc..Wherein, preferably Gravure coating process and stick coating method, more preferable stick coating method.In addition, heating/drying side as release layer formation resin combination Method can enumerate the method etc. that heated drying is carried out such as using hot-air drying stove.Drying temperature is such as 50 DEG C or more and 150 DEG C or less.In addition, drying time is preferably such as 10 seconds~5 minutes.

(adhesive phase 14)

Adhesive phase 14 can be used acrylic adhesives, natural rubber based binder, synthetic rubber class adhesive, gather Ethers adhesive, polyester adhesive, polyurethane binding and polyurethane acrylates adhesive etc. are known viscous Mixture composite is formed.It, can be with solvent type, emulsion-type, hot melt no-solvent type and ultraviolet curing without molten as adhesive The supply of the forms such as dosage form forms adhesive phase 14 using various forms of coating methods are corresponded to.

As acrylic adhesives, adhesive composition for example containing acrylic polymer can be enumerated.Propylene Acids polymers can be by the vinyl monomer comprising (methyl) acrylate and containing hydroxyl and carboxyl isoreactivity group Deng monomer be synthesized into.

It as (methyl) acrylate, can enumerate for example: (methyl) methyl acrylate, (methyl) ethyl acrylate, (first Base) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (first Base) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid n-pentyl ester, (methyl) the just own ester of acrylic acid, (first Base) cyclohexyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) decyl acrylate, (methyl) dodecylacrylate, (methyl) acrylic acid tetradecane base ester, (methyl) aliphatic acrylate and (first Base) atomic number of alkyl carbon of the ester moieties such as octadecyl acrylate is 1 or more and 20 (methyl) alkyl acrylates below. Here, " (methyl) acrylic acid " expression " acrylic acid " or " methacrylic acid ".These acrylic monomers can be used alone one Kind, it can also be applied in combination two or more.

As the vinyl monomer containing reactive functional groups, can enumerate for example: (methyl) Hydroxyethyl Acrylate, (methyl) acrylate of the hydroxyls such as (methyl) hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate；Bis- (first of 1,4- Base) acryloyl-oxyethyl pyromellitic dianhydride, 4- (methyl) acryloyl-oxyethyl trimellitic anhydride, N- (methyl) acryloyl Base p-aminobenzoic acid, 2- (methyl) acryloyl-oxy yl benzoic acid, N- (methyl) acryloyl group -5-aminosalicylic acid, acrylic acid, Carboxylic (methyl) acrylate such as methacrylic acid；(methyl) acrylate, (methyl) acrylic acid ethyl amino (methyl) containing primary amino group and secondary amino group such as ethyl ester, (methyl) acrylic-amino propyl ester, (methyl) acrylic acid ethyl amino propyl ester Acrylate；(methyl) acrylate containing sulfydryl such as methacrylic acid 2- (methyl mercapto) ethyl ester etc..These monomers can be independent Using one kind, can also be applied in combination two or more.

In acrylic polymer, from the content of the structural unit of the vinyl monomer containing reactive functional groups Preferably 0.01 mole of % or more, more preferably 0.1 mole of % or more, and preferably 20 moles of % or less, more preferably 10 Mole % or less.

As adhesive composition, crosslinking agent (curing agent) is preferably comprised.As crosslinking agent, it is preferably selected from multifunctional ammonia The polyfunctional isocyanate compounds such as based compound and polyisocyanate compound, multi-functional epoxy compound, multifunctional azepine At least one of cyclopropane compound, multifunctional oxazoline compound and multifunctional metallic compound.As crosslinking agent, such as It can be used and reacted by the reactive functional groups with acrylic polymer and make crosslinking obtained from adhesive crosslinking Agent.In addition, the composition containing curing accelerator, cure retarder etc. also can be used as adhesive composition.

From the viewpoint of being capable of forming bond properties and the excellent adhesive phase of cohesiveness, the use level of crosslinking agent is preferred It is 0.1 mass parts or more relative to 100 mass parts of acrylic polymer, is more preferably 1 mass parts or more, and preferably 30 Below the mass, 20 are more preferably below the mass.

As core material 141, can suitably select to use from well known plastic foil, paper and non-woven fabrics, preferably as substrate The plastic foil of film 22 and illustration.

The thickness of adhesive phase 14 is not particularly limited as long as the range that can play effect of the present invention, for example, it is preferable to Be 3 μm or more, more preferably 10 μm or more, further preferably 20 μm or more, and preferably 500 μm or less, be more preferably 400 μm or less, further preferably 300 μm or less.

In addition, the case where adhesive phase 14 is made of the 1st adhesive phase 142, the 2nd adhesive phase 143 and core material 141 Under, preferably core material 141 with a thickness of 2 μm or more, more preferably 5 μm or more, and preferably 50 μm or less, be more preferably 45 μm Below.The thickness of 1st adhesive phase 142 and the 2nd adhesive phase 143 is respectively preferably 1 μm or more and 50 μm or less.

21 > of the 2nd mold release film of <

It, can by the way that the 2nd mold release film 21 is arranged in the outer surface of adhesive phase 14 in the bonding sheet 1 of present embodiment The adhesive surface of adhesive phase 14 is protected (when unused) when bonding sheet 1 is taken care of.

As the 2nd mold release film 21, the polyester film such as polyethylene terephthalate, polyethylene and poly- third can be used Synthetic resin films such as the polyolefin films such as alkene etc..In addition, can according to need use in one or both sides as the 2nd mold release film 21 The upper mold release film that lift-off processing is implemented by polyorganosiloxane resin, alkyd resin and resin containing chain alkyl etc..

As the thickness of stripping film, such as preferably 10 μm or more, more preferably 15 μm or more, and preferably 200 μm Below, 100 μm or less are more preferably.

It should be noted that the 2nd mold release film 21 is shown as simple layer, but the 2nd mold release film 21 is not limited in Fig. 1 Centainly it is made of simple layer.2nd mold release film 21 can also be by structure in a manner of 2 tunics of such as lamination base material film and release layer At can also be constituted in a manner of 3 tunics in the same manner as the 1st mold release film 10.

23 > of < functional layer

As functional layer, transparent conductive film can be used for example.As transparent conductive film, as long as having both the transparency and leading Electrical material, so that it may use without particular limitation.As transparent conductive film, can enumerate for example: indium oxide, oxidation Zinc, tin oxide, indium-tin composite oxides, tin-antimony composite oxides, zinc-aluminium composite oxide and indium-zinc composite oxide Deng film.These compound films form the transparent conductive film for having both the transparency and electric conductivity according to membrance casting condition.

It is examined from forming continuous film and obtaining the viewpoint of stable electric conductivity and obtain the viewpoints of enough transparencys Consider, the film thickness of transparent conductive film is preferably 4nm or more, more preferably 5nm or more, further preferably 10nm or more, and excellent It is selected as 800nm or less, more preferably 500nm or less, further preferably 100nm or less.

< oligomer leakproofness >

Oligomer precipitation is evaluated for progress ocular estimate is only observed by the naked eye in the prior art, this hair Bright people etc. be conceived to by measure bonding sheet haze value can the degree to oligomer precipitation quantitatively evaluated.And And the inventors of the present invention have found: quantitative assessment is carried out to oligomer precipitation by measuring the haze value of bonding sheet, it can be effectively The damage of transparent electrode layer, foreign matter is prevented to be mixed into.

In the bonding sheet 1 of present embodiment, the oligomer on 10 surface layer of the 1st mold release film, which is precipitated, makes 11 (polyester of base material film Film) it is fuzzy, so that the haze value of bonding sheet 1 is changed.Therefore, in the present embodiment, pass through the initial haze to bonding sheet 1 Value heated 2 hours at 150 DEG C with the bonding sheet 1 after heating after the absolute value of the difference of haze value, i.e. Δ haze value surveyed It is fixed, the oligomer leakproofness being able to confirm that in resin layer 12.But in order to exclude to be gone (when annealing) when heating and using The measurement of haze value is removing the 2nd mold release film 21, is taking off with the 1st after the influence for the 2nd mold release film 21 removed, initial haze value and heating Mould film 10 and the state of the laminated body of adhesive phase 14 are measured.

In the present embodiment, due to using above-mentioned resin combination to form resin layer 12, and in order to prevent oligomer from Base material film 11 is precipitated and makes the composition of (A)~(C) ingredient in appropriate range, therefore Δ haze value can be 0.15% or less.It needs It is noted that the initial haze value of bonding sheet 1 refers to the haze value before heating bonding sheet 12 hours at 150 DEG C.Δ Haze value is preferably 0.1% hereinafter, more preferably 0.08% hereinafter, further preferably 0.04% or less.

It should be noted that in the present embodiment, Δ haze value can calculate as follows.Firstly, using mist degree instrument (trade name: NDH-2000, Nippon Denshoku Industries Co., Ltd.'s manufacture), according to the initial haze of JIS K7105 measurement bonding sheet 1 It is worth (%) (average value of N=5).Then, bonding sheet 1 is hung in 150 DEG C of drying machine and is heated 2 hours, then according to JIS Haze value (%) (average value of N=5) after K7105 measurement heating.Then, the haze value after heating is subtracted into initial haze value The absolute value of value afterwards is as Δ haze value.

< purposes >

The bonding sheet 1 of present embodiment for example can be used as in the touch panel manufacturing process of electrostatic capacity type for inciting somebody to action The optics that transparent conductive film and glass substrate etc. are bonded is used with adhesive (OCA) etc..Especially in the annealing of transparent conductive film Fitting before processing, in annealing, the 1st mold release film 10 in bonding sheet 1 also acts as the effect of screening glass, can be preferred for Oligomer precipitation becomes the annealing at a temperature of 150 DEG C or so of problem.It should be noted that the bonding sheet of present embodiment 1 can be used for having used the purposes that the needs other than the manufacturing process of the touch panel of transparent conductive film heat.

Fig. 5 is the explanatory diagram for having used the transparent conductive film 5 of bonding sheet 1 of present embodiment.As shown in figure 5, transparent In conductive film 5, it is equipped with hard conating 52b on a surface of supporter 51, passes through sputtering, CVD, PVD on hard conating 52b Deng provided with transparency conducting layer 53 (transparent conductive film: indium oxide tin film).Hard conating is equipped on another surface of supporter 51 52a, across 14 lamination of adhesive phase bonding sheet 1 on hard conating 52a.It is arranged as a result, with bonding sheet 1 in transparent conductive film When state on 5 is made annealing treatment, ITO is crystallized, and low-resistance transparent electrode layer 53 can be made.

Here, by using the bonding sheet of present embodiment, even if in annealing, other heat treatment, it can also be with Inhibit the exudation of the oligomer contained in the polyester film of base material film 11 well, and is able to suppress the crystallization from oligomer Therefore precipitation to 12 surface of resin layer is able to suppress as undesirable from the small different of oligomer for touch panel Object be mixed into and the damage of transparent electrode layer.

Embodiment

Hereinafter, based on embodiment, the present invention will be described in more detail, to further clarify effect of the invention.It needs It is noted that the present invention is not by any restriction of following embodiment and comparative example.

The calculating > of < Δ haze value

The bonding sheet made in embodiment and comparative example is cut into 5cm square respectively, by the 2nd mold release film 21 from bonding sheet After being removed on 1, as test film.Using mist degree instrument (trade name: NDH-2000, Nippon Denshoku Industries Co., Ltd. manufacture) according to JIS K7105 carries out the measurement (average value of N=5) of initial haze value (%) to the test film.In addition, with fixture by each test One jiao of piece is fixed, and is hung in 150 DEG C of drying machine after heating 2 hours, according to the haze value after JIS K7105 measurement heating (%) (average value of N=5).

The absolute value of value after haze value after heating is subtracted initial stage haze value as Δ haze value, by following standard into Evaluation is gone.It should be noted that if Δ haze value be 0.15% hereinafter, if oligomer from using as the 1st base material film The amount being precipitated in polyester film is considerably less, can reduce the influence to process thereafter.

0.15% or less zero (good):

× (bad): 0.15% or more

(embodiment 1)

By (A) bisphenol A type epoxy compound (trade name: EPICLON H-360, DIC company manufacture: solid component concentration 40 mass %, weight average molecular weight 25000) 100 mass parts, (B) petchem (trade name: VYLON GK680, Japan's weaving Co., Ltd. manufacture, number-average molecular weight 6000,10 DEG C of glass transition temperature) toluene solution (30 matter of solid component concentration Measure %) 19.0 mass parts and (C) hexamethoxymethyl melamine (trade name: CYMEL 303, solid component concentration 100 Quality %, Nihon Cytec Industries Ltd. manufacture) mixing of 11.4 mass parts.It is (following to be also referred to as with toluene/methyl ethyl ketone Mixed solvent for the mass of mass %/50 of " MEK ")=50 % dilutes mixed liquor, so that solid component is 3 mass %, goes forward side by side Row stirring.Then, methanol solution (50 mass % of solid component concentration) 2.9 mass parts for adding (D) p-methyl benzenesulfonic acid, obtain Composition is used in resin layer formation.

The tree that stick rubbing method (Meyer bar coat) will be obtained is strangled by roll-to-roll (Roll to Roll) mode, with wheat Rouge layer formation uses composition to be evenly coated at the biaxial tension polyethylene terephthalate film (commodity as base material film Name: E5001, Toyo Boseki K.K manufacture, 75 μm of thickness) a surface on.Then, it is coated with resin formation group The base material film for closing object blows out the baking oven of 150 DEG C of hot winds in 20 seconds by the wind speed divided with 8m/, forms with a thickness of 150nm Resin layer, the base material film for foring resin layer is rolled into a roll on ABS coremaking material then, has obtained being formed with width The polyester film of the resin layer of 1050mm, long 4000m.

Then, with the toluene/MEK=50 mass mass of %/50 % mixed solvent by addition reaction-type polyorganosiloxane resin (trade name: KS-774, Shin-Etsu Chemial Co., Ltd's manufacture) 100 mass parts dilution, so that solid component is 1.5 matter % is measured, and is stirred.Then, platinum catalyst (trade name: PL-50T, Shin-Etsu Chemial Co., Ltd's manufacture) 1 matter is added Part is measured, release layer formation composition has been obtained.

Then, stick rubbing method being strangled by roll-to-roll mode, with wheat, release layer formation is homogeneously applied to base with composition The face with resin layer opposite side of material film so that after dry with a thickness of 150nm.Then, it is coated with release layer formation group The base material film for closing object blows out the baking oven of 150 DEG C of hot winds in 20 seconds by the wind speed divided with 8m/, forms release layer, obtains 1st mold release film.

Then, by acrylic adhesives, (Soken Chemical & Engineering Co., Ltd. is manufactured, and trade name " SK-Dyne2971 " is divided equally again Son amount: 400,000, solid component: 40%) 100 mass parts, toluene di-isocyanate(TDI) class curing agent (trade name " TD-75 ", solid at Point: 75%, Soken Chemical & Engineering Co., Ltd. manufacture) 0.5 mass parts, silane coupling agent (trade name " A-50 ", solid component: 50%, Soken Chemical & Engineering Co., Ltd. manufacture) 0.2 mass parts and 40 mass parts of ethyl acetate mixing, be prepared for the coating liquid of adhesive.

Then, the coating liquid of above-mentioned adhesive is coated on stripping film with roll-to-roll mode, the heat drying 5 at 100 DEG C Minute, obtain the adhesive phase with a thickness of 75 μm.Then, over the binder layer be bonded stripping film (trade name: P50LT-H, Lintec company manufacture: 50 μm of thickness), it rolls up on the core material of ABS, results in the bonding sheet being rolled into a roll.To obtaining Bonding sheet evaluated.By the composition of resin layer formation composition, the weight average molecular weight of (A) ingredient, (B) ingredient glass Glass transition temperature (Tg), it is dry after the film thickness of resin layer be shown in following table 1, by initial haze value, Δ haze value and The evaluation result of oligomer leakproofness is shown in following table 2.

(embodiment 2)

In addition to (B) petchem is 22.22 mass parts, (C) hexamethoxymethyl melamine is 20 mass parts, (D) The methanol solution of p-methyl benzenesulfonic acid is to be operated similarly to Example 1 other than 3.3 mass parts, obtained bonding sheet.Resin The composition etc. of layer formation composition remembers in following table 1 that evaluation result is remembered in following table 2 together together.

(embodiment 3)

In addition to (B) petchem is 44.4 mass parts, (C) hexamethoxymethyl melamine is 13.3 mass parts, (D) The methanol solution of p-methyl benzenesulfonic acid is to be operated similarly to Example 1 other than 3.3 mass parts, obtained bonding sheet.Resin The composition etc. of layer formation composition remembers in following table 1 that evaluation result is remembered in following table 2 together together.

(embodiment 4)

In addition to be changed to (A) bisphenol A type epoxy compound (trade name: EPICLON EXA-123, DIC company manufacture, Gu Body constituent concentration 30%, weight average molecular weight 45000) 100 mass parts, and (B) petchem is 14.3 mass parts, (C) pregnancy Oxygroup methyl melamine is 8.6 mass parts, and adds methanol solution (50 matter of solid component concentration of (D) p-methyl benzenesulfonic acid Amount %) 2.1 mass parts obtain being operated, bonded similarly to Example 1 other than resin layer formation composition Piece.The composition etc. of resin layer formation composition remembers in following table 1 that evaluation result is remembered in following table 2 together together.

(embodiment 5)

In addition to being changed to (B) petchem, (trade name: VYLON GK810, Toyo Boseki K.K's manufacture, number are equal Molecular weight 6000,46 DEG C of glass transition temperature) toluene solution (30 mass % of solid component concentration) other than, with embodiment 1 It is carried out similarly operation, has obtained bonding sheet.The composition etc. of resin layer formation composition is remembered in following table 1 together, evaluates As a result remember in following table 2 together.

(embodiment 6)

In addition to changing coating amount, so that the film thickness after resin layer is dry is to be grasped similarly to Example 1 other than 75nm Make, has obtained bonding sheet.The composition etc. of resin layer formation composition remembers in following table 1 that evaluation result is remembered together together In following table 2.

(comparative example 1)

In addition to unmated (B) ingredient and (C) hexamethoxymethyl melamine is 10 mass parts, (D) p-methyl benzenesulfonic acid Methanol solution is to be operated similarly to Example 1 other than 2.5 mass parts, obtained bonding sheet.Resin layer is formed with combination The composition etc. of object remembers in following table 1 that evaluation result is remembered in following table 2 together together.

(comparative example 2)

In addition to (B) petchem is 222.2 mass parts, (C) hexamethoxymethyl melamine be 26.7 mass parts, (D) methanol solution of p-methyl benzenesulfonic acid is to be operated similarly to Example 1 other than 6.7 mass parts, obtained bonding sheet. The composition etc. of resin layer formation composition remembers in following table 1 that evaluation result is remembered in following table 2 together together.

[table 1]

[table 2]

	Initial haze value (%)	Δ haze value (%)	Oligomer leakproofness
				Embodiment 1	1.51	0.02	○
Embodiment 2	1.55	0.03	○
				Embodiment 3	1.55	0.02	○
Embodiment 4	1.53	0.03	○
				Embodiment 5	1.55	0.04	○
Embodiment 6	1.68	0.08	○
				Comparative example 1	1.54	0.41	×
Comparative example 2	1.58	0.32	×

As shown in Table 2, the oligomer leakproofness of the bonding sheet of 1~embodiment of embodiment 6 is good.It can consider the knot Fruit is due to, resin layer be using being formed with composition from (A) ingredient~(C) ingredient by resin layer made of with specified rate and It is formed, also, Δ haze value is 0.15%, therefore can be substantially sealed by oligomer.In comparative example 1, comparative example 2 In, only obtain the undesirable bonding sheet of oligomer leakproofness.

Claims (13)

1. a kind of bonding sheet, the adhesive phase for having mold release film and being arranged in the demoulding film surface,

The mold release film includes the 1st base material film formed by polyester film, is arranged on a surface of the 1st base material film Resin layer and the release layer being arranged on another surface of the 1st base material film,

Wherein, the resin layer is solidified by resin combination, and the resin combination contains: (A) 50 mass % or more and 80 Quality % bisphenol A type epoxy compound below, (B) 5 mass % or more and 30 mass % petchem below and (C) 10 Quality % or more and 40 mass % multifunctional amino-compound below.

2. bonding sheet according to claim 1 is also equipped with the 2nd base material film being arranged on described adhesive layer.

3. bonding sheet according to claim 2 is also equipped with the functional layer being arranged on the 2nd base material film.

4. bonding sheet according to claim 3, wherein the functional layer is transparency conducting layer.

5. bonding sheet according to claim 1, wherein described adhesive layer includes core layer, is arranged in the core layer The side that connects with release layer surface on the 1st adhesive phase and be arranged on another surface of the core layer the 2nd bonding Oxidant layer.

6. bonding sheet according to claim 5 is also equipped with the 2nd base material film being arranged on the 2nd adhesive phase.

7. bonding sheet according to claim 6 is also equipped with the functional layer being arranged on the 2nd base material film.

8. bonding sheet according to claim 7, wherein the functional layer is transparency conducting layer.

9. bonding sheet according to claim 1, wherein the release layer is solidified by addition reaction-type polysiloxanes.

10. bonding sheet according to claim 1, wherein the weight average molecular weight of the bisphenol A type epoxy compound is 10000 or more and 50000 or less.

11. bonding sheet according to claim 1, wherein the glass transition temperature (Tg) of the petchem is 0 DEG C Above and 50 DEG C or less.

12. bonding sheet according to claim 1, wherein the resin layer is by the solution coating of the resin combination Form coating layer on the 1st base material film, then the coating layer is heated and the cured film that is formed.

13. bonding sheet according to claim 1, wherein the film thickness of the resin layer is 50nm or more and 500nm or less.