CN104781359B - Without base material double-sided adhesive sheet - Google Patents

Without base material double-sided adhesive sheet Download PDF

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Publication number
CN104781359B
CN104781359B CN201380058232.6A CN201380058232A CN104781359B CN 104781359 B CN104781359 B CN 104781359B CN 201380058232 A CN201380058232 A CN 201380058232A CN 104781359 B CN104781359 B CN 104781359B
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CN
China
Prior art keywords
mold release
release film
film
layer
methyl
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CN201380058232.6A
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Chinese (zh)
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CN104781359A (en
Inventor
斋藤智久
井崎公裕
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Chemical Corp
Mitsubishi Rayon Co Ltd
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Mitsubishi Plastics Inc
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Priority claimed from JP2012255751A external-priority patent/JP6046463B2/en
Priority claimed from JP2012255750A external-priority patent/JP6046462B2/en
Application filed by Mitsubishi Plastics Inc filed Critical Mitsubishi Plastics Inc
Publication of CN104781359A publication Critical patent/CN104781359A/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/21—Anti-static
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/208—Touch screens
    • 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
    • C09J2469/00—Presence of polycarbonate
    • C09J2469/006—Presence of polycarbonate in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2483/00—Presence of polysiloxane
    • C09J2483/005—Presence of polysiloxane in the release coating

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)

Abstract

The present invention provide as such as liquid crystal polarization plate manufacture use, the various optics part such as the touch panel member for producing of capacitance-type it is suitable without base material double-sided adhesive sheet.This is on two sides difference lamination mold release film (31,32) of bond layer (11) without base material double-sided adhesive sheet (10), the peeling force of one mold release film (the first mold release film) (31) is less than another mold release film (the second mold release film) (32), and the second mold release film (32) is while meet the condition of following (a)～(c) for recording：(a) its be that the surface of the set coating layer containing water-disintegrable silicon compound (24) on biaxially oriented polyester film is provided with the mold release film of release layer (25)；B the variation of the angle of orientation in () above-mentioned biaxially oriented polyester film face is 6 degree/below 500mm；C () is 0.5mg/m by the oligomer amount extracted by dimethylformamide from release layer (25) surface of above-mentioned mold release film (32)2Below.

Description

Without base material double-sided adhesive sheet
Technical field
The present invention relates to one kind is without base material double-sided adhesive sheet, its static electricity resistance, release property, oligomer sealing, inspection are held Easily property is good, when mold release film is peeled off it is not peeling-off it is powered, can be peeled off with good fissility.Additionally have such as Lower feature：After coating adhesive, after laminating mold release film, the stripping relative to bond layer changes little, to the low of bond layer The transfer of polymers, precipitation are few.The Jing such as the touch panel manufacture use for such as liquid crystal polarization plate manufacture use, capacitance-type The various uses fitted by bond layer, there is provided suitable without base material double-sided adhesive sheet.
Background technology
Conventionally, there is known various will carry out the adhesive sheet of face engagement between object, base material is whether there is as one of adhesive sheet is known Double-sided adhesive sheet.It is following double-sided adhesive sheet without base material double-sided adhesive sheet：With the two sides lamination peeling force phase in adhesive linkage Laminate structure obtained from the re-release film relatively high to low light stripping film and peeling force, after removing the stripping film on two sides, Only there is no the adhesive linkage of supporting base material.
As the using method without base material double-sided adhesive sheet, following manufacturing procedure can be illustrated：Light stripping is peeled first Film, a surface of the adhesive linkage for exposing is engaged with the object plane of the object fitted, after the engagement, then re-release film is peeled, Another face for the adhesive linkage for being exposed is engaged from different object planes, thus quilt cover engagement between object.
In recent years, enjoy at the good aspect of its workability without base material double-sided adhesive sheet and gaze at, purposes is constantly widened, each The part of kind of optical applications, for example, also using in portable phone etc..Particularly the touch panel of capacitance-type, passes through The multi-point touch operation of screen operation is carried out with two fingers, the rapid situation for expanding is in as the purposes of information terminal.It is quiet The touch panel of capacitance mode compared with resistive film mode exists and constitutes the thickening tendency of upper, printing step difference, therefore carry The scheme for making bond layer thickening and eliminating the step difference for printing is gone out.In the case where making bond layer thickening, the demoulding is peeled off During film, the part for producing bond layer sometimes is attached to mold release film or the bonding agent in the part for being needed on mold release film A problem that bubble is mixed in layer.Therefore, when used in optical applications without base material double-sided adhesive sheet, not only double without base material In the adhesive sheet of face, and in the mold release film of combination, being also at needs than ever the more strict, shape of the mold release film of higher quality Condition.
On the other hand, when using mold release film, when making which peel off from bond layer, it some times happens that stripping charge, its As a result, in processing site, produce sometimes because foreign body etc. attachment or be involved in the product for causing it is bad occur etc. bad feelings Condition.
Therefore, only with manufacturing process in by the corresponding antistatic countermeasure of equipment, might not be abundant, in urgent uncommon Hope the situation of the antistatic process from mold release film itself.Additionally, in the mold release film of release layer of heavy peeling type is provided with, When being peeled off after the state fitted with bond layer long-time, there is the tendency of re-separation.As the present invention, In the purposes that bond layer fits mold release film, in the case that the ratio of peeling force deviates desired scope, needing originally During situation to be peeled off, a problem that be peeling difficulty sometimes.
Additionally, in the state of being provided with bond layer on the second mold release film (re-release side), it is right to fit in sometimes As part, implement the inspection with optical assessment.Now, when the opticses by acting on polarisation are checked, have When can check that the visual field is dimmed because of angle.
Prior art literature
Patent documentation
Patent documentation 1：Japanese Patent Application 2010-56884 publication
Patent documentation 2：Japanese Patent Application 2010-121101 publication
Patent documentation 3：Japanese Patent Application 2010-97765 publication
Patent documentation 4：Japanese Patent Application 2010-97925 publication
Patent documentation 5：Japanese Patent Application 2010-165733 publication
Patent documentation 6：Japanese Patent Application 2011-48410 publication
Patent documentation 7：Japanese Patent Application 2011-75120 publication
The content of the invention
Invent problem to be solved
The present invention be in view of above-mentioned practical situation and complete, its solve problem be provide one kind without base material double-sided adhesive Piece, its be the two sides of bond layer respectively lamination have mold release film without base material double-sided adhesive sheet, be suitable as such as direct capacitance The touch panel of amount mode is used with part, and static electricity resistance, release property, oligomer sealing, inspection easiness are good, and the demoulding Film itself has oligomer sealing property.
Method for solving problem
As a result the present inventors are had found, according to specific in view of above-mentioned actual state has made intensive studies Constitute without base material double-sided adhesive sheet, can easily solve above-mentioned problem, so as to complete the present invention.The present invention includes association 2 inventions, the purport of each invention is as follows.
That is, the purport of the first invention is one kind without base material double-sided adhesive sheet, it is characterised in that：Which is in bond layer Two sides lamination mold release film respectively, the peeling force of mold release film (the first mold release film) are less than another mold release film (second Mold release film) peeling force, the second mold release film simultaneously meets the condition of following (a)～(c) for recording.
A () is that the surface of the set coating layer containing water-disintegrable silicon compound on biaxially oriented polyester film is provided with The mold release film of release layer.
B the variation of the angle of orientation in () above-mentioned biaxially oriented polyester film face is 6 degree/below 500mm.
C () is 0.5mg/m by the oligomer amount extracted by dimethylformamide from the demoulding layer surface of above-mentioned mold release film2 Below.
And, the purport of the second invention is one kind without base material double-sided adhesive sheet, it is characterised in that be related in the first purport Without in base material double-sided adhesive sheet, the film mist degree of the first mold release film is more than 6%.
The effect of invention
First invention is due to static electricity resistance, release property is good and has oligomer sealing property, so being suitable as example The touch panel of capacitance-type used without base material double-sided adhesive sheet, the value of its industry is high.Second invention and then inspection Look into easiness, identity good.
Description of the drawings
Fig. 1 is to represent the schematic profile without base material double-sided adhesive sheet that embodiments of the present invention are related to.
Specific embodiment
＜ the first invention ＞
The polyester film of the first and second mold release film of composition in the present invention both can also can be tied for lamination for single layer structure Structure, such as in addition to 2 layers, 3-tier architecture, as long as less than the purport of the present invention, can also be 4 layers or the multilamellar more than which, not have It is particularly limited to.
In the present invention polyester used by polyester film can both be homopolymerization polyester, or copolyester.By homopolymerization In the case that polyester is constituted, aromatic dicarboxylic acid and material obtained from aliphatic diol polycondensation are preferably made.As aromatic series two Carboxylic acid, can enumerate p-phthalic acid, 2,6- naphthalene dicarboxylic acids etc., as aliphatic diol, can enumerate ethylene glycol, a contracting diethyl Glycol, 1,4 cyclohexane dimethanol etc..As representational polyester, polyethylene terephthalate (PET) etc. can be illustrated. On the other hand, as the dicarboxylic acid component of copolyester, can enumerate M-phthalic acid, phthalic acid, p-phthalic acid, 2, One or two or more kinds in 6- naphthalene dicarboxylic acids, adipic acid, decanedioic acid, hydroxy carboxylic acid (such as P-hydroxybenzoic acid etc.) etc., makees For diol component, can enumerate ethylene glycol, diglycol, Propylene Glycol, butanediol, 1,4-CHDM, new penta 2 One or two or more kinds in alcohol etc..In either event, the polyester described in the present invention is referred to as usual 60 moles of % The above, the polyester that preferably 80 moles more than % are the polyethylene terephthalate of ethylene glycol terephthalate unit etc..
In the present invention, coordinate granule as main purpose to give easy slip preferably in polyester layer.The granule of cooperation As long as species be just not particularly limited for the granule that can give easy slip, as concrete example, can enumerate for example：Titanium dioxide The granule of silicon, Calcium Carbonate, magnesium carbonate, brium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, Kaolin, aluminium oxide, titanium oxide etc..Separately Outward, it is also possible to using heat-resisting described in Japanese Patent Publication 59-5216 publication, Japanese Unexamined Patent Application 59-217755 publication etc. Property organic granular.As the example of other thermostability organic granulars, thermosetting urea resin, thermosetting phenolic tree can be enumerated Fat, thermosetting epoxy resin, benzoguanamine resin etc..It is further possible to use make catalysis in polyester manufacturing process The part precipitation of the metallic compounds such as agent, differential dissipate the precipitation granule for obtaining.
On the other hand, with regard to using the shape of granule be also not particularly limited, it is possible to use it is spherical, block, bar-shaped, flat It is flat-shaped to wait arbitrary shape.In addition, being also not particularly limited with regard to its hardness, proportion, color etc..These a series of granules according to Needs and can also use two or more.
In addition, the mean diameter of the granule for using is usually 0.01～3 μm, is preferably 0.01～1 μm of scope.Average When particle diameter is less than 0.01 μm, granule is easy to coagulation, and dispersibility is insufficient sometimes, on the other hand, when mean diameter is more than 3 μm, The surface roughness of film becomes excessively thick, produces unfavorable condition sometimes when release layer is coated with subsequent handling etc..
Additionally, the granule content in polyester layer is usually 0.001～5 weight %, is preferably the model of 0.005～3 weight % Enclose.When granule content is less than 0.001 weight %, the easy slip of film is insufficient sometimes, on the other hand, in addition more than 5 weights During amount %, film is transparent insufficient sometimes.
Method as granule is added in polyester layer, is not particularly limited, can be using existing known method.Example Such as, can add in any stage of the polyester that manufacture constitutes each layer, but preferably can be in the stage of esterification or ester exchange After reaction terminates, polycondensation reaction is carried out.
Furthermore it is possible to carry out by the following method, i.e. using the mixing extruder with vent, will be dispersed in second two The method that the slurry of the granule in alcohol or water etc. is blended with polyester raw material；Or mixing extruder is used, by dried granule Method blended with polyester raw material etc..
Additionally, in the polyester film of the present invention in addition to above-mentioned granule, can also add existing known as needed Antioxidant, antistatic agent, heat stabilizer, lubricant, dyestuff, pigment etc..
As long as constituting the thickness of the polyester film of first mold release film and the second mold release film of the present invention being capable of masking as film Scope be just not particularly limited, usually 25～250 μm, be preferably 38～188 μm, more preferably 50～125 μm of scope.
Then, it is for the Production Example of the polyester film of the present invention is specifically illustrated but not any by following Production Example Limit.
It is preferred that first by the polyester raw material for describing before, the molten sheet chill roll extruded from die head is cooled and solidified To the method for non-stretched.Now, in order that the flatness of piece is improved, need to improve the adaptation of piece and rotation cooling drum, it is excellent Choosing applies closely sealed method and/or the closely sealed method of liquid spreading using electrostatic.Then resulting non-stretched is drawn on biaxially oriented Stretch.Now, first, above-mentioned non-stretched is used in one direction the stretching-machine stretching of roller or stenter mode.Draft temperature Usually 70～120 DEG C, preferably 80～110 DEG C, stretching ratio is usually 2.5～7 times, preferably 3.0～6 times.Then, with The orthogonal draft temperature of first paragraph draw direction is usually 70～170 DEG C, and stretching ratio is usually 3.0～7 times, and preferably 3.5 ～6 times.Then, continue with 180～270 DEG C of temperature strain at it is lower or 30% within it is lax under carry out heat treatment, obtain double Axle alignment films.In above-mentioned stretching, it is also possible to the method for adopting the stretching that a direction more than the stage is carried out with 2.Now, preferably Carry out in the way of the stretching ratio of final both direction respectively becomes above range.
In addition, manufacturing with regard to the polyester film in the present invention, it is also possible to using simultaneously biaxial drawing method.With regard to simultaneously biaxial drawing For method, using in the state of being controlled as usual 70～120 DEG C, preferably 80～110 DEG C in temperature by above-mentioned non-stretched Stretching simultaneously on operating direction and width makes the method which is orientated, and as stretching ratio, with area dynameter, is 4～50 Times, preferably 7～35 times, more preferably 10～25 times.Then, continue with 170～250 DEG C of temperature strain at it is lower or 30% with It is interior it is lax under carry out heat treatment, obtain stretching alignment films.With regard to using biaxial stretch-formed device, energy while above-mentioned stretching mode The known stretching mode all the time such as spiral way, scalable manner, linear drive mode is adopted enough.
Furthermore it is possible to be implemented in process film surface, so-called coating pulling method in the stretching process of above-mentioned polyester film (online to coat).In the case where coating layer is arranged by coating pulling method on polyester film, can be applied with stretching simultaneously Cloth, and make the thickness of coating layer thinning corresponding to stretching ratio, film suitable as polyester film can be manufactured.
Coating layer with regard to constituting the mold release film of the present invention is illustrated.
The coating layer of the mold release film of the present invention is constituted, in order that static electricity resistance, oligomer separate out preventing property and become good, and And make release layer become good with the film adaptation during Jing of polyester film, to contain water-disintegrable silicon compound as necessary bar Part.
As water-disintegrable silicon compound used in the present invention, using formula Si (OR1)x(R2)4-xShown material is at this It is preferred in the purposes of invention.In above-mentioned formula, x is preferably 2～4 integer.The R in above-mentioned formula1Can be alkyl or Any one of acyl group.As alkyl, can enumerate for example：Methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, uncle The alkyl of the carbon numbers such as butyl 1～5, can enumerate for example as acyl group：The acyl group of the carbon numbers such as acetyl group 1～4.Upper State in formula, R2For the organic group of carbon number 1～10, the alkyl of for example, unsubstituted or replacement.As unsubstituted hydrocarbon Base, can enumerate：It is methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, n-hexyl, cyclohexyl, n-octyl, tertiary pungent Thiazolinyls such as the aryl such as the alkyl such as base, positive decyl, phenyl, vinyl, pi-allyl etc..In addition, as substituted hydrocarbon radical, can enumerate： γ-glycidoxypropyl group, γ-mercaptopropyi, 3,4- epoxycyclohexylethyls, gamma-methyl allyl acyloxypropyl etc..These water Solution property silicon compound both can be used alone, or can also combine two or more and be used in combination.
As the concrete example of the water-disintegrable silicon compound of x=4, can illustrate：Tetramethoxy-silicane, tetraethoxysilane, Four positive propoxy silane, four n-butoxy silanes, four acetoxylsilanes etc..As the concrete example of x=3, can enumerate：Methyl Trimethoxy silane, MTES, ethyl trimethoxy silane, ethyl triethoxysilane, n-pro-pyl trimethoxy Base silane, n-pro-pyl triethoxysilane, isopropyltri-methoxysilane, isopro-pyltriethoxysilane, γ-chloropropyl front three TMOS, γ-chloropropyl triethoxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy third Ethyl triethoxy silicane alkane, gamma-methyl allyl acyloxypropyl trimethoxysilane, γ-Mercaptopropyltriethoxysilane, phenyl three Methoxy silane, VTES, 3,4- epoxycyclohexylethyl trimethoxy silanes, 3,4- epoxycyclohexyl second Ethyl triethoxy silicane alkane etc..As the alkoxysilane compound containing trialkylsilyl group in molecular structure of x=2, can illustrate：Dimethyldimethoxysil,ne, diformazan Base diethoxy silane, aminomethyl phenyl dimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, two N-pro-pyl dimethoxysilane, diη-propyl diethoxy silane, diisopropyl dimethoxy silane, diisopropyl diethoxy Silane, dimethoxydiphenylsilane, divinyl diethoxy silane etc..
In addition, as the material of the coating layer for constituting the present invention, in order that oligomer sealing is better, being preferably used in combination Organic compound containing metallic element.
Specifically, containing selected from more than at least one in aluminum, titanium, zirconium organic compound containing metallic element in coating layer Thing.
As the concrete example of the organic compound with aluminium element, can illustrate：Aluminium tris(acetylacetonate), aluminum single acetyl third Ketonates double (ethyl acetoacetate) ,-two positive fourth oxide-acetoacetic acid mono ethyl ester of aluminum, aluminum-diisopropyl oxide-acetyl second Sour mono-methyl etc..
As the concrete example of the organic compound with titanium elements, can enumerate for example：Tetra-n-butyl titanate, metatitanic acid four are different The titanium ortho acid esters such as propyl ester, butyltitanate dimer, four (2- ethylhexyls) titanate esters, tetramethoxy titanate ester；Pentanedione titanium, Tetra-acetylated acetone titanium, poly- titanium acetylacetonate, ethohexadiol titanium, lactic acid titanium, titanium triethanolamine compound, oacetic acid titanium Deng titanium chelate class etc..
As the concrete example of the organic compound with zr element, can enumerate for example：Zirconium acetate, n Propanoic acid zirconium, positive fourth Sour zirconium, zirconium, monoacylphosphine acetone zirconium, diacetyl group acetone zirconium etc..
Wherein, particularly separating out in oligomer prevents aspect of good performance, preferably comprises the metal unit in aluminum, zirconium The organic compound of element, the more preferably organic compound with chelate structure.Additionally, in " frame Bridge agent Ha Application De Block ッ Network (friendship Connection agent handbook) " also there is concrete record in (Shanxi three, gold east help editor's (strain) great achievement society 2 years versions of Heisei under mountain).
It is in the coating layer of mold release film of the present invention is constituted, preferred to making oligomer sealing become good, preferably mixed Close water-disintegrable silicon compound (A) and organic compound containing metallic element (B).Both compounding ratios (weight ratio) are preferably (A)： (B)=1：0.001～1：0.01 scope.When the scope is deviateed, the surface of the demoulding layer surface in mold release film is intrinsic sometimes Not a problem that resistance (R) does not reach desired level or can produce oligomer sealing property deficiency.
Formation sequentially for the release layer of the present invention is illustrated.
The first mold release film and the release layer of the second mold release film for constituting the present invention refers to the layer with release property, it is concrete and Speech, can complete the present invention in certain limit by making acrylic acid seriess splicing tape and the peeling force (F) of release layer.
5～40mN/cm is preferably equivalent to the peeling force relative to adhesive linkage 11 of light the first mold release film 31 for peeling off side. When the peeling force of the first mold release film is less than 5mN/cm, under the situation that need not be peeled off originally, mold release film can be easily sometimes Peel off.In addition, when the peeling force of the first mold release film is more than 40mN/cm, sometimes second in the operation for peeling off the first mold release film The peeling for floating can be referred to as between mold release film and adhesive linkage.
By suppressing relatively low the absolute value of the peeling force of the first mold release film 31, even if reducing the stripping of the second mold release film 32 From the absolute value of power, it is also possible to which the peeling force for increasing two mold release films 31,32 is poor.In addition, the stripping by making the first mold release film 31 Power is more than certain value, using front, under the situation that need not be peeled off originally, is prevented from the first mold release film 31 from adhesive linkage 11 are easily peeled off or phenomenon that the first mold release film 31 floats from adhesive linkage 11.
On the other hand, the peeling force equivalent to the second mold release film 32 of re-release side is preferably 45～100mN/cm, more excellent Elect 50～80mN/cm as.When the peeling force of the second mold release film is less than 45mN/cm, when the first mold release film is peeled off, produce sometimes An a problem that part for raw second mold release film is peeled off.In addition, when the peeling force of the second mold release film is more than 100mN/cm, sometimes Can produce a problem that the second mold release film is remained from the composition of adhesive linkage.
The present invention without base material double-sided adhesive sheet in addition to above-mentioned peeling force is adjusted, be also preferably provided with the first mold release film It is poor with the peeling force of the second mold release film.
It is preferred that the peeling force of the second mold release film 32 is usual more than 2.0 times of the peeling force of the first mold release film 31, preferably sets For more than 3.0 times.When the peeling force of the second mold release film 32 is less than 2.0 times of the peeling force of the first mold release film 31, light stripping is being peeled off From the first mold release film 31 of side when, it some times happens that the second mold release film 32 float from bond layer 11 phenomenon, bonding composition of layer To the second mold release film 32 residual or it is discontinuous peel off (Zipping) a problem that.
The release layer for constituting first mold release film of the present invention can also be set by above-mentioned coating pulling method (online to coat) Put on polyester film.Following methods are not limited to regard to being coated with pulling method (online to coat), for example, can be drawn in gradually twin shaft Stretch particularly the 1st section of stretching to terminate, implement coating processing before the 2nd section of stretching.By being coated with pulling method in polyester film During upper setting release layer, it can be coated with stretching simultaneously, and makes the thickness of release layer thinning corresponding to stretching ratio, system Make as the suitable film of polyester film.
In addition, constituting the release layer of the mold release film of the present invention in order that release property becomes good, preferably comprising curing type has Machine silicones.Can both be the type with curing type silicone resin as main component, it is also possible in the master for not damaging the present invention In the range of purport, using by obtaining with the glycerol polymerization of organic resin such as polyurethane resin, epoxy resin, alkyd resin etc. Modified organic silicon type etc..
As the species of curing type silicone resin, add-on type, condensed type, ultraviolet hardening, electronic beam solidified, nothing Any curing reaction type such as solvent-borne type can be used.Concrete example is enumerated, then can be illustrated：SHIN-ETSU HANTOTAI's chemical industry (strain) is made KS-774、KS-775、KS-778、KS-779H、KS-847H、KS-856、X-62-2422、X-62-2461、X-62-1387、X- 62-5039、X-62-5040、KNS-3051、X-62-1496、KNS320A、KNS316、X-62-1574A/B、X-62-7052、X- 62-7028A/B, X-62-7619, X-62-7213, Momentive Performance Materials Inc. YSR- 3022、TPR-6700、TPR-6720、TPR-6721、TPR6500、TPR6501、UV9300、UV9425、XS56-A2775、 XS56-A2982, UV9430, TPR6600, TPR6604, TPR6605, Dow Corning Toray Co., Ltd. (Dong Lidaokang Ning companies) SRX357, SRX211, SD7220, SD7292, LTC750A, LTC760A, LTC303E, SP7259, BY24- processed 468C, SP7248S, BY24-452, DKQ3-202, DKQ3-203, DKQ3-204, DKQ3-205, DKQ3-210 etc..And then in order to Fissility of adjustment release layer etc., it is also possible to and use release control agent.
In the present invention, it is not particularly limited with regard to condition of cure when release layer is formed on polyester film, by offline Coating arrange release layer when, generally with 120～200 DEG C, 3～40 seconds, preferably carried out with 100～180 DEG C, 3～40 seconds as standard Heat treatment.Alternatively, it is also possible to as needed and with heat treatment and ultraviolet irradiation isoreactivity energy line irradiation.Additionally, making It is the energy source for being solidified using active energy ray irradiation, can be using known device, energy source all the time.It is de- The coating amount (be dried after) of mold layer from screening characteristics aspect, usually 0.005～1g/m2, preferably 0.005～0.5g/ m2, more preferably 0.01～0.2g/m2Scope.Coating amount (after being dried) is less than 0.005g/m2When, from from the aspect of screening characteristics Deficient in stability, is difficult to obtain uniform film sometimes.On the other hand, apply more than 1g/m thick2When, release layer itself sometimes Film adaptation, curable etc. can be reduced.
It is 6 degree/below 500mm that second mold release film of the present invention needs the variation of the angle of orientation in film.In the change of the angle of orientation When moving more than 6 degree/500mm, this purposes can be not suitable for.
In the present invention, the method as release layer is arranged in polyester film can be applied using reverse intaglio plate coating, direct intaglio plate The existing known application pattern such as cloth, roller coat, die coating, rod painting, curtain coating.With regard to application pattern in “ コ ー テ ィ Application グ modes (coating method) " Omaki bookstore writes example on the books in distribution in 1979 former rugged brave time.
With regard to first mold release film and the second mold release film of the present invention, the face of release layer is being not provided with, this is not being damaged In the range of the purport of invention, it is also possible to arrange bonding layer, antistatic backing, oligomer separate out prevent the coating layers such as layer.
Alternatively, it is also possible to the polyester film to constituting the first mold release film and the second mold release film implement in advance sided corona treatment, etc. from The surface treatments such as daughter process.
In the present invention, when mold release film is manufactured, after both being coated with coating layer on polyester film, after at one end rise film roll Release layer is set on coating layer again, it is also possible to is coated with polyester film after coating layer is dried, is continuously set on coating layer Release layer is put, can be using any method in the present invention.
Constitute the present invention the mold release film without substrate bonding piece in, from prevent to bond layer surface foreign body attachment or From the viewpoint of person peels off electrostatic, surface intrinsic resistance (R) value of stripping surface is preferably 1 × 1012(Ω) below.It is with regard to R values, excellent Elect 1 × 10 as11(Ω) below, more preferably 1 × 1010(Ω) below.When R deviates above range, mold release film is being peeled off sometimes When can produce a problem that being involved in foreign body.
Additionally, in the mold release film of the present invention, (180 DEG C, 10 minutes) after preferred heat treatment, from release layer surface extraction Oligomer amount (OL) is 0.5mg/m2Below.OL is more than 0.5mg/m2When, when the stripping surface of mold release film is fitted with bond layer, During oligomer Jing, ground is separated out, and in the inspection operation with optical assessment, can bring obstacle when checking sometimes.
Then, below explanation constitutes the bond layer without base material double-sided adhesive sheet of the present invention.Bonding agent in the present invention Layer refer to the layer being made up of the material with cementability, do not damage the present invention purport in the range of, can using always with Carry out known material.As one of concrete example, for using during acrylic acid series bonding agent described below.
In the present invention, acrylic acid series bonding agent refer to containing using acrylic monomer as must monomer (Monomer) into The bond layer of polymer based on point formed acrylic acid series polymeric compounds.The acrylic acid series polymeric compounds are preferably to have (methyl) alkyl acrylate and/or (methyl) alkoxyalkyl acrylate of the alkyl of straight or branched is used as necessary The acrylic acid series polymeric compounds formed by monomer component (more preferably as main monomer component).Additionally, acrylic acid series polymeric compounds (methyl) alkyl acrylate and alkoxyalkyl acrylate preferably using the alkyl with straight or branched is used as must The acrylic acid series polymeric compounds formed by the monomer component of palpus.
The bond layer of the present invention be preferably with (methyl) alkyl acrylate of the alkyl with straight or branched and The acrylic acid series bonding agent layer formed as necessary monomer component by alkoxyalkyl acrylate.
In addition, formed the present invention bond layer in based on polymer acrylic acid series polymeric compounds monomer into Point in, it is also possible to also the monomer containing polar functionalities, multi-functional monomer, other co-polymerized monomers as comonomer into Point.Additionally, above-mentioned " (methyl) acrylic acid " expression " acrylic acid " and/or " methacrylic acid ", other are similarly.In addition, not having Be particularly limited to, based on polymer acrylic acid series polymeric compounds the present invention bond layer in content relative to bonding The gross weight (100 weight %) of oxidant layer is preferably more than 60 weight %, more than more preferably 80 weight %.
As the monomer component for forming aforesaid propylene acid based polymer, suitably can use with straight or branched (methyl) alkyl acrylate (below, being only abbreviated as sometimes " (methyl) alkyl acrylate ") of alkyl.As above-mentioned (first Base) alkyl acrylate concrete example, can illustrate：(methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) propylene Propyl propionate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) acrylic acid are secondary Butyl ester, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) isoamyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 1-Octyl acrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid nonyl ester, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (first Base) acrylic acid hendecane base ester, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) propylene Sour tetradecane base ester, (methyl) acrylic acid pentadecane base ester, (methyl) aliphatic acrylate, (methyl) acrylic acid heptadecane The alkane such as base ester, (methyl) octadecyl acrylate, (methyl) acrylic acid nonadecane base ester, (methyl) acrylic acid eicosane base ester The carbon number of base is 1～20 (methyl) alkyl acrylate etc..In addition, (methyl) alkyl acrylate can be used alone Or and use two or more.Wherein, the carbon number of preferred alkyl is 2～14 (methyl) alkyl acrylate, more preferably alkyl Carbon number is 2～10 (methyl) alkyl acrylate.
As the monomer of above-mentioned polar functionalities, can enumerate for example：(methyl) acrylic acid, itaconic acid, maleic acid, rich horse The carboxyl group-containing monomers such as acid .beta.-methylacrylic acid, iso-crotonic acid or its anhydride (maleic anhydride etc.)；(methyl) acrylic acid 2- hydroxy methacrylates, (first Base) (methyl) propylene such as acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 4- hydroxybutyls, the own ester of (methyl) acrylic acid 6- hydroxyls The hydroxyls such as sour hydroxyalkyl acrylate, vinyl alcohol, 1-propenol-3 (hydroxyl) monomer；(methyl) acrylamide, N, N- dimethyl (methyl) Acrylamide, N- methylols (methyl) acrylamide, N- methoxies (methyl) acrylamide, N- butoxymethyls (methyl) The amide-containing monomers such as acrylamide, N- hydroxyethyl acrylamides；(methyl) acrylate, (methyl) acrylic acid diformazan The emulsion stabilities such as base amino ethyl ester, (methyl) tbutylaminoethylacrylate；(methyl) glycidyl acrylate, (first Base) acrylic acid methylglycidyl esters etc. contain glycidyl monomer；The cyano-containing monomer such as acrylonitrile or methacrylonitrile；N- second Thiazolinyl -2-Pyrrolidone, (methyl) acryloyl morpholine and N- vinylpyridines, N- vinylpiperidones, N- vinyls are phonetic The vinyl monomers containing heterocycle such as pyridine, N- vinyl piperazines, N- vinyl pyrroles, N- vinyl imidazoles, N- Yi Xi Ji oxazoles； The monomers containing sulfonic group such as sodium vinyl sulfonate；The phosphorous acid-based monomers such as 2- hydroxyethyl acryloyl phosphates；Cyclohexyl Malaysia The monomers containing imido grpup such as acid imide, isopropylmaleimide；2- methylacryoyloxyethyl isocyanates etc. contain isocyanates Base monomer etc..The monomer of above-mentioned polar functionalities can also be used alone or in combination of two or more kinds.
As above-mentioned multi-functional monomer, can enumerate for example：Hexanediol two (methyl) acrylate, two (first of butanediol Base) acrylate, (gathering) ethylene glycol bisthioglycolate (methyl) acrylate, (gathering) Propylene Glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, dipentaerythritol six (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylol methane three (methyl) acrylate, allyl It is base (methyl) acrylate, vinyl (methyl) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, poly- Urethane acrylate etc..Above-mentioned multi-functional monomer can also be used alone or in combination of two or more kinds.
The content of above-mentioned multi-functional monomer is preferred relative to 100 weight % of monomer component for forming acrylic acid series polymeric compounds Below 0.5 weight %.When the content is more than 0.5 weight %, the cohesive force of such as bond layer becomes too high, sometimes stress Lusitropic can be reduced.
In addition, co-polymerized monomer beyond monomer and multi-functional monomer as above-mentioned polar functionalities (other altogether Poly- property monomer), can enumerate for example：(methyl) acrylic acid cyclopentyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid (methyl) acrylate with alicyclic type hydrocarbon such as iso-bornyl ester or (methyl) phenyl acrylate etc. have aromatic hydrocarbyl Above-mentioned (methyl) alkyl acrylate such as (methyl) acrylate, (methyl) alkoxyalkyl acrylate, containing polar group (methyl) acrylate beyond the monomer and multi-functional monomer of group；The vinyl esters such as vinyl acetate, propionate； The aromatic ethenyl compounds such as styrene, vinyltoluene；The alkene such as ethylene, butadiene, isoprene, isobutene. or diene Class；The vinyl ethers such as vinyl alkyl ethers；Vinyl chloride etc..
Above-mentioned monomer component can be utilized all the time known or usual polymerization by aforesaid propylene acid based polymer Method is polymerized to prepare.As the polymerization of acrylic acid series polymeric compounds, can enumerate for example：Solution polymerization process, breast Liquid polymerization, bulk polymerization method or the polymerization (active energy ray polymerization) using active energy ray irradiation etc.. Among above-mentioned, from the aspects such as the transparency, resistance to water, manufacturing cost, preferred solution polymerization process, active energy ray polymerization side Method.
As the active energy ray irradiated in above-mentioned active energy ray polymerization (photopolymerization), can enumerate for example：α The ionization such as line, β lines, γ lines, middle sub-line, electron beam property lonizing radiation or ultraviolet etc., wherein, ultraviolet is in the purposes of the present invention It is adapted to.As long as in addition, the irradiation energy of active energy ray, irradiation time, illuminating method etc. are in the purport for not damaging the present invention In the range of, just it is not particularly limited.
In addition, in above-mentioned polymerisation in solution, various general solvents can be used.As such solvent, can enumerate： The esters such as ethyl acetate, n-butyl acetate；Toluene, benzene etc. are aromatic hydrocarbon；The aliphatic hydrocarbons such as normal hexane, normal heptane；Hexamethylene The ester ring type hydro carbons such as alkane, hexahydrotoluene；The organic solvents such as the ketones such as butanone, methyl iso-butyl ketone (MIBK).Solvent individually can make With or combine two or more use.
When above-mentioned acrylic acid series polymeric compounds are prepared, can according to the species of polyreaction using thermal polymerization, The polymerization initiators such as Photoepolymerizationinitiater initiater (light trigger).Polymerization initiator can also be used alone or in combination of two or more kinds.
With regard to above-mentioned Photoepolymerizationinitiater initiater, it is not particularly limited, benzoin ether system Photoepolymerizationinitiater initiater, benzene second can be used Ketone system Photoepolymerizationinitiater initiater, alpha-ketol system Photoepolymerizationinitiater initiater, aromatic sulfonyl system Photoepolymerizationinitiater initiater, photolytic activity oxime system Photoepolymerizationinitiater initiater, benzoin system Photoepolymerizationinitiater initiater, benzyl system Photoepolymerizationinitiater initiater, benzophenone series Photoepolymerizationinitiater initiater, Ketal system Photoepolymerizationinitiater initiater, thioxanthone system Photoepolymerizationinitiater initiater etc..With regard to the usage amount of Photoepolymerizationinitiater initiater, as long as not Infringement the present invention purport in the range of, be just not particularly limited, for example relative to formed acrylic acid series polymeric compounds monomer into Point 100 weight portion of total amount is the scope of 0.01～0.2 weight portion.
As the concrete example of benzoin ether system Photoepolymerizationinitiater initiater, can enumerate for example：Benzoin methylether, benzoin second Ether, benzoin propyl ether, benzoin iso-propylether, benzoin isobutyl ether, 2,2- dimethoxy -1,2- diphenylethane -1- ketone, benzene first Ether methyl ether etc..As 1-Phenylethanone. system Photoepolymerizationinitiater initiater, can enumerate for example：2,2- diethoxy acetophenones, 2,2- diformazans Epoxide -2- phenyl acetophenones, 1- hydroxycyclohexylphenylketones, 4- phenoxydichloroacetophenones, 4- (tert-butyl group) dichloroacetophenone Deng.As alpha-ketol system Photoepolymerizationinitiater initiater, can enumerate for example：2- methyl -2- hydroxypropiophenonepreparations, 1- [4- (2- hydroxyl second Base) phenyl] -2- methylpropane -1- ketone etc..As the concrete example of aromatic sulfonyl system Photoepolymerizationinitiater initiater, 2- can be enumerated Naphthalene sulfonyl chloride etc..As photolytic activity oxime system Photoepolymerizationinitiater initiater, can enumerate for example：1- phenyl -1,1- pentanedione -2- are (adjacent Ethoxy carbonyl)-oxime etc..Benzoin system Photoepolymerizationinitiater initiater includes such as benzoin etc..In benzyl system Photoepolymerizationinitiater initiater Including such as benzyl etc..As the concrete example of benzophenone series Photoepolymerizationinitiater initiater, can illustrate：Benzophenone, benzoyl Benzoic acid, 3,3 '-dimethyl -4- methoxy benzophenones, polyvinyl benzophenone, Alpha-hydroxy cyclohexyl-phenyl ketone etc..Make For the concrete example of ketal system Photoepolymerizationinitiater initiater, including benzyl dimethyl ketal etc..As thioxanthone system Photoepolymerizationinitiater initiater Concrete example, including thioxanthone, 2- chlorothiaxanthenones, 2- methyl thioxanthones, 2,4- dimethyl thioxanthones, isopropyl sulfur Miscellaneous anthrone, 2,4- diisopropyl thioxanthones, dodecyl thioxanthone etc..
As the concrete example of above-mentioned thermal polymerization, can enumerate：Azo system polymerization initiator [for example, 2,2 '-azo Double -2- the methylbutyronitriles of double isopropyl cyanides, 2,2 '-azo, double (2 Methylpropionic acid) dimethyl esters of 2,2 '-azo, the double -4- of 4,4 '-azo Double (2- amidine propanes) dihydrochlorides of the double isobutyl cyanide of cyanopentanoic acid, azo, 2,2 '-azo, 2,2 '-azo it is double [2- (5- methyl- 2- imidazoline -2- bases) propane] dihydrochloride, double (the 2- methyl-prop amidines) dithionate of 2,2 '-azo, 2,2 '-azo it is double (N, N ' - Dimethyleneisobutylamidine) dihydrochloride etc.], peroxide system polymerization initiator (for example, dibenzoyl peroxide, mistake Oxidation Malaysia tert-butyl acrylate etc.), redox system polymerization initiator etc..As the usage amount of thermal polymerization, as long as not In the range of the purport of the infringement present invention, just it is not particularly limited.
In the acrylic acid series bonding agent layer that a kind of mode of the bond layer as the present invention is used, as needed, energy Enough scopes not damage the characteristic of the present invention use cross-linking agent, crosslinking accelerator, bonding imparting agent (for example, rosin derivative Resin, polyterpene resin, Petropols, oil-soluble phenolic resin etc.), age resister, filler, coloring agent (pigment or dyestuff Deng), UV absorbent, antioxidant, chain-transferring agent, plasticizer, softening agent, surfactant, antistatic agent etc. it is known Additive.In addition, when bond layer is formed, it is also possible to using various general solvents.As the species of solvent, without special Limit, can use as material illustrated in the solvent used in above-mentioned polymerisation in solution etc..
Above-mentioned cross-linking agent is crosslinked by the base polymer by bond layer, can control the gel fraction of bond layer. As cross-linking agent, except isocyanates system cross-linking agent, epoxy cross-linking agent, melamine series cross-linking agent, peroxide system cross-linking agent In addition, Urea Series cross-linking agent, metal alkoxide system cross-linking agent, metallo-chelate system cross-linking agent, slaine system can also be enumerated Cross-linking agent, cross-linking agent, oxazolines system of carbodiimides system cross-linking agent, aziridine system cross-linking agent, amine system cross-linking agent etc., can be suitable Ground uses isocyanates system cross-linking agent, epoxy cross-linking agent.Cross-linking agent can also be used alone or in combination of two or more kinds.
Then, in the present invention is without base material double-sided adhesive sheet, use as its Component units, when bond layer is formed In the case of acrylic acid series bonding agent compositionss, for example, by will be present in opticses (such as, sealer, touch surface Display surface of plate and image-display units etc.) between space refractive index it is transparent closer to opticses compared with air Adhesive sheet replaces, and improves photopermeability, suppresses brightness, the reduction of contrast of image display device, is considering the above In the case of, preferably flexibly design bond layer itself.For example, the store elastic modulus (G`) of dynamic viscoelastic are preferably 1.0×105Below Pa, more preferably 5.0 × 104Below Pa.In store elastic modulus (G`) more than 1.0 × 105During Pa, for example, When landfill is present in the space between opticses, the bond layer for producing sometimes filling cannot reach corner, occur in end Peel off or produce a problem that floating.
As the thickness of the bond layer without base material double-sided adhesive sheet for constituting the present invention, can be 25 μm～200 μm, it is excellent Elect 50 μm～150 μm of scope as.When the thickness of adhibited layer is less than 25 μm, for example, the space produced between opticses Become too much, be difficult to be filled into corner in bond layer sometimes.On the other hand, when bond layer thickness is more than 200 μm, compare In the space produced between opticses, bond layer thickness becomes blocked up, it some times happens that the bond layer of redundance into Divide a problem that oozing out between opticses.
＜ the second invention ＞
It is of the invention compared with the first above-mentioned invention, for making to become easy viewpoint from outside identification, only will The film mist degree of the first mold release film is more than 6% different as the aspect of constitutive requirements.The film mist degree of the first mold release film is preferably More than 10%.When the film mist degree is less than 6%, when mold release film is peeled off without base material double-sided adhesive sheet, misunderstand sometimes.
Embodiment
Hereinafter, the present invention is illustrated in greater detail according to embodiment, the present invention without departing from its purport, be just not limited to Under embodiment.In addition, the algoscopy used in the present invention is as follows.
(1) measure of the intrinsic viscosity of polyester：
Polyester 1g after accurate weighing removing other polymers composition non-compatibility in the polyester and pigment, addition phenol/ The mixed solvent 100ml of sym-tetrachloroethane=50/50 (weight ratio) dissolves which, is measured at 30 DEG C.
(2) mean diameter (d50：μm) measure：
To be determined using centrifugal type particle size distribution device (Shimadzu Scisakusho Ltd's SA-CP3 types) To equivalent spherical distribution in accumulative (weight basis) 50% value as mean diameter.
The film mist degree of (3) first mold release films is determined：
According to JIS-K6714, film mist degree is determined using electricity Se Industrial Co., Ltd of Japan system bulb separation formula scopometer NDH-20D (turbidity).
(4) measure of the variation of the angle of orientation in main axis of orientation and film：
Position from centered on the width relative to the polyester film for constituting the second mold release film, towards two ends, per 500mm Position and cut out sample from most two ends, respectively using Carl Zeiss company system polarizing microscopes, observe polyester film orientation, How many degree inclined relative to the MD of polyester film for the direction for obtaining the main axis of orientation in polyester face.Additionally, in measure, master take To axle more than 90 degree when, using its supplementary angle as the MD directions relative to main axis of orientation angle.In addition, calculating comprising most two ends Position the angle of orientation variation when, between sample position less than 500mm in the case of, be calculated by every 500mm's with ratio The variation of the angle of orientation.So obtain the variation of the angle of orientation of every 500mm of width, using meansigma methodss as each film width The orientation angular variable in degree direction.
(determinating reference)
The variation of the A angles of orientation is 6 degree/below 500mm.
The variation of the B angles of orientation is more than 6 degree/500mm.
The measure postponed in the face of (5) second mold release films：
Thickness of liquid crystal box (cell gap) check device RETS-1100A of Shi Yong Otsuka Electronics Co., Ltd., determines phase For delay in the face of the position centered on film width.Optical interferometry used in the measure postponed in the face of film, is set to Aperture 5mm is carried out at 23 DEG C.
(6) peeling force (F1F2) of mold release film is determined：
After the demoulding layer surface of sample film attaches a face of double-sided adhesive tape (day east electrician's system " No.502 "), cutting Into the size of 50mm × 300mm, the peeling force after room temperature is placed 1 hour is determined.Peeling force uses cupping machine ((strain) Intesco systems " Intesco model2001 types "), under conditions of draw speed 300mm/ minutes, carry out 180 ° of strippings.
(7) the surface intrinsic resistance (R) of mold release film is determined：
The surface intrinsic resistance (R) of stripping surface in sample film, is determined, is judged according to following determinating references.Determine Condition is carried out under 23 DEG C, the atmosphere of 50%RH.Will be the medial electrode 50mm diameters of Yokogawa Hewlett-Packard, lateral electrode 70mm straight The concentric electrode 16008A (trade name) in footpath is arranged at sample under 23 DEG C, the atmosphere of 50%RH, applies the voltage of 100V, uses The meter 4329A (trade name) of the said firm determines the surface intrinsic resistance value of sample.
(determinating reference)
AR (Ω) is 1012Below (level that can be practical).
BR (Ω) is more than 1012(being difficult to the level of practicality).
(8) from the measure of the oligomer amount (OL) of the release layer surface extraction of mold release film：
In advance by nonheat-treated mold release film in atmosphere, 180 DEG C heat 10 minutes.Then, by the heat treatment after should Film is attached to length and width 10cm, the inner surface of the case of high 3cm of opened upper end as far as possible, makes the shape of box-shaped.It is being provided with coating During layer, coating aspect is made to be inner side.Then, among the case by made by said method DMF (dimethylformamide) 4ml is added to put After putting 3 minutes, DMF is reclaimed.By DMF supply liquid chromatograph (Shimadzu Seisakusho Ltd.'s systems for reclaiming：LC-7A), obtain oligomeric in DMF Thing amount, by the value divided by the membrane area of contact DMF, obtains film surface oligomers amount (mg/m2)。
Oligomer amount in DMF is tried to achieve (definitely with the peak area ratio for determining sample peak area by standard specimen peak area Standard curve method).The precise that is made through of standard specimen divides the oligomer (cyclic trimer) for taking in advance, is dissolved in accurately The DMF of weighing and make.The concentration of standard specimen is preferably the scope of 0.001～0.01mg/ml.
Wherein, the condition of liquid chromatograph is as follows.
Mobile phase A：Acetonitrile
Mobile phase B：2% acetic acid aqueous solution
Post：Mitsubishi Chemical's (strain) makes " MCI GEL ODS 1HU "
Column temperature：40℃
Flow velocity：1ml/ minutes
Detection wavelength：254nm
(9) metallic element from the demoulding surface side of mold release film measures fixed：
Device ((strain) Shimadzu Seisakusho Ltd. is determined using fluorescent X-ray by the face for being provided with release layer of specimen sample in advance (system) pattern " XRF-1500 ") using FP (fundamental parameters method, Fundamental Parameter Method) method, in following tables Under condition determination shown in 1, metallic element amount is determined.
[table 1]
(condition determination)
Setting item Zr Al Ti
X-ray tube target Rh4.0kW Rh4.0kW Rh4.0kW
Light splitting is crystallized LiF PET LiF
2θ 22.550 144.58 86.14
Detector SC FPC FPC
Tube current 95mA 95mA 95mA
Tube voltage 40kv 40kv 40kv
(10) the film adaptation of mold release film promotes to evaluate (practical characteristic alternative evaluation)：
By sample film in constant temperature and humidity cabinet, 60 DEG C, place after 4 weeks under 80%RH atmosphere, take out sample film.Then, profit With the stripping surface 5 times of tentacle friction sample film, the degree of coming off of release layer is judged according to following determinating references.
(determinating reference)
A does not observe come off (the level that can be practical) of film.
B films bleach but do not come off (level that can be practical).
C confirms come off (level for being difficult to practicality) of film.
(11) store elastic modulus (G`) of bond layer are determined：
Double-sided adhesive sheet from obtained by embodiment and comparative example peels off separator, only lamination acrylic acid series bonding agent layer, The laminated body of the acrylic acid series bonding agent layer of thickness (after being dried) 1.5mm ± 0.1mm is made, as determination sample.To above-mentioned survey Random sample product, using " the Advanced Rheometric Expansion System of Rheometric Scientific company systems (ARES) ", under conditions of frequency 1Hz, it is measured with -70～200 DEG C of scope, 5 DEG C/min of programming rate, obtains temperature Degree 23 DEG C when store elastic modulus (G`).Additionally, the storage of bond layer used by the embodiment and comparative example in the present invention Energy elastic modelling quantity (G`) is 5.0 × 104Pa。
(12) discontinuous fissility evaluation (practical characteristic alternative evaluation)：
Following adhesive composites are coated into the second mold release film, after 5 minutes heat treatments being carried out at 100 DEG C, obtain thickness (after drying) is 50 μm of adhesive linkage.Then, it is two-sided without base material what the first mold release film fitted in bond layer surface obtains In adhesive sheet, stripping situation is observed when the first mold release film is peeled off, for the discontinuous situation occurred peeled off, according to following judgements Benchmark is judged.
＜ acrylic acid series bonding agent compositionss ＞
(monomer be combined into)
70 weight % of 2-EHA
29 weight % of acrylic acid 2- methoxy acrylates
1 weight % of acrylic acid 4- hydroxybutyls
Relative to 100 weight portion of above-mentioned monomer composition, add Japanese polyurethane CORONATE L0.1 parts, obtain propylene Acid is bond layer formation compositionss.
(determinating reference)
A：Extremely successfully peel off, do not peel off vestige, also do not peel off sound generation.
B：It can be seen that slight stripping vestige, produce very little peels off the slight discontinuous stripping (practicality of sound or generation On the level that throws into question sometimes).
C：It can be seen that stripping vestige, is peeling sound.There is discontinuous stripping (level thrown into question in practicality).
The fissility evaluation (practical characteristic alternative evaluation) of (13) first, second mold release films：
In (7) item, for when peeling off the first mold release film, the situation at the second release layer and bond layer interface, according under Stating determinating reference carries out sense evaluation.
(determinating reference)
A：At the second release layer and bond layer interface, abnormal (level having no problem in practicality) is not seen.
B：At the second release layer and bond layer interface, it is seen that slightly float the (water for being thrown into question in practicality sometimes It is flat).
C：At the second release layer and bond layer interface, it is seen that significantly float (problematic level in practicality).
(14) check easiness evaluation (practical characteristic alternative evaluation)：
It is each without base material double-sided adhesive sheet obtained by using embodiment and comparative example, after peeling off the first mold release film, will expose Bond layer surface fit with Polarizer, obtain the laminated body of the composition with Polarizer/bond layer/the second mold release film.
Laminated body obtained by being then used by, carries out the inspection of Polarizer using Nicol crossed method.
Each inspection easiness without base material double-sided adhesive sheet obtained by embodiment is good, but in comparative example obtained by It is each without base material double-sided adhesive sheet among, the variation of the angle of orientation more than 6 degree/500mm adhesive sheet in Nicol crossed observation When light and shade it is unobvious, to be difficult to the situation for checking.
(determinating reference)
The variation of the A angles of orientation is 6 degree/below 500mm.
The variation of the B angles of orientation is more than 6 degree/500mm.
(15) oligomer sealing evaluates (practical characteristic alternative evaluation)：
Oligomer amount obtained by utilization (8) item, is judged according to following determinating references.
(determinating reference)
A oligomer amount is 0.5mg/m2Below.
B oligomer amounts are more than 0.5mg/m2。
(16) identity evaluation (practical characteristic alternative evaluation)
Visual observations fit to which side without base material double-sided adhesive sheet, the mold release film of the side light for peeling force, according to Following determinating references are judged.
(determinating reference)
A is capable of identify that.
B is difficult to.
(17) static electricity resistance evaluation (practical characteristic alternative evaluation)
Under 23 DEG C, the measure atmosphere of 50%RH, will be without the abundant damping of base material double-sided adhesive sheet after, peel off first demoulding Film.Then, the bond layer surface exposed is close at leisure on the ash of the Nicotiana tabacum L. crushed in advance, according to following judgement base The accurate attachment to ash now judges.
(determinating reference)
A：Even if film contact ash does not also adhere to.
B：Only make film be close to ash to adhere in large quantities.
(18) overall merit (practical characteristic alternative evaluation)：
Using manufacturing in embodiment and comparative example without base material double-sided adhesive sheet, situation occurred, stripping are peeled off for discontinuous From property, static electricity resistance, oligomer sealing, adaptation, each assessment item for checking easiness, carried out according to following determinating references Overall merit.
(determinating reference)
A：Discontinuous stripping situation occurred, fissility, static electricity resistance, oligomer sealing, adaptation, inspection easiness are equal For " A " (level having no problem in practicality).
B：It is discontinuous peel off situation occurred, fissility, static electricity resistance, oligomer sealing, adaptation, check easiness it In at least one be " B " (in practicality, the level for throwing into question sometimes).
C：It is discontinuous to peel off in situation occurred, fissility, static electricity resistance, oligomer sealing, adaptation, inspection easiness At least one be " C " (problematic level in practicality).
＜ the first invention ＞
Polyester used in embodiment and comparative example is to be carried out as follows the polyester for preparing to obtain.
The manufacture ＞ of ＜ polyester
Production Example 1 (polyethylene terephthalate A1)
0.09 part of 100 parts of dimethyl terephthalate (DMT), 60 parts of ethylene glycol and four acetate hydrate magnesium are taken into reactor, companion With heat temperature raising, methanol is distilled off, carries out ester exchange reaction, start to need to be warmed up within 4 hours 230 DEG C from reaction, essence On ester exchange reaction is terminated.Then, after adding 0.04 part of ethylene glycol slurry acid phosphate ester, 0.03 part of antimony trioxide, use Make within 100 minutes temperature reach 280 DEG C, pressure reach 15mmHg, also slowly reduce pressure later, be finally reached 0.3mmHg.4 is little Shi Hou, will return normal pressure in system, obtains polyethylene terephthalate A1 of intrinsic viscosity 0.61.
Production Example 2 (polyethylene terephthalate A2)
Add 0.6 part of the silica dioxide granule of 2.5 μm of mean diameter in Production Example 1, it is same with Production Example 1 in addition Manufactured, obtained polyethylene terephthalate A2 of intrinsic viscosity 0.62.
Production Example 3 (polyester film F1a)
Polyethylene terephthalate A1, A2 is blended into the raw material for obtaining as table using 80%, 20% ratio respectively Layer raw material, using the raw material of polyethylene terephthalate A1=100% as the raw material in intermediate layer, supplies 2 with ventilation Mouthful extruder, extruder of the supply with vent, after 290 DEG C of melting extrusions, apply closely sealed method by table using electrostatic Face temperature is set on 40 DEG C of chill roll and cools and solidifies, and obtains the amorphous membrance of about 1300 μm of thickness.
The film is stretched into 3.5 times in the vertical at 90 DEG C, 4.1 times is stretched in the horizontal at 130 DEG C, is carried out heat at 230 DEG C Process, then, carry out 4.3% relaxation processes in the direction of the width, (thickness constitutes=2.5 μm/45 μ of ratio to obtain 50 μm of thickness M/2.5 μm) polyester film F1a.
Production Example 4 (polyester film F2a)
Polyethylene terephthalate A1, A2 is blended into the raw material for obtaining as table using 80%, 20% ratio respectively Layer raw material, using the raw material of polyethylene terephthalate A1=100% as the raw material in intermediate layer, supplies 2 with ventilation The extruder of mouth, after 290 DEG C of melting extrusions, applies closely sealed method in the chill roll that surface temperature is set as 40 DEG C using electrostatic Upper cooling and solidifying, obtains the amorphous membrance of about 740 μm of thickness.
The film is stretched into 3.5 times in the vertical at 90 DEG C, at 130 DEG C in 4.1 times of cross directional stretch, hot place is carried out at 230 DEG C Reason, then, carry out 4.3% relaxation processes in the direction of the width, obtain 50 μm of thickness (thickness constitute than=2.5 μm/45 μm/ 2.5 μm) polyester film.Then the coating that constituted is constituted by following smearss to be coated with using reverse plate gravure coating method offline Layer so that coating weight (after being dried) is 0.05g/m2, then, 30 seconds heat treatments are carried out at 120 DEG C, obtain being provided with coating layer The polyester film F2a of 50 μm of thickness.
(coating layer composition)
AC1：Colcoat N-103X (Colcoat company systems)
AC2：Aluminium tris(acetylacetonate)
AC3：Four acetylacetone,2,4-pentanedione zirconiums
AC4：Four titanium acetylacetones
(matching requirements)
Production Example 5 (polyester film F3a)
In addition to the cooperation difference of coating layer in Production Example 4, equally manufactured with Production Example 4, obtained polyester film F3a。
Production Example 6 (polyester film F4a)
In addition to the cooperation difference of coating layer in Production Example 4, equally manufactured with Production Example 4, obtained polyester film F4a。
Production Example 7 (polyester film F5a)
In addition to the cooperation difference of coating layer in Production Example 4, equally manufactured with Production Example 4, obtained polyester film F5a。
Production Example 8 (polyester film F6a)
Polyethylene terephthalate A1, A2 is blended into the raw material for obtaining as table using 80%, 20% ratio respectively Layer raw material, using the raw material of polyethylene terephthalate A1=100% as the raw material in intermediate layer, supplies 2 with ventilation The extruder of mouth, after 290 DEG C of melting extrusions, applies closely sealed method in the chill roll that surface temperature is set as 40 DEG C using electrostatic Upper cooling and solidifying, obtains the amorphous membrance of about 740 μm of thickness.
The film is stretched into 2.8 times in the vertical at 90 DEG C, 5.4 times is stretched in the horizontal at 120 DEG C, is carried out heat at 200 DEG C Process, then, carry out 4.3% relaxation processes in the direction of the width, (thickness constitutes=2.5 μm/45 μ of ratio to obtain 50 μm of thickness M/2.5 μm) polyester film.Then the coating that constituted is constituted by following smearss to be coated with using reverse plate gravure coating method offline Layer so that coating weight (after being dried) is 0.05g/m2, then, 30 seconds heat treatments are carried out at 120 DEG C, obtain being provided with coating layer The polyester film F6a of 50 μm of thickness.
(coating layer composition)
AC1：Colcoat N-103X (Colcoat company systems)
AC2：Aluminium tris(acetylacetonate)
AC3：Four acetylacetone,2,4-pentanedione zirconiums
AC4：Four titanium acetylacetones
(matching requirements)
Production Example 9 (polyester film F7a)
In addition to coating layer being not provided with Production Example 4, equally manufactured with Production Example 4, obtained polyester film F7a.
(release layer composition-A)
Curing type silicone resin
(LTC303E：Dow Corning Toray Co., Ltd. systems) 100 parts
Firming agent (SRX212：Dow Corning Toray Co., Ltd. systems) 1 part
(blending ratio is 1 to MEK/ toluene Mixed Solvents：1) 1500 parts
(release layer composition-B)
Curing type silicone resin (KS-847H：SHIN-ETSU HANTOTAI's chemistry system) 100 parts
Firming agent (PL-50T：SHIN-ETSU HANTOTAI's chemistry system) 1 part
(blending ratio is 1 to MEK/ toluene Mixed Solvents：1) 1500 parts
(release layer composition-C)
(release layer composition-D)
Embodiment 1：
The manufacture ＞ of the first mold release films of ＜
In polyester film F1a with offline using the following release layer composition-A of reverse plate gravure coating method coating so that coating weight (after drying) is 0.1g/m2, then, 30 seconds heat treatments are carried out at 120 DEG C.
(release layer composition-A)
Curing type silicone resin
(LTC303E：Dow Corning Toray Co., Ltd. systems) 100 parts
Firming agent (SRX212：Dow Corning Toray Co., Ltd. systems) 1 part
(blending ratio is 1 to MEK/ toluene Mixed Solvents：1) 1500 parts
By the personality presentation of the first mold release film derived above in table 2～4.Additionally, the embodiment numbering in table 4 is referred to Embodiment numbering (same as below) in table described later 5.
The manufacture ＞ of the second mold release films of ＜
In polyester film F2a, on coating layer with offline using reverse plate gravure coating method be coated with following release layers composition- It is 0.1g/m that D causes coating weight2(after drying), then, carries out 30 seconds heat treatments at 120 DEG C.The second resulting mold release film Personality presentation is in table 1～4.
(release layer composition-C)
Manufacture ＞s of the ＜ without base material double-sided adhesive sheet
Applied by following acrylic acid seriess with coating machine (applicator) on the release layer of the second resulting mold release film The coating fluid that adhesive composite is constituted, then carries out 5 minutes heat treatments using hot air type circulatory stove, is coated with 100 DEG C Amount (after being dried) is 50g/m2Bond layer.
＜ acrylic acid series bonding agents layer is formed and uses compositionss ＞
(monomer be combined into)
70 weight % of 2-EHA
29 weight % of acrylic acid 2- methoxy acrylates
1 weight % of acrylic acid 4- hydroxybutyls
Relative to 100 weight portion of above-mentioned monomer composition, add Japanese polyurethane CORONATE L0.1 parts, obtain propylene Acid is bond layer formation compositionss.
The rubber rollers of 2kg are then used by, are made the release layer of the first mold release film fit with bond layer, is obtained two-sided without base material Adhesive sheet.By the resulting personality presentation without base material double-sided adhesive sheet in table 5.
2～embodiment of embodiment 6 and 1～comparative example of comparative example 3：
In embodiment 1, by smearss composition, releasing agent composition, polyester film base material thickness as shown in table 2 below and table 3 Change, in addition, is manufactured similarly to Example 1, is obtained the first mold release film and the second mold release film shown in table 4.Then, Fitted across bond layer using both, obtained without base material double-sided adhesive sheet.By gained in above-described embodiment and comparative example To each mold release film and the personality presentation without base material double-sided adhesive sheet in 2～table of table 5.
[table 2]
Project Unit F1a F2a F3a F4a F5a F6a F7a
Film thickness μm 38 50 50 50 50 50 50
Longitudinal stretching multiplying power - 3.5 3.5 3.5 3.5 3.5 2.8 3.5
Longitudinal drawing temperature ℃ 90 90 90 90 90 90 90
Cross directional stretch multiplying power - 4.1 4.1 4.1 4.1 4.1 5.4 4.1
Transverse drawing temperature ℃ 130 130 130 130 130 120 130
Heat-fixing temperature ℃ 230 230 230 230 230 200 230
Relaxation rate % 4.3 4.3 4.3 4.3 4.3 4.3 4.3
The variation of the angle of orientation Degree/500mm 7 7 7 7 7 3 7
Postpone nm 1340 1620 1620 1620 1620 1860 1620
[table 3]
[table 5]
＜ the second invention ＞
Polyester used in embodiment and comparative example is to be carried out as follows the polyester for preparing to obtain.
The manufacture ＞ of ＜ polyester
Production Example 10 (polyethylene terephthalate A1)
0.09 part of 100 parts of dimethyl terephthalate (DMT), 60 parts of ethylene glycol and four acetate hydrate magnesium are taken into reactor, companion With heat temperature raising, methanol is distilled off, carries out ester exchange reaction, start to need to be warming up within 4 hours 230 DEG C from reaction, essence On terminate ester exchange reaction.Then, after adding 0.04 part of ethylene glycol slurry acid phosphate ester, 0.03 part of antimony trioxide, with Make within 100 minutes temperature reach 280 DEG C, make pressure reach 15mmHg, also slowly reduce pressure later, be finally reached 0.3mmHg.4 After hour, normal pressure will be returned in system, obtain polyethylene terephthalate A1 of intrinsic viscosity 0.61.
Production Example 11 (polyethylene terephthalate A2)
In Production Example 10, add 0.6 part of the silica dioxide granule of 2.5 μm of mean diameter, in addition, with Production Example 1 Equally manufactured, obtained polyethylene terephthalate A2 of intrinsic viscosity 0.62.
Production Example 12 (polyethylene terephthalate A3)
In Production Example 1, add 1.0 parts of the synthetic calcium carbonate particle of 0.8 μm of mean diameter, in addition, with Production Example 10 are equally manufactured, and obtain polyethylene terephthalate A3 of intrinsic viscosity 0.62.
Production Example 13 (polyester film F1b)
Polyethylene terephthalate A1, A3 is blended into the raw material for obtaining as top layer using 92%, 8% ratio respectively Polyethylene terephthalate A1, A3 is blended the raw material for obtaining as intermediate layer using 80%, 20% ratio by raw material respectively Raw material, supply 2 extruders with vent, extruder of the supply with vent, after 290 DEG C of melting extrusions, makes Apply closely sealed method with electrostatic be set as cooling and solidifying surface temperature on 40 DEG C of chill roll, obtain the nothing of about 1300 μm of thickness Setting film.
The film is stretched into 3.5 times in the vertical at 90 DEG C, 4.1 times is stretched in the horizontal at 130 DEG C, is carried out heat at 230 DEG C Process, then carry out 4.3% relaxation processes in the direction of the width, obtain 50 μm of thickness (thickness constitute than=2.5 μm/45 μm/ 2.5 μm) polyester film F1b.
Production Example 14 (polyester film F2b)
Polyethylene terephthalate A1, A3 is blended into the raw material for obtaining as top layer using 92%, 8% ratio respectively Polyethylene terephthalate A1, A3 is blended the raw material for obtaining as intermediate layer using 80%, 20% ratio by raw material respectively Raw material, supply 2 extruders with vent, after 290 DEG C of melting extrusions, apply closely sealed method by surface using electrostatic Temperature is set as cooling and solidifying on 40 DEG C of chill roll, obtains the amorphous membrance of about 740 μm of thickness.
The film is stretched into 3.5 times in the vertical at 90 DEG C, 4.1 times is stretched in the horizontal at 130 DEG C, is carried out heat at 230 DEG C Process, then, carry out 4.3% relaxation processes in the direction of the width, (thickness constitutes=2.5 μm/45 μ of ratio to obtain 50 μm of thickness M/2.5 μm) polyester film.Then, the painting that constituted is constituted by following smearss to be coated with using reverse plate gravure coating method offline Layer of cloth so that coating weight (after being dried) is 0.05g/m2, 30 seconds heat treatments are then carried out at 120 DEG C, obtain being provided with coating layer 50 μm of thickness polyester film F2b.
(coating layer composition)
AC1：Colcoat N-103X (Colcoat company systems)
AC2：Aluminium tris(acetylacetonate)
AC3：Four acetylacetone,2,4-pentanedione zirconiums
AC4：Four titanium acetylacetones
(matching requirements)
Production Example 15 (polyester film F3b)
In addition to the cooperation difference of coating layer in Production Example 14, equally manufactured with Production Example 14, obtained polyester film F3b。
Production Example 16 (polyester film F4b)
In addition to the cooperation difference of coating layer in Production Example 14, equally manufactured with Production Example 14, obtained polyester film F4b。
Production Example 17 (polyester film F5b)
In addition to the cooperation difference of coating layer in Production Example 14, equally manufactured with Production Example 14, obtained polyester film F5b。
Production Example 18 (polyester film F6b)
Polyethylene terephthalate A1, A3 is blended into the raw material for obtaining as top layer using 92%, 8% ratio respectively Polyethylene terephthalate A1, A3 is blended the raw material for obtaining as intermediate layer using 80%, 20% ratio by raw material respectively Raw material, supply 2 extruders with vent, after 290 DEG C of melting extrusions, apply closely sealed method by surface using electrostatic Temperature is set as cooling and solidifying on 40 DEG C of chill roll, obtains the amorphous membrance of about 740 μm of thickness.By the film at 90 DEG C in longitudinal direction 2.8 times of upper stretching, stretches 5.4 times in the horizontal at 120 DEG C, carries out heat treatment at 200 DEG C, then, carry out in the direction of the width 4.3% relaxation processes, obtain the polyester film of 50 μm of thickness (thickness constitutes=2.5 μm/45 μm/2.5 μm of ratio).Then, with from Line be made up of the coating layer that constitutes using the coating of reverse plate gravure coating method following smearss so that coating weight (after drying) is 0.05g/m2Afterwards, 30 seconds heat treatments are carried out at 120 DEG C, the polyester film F6b of 50 μm of thickness for obtaining being provided with coating layer.
(coating layer composition)
AC1：Colcoat N-103X (Colcoat company systems)
AC2：Aluminium tris(acetylacetonate)
AC3：Four acetylacetone,2,4-pentanedione zirconiums
AC4：Four titanium acetylacetones
(matching requirements)
Production Example 19 (polyester film F7b)
In addition to coating layer being not provided with Production Example 14, equally manufactured with Production Example 14, obtained polyester film F7b.
Production Example 20 (polyester film F8b)
In Production Example 14, top layer, the raw material cooperation in intermediate layer change as described as follows, and are not provided with coating layer, remove Beyond this, equally manufactured with Production Example 14, obtained polyester film F8b.
Top layer raw material：Obtained using polyethylene terephthalate A1, A2 is blended with 80%, 20% ratio respectively Raw material.
Intermediate layer raw material：Using the raw material of polyethylene terephthalate A1=100%.
(release layer composition-A)
Curing type silicone resin
(LTC303E：Dow Corning Toray Co., Ltd. systems) 100 parts
Firming agent (SRX212：Dow Corning Toray Co., Ltd. systems) 1 part
(blending ratio is 1 to MEK/ toluene Mixed Solvents：1) 1500 parts
(release layer composition-B)
Curing type silicone resin (KS-847H：SHIN-ETSU HANTOTAI's chemistry system) 100 parts
Firming agent (PL-50T：SHIN-ETSU HANTOTAI's chemistry system) 1 part
(blending ratio is 1 to MEK/ toluene Mixed Solvents：1) 1500 parts
(release layer composition-C)
(release layer composition-D)
Embodiment 7：
The manufacture ＞ of the first mold release films of ＜
In polyester film F1b with offline using the following release layer composition-A of reverse plate gravure coating method coating so that coating weight (after drying) is 0.1g/m2Afterwards, 30 seconds heat treatments are carried out at 120 DEG C.
(release layer composition-A)
Curing type silicone resin
(LTC303E：Dow Corning Toray Co., Ltd. systems) 100 parts
Firming agent (SRX212：Dow Corning Toray Co., Ltd. systems) 1 part
(blending ratio is 1 to MEK/ toluene Mixed Solvents：1) 1500 parts
By by the personality presentation of the first mold release film derived above in table 6～8.Additionally, the embodiment numbering in table 8 is Refer to that the embodiment in table described later 9 numbers (same as below).
The manufacture ＞ of the second mold release films of ＜
In polyester film F2b, on coating layer with offline using reverse plate gravure coating method be coated with following release layers composition- D so that coating weight is 0.1g/m2After (after drying), 30 seconds heat treatments are carried out at 120 DEG C.By the second resulting mold release film Personality presentation is in table 6～8.
(release layer composition-C)
Manufacture ＞s of the ＜ without base material double-sided adhesive sheet
On the release layer of the second resulting mold release film, applied using coating machine and combined by following acrylic acid series bonding agents After the coating fluid that thing is constituted, using hot air type circulatory stove, 5 minutes heat treatments are carried out at 100 DEG C, obtaining coating weight (after being dried) is 50 μm of bond layer.
＜ acrylic acid series bonding agents layer is formed and uses compositionss ＞
(monomer be combined into)
70 weight % of 2-EHA
29 weight % of acrylic acid 2- methoxy acrylates
1 weight % of acrylic acid 4- hydroxybutyls
Relative to 100 weight portion of above-mentioned monomer composition, add Japanese polyurethane CORONATE L0.1 parts, obtain propylene Acid is bond layer formation compositionss.
The rubber rollers of 2kg are then used by, are made the release layer of the first mold release film fit with bond layer, is obtained two-sided without base material Adhesive sheet.
8～embodiment of embodiment 12 and 4～comparative example of comparative example 7：
In embodiment 7, by smearss composition, releasing agent composition, polyester film base material thickness as shown in table 6 below and table 7 Change like that, in addition, manufactured similarly to Example 7, obtain the first mold release film and the second mold release film shown in table 8. Then, fitted across bond layer using both, obtained without base material double-sided adhesive sheet.By in above-described embodiment and comparative example Resulting each mold release film and the personality presentation without base material double-sided adhesive sheet are in 6～table of table 9.
[table 6]
Project Unit F1b F2b F3b F4b F5b F6b F7b F8b
Film thickness μm 38 50 50 50 50 50 50 38
Longitudinal stretching multiplying power - 3.5 3.5 3.5 3.5 3.5 2.8 3.5 3.5
Longitudinal drawing temperature ℃ 90 90 90 90 90 90 90 90
Cross directional stretch multiplying power - 4.1 4.1 4.1 4.1 4.1 5.4 4.1 4.1
Transverse drawing temperature ℃ 130 130 130 130 130 120 130 130
Heat-fixing temperature ℃ 230 230 230 230 230 200 230 230
Relaxation rate % 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3
The variation of the angle of orientation Degree/500mm 7 7 7 7 7 3 7 7
Postpone nm 1340 1620 1620 1620 1620 1860 1620 1340
[table 7]
[table 9]
Industrial utilizability
The static electricity resistance without base material double-sided adhesive sheet of the present invention, release property, oligomer sealing, inspection easiness are good It is good, it is suitable as such as various optics such as liquid crystal polarization plate manufacture use, touch panel member for producing of capacitance-type and uses Part.
Symbol description
10：Without base material double-sided adhesive sheet
11：Bond layer
13：First demoulding film base material
14：First coating layer
15：First releasing agent layer
23：Second demoulding film base material
24：Second coating layer
25：Second releasing agent layer
31：First mold release film (light stripping film)
32：Second mold release film (re-release piece)

Claims (2)

1. one kind is without base material double-sided adhesive sheet, it is characterised in that：
Which is in the two sides of bond layer lamination mold release film respectively, as the stripping of a mold release film of the first mold release film Peeling force of the power less than another mold release film as the second mold release film,
Second mold release film meets the condition of following (a)～(c) for recording simultaneously：
(a) its be the set coating layer containing water-disintegrable silicon compound on biaxially oriented polyester film surface be provided with it is de- The mold release film of mold layer；
B the variation of the angle of orientation in () described biaxially oriented polyester film face is 6 degree/below 500mm；
C () is 0.5mg/m by the oligomer amount extracted by dimethylformamide from the demoulding layer surface of the mold release film2Hereinafter,
The coating layer of the second mold release film contains organic compound containing metallic element,
Water-disintegrable silicon compound and the compounding ratio containing metallic element organic compound are with water-disintegrable silicon compound：Containing metallic element The weight ratio meter of organic compound, is 1：0.001～1：0.01 scope,
The film mist degree of the first mold release film is more than 6%.
2. as claimed in claim 1 without base material double-sided adhesive sheet, it is characterised in that：
Water-disintegrable silicon compound is the compound shown in following formula,
Si(OR1)x(R2)4-x
Wherein, x represents 2～4 integer, R1Represent alkyl or acyl group, R2Represent the organic group of carbon number 1～10.
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JP2012-255750 2012-11-22
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WO2014080715A1 (en) 2014-05-30

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