CN106103622B - Sticker and adhesive sheet - Google Patents
Sticker and adhesive sheet Download PDFInfo
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- CN106103622B CN106103622B CN201480077488.6A CN201480077488A CN106103622B CN 106103622 B CN106103622 B CN 106103622B CN 201480077488 A CN201480077488 A CN 201480077488A CN 106103622 B CN106103622 B CN 106103622B
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- Prior art keywords
- methyl
- sticker
- agent layer
- polymer
- adhering agent
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Abstract
The sticker of the present invention is formed by carrying out crosslinking to adherence composition, and the adherence composition contains：(methyl) acrylate polymer (A), its weight average molecular weight is 200,000~900,000, as the monomeric unit for forming polymer, containing the monomer with hydroxyl for having more than 10 mass % and below 30 mass %；Crosslinking agent (B)；And crosslinking accelerator (C), wherein, the gel fraction of the sticker is 40~90%.Both the blister resistance and segment difference tracing ability of the adhering agent layer being made up of the sticker are excellent.
Description
Technical field
The present invention relates to a kind of sticker and adhesive sheet that can be used in touch panel etc..
Background technology
In recent years, the various mobile electronic devices such as portable phone or tablet personal computer possess the display using display body module
Device, the display mould have liquid crystal cell, light-emittingdiode (LED element), organic electroluminescent (organic EL) element etc., should
The situation that display turns into touch panel also gradually increases.
In such as above-mentioned display, the face side of display body module is generally provided with protection panels.With electronics
The slimming and lightweight of equipment, above-mentioned protection panels are gradually changed to acrylic panel or polycarbonate plate from known glass plate
Deng plastic plate.
Here, space is provided between protection panels and display body module, in order to which protection panels deform because of external force
When, the protection panels deformed will not also encounter display body module.
If however, in the presence of such as above-mentioned space namely air layer, the refractive index by protection panels and air layer be present
The reflection loss of difference and air layer and light caused by the refringence of display body module becomes big, and the image quality of display reduces
The problem of.
Then, propose to have and improved aobvious by using adhering agent layer filling the space between protection panels and display body module
Show the scheme of the image quality of device.But border shape printing layer be present as segment difference in the display body module side of protection panels sometimes.If
Adhering agent layer does not follow the segment difference, then the adhering agent layer near segment difference will be caused to tilt, thus, produce the reflection loss of light.Cause
This, segment difference tracing ability is required to above-mentioned adhering agent layer.
In order to solve above-mentioned problem, there is following adhering agent layer disclosed in patent document 1, as filling protection panels and display
The adhering agent layer in the space between body module, the storage shear modulus (G ') under 25 DEG C, 1Hz are 1.0 × 105Below Pa, and
Gel fraction is more than 40%.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2010-97070 publications
The content of the invention
The technical problem to be solved in the present invention
In patent document 1, it is intended to chase after to improve segment difference by storage elastic modulus when reducing the normal temperature in adhering agent layer
It is casual.If however, storage elastic modulus when reducing normal temperature as described above, needed for storage elastic modulus during high temperature is decreased to
More than value, therefore problem is produced under the conditions of durable.For example, when applying hot and humid condition, it can produce and be produced near segment difference
Anger bubble produces the problem of bubble, tilting, stripping etc. expand because producing gas leakage from the plastic plate as protection panels.Separately
On the one hand, if making adhering agent layer become hard to improve blister resistance, segment difference tracing ability declines.
The present invention in view of such as above-mentioned actual conditions and complete, its purpose should to provide a kind of blister resistance and segment difference tracing ability
Both excellent sticker and adhesive sheet.
Solves the technological means of technical problem
To achieve these goals, first, the present invention provides a kind of sticker, and it is formed by the crosslinking of adherence composition,
The adherence composition contains：(methyl) acrylate polymer (A), its weight average molecular weight is 200,000~900,000, as structure
Into the monomeric unit of polymer, containing the monomer with hydroxyl for having more than 10 mass % and below 30 mass %；Crosslinking agent (B)；
And crosslinking accelerator (C), wherein, gel fraction is 40~90% (inventions 1).
In foregoing invention (invention 1), crosslinking agent (B) is activated by the catalytic action of crosslinking accelerator (C),
The cross-linking reaction of (methyl) acrylate polymer (A) and crosslinking agent (B) is effectively carried out, the cohesive force of the sticker obtained
Improve.With this stronger cohesive force and by by gel fraction within the above range in a manner of the sticker that is crosslinked formed
Adhering agent layer, its blister resistance is excellent, and is not easy to become really up to the mark, therefore segment difference tracing ability is also excellent.That is, according to above-mentioned hair
The sticker of bright (invention 1), balance blister resistance and segment difference tracing ability the two performances usually can be realized.
In foregoing invention (invention 1), the content of the crosslinking accelerator (C) in the adherence composition is preferred
To be 0.001~1 mass parts (invention 2) relative to the mass parts of (methyl) acrylate polymer (A) 100.
In foregoing invention (invention 1), the crosslinking accelerator (C) is preferably organo-tin compound (invention 3).
In foregoing invention (invention 1~3), in (methyl) acrylate polymer (A), as the composition polymer
Monomeric unit, preferably do not contain the monomer (invention 4) with carboxyl.
In foregoing invention (invention 1~4), the crosslinking agent (B) is preferably isocyanates crosslinking agent (invention 5).
It is poly- as this is formed in preferably described (methyl) acrylate polymer (A) in foregoing invention (invention 1~5)
The monomeric unit of compound, contain the hard monomer (invention 6) that the glass transition temperature as homopolymer is more than 70 DEG C.
It is poly- as this is formed in preferably described (methyl) acrylate polymer (A) in foregoing invention (invention 1~6)
The monomeric unit of compound, contain (methyl) 2-EHA (invention 7).
In foregoing invention (invention 1~7), preferably described adherence composition is further containing silane coupler (D) (hair
It is bright 8).
Second, the present invention provides a kind of adhesive sheet, and this kind of adhesive sheet is characterised by possessing：Two panels stripping film；And with
The adhering agent layer that the mode of the release surface contact of the two panels stripping film is clamped by the stripping film, the adhering agent layer is by described
Sticker (invention 1~8) is formed (invention 9).
In foregoing invention (invention 9), preferably described adhering agent layer be configured at two nesa coatings patterned it
Between, or (invention 10) between the nesa coating and covering material or display body module patterned.
Invention effect
The rwo is excellent for the sticker of the present invention and the blister resistance and segment difference tracing ability of adhesive sheet.
Brief description of the drawings
Fig. 1 is the sectional view of the adhesive sheet of an embodiment of the invention.
Fig. 2 is the sectional view for a configuration example for representing touch panel.
Embodiment
Hereinafter, embodiments of the present invention are illustrated.
(sticker)
The sticker of present embodiment by adherence composition (hereinafter sometimes referred to " adherence composition P ") crosslinking and
Into the adherence composition contains：(methyl) acrylate polymer (A), its weight average molecular weight are 200,000~900,000, as
The monomeric unit of polymer is formed, containing monomer (the hydroxyl list with hydroxyl for having more than 10 mass % and below 30 mass %
Body)；Crosslinking agent (B)；And crosslinking accelerator (C), the gel fraction of the sticker is 40~90%.In addition, in this specification,
(methyl) acrylic acid refers to both acrylic acid and methacrylic acid.Other similar terms are also identical.Also, also wrapped in " polymer "
Concept containing " copolymer ".
In the sticker formed by being crosslinked above-mentioned adherence composition P, crosslinking agent (B) passes through crosslinking accelerator (C)
Catalytic action and be activated, the cross-linking reaction of (methyl) acrylate polymer (A) and crosslinking agent (B) is effectively carried out.
Compound as crosslinking agent (B) has multiple functional groups in a molecule, several in a molecule in common reaction
Individual functional group does not react and remained, but due to crosslinking accelerator (C) be present, therefore can estimate in a molecule of above-claimed cpd
All functional groups can be reacted with the reactive functional groups (hydroxyl) of (methyl) acrylate polymer (A).Therefore, it is crosslinked
Structure is stronger, and the cohesive force of the sticker obtained improves.With this stronger cohesive force, and by with gel fraction upper
The blister resistance for the adhering agent layer that the sticker that mode in the range of stating is crosslinked is formed is excellent, and will not be really up to the mark, therefore segment difference
Tracing ability is also excellent.That is, the sticker according to present embodiment, can take into account the blister resistance and section for being generally in trade-off relationship
Poor tracing ability.
Therefore, as one, when the adhering agent layer being made up of above-mentioned sticker to be attached to the presence segment difference in plastic plate
During the surface of side, because adhering agent layer follows the segment difference, therefore without tilting or bubble etc. near segment difference.Also, even if
By the layered product of above-mentioned adhering agent layer and above-mentioned plastic plate be placed in it is durable under the conditions of, can also suppress to produce bubble near segment difference
Deng, and even if producing gas leakage from plastic plate, can also suppress to produce the expansion such as bubble, tilting, stripping.
(1) (methyl) acrylate polymer (A)
As the monomeric unit namely hydroxyl list that form the polymer contained by (methyl) acrylate polymer (A)
Body, for example, (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 3- hydroxyls can be enumerated
Base propyl ester, (methyl) acrylic acid 2- hydroxybutyls, (methyl) acrylic acid 3- hydroxybutyls, (methyl) acrylic acid 4- hydroxybutyls etc.
(methyl) hydroxyalkyl acrylates etc..Wherein, from the hydroxyl in (methyl) acrylate polymer (A) obtained and crosslinking
From the viewpoint of the reactivity of agent (B) and the copolymerizable of other monomers, preferred (methyl) acrylic acid 2- hydroxyethyl esters.These
Material can be used alone, and also can be combined using two or more.
As described above, in (methyl) acrylate polymer (A), as the monomer for forming the polymer, containing having more than
10 mass % and below 30 mass % hydroxyl monomeric unit.If the content of hydroxyl monomer is below 10 mass %, no
The stronger cross-linked structure can be formed, and the blister resistance of the sticker obtained is poor.On the other hand, if hydroxyl monomer
Content can not then obtain desired adherence more than 30 mass %.
Here, if touch panel etc. is placed under hot and humid environment, moisture is immersed in adhering agent layer, works as touch surface
When plate etc. reverts to normal temperature, with adhering agent layer albefaction the problem of " the damp and hot albefaction " of transparency decline.(if methyl) propylene
Acid ester polymer (A) contains hydroxyl monomer with above range, then the hydroxyl of ormal weight can be residued in adhering agent layer.Hydroxyl is
It is hydrophilic, if this hydrophily base of ormal weight is present in adhering agent layer, high temperature height is placed in even in adhering agent layer
In the case of under the conditions of wet, the compatibility for the moisture being immersed in this under the conditions of hot and humid in adhering agent layer is also good, and it is tied
Fruit, the albefaction of adhering agent layer are inhibited, and adhering agent layer wet-heat resisting albefaction is excellent.
Consider from above-mentioned viewpoint, it is excellent as the monomeric unit for forming the polymer in (methyl) acrylate polymer (A)
Choosing contains the mass % of hydroxyl monomer 12~25, particularly preferably containing 15~20 mass %.
In (methyl) acrylate polymer (A), as the monomeric unit for forming the polymer, preferably do not contain containing carboxylic
Base monomer.Carboxyl (acid) has the tendency of reduction crosslinking accelerator (C) catalytic action, but due to (methyl) acrylate polymer
(A) do not have carboxyl, therefore crosslinking accelerator (C) catalytic action can be given full play to.Also, due to (methyl) acrylate
Polymer (A) does not have a carboxyl, therefore even if the sticker obtained is attached in producing the object of unfavorable condition, example by acid
Such as, even if attaching in the case of nesa coating or metal wiring etc., the unfavorable condition as caused by acid can also be suppressed.
For example, nesa coating or metal wiring corrosion can be suppressed, or the resistance value of nesa coating is set to change.
Here, " not containing the monomer with carboxyl ", which refers to, does not contain the monomer with carboxyl actually, except being entirely free of
There is the outer of carboxyl group-containing monomer, allow not produce the catalytic action based on carboxyl reduction crosslinking accelerator (C), or not produce
The degree of a problem that nesa coating or metal wiring contains carboxyl group-containing monomer.Specifically, (methyl) acrylic acid is allowed
In ester polymer (A), as monomeric unit, containing the carboxyl group-containing monomer below 0.1 mass %, preferably comprise 0.01 mass % with
Under amount.
In (methyl) acrylate polymer (A), as the monomeric unit for forming the polymer, the carbon of alkyl is preferably comprised
Atomicity is 1~20 (methyl) alkyl acrylate.Thus, the sticker obtained, which can show that, more preferably adheres
Property.In addition, hard monomer described later removes from (methyl) alkyl acrylate.
As alkyl carbon number be 1~20 (methyl) alkyl acrylate, such as can enumerate methyl acrylate,
(methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid n-pentyl ester, (first
Base) the just own ester of acrylic acid, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid,
(methyl) acrylic acid n-dodecane ester, (methyl) tetradecyl acrylate, (methyl) acrylic acid hexadecane ester, (methyl) acrylic acid
Stearic alcohol ester etc..Wherein, from the viewpoint of further raising adherence, preferably the carbon number of alkyl is 1~8 (methyl)
Acrylate, particularly preferred (methyl) n-butyl acrylate and (methyl) 2-EHA, further preferred (first
Base) 2-EHA.By (methyl) 2-EHA, the dielectric constant of resulting sticker can be made
Reduce, and the response accuracy of touch panel can be improved.In addition, these materials can be used alone, it also can be combined and use two kinds
More than.
In (methyl) acrylate polymer (A), as the monomeric unit for forming the polymer, the carbon of alkyl is preferably comprised
Atomicity is 1~20 mass % of (methyl) alkyl acrylate 30~85, particularly preferably containing 40~75 mass %, further
Preferably contain 50~65 mass %.
Also, in (methyl) acrylate polymer (A), as the monomeric unit for forming the polymer, preferably comprise work
The hard monomer that glass transition temperature (Tg) for homopolymer is more than 70 DEG C.It is used as composition (first by containing above-mentioned hard monomer
Base) acrylate polymer (A) monomeric unit, the cohesive force of resulting sticker is further enhanced, so as to resist
Bubble property is more excellent.Particularly, when use (methyl) 2-EHA as form (methyl) acrylate polymer
(A) during monomeric unit, there is the tendency that cohesive force reduces, therefore preferably use above-mentioned hard monomer.As above-mentioned hard monomer
The glass transition temperature (Tg) of homopolymer is preferably 75~200 DEG C, particularly preferred 80~180 DEG C.
As above-mentioned hard monomer, for example, methyl methacrylate (Tg105 DEG C), isobornyl acrylate can be included
(Tg94 DEG C), isobornyl methacrylate (Tg180 DEG C), acryloyl morpholine (Tg145 DEG C), acrylic acid Buddha's warrior attendant alkyl ester (Tg115
DEG C), methacrylic acid Buddha's warrior attendant alkyl ester (Tg141 DEG C), DMAA (Tg89 DEG C), acrylamide (Tg165 DEG C) etc..This
A little materials can be used alone, and also can be combined using two or more.
In above-mentioned hard monomer, from prevent to adherence and the transparency wait other characteristics harmful effect while further send out
From the viewpoint of the performance for waving hard monomer, more preferably methyl methacrylate, isobornyl acrylate and acryloyl morpholine, especially
It is preferred that methyl methacrylate.
In (methyl) acrylate polymer (A), as the monomeric unit for forming the polymer, 10~45 matter are preferably comprised
% above-mentioned hard monomer is measured, particularly preferably containing 15~30 mass %.Pass through the above-mentioned hard monomer containing more than 10 mass %, energy
Enough improvements for expecting the blister resistance based on the monomeric unit.On the other hand, by the way that above-mentioned hard monomer is set into 45 matter
Below % content is measured, prevents the monomeric unit relative deficiency in addition in (methyl) acrylate polymer (A), can
Make obtained sticker adherence and segment difference tracing ability is excellent.
(methyl) acrylate polymer (A) as needed also contain as composition the polymer monomeric unit its
His monomer.As other monomers, in order to not damage the effect of hydroxyl monomer, preferably do not contain the functional group's with reactivity
Monomer.As the other monomers, such as (methyl) acrylic acid methoxy ethyl ester, (methyl) acrylic acid ethoxy ethyl ester etc. can be enumerated
(methyl) alkoxyalkyl acrylate, (methyl) cyclohexyl acrylate etc. has (methyl) acrylate of aliphatic ring,
(methyl) acrylic acid-N, N- dimethylaminoethyl, (methyl) acrylic acid-N, N- dimethylamino propyl ester etc. have the non-crosslinked tertiary ammonia of property
(methyl) acrylate of base, vinyl acetate, styrene etc..These materials can be used alone, also can be combined using two kinds with
On.
The polymeric species of (methyl) acrylate polymer (A) can be random copolymer, or block copolymer.
The weight average molecular weight of (methyl) acrylate polymer (A) is 200,000~900,000, preferably 300,000~800,000, especially excellent
Select 400,000~600,000.In addition, the weight average molecular weight in this specification is the polyphenyl second determined by gel permeation chromatography (GPC) method
The value of alkene conversion.
, can by the weight average molecular weight of (methyl) acrylate polymer (A) as described above than in relatively low scope
To obtain blister resistance and segment difference tracing ability the rwo excellent sticker.The weight of (if methyl) acrylate polymer (A) is equal
Molecular weight be less than 200,000, then blister resistance is poor, if the weight average molecular weight of (methyl) acrylate polymer (A) more than 900,000,
Then segment difference tracing ability is poor.
In addition, in adherence composition P, (methyl) acrylate polymer (A) can be used alone one kind, and also can be combined makes
With two or more.
(2) crosslinking agent (B)
If being crosslinked adherence composition P, crosslinking agent (B) and containing from composition (methyl) acrylate polymer (A)
The hydroxyl of carboxylic monomer is reacted.Thus, (methyl) acrylate polymer (A) is formed to be crosslinked by crosslinking agent (B)
Structure.
As crosslinking agent (B), if for (methyl) acrylate polymer (A) possessed by reactive group (as
The hydroxyl of the hydroxyl monomer of monomeric unit) reactor, for example, isocyanates crosslinking agent can be included, epoxies is handed over
Join agent, amine cross-linking agent, melamine crosslinkers, ethylene imide class crosslinking agent, hydrazine crosslinking agent, aldehyde crosslinking agent, oxazoline classes
Crosslinking agent, metal alkoxide class crosslinking agent, metal-chelating species crosslinking agent, metallic salt crosslinking agent, ammonium salt class crosslinking agent etc..It is above-mentioned
In material, preferably use with the reactive excellent of hydroxyl and the isocyanic acid of the excellent catalytic action of crosslinking accelerator (C) can be played
Esters crosslinking agent.In addition, one kind can be used alone in crosslinking agent (B), or it is applied in combination two or more.
Isocyanates crosslinking agent at least contains polyisocyanate compounds.As polyisocyanate compounds, such as can
Enumerate the aromatic poly-isocyanates such as toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, xylylene diisocyanate；Six
The aliphatic polymeric isocyanates such as methylene diisocyanate；IPDI, hydrogenated diphenyl methane diisocyanate
Deng ester ring type PIC etc.；And their biuret body, isocyanuric acid ester body；And with ethylene glycol, propane diols, new penta
The reactant of the active dydrogen compounds containing low molecule such as glycol, trimethylolpropane, castor oil namely addition product etc..Wherein, from
From the viewpoint of the reactivity of hydroxyl and the catalytic action of crosslinking accelerator (C), preferably trimethylolpropane modified aromatic adoption
Isocyanates, particularly preferred trimethylolpropane modified toluene diisocyanate.
One molecule of above-mentioned polyisocyanate compounds has multiple NCOs.In the sticker of present embodiment
In, because adherence composition P contains crosslinking accelerator (C), therefore one point of above-mentioned polyisocyanate compounds can be estimated
All NCOs possessed by son with the reactive functional groups (hydroxyl) of (methyl) acrylate polymer (A) due to reacting
And cohesive force improves, and the rwo is excellent for blister resistance and segment difference tracing ability.
The content of crosslinking agent (B) in adherence composition P is, relative to the matter of (methyl) acrylate polymer (A) 100
It is preferably 0.01~2 mass parts to measure part, particularly preferred 0.05~1 mass parts, further preferred 0.10~0.20 mass parts.If hand over
Join the content of agent (B) within the above range, then the rwo is excellent for the blister resistance and segment difference tracing ability of the sticker obtained
It is different.
(3) crosslinking accelerator (C)
Crosslinking accelerator (C) if can make crosslinking agent (B) activate, and make (methyl) acrylate polymer (A) and
The reaction efficiency of crosslinking agent (B) improves, then is not particularly limited.As crosslinking accelerator (C), such as can enumerate：Organotin
Compound；The amino-compounds such as N, N, N', N'- 4-methyl hexamethylene diamine, triethylamine, imidazoles；The metal complexs such as aluminium complex；To first
Acid catalysts such as benzene sulfonic acid, phosphoric acid, hydrochloric acid, ammonium chloride etc..Wherein, from the viewpoint of catalytic action, preferred organotin chemical combination
Thing.
As organo-tin compound, for example, can enumerate：The organo-tin compounds such as dimethyltin chloride；Tin dilaurate two
Methyl tin, two (2 ethyl hexanoic acid) stannous methides, dimethyltin diacetate, dibutyl tin laurate, oxalic acid dihexyl tin,
The soap of the organo-tin compounds such as tin dilaurate dioctyl tin；It is double (the different monooctyl ester mercaptoacetate) salt of stannous methide, two pungent
The mercaptoacetate salt of the organo-tin compounds such as double (the different monooctyl ester mercaptoacetate) salt of base tin；The metals such as octyl group acid tin, capric acid tin
Soap etc..Wherein, from the viewpoint of catalytic action, the soap of preferred organo-tin compound in above-mentioned substance, particularly preferably
Dibutyl tin laurate.In addition, crosslinking accelerator (C) can be used alone, also can be combined using two or more.
The content of crosslinking accelerator (C) in adherence composition P is, relative to (methyl) acrylate polymer (A)
100 mass parts be preferably 0.001~1 mass parts, particularly preferred 0.005~0.8 mass parts, further preferred 0.01~0.7
Mass parts.Due to crosslinking accelerator (C) content within the above range, therefore can effectively play based on crosslinking accelerator (C)
Catalytic action, and adherence will not be hindered.
(4) silane coupler (D)
Adherence composition P further preferably contains silane coupler (D).Therefore, if glass component in adherend be present, institute
The adaptation raising with the glass component of the sticker of acquisition.Also, even if adherend is plastic plate, the sticker obtained
Also improved with the adaptation of plastic plate, and blister resistance is further excellent.
It is the organo-silicon compound that intramolecular at least has an alkoxysilyl as silane coupler (D), it is excellent
Choosing is good with the compatibility of (methyl) acrylate polymer (A), and has translucency.
As the silane coupler (D), for example, can enumerate vinyltrimethoxy silane, VTES,
The silicon compound of the unsaturated groups containing polymerism such as methyl allyl acyloxypropyl trimethoxysilane, 3- glycidol ether propyl group front threes
TMOS, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane etc. have the silicon compound of epoxy construction, 3- sulfydryls third
The silication containing sulfydryl such as base trimethoxy silane, 3- Mercaptopropyltriethoxysilanes, 3- mercaptopropyi dimethoxymethylsilanes
Compound, 3- TSL 8330s, N- (2- amino-ethyls) -3- TSL 8330s, N- (2- amino second
Base) -3- amino propyl methyl dimethoxysilanes etc. contain aminosilicon compounds, 3- r-chloropropyl trimethoxyl silanes, 3- isocyanic acids
Ester propyl-triethoxysilicane, or these at least one and MTES, ethyl triethoxysilane, methyl three
Condensation product of the silicon compounds containing alkyl such as methoxy silane, ethyl trimethoxy silane etc..These materials can be used alone one kind,
Also can be combined using two or more.
The content of silane coupler (D) in adherence composition P is relative to (methyl) acrylate polymer (A) 100
Mass parts are preferably 0.01~1 mass parts, particularly preferred 0.05~0.5 mass parts, further preferred 0.1~0.3 mass parts.
(5) various additives
In adherence composition P, the various additives for being typically used as acrylic compounds sticker, example can be added as needed
Such as, reaction suppressor is refractive index adjusters, antistatic additive, tackifier, antioxidant, ultra-violet absorber, light stabilizer, soft
Agent, filler etc..
In adherence composition P in the present embodiment, pass through crosslinking accelerator (C) catalytic action, (methyl) third
Olefine acid ester polymer (A) and crosslinking agent (B) are easily reacted, therefore preferably comprise response inhabitation in order to ensure working life
Agent.
As reaction suppressor, such as acetylacetone,2,4-pentanedione, ethyl acetoacetate, ethohexadiol etc. can be enumerated, wherein, preferred acetyl
Acetone.These materials can be used alone one kind, also can be combined using two or more.In addition, above-mentioned reaction suppressor is generally in shape
The volatilization into drying process during adhering agent layer.
The content of reaction suppressor in adherence composition P is, relative to (methyl) acrylate polymer (A) 100
Mass parts are preferably 0.01~10 mass parts, particularly preferred 0.05~8 mass parts, further preferred 0.1~5 mass parts.
(6) preparation of adherence composition
(methyl) acrylate polymer (A) is prepared, and is added in (methyl) acrylate polymer (A) obtained
Crosslinking agent (B), crosslinking accelerator (C) and silane coupler (D) and additive are added as needed on, so as to prepare adhesion
Property composition P.
It polymerize the mixture for the monomeric unit for forming polymer by using common radical polymerization, so as to
Prepare (methyl) acrylate polymer (A).As needed, can be carried out using polymerization initiator and by solution polymerization process etc.
The polymerization of (methyl) acrylate polymer (A).As polymer solvent, such as ethyl acetate, n-butyl acetate, acetic acid can be enumerated
Isobutyl ester, toluene, acetone, hexane, MEK etc., also can and with two or more.
As polymerization initiator, azo compound, organic peroxide etc. can be enumerated, also can and with two or more.Make
For azo compound, for example, 2,2'- azodiisobutyronitriles, 2,2'- azos double (2- methylbutyronitriles), the double (rings of 1,1'- azos
Hexane -1- carboxylics nitrile), 2,2'- azos double (2,4- methyl pentane nitriles), the double (2,4- dimethyl -4- methoxyl groups penta of 2,2'- azos
Nitrile), dimethyl 2,2'- azos double (2 Methylpropionic acid esters), 4,4'- azos double (4- cyanopentanoic acids), double (the 2- hydroxyls of 2,2'- azos
Methyl propionitrile), 2,2'- azos double [2- (2- imidazoline -2- bases) propane] etc..
As organic peroxide, such as benzoyl peroxide can be enumerated, TBPB tertiary butyl perbenzoate, cumene peroxidating
Hydrogen, diisopropyl peroxydicarbonate, di n propyl peroxy dicarbonate, two (2- ethoxyethyl groups) peroxydicarbonates, mistake
Aoxidize the neodecanoic acid tert-butyl ester, tert-Butyl peroxypivalate, (3,5,5- trimethyl acetyls base) peroxide, peroxidating dipropyl
Acyl, diacetyl peroxide etc..
In addition, in above-mentioned polymerization process, by adding the chain-transferring agents such as 2 mercapto ethanol, obtained polymerization can be adjusted
The weight average molecular weight of thing.
If obtaining (methyl) acrylate polymer (A), added in the solution of (methyl) acrylate polymer (A)
Crosslinking agent (B), crosslinking accelerator (C) and it is added as needed on silane coupler (D), retarder thinner and additive and fully mixed
Close, the adherence composition P (coating solution) diluted so as to acquisition solvent.
As above-mentioned retarder thinner, the virtue such as aliphatic hydrocarbon, toluene, dimethylbenzene such as hexane, heptane, hexamethylene can be used
The alcohol such as the chlorinated hydrocabons such as fragrant race's hydrocarbon, dichloromethane, ethlyene dichloride, methanol, ethanol, propyl alcohol, butanol, 1- methoxy-2-propanols, third
The cellosolves such as the ester such as the ketone such as ketone, MEK, 2 pentanone, isophorone, cyclohexanone, ethyl acetate, butyl acetate, ethyl cellosolve
Class solvent etc..
Concentration, viscosity as the coating solution so prepared, as long as in the scope that can be coated with, have no special limit
System, can suitably be selected according to situation.For example, so that adherence composition P concentration is 10~60 mass % side
Formula dilutes.In addition, when obtaining coating solution, the addition of retarder thinner etc. not necessarily condition, if adherence composition P is can
Viscosity of coating etc., then it can not also add retarder thinner.In this case, adherence composition P turns into (methyl) propylene directly
Coating solution of the polymer solvent of acid ester polymer (A) as retarder thinner.
(7) preparation of sticker
The sticker of present embodiment is preferably by forming adherence composition P crosslinkings.Adherence composition P friendship
UNICOM can often be carried out by heating.In addition, when being volatilized using retarder thinner for making adherence composition P etc. dry at
Reason can double as the heating.
When being heated, heating-up temperature is preferably 50~150 DEG C, particularly preferred 70~120 DEG C.Also, heat
Time is preferably 30 seconds~10 minutes, particularly preferred 50 seconds~2 minutes.After heating, as needed, normal temperature can be configured as
During (for example, 23 DEG C, 50%RH) and the maintenance of 1~2 week or so.In the case of during needing the maintenance, during maintenance
Through forming sticker later, in the case of during maintenance, sticker is formed after heating terminates.
By above-mentioned heating (and maintenance), (methyl) acrylate polymer (A) is fully handed over via crosslinking agent (B)
Connection, and the effect can be played.
(8) gel fraction
The gel fraction of the sticker of present embodiment is 40~90%, preferably 50~85%, particularly preferred 60~80%.
If gel fraction is less than 40%, the cohesive force deficiency of sticker, so as to which blister resistance declines.On the other hand, if gel fraction
More than 90%, then adhesion strength becomes too low, and so as to which durability declines, or segment difference follows performance reduction.In addition, gel fraction
Shown in the test example of assay method as be described hereinafter.
(adhesive sheet)
As shown in figure 1, the adhesive sheet 1 of present embodiment by two panels stripping film 12a, 12b and with the two panels stripping film
The adhering agent layer 11 that the mode of 12a, 12b release surface contact is held in the two panels stripping film 12a, 12b is formed.In addition,
The release surface of stripping film in this specification refer in stripping film have fissility face, including implement lift-off processing face and
Any of the face of fissility can be also shown even if lift-off processing is not carried out.
(1) adhering agent layer
Adhering agent layer 11 is made up of the sticker, i.e., is made up of the sticker formed by being crosslinked adherence composition P.
The thickness (value determined on the basis of JIS K7130) of adhering agent layer 11 depends on segment difference highly, and preferably 10~400
μm, particularly preferred 20~300 μm, further preferred 50~250 μm.Because the thickness of adhering agent layer 11 is more than 10 μm, therefore
Good segment difference tracing ability can be played, and because the thickness of adhering agent layer 11 is less than 400 μm, therefore processability is good.Separately
Outside, adhering agent layer 11 can be formed with individual layer, also can laminated multi-layer and formed.
(2) stripping film
As stripping film 12a, 12b, it is not particularly limited and known plastic sheeting can be used.It is it is, for example, possible to use poly-
Vinyl film, polypropylene film, polybutene film, polybutadiene membrane, poly-methyl pentene film, polyvinyl chloride film, chloroethene
Alkene copolymer film, pet film, polyethylene naphthalate film, polybutylene terephthalate
Ester film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethene-(methyl) acrylic copolymer are thin
Film, ethene-(methyl) acrylate copolymer film, polystyrene film, polycarbonate film, Kapton, fluorine tree
Membrane of lipoprotein etc..And, it is possible to use their crosslinked film.Their laminate film can also be used.
Above-mentioned stripping film 12a, 12b release surface (face that particularly adhering agent layer 11 contacts) are preferably carried out at stripping
Reason.As the remover for being used in lift-off processing, for example, alcohol acids, silicone, fluorine class, unsaturated polyester (UP) class, polyene can be enumerated
The removers such as hydro carbons, wax class.In addition, in stripping film 12a, 12b, side's stripping film is preferably set to the larger re-release of peeling force
Type stripping film, the opposing party's stripping film is set to the less light exfoliated stripping film of peeling force.
On stripping film 12a, 12b thickness, there is no particular restriction, usually 20~150 μm or so.
(3) preparation of adhesive sheet
As a preparation example of adhesive sheet 1, above-mentioned adherence is coated with the release surface of a stripping film 12a (or 12b)
Composition P coating fluid, and heated so that adherence composition P crosslinkings, after coating layer is formed, make another stripping
Release surface from piece 12b (or 12a) coincides with the coating layer.In the case of during needing to conserve, during maintenance is set in advance,
In the case of during need not conserving, above-mentioned coating layer is directly becoming adhering agent layer 11.Thus, above-mentioned adhesive sheet 1 can be obtained.
Condition on heating and conserving is as described above.
As other preparation examples of adhesive sheet 1, above-mentioned adherence composition P is coated with stripping film 12a release surface
Coating fluid, and heated so that adherence composition P be crosslinked, formed coating layer, so as to obtain the stripping with coating layer
From piece 12a.Also, above-mentioned adherence composition P coating fluid is coated with another stripping film 12b release surface, and is heated
Handle so that adherence composition P crosslinkings, form coating layer, so as to obtain the stripping film 12b with coating layer.Then, will be with painting
The stripping film 12a of layer of cloth is bonded with the stripping film 12b with coating layer in a manner of two coating layers are in contact with each other.Work as needs
In the case of during maintenance, during setting maintenance in advance, in the case of during need not conserving, the coating layer of above-mentioned stacking is straight
It is connected into as adhering agent layer 11.Thus, above-mentioned adhesive sheet 1 can be obtained.According to the preparation example, even if in the thicker feelings of adhering agent layer 11
Also can stably it be prepared under condition.
As the method for the coating fluid for being coated with above-mentioned adherence composition P, such as rod coating method, scraper for coating can be utilized
Method, roller rubbing method, scraper plate rubbing method, die coating methods, gravure coating process etc..
(4) adhesion strength
Adhering agent layer 11 is laminated on the base material being made up of the pet film that thickness is 100 μm
Layered product the side of adhering agent layer 11 face, be pasted on and be provided with the nesa coating that is made up of tin-doped indium oxide (ITO)
In the case of the nesa coating of transparent conducting film, the layered product is preferably 5 to the adhesion strength of transparent conducting film
~80N/25mm, particularly preferred 10~70N/25mm, further preferred 15~50N/25mm.Because adhesion strength is in above range
It is interior, such as therefore the constituent components of touch panel can be reliably bonded.
In addition, so-called adhesion strength refers to substantially with JIS Z0237 herein：Surveyed on the basis of 2009 and by 180 ° of stripping methods
Fixed adhesion strength, determination sample is set to wide 25mm, long 100mm, by the determination sample to adherend at 0.5MPa, 50 DEG C plus
Pressure 20 minutes and after being pasted, placed 24 hours under conditions of normal pressure, 23 DEG C, 50%RH, then with peeling rate
300mm/min is measured.
(5) use of adhesive sheet
By using above-mentioned adhesive sheet 1, it is capable of the touch panel 2 of preparation example electrostatic capacitance mode as shown in Figure 2.Touch
Panel 2 is configured to possess：Display body module 3；The first film sensor 5a, it is laminated in display body module via adhering agent layer 4a
On 3；Second thin film sensor 5b, it is laminated on the first film sensor 5a via adhering agent layer 4b；Covering material 6, it is passed through
It is laminated in by adhering agent layer 11 on the second thin film sensor 5b.
Adhering agent layer 11 in above-mentioned touch panel 2 is the adhering agent layer 11 of above-mentioned adhesive sheet 1.
As above-mentioned display body module 3, such as liquid crystal (LCD) module, light-emittingdiode (LED) module, organic can be enumerated
Electroluminescent (organic EL) module, Electronic Paper etc..
Adhering agent layer 4a, 4b can be formed by the adhering agent layer 11 of above-mentioned adhesive sheet 1, also can by other stickers or
Adhesive sheet is formed.In the case of the latter, as the sticker for forming adhering agent layer 4, acrylic compounds sticker, rubber-like can be enumerated
Sticker, silicone sticker, urethane class sticker, polyesters sticker, glymes sticker etc., wherein, preferably third
Olefin(e) acid class sticker.
The first film sensor 5a and the second thin film sensor 5b generally by base film 51 and has been patterned respectively
Nesa coating 52 is formed.It is not particularly limited as base film 51, such as can be used polyethylene terephthalate thin
Film, acrylate film, polycarbonate film etc..
As nesa coating 52, such as the metals such as platinum, gold, silver, copper can be enumerated, tin oxide, indium oxide, cadmium oxide, oxygen
Change the oxides such as zinc, zinc oxide, tin-doped indium oxide (ITO), Zinc oxide doped indium oxide, Fluorin doped indium oxide, Sb doped
The composite oxides such as tin oxide, fluorine-doped tin oxide, aluminium-doped zinc oxide, chalkogenide, lanthanum hexaboride, titanium nitride, titanium carbide
Deng non-oxidized compound etc., wherein, preferably it is made up of tin-doped indium oxide (ITO).
The first film sensor 5a thin film sensor 5b of nesa coating 52 and second nesa coating 52, lead to
Often, a side forms the circuit pattern of X-direction, and the opposing party forms the circuit pattern of Y direction.
In fig. 2, the nesa coating 52 of the second thin film sensor 5b in present embodiment is located at the second film-sensing
Device 5b upside, but this is not limited to, the second thin film sensor 5a downside can also be located at.Also, in fig. 2, first
Thin film sensor 5a nesa coating 52 is located at the first film sensor 5a upside, but is not limited to this, can also position
In the first film sensor 5a downside.
Covering material 6 is generally used as main body using glass plate or plastic plate.It is not particularly limited as glass plate, such as can example
Lift chemically reinforced glass, alkali-free glass, quartz glass, soda-lime glass, containing barium strontium glass, sillico aluminate glass acid, lead glass, boron
Silicate glass, barium borosilicate glass etc..It is not particularly limited, such as can be enumerated by poly-methyl methacrylate as plastic plate
The acrylic panels of the compositions such as ester, polycarbonate plate etc..
In addition, the one or two sides of above-mentioned glass plate or plastic plate, can be set the work(such as hard conating, anti-reflection layer, antiglare layer
Ergosphere, it can also be laminated the optical modules such as hard coat film, antireflection film, antiglare film.
In present embodiment, above-mentioned covering material 6 has segment difference in the face of the side of adhering agent layer 11, specifically, have because
The presence or absence of printing layer 7 and formed segment difference.Adhering agent layer 11 side of the printing layer 7 typically in covering material 6 is formed with border shape.
The material for forming printing layer 7 is not particularly limited, the well known materials of usable printing.The thickness of printing layer 7,
It is 3~45 μm that i.e. segment difference is highly preferred, more preferably 5~35 μm, particularly preferred 7~25 μm, further preferred 7~15 μm.
Also, the thickness (segment difference height) of printing layer 7 is preferably the 3~30% of the thickness of adhering agent layer 11, particularly preferably
3.2~20%, further preferred 3.5~15%.Thus, adhering agent layer 11 easily follows the segment difference formed by printing layer 7, can
Suppress to produce near segment difference and float or bubble etc..
Hereinafter, one of the preparation method of above-mentioned touch panel 2 is illustrated.
From adhesive sheet 1 peel off a stripping film 12a, by the adhering agent layer 11 exposed with the second thin film sensor 5b
The mode that the nesa coating 52 of patterning contacts is bonded with second thin film sensor 5b.On the other hand, stripping will be arranged at
Adhering agent layer 4b on piece is in a manner of the nesa coating 52 patterned with the first film sensor 5a contacts with first
Thin film sensor 5a is bonded.
Also, the stripping film that residues on adhering agent layer 4b is peeled off, with the adhering agent layer 4b that exposes and above-mentioned second thin
(the second thin film sensor 5b base material is thin in the face of the opposite side of the side with being laminated with adhering agent layer 11 in film sensors 5b
The exposed surface of film 51) contact mode be bonded both.Thus, stripping film 12b, adhering agent layer 11, the second thin film sensor are obtained
The layered product that 5b, adhering agent layer 4b and the first film sensor 5a are stacked gradually.
Then, on the surface of the first film sensor 5a sides of above-mentioned layered product, (the first film sensor 5a base material is thin
The exposed surface of film 51), fitting is arranged at the adhering agent layer 4a on stripping film.Then, another stripping is peeled off from above-mentioned layered product
Piece 12b, the adhering agent layer 11 exposed is bonded in a manner of the side of printing layer 7 of covering material 6 contacts with the adhering agent layer 11 and covered
Cover material 6.Thus, covering material 6, adhering agent layer 11, the second thin film sensor 5b, adhering agent layer 4b, the first film is obtained to pass
The composition body that sensor 5a, adhering agent layer 4a and stripping film stack gradually.
Finally, stripping film, and the side that the adhering agent layer 4a to expose contacts with display module 3 are peeled off from above-mentioned composition body
Formula, this composition is shown consideration for together in display module 3.Thus, the touch panel 2 shown in Fig. 2 can be prepared.
In above-mentioned operation, when being bonded adhering agent layer 11 and covering material 6, because the segment difference tracing ability of adhering agent layer 11 is excellent
It is different, therefore, space is not likely to produce between the segment difference and adhering agent layer 11 formed by printing layer 7, adhering agent layer 11 can be filled out
Fill the segment difference.Also, even if touch panel 2 be placed in it is hot and humid under the conditions of in the case of, produced prevented also near segment difference
Anger bubble, tilting, stripping etc..
Also, when covering material 6 is plastic plate, gas leakage is produced from the plastic plate under the conditions of hot and humid, by
It is also excellent in the blister resistance of above-mentioned adhering agent layer 11, therefore can suppress to produce the expansion such as bubble, tilting, stripping.
Embodiments described above is recorded to be readily appreciated that the present invention, is not recorded to limit the present invention.From
And each key element purport disclosed in above-mentioned embodiment includes belonging to all design alterations of the technical scope of the present invention or equivalent
Thing.
For example, it can also omit any one in stripping film 12a, 12b in adhesive sheet 1.
Embodiment
Hereinafter, further the present invention is specifically described by embodiment etc., but the scope of the present invention does not limit
In these embodiments etc..
(embodiment 1)
The preparation of (1. methyl) acrylate copolymer
Make the mass parts of 2-EHA 62.5, the mass parts of methyl methacrylate 22.5 and acrylic acid 2- hydroxyls
The mass parts of ethyl ester 15 are copolymerized, so as to prepare (methyl) acrylate polymer (A).Should (methyl) propylene with aftermentioned method measure
The result of the molecular weight of acid ester polymer (A), weight average molecular weight (Mw) are 500,000.
2. the preparation of adherence composition
(solid constituent converts the mass parts of (methyl) acrylate polymer (A) 100 obtained in mixing above-mentioned operation (1)
Value；It is same as below), the trimethylolpropane modified toluene diisocyanate (Nippon as crosslinking agent (B)
Polyurethane Industry Co., Ltd.s system, name of product " CORONATE L ") 0.23 mass parts, as crosslinking promote
Dibutyl tin laurate (Toyokemu Co., Ltd.s system, name of product " BXX3778-10 ") 0.005 mass parts of agent (C),
3- glycidol ethers propyl trimethoxy silicane (Shin-Etsu Chemical Co., Ltd. as silane coupler (D)
System, name of product " KBM-403 ") 0.25 mass parts, the mass parts of acetylacetone,2,4-pentanedione 2.5 as reaction suppressor and it is sufficiently stirred,
And diluted with MEK, be derived from the coating solution for the adherence composition that solid component concentration is 36 mass %.
Here, the proportioning of the adherence composition is shown in table 1.In addition, the detailed content of contracted notation described in table 1 etc. is such as
Under.
[(methyl) acrylate polymer (A)]
2EHA：2-EHA
MMA：Methyl methacrylate
HEA：Acrylic acid 2- hydroxy methacrylates
3. the preparation of adhesive sheet
In a manner of dried thickness is turned into 25 μm, with knife type coater, by the adherence composition obtained
Coating solution is coated on silicone remover to carry out lift-off processing to the one side of pet film
Behind the lift-off processing face of re-release type stripping film (Lintec Corporation systems, name of product " SP-PET752150 "),
Heat 1 minute at 90 DEG C, so as to form coating layer.Similarly, in a manner of dried thickness turns into 25 μm, scraper is used
Coating machine, the coating solution of the adherence composition obtained is coated on silicone remover come to poly terephthalic acid
The one side of glycol ester film carries out light exfoliated stripping film (Lintec Corporation systems, the name of product of lift-off processing
" SP-PET382120 ") lift-off processing face after, heat 1 minute at 90 DEG C, so as to form coating layer.
Secondly, by above-mentioned the obtained re-release type stripping film with coating layer and above-mentioned obtained with the light of coating layer
Exfoliated stripping film, it is bonded in a manner of two coating layers are in contact with each other, and 7 is conserved under conditions of 23 DEG C, 50%RH
My god, thus, produce by re-release type stripping film/adhering agent layer (thickness：50 μm) composition of/light exfoliated stripping film and form
Adhesive sheet.In addition, the thickness of adhering agent layer is as foundation and using constant pressure thickness tester (TECLOCK using JIS K7130
Company Inc. systems, name of product " PG-02 ") measure value.
(embodiment 2~6, comparative example 1~2)
In addition to the combined amount of change crosslinking agent (B), crosslinking accelerator (C) and silane coupler (D) as shown in table 1,
Adhesive sheet is prepared in the same manner as example 1.
Here, the weight average molecular weight (Mw) is to determine (GPC measure) in following condition using gel permeation chromatography (GPC)
Polystyrene conversion weight average molecular weight.
＜ condition determinations ＞
GPC determines device：Tosoh Corporation systems, HLC-8020
GPC posts (pass through) in the following order：Tosoh Corporation systems
TSK guard column HXL-H
TSK gel GMHXL(×2)
TSK gel G2000HXL
Determine solvent：Tetrahydrofuran
Measurement temperature：40℃
(test example 1) (measure of adhesion strength)
Light exfoliated stripping film, and the sticker that will expose are peeled off on adhesive sheet obtained in from embodiment and comparative example
Layer fits in the pet film with adhesive layer, and (Toyobo Co., Ltd.s system, PET A4300 are thick
Degree：100 μm) adhesive layer on.The layered product is cut into width 25mm, length 100mm, as sample.From the sample
Product peel off re-release type stripping film, and the adhering agent layer exposed is attached and is provided with one side by tin-doped indium oxide (ITO) structure
Into the pet film of nesa coating (Oike Industry Co., Ltd.s system, ito thin film are thick
Degree：125 μm) nesa coating on.
Afterwards, after being placed 24 hours under conditions of normal pressure, 23 DEG C, 50%RH, cupping machine (Orientec is utilized
Company Inc. systems, Tensilon), with JIS Z0237：On the basis of 2009, in peeling rate 300mm/min, peel angle
Adhesion strength (N/25mm) is determined under conditions of 180 °.As a result shown in table 1.
(test example 2) (measure of gel fraction)
Adhesive sheet obtained in embodiment and comparative example is cut into 80mm × 80mm size, and makes the adhering agent layer
Surrounded by polyester net (size of mesh 200), and with accurate Libra come its quality of weighing, by subtracting the single matter of above-mentioned net
Amount, thus only calculate the quality of sticker.Quality now is set to M1.
Secondly, by the above-mentioned sticker surrounded by polyester net at room temperature (23 DEG C) to be impregnated in ethyl acetate 24 small
When.Then, the sticker is taken out, and is air-dried 24 hours in the environment of 23 DEG C of temperature, relative humidity 50%, and then, at 80 DEG C
Baking box in dry 12 hours.After being dried, with accurate Libra come its quality of weighing, and the single matter of above-mentioned net is subtracted
Amount, thus only calculate the quality of sticker.Quality now is set to M2.Gel fraction is represented with (M2/M1) × 100
(%).Show the result in table 1.
(test example 3) (evaluation of segment difference tracing ability)
(a) making of sample for evaluation
In glass plate (NSG Precision Company Inc. systems, name of product " Corning Glass Eagle
XG ", lengthwise 90mm × grow crosswise 50mm × thickness 0.5mm) surface, using coating thickness as any one of 5 μm, 10 μm and 15 μm,
Ultraviolet ray hardening type ink (Teikoku Ink Mfg.Co., Ltd. systems, name of product " POS-911 ink ") is (outer with border shape
Shape：Lengthwise 90mm × grow crosswise 50mm, width 5mm) carry out silk-screen printing.Secondly, irradiation ultraviolet (80W/cm2, metal halide
Two, thing lamp, lamp height 15cm, belt speed 10~15m/ minutes), make the above-mentioned ultraviolet ray hardening type ink hardening of printing, make
Go out based on printing and with segment difference (segment difference height：Any one of 5 μm, 10 μm and 15 μm) band segment difference glass plate.
Light exfoliated stripping film, and the sticker that will expose are peeled off on adhesive sheet obtained in from embodiment and comparative example
Layer fits in the pet film with adhesive layer, and (Toyobo Co., Ltd.s system, PET A4300 are thick
Degree：100 μm) adhesive layer.Then, re-release type stripping film is peeled off, appears adhering agent layer.Also, utilize laminating machine
(Fujipura Company Inc. systems, name of product " LPD3214 "), the whole printing surface of border shape is covered with adhering agent layer
Mode, above-mentioned laminate layers are pressed on each band segment difference glass plate, as sample for evaluation.
(b) evaluation of sample for evaluation
Under conditions of 50 DEG C, 0.5MPa, resulting sample for evaluation is carried out 30 minutes it is autoclave treated after, enter
One step is taken care of 72 hours under 85 DEG C, 85%RH wet heat condition.Then, confirm that adhering agent layer (particularly prints by estimating
Caused by brush layer near segment difference), and segment difference tracing ability is evaluated by following benchmark.Show the result in table 1.
◎：It is completely absent bubble, tilting and stripping.
○：Only produce a diameter of below 0.1mm bubble.
△：Produce the bubble that diameter exceedes 0.1mm, a diameter of below 0.2mm of its maximum bubble.
×：Produce bubble, tilting or stripping that diameter exceedes 0.2mm.
(test example 4) (blister resistance evaluation)
By the adhering agent layer of the adhesive sheet obtained in embodiment and comparative example, it is provided with using one side by tin-doped indium oxide
(ITO) pet film (Oike Industry Co., Ltd.s system, the ITO of the nesa coating formed
Film, thickness：125 μm) nesa coating and makrolon (PC) plate (Mitsubishi Gas Chemical Co.,
Ltd. make, IUPILON SHEET MR58, thickness：Acrylic panel 1mm) or by polymethyl methacrylate (PMMA) formed
(Mitsubishi Gas Chemical Co., Ltd.s system, IUPILON SHEET MR200, thickness：1mm) clamped,
Obtain layered product.
Under conditions of 50 DEG C, 0.5MPa, after carrying out 30 minutes autoclave process to the layered product that is obtained, normal pressure,
23 DEG C, placed 15 hours under 50%RH.Then, 85 DEG C, 85%RH it is durable under the conditions of take care of 72 hours.Thereafter, pass through
Estimate and confirm to whether there is bubble, tilting or stripping in adhering agent layer, and blister resistance have rated by following benchmark.
Show the result in table 1.
◎：It is completely absent bubble, tilting and stripping.
○：Only produce a diameter of below 0.1mm bubble.
×：Produce bubble, tilting or stripping that diameter exceedes 0.1mm.
[table 1]
As known from Table 1, the segment difference tracing ability of the adhesive sheet obtained in embodiment and blister resistance are excellent.
Industrial applicibility
The display body module that the adhesive sheet of the present invention can for example be adapted to be used in touch panel and covering with segment difference
Cover material, particularly it is bonded with plastic plate.
Description of reference numerals
1：Adhesive sheet；11：Adhering agent layer；12a、12b：Stripping film；2：Touch panel；3：Display body module；4a、4b：It is viscous
Oxidant layer；5a：The first film sensor；5b：Second thin film sensor；51：Base film；52：Nesa coating；6：Cover material
Material；7：Printing layer.
Claims (10)
1. a kind of sticker, it carries out crosslinking by adherence composition and formed, and the adherence composition contains：
(methyl) acrylate polymer (A), its weight average molecular weight is 200,000~900,000, as the monomer list for forming polymer
Member, the monomer with hydroxyl containing more than 12 mass % and below 30 mass %；
Crosslinking agent (B)；And
Crosslinking accelerator (C),
The sticker is characterised by,
Gel fraction is 40~90%.
2. sticker according to claim 1, it is characterised in that
The content of the crosslinking accelerator (C) in the adherence composition is relative to (methyl) acrylate polymer
(A) 100 mass parts are 0.001~1 mass parts.
3. sticker according to claim 1, it is characterised in that
The crosslinking accelerator (C) is organo-tin compound.
4. sticker according to claim 1, it is characterised in that
In (methyl) acrylate polymer (A), as the monomeric unit for forming the polymer, do not contain with carboxyl
Monomer.
5. sticker according to claim 1, it is characterised in that
The crosslinking agent (B) is isocyanates crosslinking agent.
6. sticker according to claim 1, it is characterised in that
In (methyl) acrylate polymer (A), as the monomeric unit for forming the polymer, containing as homopolymer
Glass transition temperature is more than 70 DEG C of hard monomer.
7. sticker according to claim 1, it is characterised in that
In (methyl) acrylate polymer (A), as the monomeric unit for forming the polymer, contain (methyl) acrylic acid
2- ethylhexyls.
8. sticker according to claim 1, it is characterised in that
The adherence composition further contains silane coupler (D).
9. a kind of adhesive sheet, it is characterised in that possess：
Two panels stripping film；And
Adhering agent layer, it is clamped in a manner of the release surface with the two panels stripping film contacts by the stripping film,
The adhering agent layer is made up of sticker according to any one of claims 1 to 8.
10. adhesive sheet according to claim 9, it is characterised in that
Transparent led for what the adhering agent layer was configured between two nesa coatings patterned or patterned
Purposes between electrolemma and covering material or display body module.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2014/059337 WO2015145771A1 (en) | 2014-03-28 | 2014-03-28 | Adhesive and adhesive sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106103622A CN106103622A (en) | 2016-11-09 |
| CN106103622B true CN106103622B (en) | 2018-03-20 |
Family
ID=54194355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480077488.6A Active CN106103622B (en) | 2014-03-28 | 2014-03-28 | Sticker and adhesive sheet |
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| JP (1) | JP6374485B2 (en) |
| KR (2) | KR102350143B1 (en) |
| CN (1) | CN106103622B (en) |
| TW (1) | TWI727920B (en) |
| WO (1) | WO2015145771A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6525726B2 (en) * | 2015-05-21 | 2019-06-05 | リンテック株式会社 | Adhesive sheet and display |
| JP6717650B2 (en) * | 2016-04-25 | 2020-07-01 | スリーエム イノベイティブ プロパティズ カンパニー | Follow-up adhesive film for application to uneven surface of decorative member and method for producing the same |
| JP7460315B2 (en) * | 2017-03-31 | 2024-04-02 | リンテック株式会社 | Adhesive compositions, adhesives and adhesive sheets |
| KR101903888B1 (en) * | 2017-05-10 | 2018-10-02 | 동우 화인켐 주식회사 | Optical Laminate and Flexible Display Comprising the Same |
| JP6534765B1 (en) * | 2018-07-24 | 2019-06-26 | グンゼ株式会社 | Adhesive sheet for image display |
| JP6497476B1 (en) * | 2018-09-20 | 2019-04-10 | 東洋インキＳｃホールディングス株式会社 | Adhesive and adhesive sheet |
| JP2020083909A (en) * | 2018-11-15 | 2020-06-04 | 王子ホールディングス株式会社 | Adhesive sheet and laminate sheet |
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| CN101313043A (en) * | 2005-11-21 | 2008-11-26 | 综研化学株式会社 | Adhesive composition for optical film, adhesive sheet, and optical member using such adhesive composition |
| CN102757752A (en) * | 2011-04-27 | 2012-10-31 | 日东电工株式会社 | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| CN103102820A (en) * | 2011-11-15 | 2013-05-15 | 日东电工株式会社 | Pressure-sensitive adhesive sheet |
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| JP4841042B2 (en) * | 2001-02-15 | 2011-12-21 | 株式会社日本触媒 | Adhesive composition and use thereof |
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| JP5649274B2 (en) * | 2007-11-07 | 2015-01-07 | 日本合成化学工業株式会社 | Adhesive for polarizing plate and polarizing plate with adhesive layer |
| JP2010097070A (en) | 2008-10-17 | 2010-04-30 | Nitto Denko Corp | Transparent pressure-sensitive adhesive sheet for flat panel display, and flat panel display |
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| TWI447192B (en) * | 2010-11-24 | 2014-08-01 | Lg Hausys Ltd | Pressure-sensitive adhesive composition for touch panel, pressure-sensitive adhesive film and touch panel |
| JP5688338B2 (en) * | 2011-07-12 | 2015-03-25 | 綜研化学株式会社 | Adhesive, adhesive sheet and laminate for touch panel |
| JP5690241B2 (en) * | 2011-08-01 | 2015-03-25 | 日本カーバイド工業株式会社 | Adhesive composition, adhesive sheet, and optical laminated sheet |
| JP5764435B2 (en) * | 2011-08-29 | 2015-08-19 | 綜研化学株式会社 | Adhesive composition, adhesive sheet and laminate for touch panel |
| JP2013127012A (en) * | 2011-12-16 | 2013-06-27 | Toyo Ink Sc Holdings Co Ltd | Adhesive, adhesive sheet and display |
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| KR101831540B1 (en) * | 2014-03-17 | 2018-04-04 | 린텍 가부시키가이샤 | Adhesive sheet and laminate |
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- 2014-03-28 CN CN201480077488.6A patent/CN106103622B/en active Active
- 2014-03-28 KR KR1020207026026A patent/KR102350143B1/en active IP Right Grant
- 2014-03-28 WO PCT/JP2014/059337 patent/WO2015145771A1/en active Application Filing
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| CN101313043A (en) * | 2005-11-21 | 2008-11-26 | 综研化学株式会社 | Adhesive composition for optical film, adhesive sheet, and optical member using such adhesive composition |
| CN102757752A (en) * | 2011-04-27 | 2012-10-31 | 日东电工株式会社 | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| CN103102820A (en) * | 2011-11-15 | 2013-05-15 | 日东电工株式会社 | Pressure-sensitive adhesive sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI727920B (en) | 2021-05-21 |
| KR20200108114A (en) | 2020-09-16 |
| JP6374485B2 (en) | 2018-08-15 |
| TW201542738A (en) | 2015-11-16 |
| CN106103622A (en) | 2016-11-09 |
| KR102350142B1 (en) | 2022-01-11 |
| JPWO2015145771A1 (en) | 2017-04-13 |
| WO2015145771A1 (en) | 2015-10-01 |
| KR20160140749A (en) | 2016-12-07 |
| KR102350143B1 (en) | 2022-01-11 |
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