CN107077801B - Sticker, adhesive sheet and display body - Google Patents
Sticker, adhesive sheet and display body Download PDFInfo
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- CN107077801B CN107077801B CN201480082732.8A CN201480082732A CN107077801B CN 107077801 B CN107077801 B CN 107077801B CN 201480082732 A CN201480082732 A CN 201480082732A CN 107077801 B CN107077801 B CN 107077801B
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- Prior art keywords
- methyl
- sticker
- agent layer
- adhering agent
- display body
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Laminated Bodies (AREA)
Abstract
A kind of sticker, it, which is used to paste, at least has the display body component parts and another display body component parts of segment difference in the face for the side that is stuck, by forming adherence composition heat cross-linking and active energy line curing, which contains sticker: containing as active energy ray-curable ingredient (B), heat cross-linking crosslinking agents (C) more than the monomeric unit for constituting polymer, the monomer containing reactive functional groups (methyl) acrylate polymer (A), two degrees of functionality;The content of ingredient (B) is the gel fraction (G1) for making the sticker and amount that will be substantially the same from the gel fraction (G2) of sticker made of the adherence composition heat cross-linking for removing ingredient (B) in adherence composition in adherence composition;It with measured length is 20mm, tensile speed is maximum stress when being extended to elongation at break for 200mm/ minutes for 2.8N or more under 23 DEG C, 50%RH environment also, when being formed with a thickness of 600 μm, the adhering agent layer that width is 10mm.
Description
Technical field
The sticker and adhesive sheet and use the adhesive sheet that the present invention relates to a kind of for pasting display body component parts
The obtained display body of adhering agent layer.
Background technique
The various mobile electron machines of recent mobile phone and tablet computer terminating machine etc., all carrying has Liquid crystal module, shines
Diode (LED component), organic electroluminescent LED (organic EL) component etc. show the display body (display that module uses
Device).
In the display, it will usually install protection panels, protection panels and display body in display body Modular surface side
Gap is equipped between module, even if protection panels is allowed to be deformed by external force, the protection panels of deformation will not touch display module.
However, the gap, even air layer exist if it exists, then there is the refractive index because of protection panels and air layer
The problem of light reflection loss caused by the refringence of difference and air layer with display module is big, and display image quality reduces.
Therefore, it is proposed to improve display by the gap for filling protection panels and display body intermodule with sticker and draw
The motion of matter.But it can become segment difference in the printing layer of the display body module side of protection panels, border shape and exist.If adhering agent layer
The segment difference is not followed, then segment difference periphery has adhering agent layer and floats, thus generates the reflection loss of light.Therefore, the sticker
Layer requires segment difference tracing ability.
To solve the above technical problems, disclosed in patent document 1 a kind of adhering agent layer its as being filled in protection panels and aobvious
The adhering agent layer for showing gap between module, in the environment of 25 DEG C, 1Hz, storage modulus (G ') is 1.0 × 105Pa is hereinafter, and glue
Solidifying part is 40% or more.
Existing technical literature
Patent document
Patent document 1: Japanese Patent Publication 2010-97070 bulletin
Summary of the invention
The technical problem to be solved in the present invention
In patent document 1, when adhering agent layer is placed in room temperature, storage modulus is low, therefore must improve segment difference tracing ability.In addition,
As other methods, considering the crosslinking degree i.e. gel fraction for having the sticker by reducing heat cross-linking type, and improve segment difference
Tracing ability.But if storage modulus or gel fraction are reduced, the epithelium strength reduction of adhering agent layer, processability is deteriorated.For example, viscous
Piece punch process when, sticker can be attached to knife face, the problems such as generating some defect of adhering agent layer.
The present invention is completed in view of above-mentioned status, and it is an object of the present invention to provide a kind of segment difference tracing ability is excellent, shows high epithelium
The sticker and adhesive sheet of intensity and the display body obtained using the adhesive sheet.
Solve the technological means of technical problem
In order to achieve the above object, first, the present invention provides a kind of sticker, which is at least being glued for pasting
The face for pasting side has a kind of display body component parts and another display body component parts of segment difference, which is characterized in that
The sticker is by forming adherence composition heat cross-linking and active energy line curing, the adherence composition
Contain: containing as the monomeric unit for constituting polymer, the monomer containing reactive functional groups (methyl) acrylate polymer
(A), active energy ray-curable ingredients (B) and thermally crosslinkable crosslinking agent (C) more than two degrees of functionality;
The content of the active energy ray-curable ingredient (B) in the adherence composition, to make the sticker
Gel fraction (G1), with the adhesion of the active energy ray-curable ingredient (B) will be removed from the adherence composition
The gel fraction (G2) of sticker made of property composition heat cross-linking is essentially identical amount;Also,
When being formed with a thickness of 600 μm, the adhering agent layer that width is 10mm, in the environment of 23 DEG C, 50%RH, with measured length
It is 200mm/ minutes for 20mm, tensile speed, maximum stress when being extended to elongation at break is 2.8N or more (invention 1).
Sticker involved in foregoing invention (invention 1) has excellent segment difference tracing ability by meeting above-mentioned condition,
And show high epithelium intensity.
In foregoing invention (invention 1), the gel fraction (G1) is preferably 40~80% (inventions 2).
In foregoing invention (invention 1,2), when being formed with a thickness of 600 μm, the adhering agent layer that width is 10mm, 23 DEG C,
It with measured length is 20mm in the environment of 50%RH, tensile speed is that elongation at break when stretching for 200mm/ minutes is preferably
1000% or more (invention 3).
In foregoing invention (invention 1~3), the weight average molecular weight of (methyl) acrylate polymer (A) is preferably 20
Ten thousand~1,000,000 (inventions 4).
In foregoing invention (invention 1~4), (methyl) acrylate polymer (A), (methyl) acrylate polymer
(A) monomer containing the reactive functional groups (hair as the monomeric unit for constituting the polymer of 5~30 mass % is preferably comprised
It is bright 5).
In foregoing invention (invention 1~5), the reactive functional groups of the preferably described monomer containing reactive functional groups are carboxyl
And/or hydroxyl, the crosslinking agent (C) are isocyanates crosslinking agent and/or epoxies crosslinking agent (invention 6).
Second, the present invention provides a kind of adhesive sheet, which has is glued by what the sticker (invention 1~6) was formed
Oxidant layer (invention 7).
In foregoing invention (invention 7), the thickness of the sticker is preferably 10~400 μm (inventions 8).
In foregoing invention (invention 7,8), the preferably described adhesive sheet has a two panels stripping film, the adhering agent layer with it is described
The mode that the release surface of two panels stripping film is in contact is clamped by the stripping film.(invention 9).
Third, the present invention provide a kind of display body, which includes
At least the side that is stuck face have segment difference a display body component parts,
Another display body component parts and
The adhering agent layer that the one display body component parts and another display body component parts are mutually pasted, it is special
Sign is,
The adhering agent layer is the adhering agent layer (invention 10) of the adhesive sheet (invention 7~9).
In foregoing invention (invention 10), the segment difference, vertical view is seen as frame-shaped (invention 11).
Invention effect
The segment difference tracing ability of the adhering agent layer of sticker and adhesive sheet according to the present invention is excellent, and shows high epithelium
Intensity.In the display body obtained from using such adhesive sheet, in the case where pasting surface side has segment difference, adhering agent layer can be chased after
With the segment difference, even if being not easy to produce gap or bubble between the segment difference and sticker after durable condition, can maintain to adhere
Oxidant layer fills up the state of the segment difference.
Detailed description of the invention
Fig. 1 is the sectional view of adhesive sheet involved in one embodiment of the present invention.
Fig. 2 is the sectional view of laminated body involved in one embodiment of the present invention.
Specific embodiment
Hereinafter, embodiments of the present invention will be described.
[sticker]
Sticker involved in present embodiment is that at least have a display of segment difference in the face for the side that is stuck for pasting
The sticker of body component parts and another display body component parts.Display body and display body component parts are described below.
The sticker of present embodiment is by handing over adherence composition (hereinafter sometimes referred to " adherence composition P ") heat
Connection and active energy line curing form, which contains:, containing as constitute polymer monomeric unit, contain
Active energy ray-curable ingredient more than (methyl) acrylate polymer (A) of reactive functional groups monomer, two degrees of functionality
(B) and thermally crosslinkable crosslinking agent (C).It is assumed that (methyl) acrylate polymer (A) passes through friendship in the sticker
Join agent (C) and be crosslinked, form space network, active energy ray-curable ingredient (B) mutually polymerize, and is wound in above-mentioned vertical
Body reticular structure.The structure is known as " structure X " sometimes below.In addition, in the present specification, so-called (methyl) acrylic acid is
Refer to both acrylic acid and methacrylic acid.Other similar term is also identical.In addition, also including " copolymer " in " polymer "
Concept.
The content of active energy ray-curable ingredient (B) in above-mentioned adherence composition P, to make involved by present embodiment
And sticker gel fraction (G1), with will remove active energy ray-curable ingredient (B) from above-mentioned adherence composition P
Adherence composition heat cross-linking after made of sticker (hereinafter sometimes referred to " sticker H ") gel fraction (G2) it is substantial
Identical amount.In addition, it is so-called herein " practically identical ", refer to that the gel fraction change rate of following presentation is 15% below
It is horizontal.
Gel fraction change rate, the gel fraction of the sticker of present embodiment is set as G1 (%), will be from adherence
The gelling portion of sticker H made of the adherence composition heat cross-linking of active energy ray-curable ingredient (B) is removed in composition P
When being divided into G2 (%), indicated by following formula.
Gel fraction change rate (%)={ (G1-G2)/G2 } × 100
For sticker involved in present embodiment, gel fraction change rate is preferably 0~15%, and particularly preferably 0
~10%, further preferably 0~4%.In addition, the measuring method of gel fraction is identical as shown in subsequent test example.
In addition, sticker involved in present embodiment, forms with a thickness of the feelings of 600 μm, the adhering agent layer that width is 10mm
Under condition, in the environment of 23 DEG C, 50%RH, when being stretched to elongation at break with measured length 20mm, tensile speed 200mm/ minutes,
Maximum stress must be 2.8N or more.The problems such as can get starved (paste and owe け) of adhering agent layer when can prevent from cutting as a result,
Epithelium intensity.From the point of view of same insight, above-mentioned maximum stress is preferably 3N or more, particularly preferably 4N or more.On the other hand, though
The upper limit of right above-mentioned maximum stress is not particularly limited, but follows segment difference from the viewpoint of rate is deteriorated, preferably 7N with
Under, particularly preferably 6N or less.In addition, the specific method of the tension test, shown in test example as be described hereinafter.The maximum stress,
It can be reached by active energy ray-curable ingredient (B) for making adherence composition P contain specified amount.
In sticker involved in present embodiment, thus it is speculated that contain active energy ray-curable ingredient by making with above-mentioned amount
(B) adherence composition P heat cross-linking and active energy line curing, be thus formed in (methyl) acrylate polymer (A) with
In the space network that crosslinking agent (C) is formed, with gel fraction essentially without the degree of variation, it is wound with the work having polymerize
The structure X of property energy line curability composition (B).X with this configuration, sticker involved in present embodiment play excellent answer
Power slackness, segment difference tracing ability also become excellent.Therefore, in the display body that at least will there is segment difference in the face for the side being stuck
When component parts and another display body component parts are pasted, sticker involved in present embodiment can follow the section well
Difference, even if being not easy to produce gap or bubble between the segment difference and sticker after defined durable condition, adhering agent layer can be tieed up
Hold the state (providing that the segment difference tracing ability after durable condition is referred to as " segment difference tracing ability " sometimes below) for filling up the segment difference.This
Outside, according to above structure X, high epithelium intensity is presented in sticker involved in present embodiment, thus, for example, adhesive sheet is rushed
When pressure processing, the problems such as sticker is attached to blade and a part of defect of adhering agent layer occurs can inhibit.
(1) (methyl) acrylate polymer (A)
(methyl) acrylate polymer (A), containing as constitute the polymer monomeric unit contain reactive functional
Single group body.Reactive functional groups from the monomer containing reactive functional groups are reacted with crosslinking agent (C), form cross-linked structure.
What (methyl) acrylate polymer (A) contained as the monomeric unit for constituting the polymer contains reactive functional
Monomer (hydroxyl monomer), intramolecular monomer with carboxyl of the intramolecular with hydroxyl is preferably listed out (containing carboxyl in single group body
Monomer), intramolecular there is monomer (emulsion stability) etc. of amino.Wherein, preferably with isocyanates crosslinking agent or epoxies
The reactivity of crosslinking agent excellent hydroxyl monomer and carboxyl group-containing monomer.
It as hydroxyl monomer, such as can enumerate: (methyl) acrylic acid 2- hydroxyl ethyl ester, (methyl) acrylic acid 2- hydroxypropyl
Ester, (methyl) acrylic acid 3- hydroxypropyl acrylate, (methyl) acrylic acid 2- hydroxy butyl ester, (methyl) acrylic acid 3- hydroxy butyl ester, (methyl) propylene
(methyl) acrylic acid hydroxy alkyl ester of sour 4- hydroxy butyl ester etc. etc..Wherein, from (methyl) acrylate polymer (A) obtained
Hydroxyl and crosslinking agent (C) reactivity and with from the point of view of the copolymerizable of other monomers, preferred (methyl) acrylic acid 2- hydroxyl ethyl ester
Or (methyl) acrylic acid 4- hydroxy butyl ester.They may be used alone, two or more kinds can also be used in combination.
It as carboxyl group-containing monomer, such as can enumerate: acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, lemon
Ethylenically unsaturated carboxylic acids such as health acid etc..Wherein, hydroxyl and crosslinking agent from (methyl) acrylate polymer (A) obtained
(C) reactivity and with from the point of view of the copolymerizable of other monomers, preferred acrylic acid.They can be used alone, can also with 2 kinds with
On be applied in combination.
It as emulsion stability, such as can enumerate: (methyl) acrylate, (methyl) acrylic acid normal-butyl ammonia
Base ethyl ester etc..They may be used alone, two or more kinds can also be used in combination.
(methyl) acrylate polymer (A) preferably comprise 5~30 mass %, particularly preferably containing 7~25 mass %, into
One step preferably comprises the monomer containing reactive functional groups as the monomeric unit for constituting the polymer of 10~20 mass %.Containing anti-
The content of answering property monomer then can ensure that crosslinking points if 5 mass % or more, form above structure X well.In addition,
If the monomer containing reactive functional groups content be 30 mass % hereinafter, if can be readily available required adherence.
(methyl) acrylate polymer (A), which contains, contains hydroxyl as the monomer containing reactive functional groups for constituting the polymer
In the case where base monomer, content is preferably 10~25 mass %, particularly preferably 15~20 mass %.In addition, (methyl) third
In the case that olefine acid ester polymer (A) contains the carboxyl group-containing monomer as the monomer containing reactive functional groups for constituting the polymer,
Its content is preferably 8~25 mass %, particularly preferably 10~15 mass %.
(methyl) acrylate polymer (A) preferably comprises the carbon of alkyl as the monomeric unit for constituting the polymer
(methyl) alkyl acrylate that atomicity is 1~20.Obtained sticker can show good adherence as a result,.This
Outside, aftermentioned hard monomer is removed from (methyl) alkyl acrylate.
Carbon atom number as alkyl is 1~20 (methyl) alkyl acrylate, such as can enumerate: acrylic acid first
Ester, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid n-pentyl ester,
(methyl) the just own ester of acrylic acid, (methyl) 2-EHA, the different monooctyl ester of (methyl) acrylate, (methyl) acrylic acid are just
Last of the ten Heavenly stems ester, (methyl) acrylic acid n-dodecane ester, (methyl) myristyl ester, (methyl) acrylic acid palm ester, (methyl) third
Olefin(e) acid stearoyl ester etc..Wherein, from the viewpoint of more improving adherence, (first that the carbon atom number of optimizing alkyl is 1~8
Base) acrylate, particularly preferred (methyl) n-butyl acrylate and (methyl) 2-EHA.They can individually make
With can also be applied in combination with two or more.
(methyl) acrylate polymer (A) preferably comprise 40~95 mass %, particularly preferably containing 50~93 mass %,
Further preferably the carbon atom number of the alkyl as the monomeric unit for constituting the polymer of 55~90 mass % is 1~20
(methyl) alkyl acrylate.
Here, in display body, when implementing high temperature and humidity condition, bubble can be generated near segment difference sometimes or from conduct
The plastic plates of protection panels generates exhaust, to the bubbling such as lead to the problem of bubble, float, peel off.On this basis, (methyl)
Acrylate polymer (A) preferably comprises the polymer monomer unit as composition, glass transition temperature as homopolymer
Spend the hard monomer of (Tg) at 70 DEG C or more.As the monomeric unit of composition (methyl) acrylate polymer (A), by containing upper
Hard monomer is stated, the cohesive force of obtained sticker is improved, and blister resistance is more preferable in display body.In particular, conduct
The monomeric unit of (methyl) acrylate polymer (A) is constituted, the glass of the homopolymers such as (methyl) 2-EHA is used
The low monomer of glass transition temperature (Tg) (such as: Tg is preferably -30 DEG C or less, particularly preferably -60 DEG C of monomers below) make
In situation as main component, because there is cohesive force downward trend, it is therefore preferable that using above-mentioned hard monomer.It is above-mentioned hard
The glass transition temperature (Tg) as homopolymer of monomer is preferably 75~200 DEG C, and particularly preferably 80~180 DEG C.In addition,
As the monomer containing reactive functional groups in (methyl) acrylate polymer (A), when using carboxyl group-containing monomer, pass through the list
Body can obtain a degree of cohesive force.Therefore, in this case, above-mentioned hard monomer is not used in most cases.
It as above-mentioned hard monomer, such as can enumerate: methyl methacrylate (Tg is 105 DEG C), isobornyl acrylate
(Tg is 94 DEG C), isobornyl methacrylate (Tg is 180 DEG C), acryloyl morpholine (Tg is 145 DEG C), acrylic acid adamantane
Ester (Tg is 115 DEG C), methacrylic acid Buddha's warrior attendant alkyl ester (Tg is 141 DEG C), dimethylacrylamide (Tg is 89 DEG C), acrylamide
(Tg is 165 DEG C) etc..They may be used alone, two or more kinds can also be used in combination.
In above-mentioned hard monomer, send out from the negative effect prevented for adherence and other equal characteristics of the transparency and further
From the viewpoint of the performance for waving hard monomer, more preferable methyl methacrylate, isobornyl acrylate and acryloyl morpholine;From
It is further reduced from the viewpoint of the reduction of segment difference tracing ability, particularly preferred isobornyl acrylate and acryloyl morpholine.
(methyl) acrylate polymer (A) preferably comprises 10~45 mass %, particularly preferably contains 15~30 mass %
The above-mentioned hard monomer as the monomeric unit for constituting the polymer.Pass through the above-mentioned hard monomer containing 10 mass % or more, energy
Enough improvements expected by the monomeric unit bring blister resistance.On the other hand, by making above-mentioned 45 matter of hard monomer
% content below is measured, then can prevent the opposite of the other monomers unit in (methyl) acrylate polymer (A) in addition to this its
Deficiency keeps the adherence of obtained sticker and segment difference tracing ability excellent.
(methyl) acrylate polymer (A) also can according to need containing as the monomeric unit for constituting the polymer
Other monomers.It is preferably reactive without having in order not to interfere the effect of the monomer containing reactive functional groups as other monomers
Functional group monomer.It as such other monomers, such as can enumerate: (methyl) methoxyethyl acrylate, (methyl)
Ethoxyethyl acrylate etc. (methyl) alkoxyalkyl acrylate;(methyl) cyclohexyl acrylate etc. has aliphatic ring
(methyl) acrylate;The tool such as (methyl) acrylic acid N, N- dimethylamino ethyl ester, (methyl) acrylic acid N, N- dimethylamino propyl ester
There is (methyl) acrylate of the tertiary amino of non-crosslinked property;Vinyl acetate, styrene etc..They can be used alone, can also
It is applied in combination with two or more.
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 preferably 200,000~1,000,000, particularly preferably 300,000~
900000, further preferably 400,000~700,000.In addition, the weight average molecular weight in this specification is to utilize gel permeation chromatography
(GPC) what is measured is converted into the value of standard polystyren.
Weight average molecular weight by making (methyl) acrylate polymer (A) is in as described above in lower range, energy
Access the superior sticker of segment difference tracing ability.(methyl) acrylate polymer (A) if weight average molecular weight more than 100
Ten thousand, it will cause segment difference tracing ability variation sometimes.On the other hand, (methyl) acrylate polymer (A) if weight average molecular weight it is small
In 200,000, then the durability that will cause sticker sometimes is deteriorated.
In addition, (methyl) acrylate polymer (A) can be used alone in adherence composition P, it can also be with 2
Kind combination of the above uses.
(2) active energy ray-curable ingredient (B)
By the active energy ray-curable that makes adherence composition P contain two degrees of functionality or more with above-mentioned additive amount at
Divide (B), so that sticker obtained from adherence composition P is solidified has excellent segment difference tracing ability, has simultaneously
There is high epithelium intensity.
Active energy ray-curable ingredient (B), as long as not interfering effect of the invention and being the photograph by active energy ray
The cured ingredient of row is injected, is just not particularly limited, is monomer, oligomer or polymer, or their mixing
Object.Wherein, preferably enumerate: the molecular weight excellent in compatibility with (methyl) acrylate polymer (A) etc. is less than 1000
Polyfunctional acrylic ester class monomer.
Polyfunctional acrylic ester class monomer as molecular weight less than 1000, such as can preferably enumerate: Isosorbide-5-Nitrae-fourth two
Alcohol two (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, poly- second two
Alcohol two (methyl) acrylate, NPGA neopentyl glycol adipate (methyl) acrylate, hydroxy new pentane acid neopentyl glycol two (methyl)
Acrylate, bicyclopentyl two (methyl) acrylate, caprolactone modification dicyclopentenyl two (methyl) acrylate, epoxy second
Alkane modified phosphate two (methyl) acrylate, two (acryloyl-oxyethyl) isocyanuric acid esters, two (first of allylation cyclohexyl
Base) acrylate, ethoxylated bisphenol a diacrylate, bis- [4- (2- acryloyloxyethoxy) phenyl] fluorenes of 9,9- etc. two
Degree of functionality acrylic ester monomer;Trimethylolpropane tris (methyl) acrylate, dipentaerythritol three (methyl) acrylate,
Propionic acid is modified dipentaerythritol three (methyl) acrylate, pentaerythrite three (methyl) acrylate, three hydroxyl of epoxy pronane modification
Modified three (the 2- (methyl) of methylpropane three (methyl) acrylate, three (acryloyl-oxyethyl) isocyanuric acid esters, 6-caprolactone
Acryloyl-oxyethyl) the three-functionality-degrees acrylic ester monomer such as isocyanuric acid ester;Two glycerol four (methyl) acrylate, season penta
The tetra functionals acrylic ester monomers such as tetrol four (methyl) acrylate;Propionic acid is modified dipentaerythritol five (methyl) acrylic acid
The five degree of functionality acrylic ester monomer such as ester;Dipentaerythritol six (methyl) acrylate, caprolactone modification dipentaerythritol six
Six degree of functionality acrylic ester monomer such as (methyl) acrylate etc..They can be used alone, can also be with two or more group
It closes and uses.
As active energy ray-curable ingredient (B), it is possible to use the esters of acrylic acid of active energy ray-curable is oligomeric
Object.The weight average molecular weight of the acrylate quasi-oligomer is preferably 50,000 or less.As such acrylate quasi-oligomer
Example, can enumerate: polyester acrylates, Epoxy Acrylates, polyurethane acrylates, polyether acrylate
Class, polybutadiene acrylic acid esters, silicon acrylate etc..
The weight average molecular weight of above-mentioned acrylate quasi-oligomer is preferably 50,000 hereinafter, particularly preferably 500~50,
000, further preferably 3,000~40,000.These acrylate quasi-oligomers can be used alone, and can also combine
Two or more is used.
In addition, also can be used to have imported in side chain has (methyl) propylene as active energy ray-curable ingredient (B)
The acrylic polymer addition product (adduct acrylate polymer) of the group of acyl group ((meta) acryloyl).
Such acrylic polymer addition product can have bridging property function by using (methyl) acrylate and intramolecular
The copolymer of the monomer of group makes the compound with the group reacted with (methyl) acryloyl group and cross-linking functional group and is somebody's turn to do
A part reaction of the cross-linking functional group of copolymer obtains.
The weight average molecular weight of above-mentioned acrylic polymer adduct is preferably 50,000~900,000 or so, particularly preferably
100000~500,000 or so.
Active energy ray-curable ingredient (B), can be oligomeric from above-mentioned polyfunctional acrylic ester class monomer, esters of acrylic acid
A kind of use is selected in object and acrylic polymer adduct, can also be used in combination of two or more, also be can be used in combination and remove
Active energy ray-curable ingredient other than this.
Active energy ray-curable ingredient (B) in adherence composition P though content as described above, but specifically, from
From the viewpoint of obtaining epithelium intensity appropriate, relative to (methyl) acrylate polymer (A) of 100 mass parts, preferably
More than 0.1 mass parts, more than particularly preferably 0.5 mass parts, more than further preferably 1 mass parts.On the other hand, Cong Benshi
It applies the gel fraction (G1) of the sticker of mode, remove active energy ray-curable ingredient (B) with to from adherence composition P
Adherence composition carry out sticker H made of heat cross-linking gel fraction (G2) it is practically identical, obtain excellent segment difference and chase after
Come from the viewpoint of casual, the content of active energy ray-curable ingredient (B), (methyl) acrylate relative to 100 mass parts
Polymer (A), preferably 4 below the mass, and more preferably 3 below the mass, and particularly preferably 2.5 below the mass, optimal
It is selected as less than 2.0 mass parts.
(3) crosslinking agent (C)
Adherence composition is crosslinked (methyl) acrylate by heating by containing thermally crosslinkable crosslinking agent (C)
Polymer (A) forms space network, improves the cohesive force of obtained sticker, and assign the sticker durability.
As above-mentioned crosslinking agent (C), as long as can be with reactive functional possessed by (methyl) acrylate polymer (A)
Group is reacted, such as can be enumerated: isocyanates crosslinking agent, epoxies crosslinking agent, amine cross-linking agent, melamine
Class crosslinking agent, aziridines crosslinking agent, hydrazine crosslinking agent, aldehyde crosslinking agent, oxazoline class crosslinking agent, the crosslinking of metal alkoxide class
Agent, metal-chelating species crosslinking agent, metallic salt crosslinking agent, ammonium salt class crosslinking agent etc..In above-mentioned crosslinking agent, (methyl) acrylic acid
, it is preferable to use the isocyanates excellent with the reactivity of hydroxyl when reactive functional groups possessed by ester polymer (A) are hydroxyl
Class crosslinking agent;, it is preferable to use with carboxyl when reactive functional groups possessed by (methyl) acrylate polymer (A) are carboxyl
The excellent epoxies crosslinking agent of reactivity.In addition, crosslinking agent (C) can be used alone, can also combine two or more makes
With.
Isocyanates crosslinking agent at least contains polyisocyanate compounds.As polyisocyanate compounds, can enumerate
Out for example: the fragrance adoption isocyanide such as toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, benzene dimethylene diisocyanate
Acid esters;The aliphatic polymeric isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated methylene diphenyld two are different
The ester ring types polyisocyanate such as cyanate;And the biuret body of these polyisocyanate compounds, isocyanuric acid ester body, Yi Jizuo
For the anti-of the active hydrogen-contg compound with the low molecular weights such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil
Answer the adduct etc. of object.Wherein, from the viewpoint of the reactivity with hydroxyl, the preferably modified fragrant adoption of trimethylolpropane
Isocyanates, the modified toluene di-isocyanate(TDI) of particularly preferred trimethylolpropane, the benzene two modified with trimethylolpropane are sub-
Methyl diisocyanate.
As epoxies crosslinking agent, can enumerate for example: 1,3- bis- (N, N'- diglycidyl aminomethyl) hexamethylene,
N, N, N', N'- four glycidyl group-m-xylene diamine, ethylene glycol diglycidylether, 1,6 hexanediol diglycidylether,
Trimethylolpropane diglycidyl ether, diglycidylaniline, diglycidyl amine etc..
The content of crosslinking agent (C) in adherence composition P, (methyl) acrylic ester polymerization relative to 100 mass parts
Object (A), preferably 0.001~2 mass parts, particularly preferably 0.01~1 mass parts, further preferably 0.02~0.3 mass
Part.When the content of crosslinking agent (C) is 0.001 mass parts or more, durability improvement effect can be assigned to obtained sticker;It hands over
Join agent (C) content be 2 below the mass when, can make crosslinking degree appropriateness, can ensure obtained sticker well
Segment difference tracing ability.
(4) various additives
Can be as needed, in adherence composition P addition be normally used for acrylic compounds sticker various additives,
Such as: silane coupling agent, Photoepolymerizationinitiater initiater, antistatic agent, tackifier, antioxidant, ultraviolet absorbing agent, light stabilizer,
Softening agent, filler, refractive index adjusters etc..
As silane coupling agent, at least there are the organo-silicon compound of 1 alkoxysilane group for intramolecular, preferably with
The good silane coupling agent of compatibility of (methyl) acrylate polymer (A).In addition, when sticker is used for optical applications, it is excellent
Select the silane coupling agent with translucency.
It as the silane coupling agent, can enumerate: vinyltrimethoxysilane, vinyltriethoxysilane, methyl
The silicon compound containing polymerism unsaturated group such as acryloyloxypropyltrimethoxysilane;3- glycidol ether oxygroup third
Base trimethoxy silane, 2- (3,4- expoxycyclohexyl) ethyl trimethoxy silane etc. have the silicon compound of epoxy construction;
3-mercaptopropyi trimethoxy silane, 3- Mercaptopropyltriethoxysilane, 3- mercaptopropyi dimethoxymethylsilane etc. contain
The silicon compound of sulfydryl;3- TSL 8330, N- (2- amino-ethyl) -3- TSL 8330,
The amino-containing silicon compounds such as N- (2- amino-ethyl) -3- aminopropylmethyldimethoxysilane;3- r-chloropropyl trimethoxyl
Silane;3- isocyanate group propyl-triethoxysilicane;Or at least one of these silane coupling agents and methyl triethoxy
The contracting of the silicon compound containing alkyl such as silane, ethyl triethoxysilane, methyltrimethoxysilane, ethyl trimethoxy silane
Close object etc..These silane coupling agents can be used alone, and can also be applied in combination with two or more.
The additive amount of silane coupling agent, relative to (methyl) acrylate polymer (A) of 100 mass parts, preferably
0.01~1.0 mass parts, particularly preferably 0.05~0.5 mass parts.
In addition, in the case where using ultraviolet light as the active energy ray for penetrating adherence composition P, adherence composition
P preferably further contains Photoepolymerizationinitiater initiater.By containing Photoepolymerizationinitiater initiater as described above, it can efficiently make active-energy
Line curability composition (B) solidification, in addition can also reduce the exposure of polymerizing curable time and active energy ray.
It as such Photoepolymerizationinitiater initiater, can enumerate: styrax, benzoin methyl ether, benzoin ethyl ether, benzoin
Isopropyl ether, benzoin n-butylether, benzoin isobutyl ether, acetophenone, dimethylamino acetophenone, 2,2- dimethoxy -2- phenyl benzene
Ethyl ketone, 2,2- diethoxy -2- phenyl acetophenone, 2- hydroxy-2-methyl -1- phenyl -propyl- 1- ketone, 1- hydroxycyclohexylphenyl
Ketone, 2- methyl-1-[4- (methyl mercapto) phenyl]-2- morpholinyl -propyl- 1- ketone, 4- (2- hydroxyl-oxethyl) phenyl-2- (hydroxyl-2-
Propyl) ketone, benzophenone, to phenyl benzophenone, 4,4'- diethylamino benzophenone, dichloro benzophenone, 2- methyl anthracene
Quinone, 2- ethyl hydrazine, 2- tert-butyl anthraquinone, 2- amino anthraquinones, 2- methyl thioxanthones, 2- ethyl thioxanthones, 2-chlorothioxanthone, 2,
4- dimethyl thioxanthone, 2,4- diethyl thioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, to dimethylamino
Benzoic ether, oligomeric [2- hydroxy-2-methyl -1 [4- (1- methyl ethylene) phenyl] acetone], 2,4,6- trimethylbenzoyl
Base-diphenyl-phosphineoxide etc..These Photoepolymerizationinitiater initiaters may be used alone, two or more kinds can also be used in combination.
Photoepolymerizationinitiater initiater, relative to the active energy ray-curable ingredient (B) of 100 mass parts, preferably with 2~15 mass
Part, particularly preferably used with the amount of the range of 4~12 mass parts.
(5) manufacture of adherence composition
Adherence composition P, can be by manufacture (methyl) acrylate polymer (A), then by obtained (methyl)
Acrylate polymer (A) is mixed with active energy ray-curable ingredient (B) and crosslinking agent (C), and is added as needed
It is prepared by additive.
(methyl) acrylate polymer (A) can will constitute the list of polymer by utilizing common radical polymerization
Body mixture polymerize to prepare.The polymerization of (methyl) acrylate polymer (A) can use polymerization initiator as needed, lead to
It crosses solution polymerization process and carries out.As polymer solvent, can enumerate: ethyl acetate, n-butyl acetate, isobutyl acetate, toluene,
Acetone, hexane, methyl ethyl ketone etc. can also use two or more side by side.
As polymerization initiator, can enumerate: azo compound, organic peroxide etc., can also side by side using 2 kinds with
On.It as azo compound, can enumerate: 2,2'- azodiisobutyronitriles, 2,2'- azo two (2- methylbutyronitrile), 1,1'-
Bis- (2, the 4- dimethyl -4- methoxies of azo two (hexamethylene -1- nitrile), 2,2'- azo two (2,4- methyl pentane nitrile), 2,2'- azo
Base valeronitrile), dimethyl 2,2'- azo bis- (2 Methylpropionic acid esters), 4,4'- azo two (4- cyanopentanoic acid), 2,2'- azo two
(2- hydroxymethyl propionitrile), 2,2'- azo two [2- (2- imidazoline -2- base) propane] etc..
It as organic peroxide, can enumerate: benzoyl peroxide, t-butyl perbenzoate, cumyl hydroperoxide, mistake
Aoxidize two diisopropyl carbonates, diη-propyl peroxy dicarbonate, two (2- ethoxyethyl group) peroxy dicarbonates, tertiary fourth
Base new decanoate ester peroxide, t-butylperoxy pivarate, (3,5,5- trimethyl acetyl base) peroxide, peroxidating dipropyl
Acyl, diacetyl peroxide etc..
In addition, by chain-transferring agents such as addition 2 mercapto ethanols, can adjust obtained polymer in above-mentioned polymerization process
Weight average molecular weight.
If obtaining (methyl) acrylate polymer (A), by the solution of (methyl) acrylate polymer (A)
Active energy ray-curable ingredient (B), crosslinking agent (C) and additive as needed are added, and is sufficiently mixed, is adhered
Property composition P.
(6) manufacture of sticker
By carrying out heat cross-linking, and pass through work after above adherence composition P to be coated on to desired object
The irradiation of property energy line is solidified (active energy line curing), to obtain sticker involved in present embodiment.
The heat cross-linking of adherence composition P, can be carried out by heat treatment.The heat treatment can also adhere in coating
It is carried out simultaneously in drying process after property composition P.The heating temperature of heat treatment, preferably 50~150 DEG C, particularly preferably
It is 70~120 DEG C.In addition, heating time is preferably 10 seconds~10 minutes, particularly preferably 50 seconds~2 minutes.
Here, so-called active energy ray, refers to the active-energy in electromagnetic wave or charged particle beam with the quanta of energy
Line specifically can enumerate ultraviolet light or electron beam etc..In active energy ray, particularly preferred maneuverable ultraviolet light.
Ultraviolet irradiation can be carried out using high-pressure sodium lamp, Fusion H lamp, xenon lamp etc., and ultraviolet irradiation amount is excellent
Selecting illumination is 50~1000mW/cm2Left and right.In addition, light quantity is preferably 50~10000mJ/cm2, more preferably 80~5000mJ/
cm2, particularly preferably 200~2000mJ/cm2.On the other hand, electron-beam accelerator etc. can be used to carry out for the irradiation of electron beam, electricity
The exposure of beamlet is preferably 10~1000krad or so.
If heat adherence composition P, (methyl) acrylate polymer (A) is reacted with crosslinking agent (C), is formed
Cross-linked structure, i.e. space network.In addition, if irradiating active energy ray, active energy line curing to adherence composition P
Property ingredient (B) polymerize, solidified while being wound in above-mentioned space network.Involved by such obtained present embodiment
And sticker, segment difference tracing ability is good, and high epithelium intensity is presented.
In addition, active energy ray can be irradiated after being heated when manufacturing the sticker of present embodiment, it can also
Both processing are carried out simultaneously.Additionally, it is preferred that after a heating treatment or irradiation active energy ray after, room temperature (such as: 23 DEG C,
1~2 week or so curing period, was set under 50%RH).
(7) gel fraction
The gel fraction (G1) of sticker involved in present embodiment is preferably 40~80%, particularly preferably 45~
70%, further preferably 50~65%.If gel fraction (G1) is 40% or more, it can ensure the epithelium of sticker well
Intensity.In addition, if gel fraction (G1) be 80% hereinafter, if can ensure the segment difference tracing ability of sticker well.
(8) elongation at break
Sticker involved in present embodiment, in the case where the adhering agent layer for being made 600 μm of thickness, width 10mm, preferably
In 23 DEG C, the environment of 50%RH, elongation at break when being extended with length 20mm, tensile speed 200mm/ minutes be 1000% with
On, particularly preferably 1100~4000%, further preferably 1200~2500%.In addition, the specific method of the stretching experiment,
As shown in subsequent test example.
Sticker involved in present embodiment, by by the adherence composition P heat cross-linking and active energy ray
Curability forms, to reach above-mentioned elongation at break.By keeping elongation at break larger as described above, so that the section of sticker
Poor tracing ability is more excellent.
(9) segment difference follows rate
Sticker involved in present embodiment, following rate (%) with segment difference shown in following formula is preferably 20% or more,
Particularly preferably 25~80%, further preferably 30~70%.
Segment difference follow rate (%)=(after defined durable test, maintenance be filled and the section of seamless or bubble state
The height (μm) of difference)/(thickness of adhering agent layer) } × 100
In addition, segment difference follows the test method of rate, as shown in the test example described below.
Sticker involved in present embodiment, it is solid by the adherence composition P heat cross-linking and active energy ray
Change, big segment difference can be reached as described above and follow rate.
[adhesive sheet]
As shown in Figure 1, adhesive sheet 1 involved in present embodiment, by two panels stripping film 12a, 12b, and with two panels
The mode of the removing face contact of stripping film 12a, 12b is constituted by two panels stripping film 12a, the 12b adhering agent layer 11 clamped.This
Outside, the release surface of the stripping film in this specification, refer in stripping film with fissility face, the face being release-treated and
Though not being release-treated but the face with fissility being all included.
(1) adhering agent layer
The adhering agent layer 11 of adhesive sheet 1 is formed by the sticker, i.e., by by adherence composition P heat cross-linking and activity
Sticker made of energy line curing is formed.
The thickness (value measured according to JIS K7130) of adhering agent layer 11, preferably 10~1000 μm, more preferably 30
~400 μm, particularly preferably 50~300 μm.In addition, adhering agent layer 11 can be formed by single layer, can also laminated multi-layer and formed.
If the thickness of adhering agent layer 11 less than 10 μm, can not obtain sufficient segment difference tracing ability sometimes.On the other hand, if
Adhering agent layer 11 with a thickness of 1000 μm hereinafter, then processability is good.
(2) stripping film
It as stripping film 12a, 12b, can enumerate: polyethylene film, polypropylene screen, polybutene film, polybutadiene film, poly- first
Base amylene film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, gathers polychloroethylene film
Butylene terephthalate film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethylene-(methyl) acrylic acid are total
Polymers film, ethylene-(methyl) acrylate copolymer film, polystyrene film, polycarbonate membrane, polyimide film, fluororesin film
Deng.In addition, it is possible to use the cross linking membrane of above-mentioned film.Further, or the stacked film of above-mentioned film.
It is preferred that the release surface (face especially contacted with adhering agent layer 11) to above-mentioned stripping film 12a, 12b is implemented at removing
Reason.It as the remover for being used for lift-off processing, can enumerate: alcohol acids, silicone, fluorine class, unsaturated polyester (UP) class, polyolefin
The remover of class, wax class.In addition, in stripping film 12a, 12b, preferably by a stripping film be set as peeling force it is big re-release type
Another stripping film is set as the small light exfoliated stripping film of peeling force by stripping film.
Although the thickness of stripping film 12a, 12b are not particularly limited, generally 20~150 μm or so.
(3) manufacture of adhesive sheet
Above-mentioned adhesion is coated in the release surface of a stripping film 12a (or 12b) as a Production Example of adhesive sheet 1
Property composition P coating fluid, then coating layer is heated, while by adherence composition P heat cross-linking, irradiation activity
Energy line solidifies adherence composition P, and forms adhering agent layer 11.It is another in being overlapped on as formed adhering agent layer 11
The release surface of one stripping film 12b (or 12a), as adhesive sheet 1.It, can also be in addition, the irradiation of above-mentioned active energy ray
Heat cross-linking is carried out to the coating layer of adherence composition P, and is overlapped the stripping of another stripping film 12b (or 12a) on the coating layer
It is carried out from after face.
As another Production Example of adhesive sheet 1, in being coated with above-mentioned adherence composition in the release surface of a stripping film 12a
The coating fluid of P, heats coating layer, while by adherence composition P heat cross-linking, irradiates active energy ray, makes
Adherence composition P solidification, forms the first adhering agent layer.In addition, in being coated with above-mentioned adhesion in the release surface of another stripping film 12b
Property composition P coating fluid, coating layer is heated, while by adherence composition P heat cross-linking, irradiation activity
Energy line solidifies adherence composition P, forms the second adhering agent layer.Then, make the stripping film with the first adhering agent layer
The 12a and stripping film 12b for having the second adhering agent layer, pastes in such a way that two adhering agent layers are in contact with each other, as adhesion
Piece 1.Alternatively, it is also possible to make it be in contact with each other by the stage before each coating layer heat cross-linking, unify to irradiate active energy later
Line is measured, and obtains adhesive sheet 1, rather than obtains adhesive sheet 1 after the first adhering agent layer and the second adhering agent layer are respectively formed.
As the method for the coating fluid for being coated with above-mentioned adherence composition P, such as it can use stick rubbing method, blade coating
Method, roller coating method, plate rubbing method, die coating methods, gravure coating method etc..Heating for the adherence composition P being coated with
The condition of processing is as described above.
In above adhesive sheet 1, since the segment difference tracing ability of adhering agent layer 11 is excellent, it is pasted on tool segment difference
After display body component parts, even in defined durable condition, being also not easy to produce between the segment difference and adhering agent layer 11
Raw gap or bubble, adhering agent layer 11 can fill up the segment difference.In addition, the epithelium intensity due to adhering agent layer 11 is high, example
Such as, when carrying out punch process to adhesive sheet 1, sticker can be inhibited to be attached to blade and a part of adhering agent layer 11 is caused to be owed
The generation for the problems such as lacking.
(4) haze value
Mist degree (Haze) value of adhering agent layer 11 involved in present embodiment (is measured according to JIS K7136:2000
Value) it is preferably 3% hereinafter, particularly preferably 2% hereinafter, further preferably 1% or less.If haze value be 3% hereinafter, if thoroughly
Bright property is very high, is suitable for optical applications.
(5) adhesion strength
The adhesive sheet 1 of present embodiment, in order to which good segment difference tracing ability, adhesion strength can also be played after durable condition
(value measured according to JIS Z0237:2009) is preferably 5N/25mm or more, more preferably 10N/25mm or more, particularly preferably
For 25N/25mm or more.In addition, above-mentioned bonding force is preferably 50N/25mm from the viewpoint of assigning 1 re-workability of adhesive sheet
Hereinafter, more preferably 40N/25mm is hereinafter, particularly preferably 35N/25mm or less.In addition, the test method of adhesion strength is detailed
Situation, as described in test example.
[display body]
As shown in Fig. 2, display body 2 involved in present embodiment, by including: that at least there is section in the face for the side that is stuck
The the first display body component parts 21 (a display body component parts) and 22 (another display body of the second display body component parts of difference
Component parts), and between the first display body component parts 21 and the second display body component parts 22, for by the two
The adhering agent layer 11 pasted each other and be configured.In the display body 2 involved in present embodiment, the first display body component parts
21, there is segment difference in the face of 11 side of adhering agent layer, specifically, segment difference caused by having because of printing layer 3.
It as display body 2, can enumerate: liquid crystal (LCD) display, light emitting diode (LED) display, organic electroluminescence hair
Light (organic EL) display, Electronic Paper etc., or touch panel.
First display body component parts 21, other than glass plate, plastic plate, preferably by the laminated body including the two
Etc. compositions protection board.Under such circumstances, it is however generally that, printing layer 3 is in the adhering agent layer of the first display body component parts 21
11 sides are formed as frame-shaped.
Second display body component parts 22, preferably show module (such as: liquid crystal (LCD) module, light emitting diode
(LED) module, organic electroluminescent (organic EL) module etc.) or part of it (such as: the optical components such as polarizing film).
As above-mentioned glass plate, be not particularly limited, can enumerate: chemically reinforced glass, alkali-free glass, quartz glass,
Soda-lime glass, containing barium strontium glass, alumina silicate glass, lead glass, pyrex, barium borosilicate glass etc..Although glass
The thickness of plate is not particularly limited, but generally 0.1~5mm, preferably 0.2~2mm.
It as above-mentioned plastic plate, is not particularly limited, can enumerate: acrylic panel, polycarbonate plate etc..The thickness of plastic plate
Degree, is not particularly limited, but generally 0.2~5mm, preferably 0.4~3mm.
In addition, various functions layers (transparent conductive film, metal can be equipped in the single or double of above-mentioned glass plate or plastic plate
Layer, silicon dioxide layer, hard conating, antiglare layer etc.), it can also laminated optical member.In addition, transparent conductive film and metal layer can also quilts
Patterning.
It as above-mentioned optical component, can enumerate: polarizing film (polarizing coating), polaroid, phase plate (phase difference film), view
Angle compensation film, brightness enhancement film, contrast enhance film, liquid crystalline polymer film, diffusion barrier, hard coating film, Transflective film etc..
The material for constituting printing layer 3, is not particularly limited, the well known material of usable printing.The thickness of printing layer 3
Degree, that is, the highly preferred of segment difference is 3~45 μm, particularly preferably 5~35 μm, further preferably 7~25 μm, most preferably 7
~15 μm.
For manufacturing above-mentioned display body 2, as an example, initially, adhesive sheet 1 is cut into and is constituted with the first display body
Component 21 and the corresponding size of the second display body component parts 22.In cutting, the thickness direction of adhesive sheet 1 can all be cut
It is disconnected, another stripping film 12b of adhesive sheet 1 can not also be truncated, and adhering agent layer 11 and a stripping film 12a are partly cut.This
When, since the epithelium intensity of adhering agent layer 11 is high, it can restrain and adhering agent layer 11 occurs because sticker is adhered to blade
The problem of a part of defect.
Then, after the stripping film 12a removing of adhesive sheet 1, the adhering agent layer 11 of the exposing of adhesive sheet 1 is pasted on the
The face of side existing for the printing layer 3 of one display body component parts 21.Later, it is removed from the adhering agent layer 11 of adhesive sheet 1 another
A stripping film 12b pastes the adhering agent layer 11 of the exposing of adhesive sheet 1 and the second display body component parts 22.
In above-mentioned operation, when pasting adhering agent layer 11 and the first display body component parts 21, due to the section of adhering agent layer 11
Poor tracing ability is good, therefore, even if being also not easy after defined durable condition in the segment difference and adhesion formed by printing layer 3
Gap is generated between oxidant layer 11, adhering agent layer 11 can fill up the segment difference.
Embodiments described above, be for easy understanding the present invention and record, and be not in order to limit the present invention
And record.Therefore, each element disclosed in above embodiment, also to include all of term technical scope of the invention
The meaning of design alteration or equivalent.
For example, it is also possible to omit any one in stripping film 12a, 12b of adhesive sheet 1.In addition, the first display body is constituted
Component 21 can have the segment difference other than printing layer 3, can also not have segment difference.It further, can also be with not only the first display body
Component parts 21, and the second display body component parts 22 also has segment difference in 11 side of adhering agent layer.
Embodiment
The present invention will be described in more detail by embodiment etc., but the scope of the present invention and be not limited below
In these embodiments etc..
[embodiment 1]
The preparation of (1. methyl) acrylate polymer
90 mass parts of n-butyl acrylate and 10 mass parts of acrylic acid are copolymerized, (methyl) acrylate polymer is prepared
(A), using aftermentioned method measurement should (methyl) acrylate polymer (A) molecular weight as a result, weight average molecular weight (Mw)
It is 400,000.
2. the preparation of adherence composition
100 mass parts of (methyl) acrylate polymer (A) obtained in above-mentioned operation (1) (are converted into solid component
Value;It is same as below), with three (acrylyl oxy-ethyl) isocyanuric acid esters as active energy ray-curable ingredient (B)
(TOAGOSEI CO., LTD. manufacture, name of product " M-315 ") 0.1 mass parts and the crosslinking agent (C) as epoxies
1,3- bis- (N, N- diglycidyl aminomethyl) hexamethylene (MITSUBISH GAS CHEMICAL COMPANY, INC. manufacture,
Name of product " TETRAD-C ", solid component concentration: 100 mass %) 0.05 mass parts and as silane coupling agent 3- shrink
Glyceryl etheroxypropyltrimethoxysilane (SHIN-ETSU CHEMICAL CO., LTD. manufacture, name of product " KBM-403 ")
The mixing of 0.2 mass parts, then the quality of the 10 mass % to be equivalent to (B) ingredient add the 1- hydroxyl ring as Photoepolymerizationinitiater initiater
Hexyl phenyl ketone (BASF AG's manufacture, name of product " IRGACURE184 "), is diluted after being sufficiently stirred with methyl ethyl ketone, thus
To the coating solution for the adherence composition that solid component concentration is 37 mass %.
Here, the mixed proportion of the adherence composition is as shown in table 1.In addition, the detailed feelings such as documented code name in table 1
Condition is as follows.
[(methyl) acrylate polymer]
BA: n-butyl acrylate
AA: acrylic acid
2EHA: acrylic acid-2-ethyl caproite
MMA: methyl methacrylate
HEA: 2-Hydroxy ethyl acrylate
IBXA: isobornyl acrylate
ACMO: acryloyl morpholine
VAc: vinyl acetate
[active energy ray-curable ingredient]
M-315: three (acryloyl-oxyethyl) isocyanuric acid esters (TOAGOSEI CO., LTD. manufacture, name of product " M-
315”)
A-400: polyethyleneglycol diacrylate (SHIN-NAKAMURA CHEMICAL CO., LTD. manufacture, name of product
" A-400 ", the molecular weight of polyethylene glycol: 400)
A-TMM-3: pentaerythritol triacrylate (SHIN-NAKAMURA CHEMICAL CO., LTD. manufacture, ProductName
Claim " A-TMM-3 ")
A-DPH: dipentaerythritol hexaacrylate (SHIN-NAKAMURA CHEMICAL CO., LTD. manufacture, ProductName
Claim " A-DPH ")
[crosslinking agent]
(N, the N'- diglycidyl aminomethyl) hexamethylene of epoxy -1:1,3- two (MITSUBISH GAS CHEMICAL
COMPANY, INC. manufacture, name of product " TETRAD-C ")
Epoxy -2:N, N, N', N'- four glycidyl group-m-xylene diamine (MITSUBISH GAS CHEMICAL
COMPANY, INC. manufacture, name of product " TETRAD-X ")
Isocyanates: modified toluene di-isocyanate(TDI) (the SOKEN CHEMICAL&ENGINEERING of trimethylolpropane
CO., LTD. is manufactured, name of product " L-45 ")
3. the manufacture of adhesive sheet
Lift-off processing is carried out using silanes remover to the single side of polyethylene terephthalate film, formation re-releases type
Stripping film (LINTEC CORPORATION manufacture, name of product " SP-PET752150 "), using scraping on its lift-off processing face
Knife coating machine is coated with the coating solution of obtained adherence composition.In addition, heating 2 points at 100 DEG C to coating layer
Zhong Hou, under it is following under conditions of irradiate ultraviolet light, the first adhering agent layer with a thickness of 25 μm is consequently formed.
[ultraviolet light irradiation condition]
Light source: high-pressure sodium lamp
Light quantity: 500mJ/cm2
Illumination: 200mW/cm2
In addition, illumination and light quantity are according to EYE GRAPHICSCO., UV illumination-quantometer " UVPF-36 " of LTD. manufacture
Confirmed.
Similarly, the single side of polyethylene terephthalate film is removed using silanes remover, forms light stripping
Release stripping film (LINTEC CORPORATION manufacture, name of product " SP-PET382120 ") is sharp on its lift-off processing face
The coating solution of obtained adherence composition is coated with knife type coater.In addition, heating at 100 DEG C to coating layer
After 2 minutes, as described above, ultraviolet light is irradiated, the second adhering agent layer with a thickness of 25 μm is consequently formed.
Then, by obtain among the above with the first adhering agent layer re-release type stripping film, with obtaining among the above
Light exfoliated stripping film with the second adhering agent layer, is pasted in such a way that two adhering agent layers are in contact with each other, and is made by weight
The adhesive sheet that exfoliated stripping film/adhering agent layer (thickness: 50 μm)/light exfoliated stripping film structure is formed.In addition, sticker
The thickness of layer is according to JIS K7130, and using constant pressure thickness measuring instrument, (TECLOCK CORPORATION is manufactured, name of product
" PG-02 ") value that is measured.
[embodiment 2~17, comparative example 1~4]
Ratio, (methyl) acrylate polymer in addition to each monomer of (methyl) acrylate polymer (A) will be constituted
(A) type of weight average molecular weight, active energy ray-curable ingredient (B) and the type and addition of additive amount, crosslinking agent (C)
Other than the additive amount of amount and silane coupling agent changes as shown in table 1, manufacture adhesion according to the same manner as in Example 1
Piece.In addition, comparative example 1 and 4 is without ultraviolet treatment with irradiation.
Here, above-mentioned weight average molecular weight (Mw) is measured under the following conditions using gel permeation chromatography (GPC)
The weight average molecular weight for being converted into polystyrene of (GPC measurement).
< determination condition >
GPC measurement device: TOSOH CORPORATION manufacture, HLC-8020
GPC column (passes through) according to following sequence: TOSOH CORPORATION manufacture
TSK guard column HXL-H
TSK gel GMHXL(×2)
TSK gel G2000HXL
Measure solvent: tetrahydrofuran
Measuring temperature: 40 DEG C
[test example 1] (measurement of adhesion strength)
Light exfoliated stripping film is peeled from adhesive sheet obtained in embodiment and comparative example, by the adhering agent layer of exposing
Being pasted on the polyethylene terephthalate film with adhesive layer, (TOYOBO CO., LTD. manufacture, PET A4300 are thick
Degree: 100 μm) adhesive layer.The laminated body is cut into the size of wide 25mm, length 100mm, as sample.From the sample
On peel and re-release type stripping film, the adhering agent layer of exposing be pasted on soda-lime glass (NIPPON SHEET GLASS CO.,
LTD. it manufactures).
Later, after being placed 24 hours under conditions of normal pressure, 23 DEG C, 50%RH, on the basis of JIS Z0237:2009,
Peeling rate 300mm/min, under conditions of 180 ° of peel angle, using measurer for pulling force (ORIENTEC CO., LTD. manufacture,
Name of product " TENSILON ") test adhesion strength (N/25mm).The results are shown in Table 2.
[test example 2] (measurement of haze value)
About the adhering agent layer of the obtained adhesive sheet in embodiment and comparative example, it is according to JIS K7361-1:1997
Benchmark is surveyed using haze meter (NIPPON DENSHOKU INDUSTRIES CO., LTD. manufacture, name of product " NDH-2000 ")
Determine haze value (%).The results are shown in Table 2.
[test example 3] (measurement of gel fraction)
The size of 80mm × 80mm, the adhering agent layer packet will be cut into obtained adhesive sheet in comparative example in embodiment
It overlays in the net (size of mesh 200) of polyester, is placed in precision balance and measures its quality;By subtracting the individual matter of above-mentioned net
Amount, can calculate the quality of only sticker.Quality at this time is denoted as M1.
Then, it by the above-mentioned sticker being covered by polyester ester net, is soaked in ethyl acetate under room temperature (23 DEG C)
24 hours.Sticker is then taken out, in the environment of 23 DEG C of temperature, relative humidity 50%, is air-dried 24 hours, further, 80
DEG C baking oven in dry 12 hours.After drying, its quality is measured using precision balance, by subtracting the individual quality of above-mentioned net,
The quality of only sticker can be calculated.Quality at this time is denoted as M2.Gel fraction (G1;%) indicated with (M2/M1) × 100.Knot
Fruit is as shown in table 2.
[test example 4] (measurement of gel fraction change rate)
In embodiment and comparative example, other than not having to add active energy ray-curable ingredient (B), with above-mentioned phase
Same method manufactures adherence composition.Using the adherence composition, other than not carrying out ultraviolet treatment with irradiation, with
Adhesive sheet is made in above-mentioned identical method.About the adhering agent layer of adhesive sheet obtained, using method identical with test example 3
Measure gel fraction (G2;%).When being denoted as G2 by the gel fraction, the gel fraction measured in test example 3 is denoted as G1, finally
Gel fraction change rate (%) shown in following formula out.The results are shown in Table 2.
Gel fraction change rate (%)={ (G1-G2)/G2 } × 100
[test example 5] (tension test)
Embodiment and the adhering agent layer stacking of adhesive sheet obtained in comparative example is several layers of, so that its overall thickness is become 600 μ
After m, it is cut into wide 10mm × length 75mm sample.With sample measurement site for the side width 10mm × length 20mm (draw direction)
Above-mentioned sample is placed in measurer for pulling force (ORIENTEC CO., LTD. manufacture, name of product " TENSILON ") by formula, 23 DEG C,
In the environment of 50%RH, using the measurer for pulling force, it is to be allowed to extend for 200mm/ minutes with tensile speed, measures elongation at break
(%).In addition, being measured maximum stress (N) until sample is stretched to elongation at break.The results are shown in Table 2.
[test example 6] (evaluation of blister resistance)
The polyethylene terephthalate film of the transparent conductive film formed by tin indium oxide (ITO) is provided with single side
The transparent conductive film of (OIKE&CO., LTD. manufacture, ito film, thickness: 125 μm), with by polycarbonate (PC) plate (MITSUBISH
GAS CHEMICAL COMPANY, INC. manufacture, name of product " IUPIRONSHEET MR58 ", thickness: 1mm) or poly- methyl
Acrylic panel (MITSUBISH GAS CHEMICAL COMPANY, INC. manufacture, the ProductName that methyl acrylate (PMMA) is formed
Claim " IUPIRONSHEET MR200 ", thickness: 1mm), the sticker of clamping embodiment and obtained adhesive sheet in comparative example
Layer, obtains laminated body.
By the laminated body of acquisition under conditions of 50 DEG C, 0.5Mpa, after carrying out the processing of 30 minutes high pressure sterilizations, normal pressure,
23 DEG C, place 15 hours under 50%RH.Then, 85 DEG C, 85%RH it is durable under the conditions of take care of 72 hours.Visual confirmation later
Whether adhering agent layer has bubble, floats or peel off, according to benchmark evaluation blister resistance below.The results are shown in Table 2.
◎ ... absolutely not bubble, float and peeling phenomenon.
Zero ... generates diameter only as 0.1mm bubble below.
× ... it generates diameter and is more than the bubble of 0.1mm, floats or peel off.
[test example 7] (evaluation of epithelium intensity)
Will be several layers of in embodiment and the adhering agent layer stacking of adhesive sheet obtained in comparative example, become its overall thickness
1mm utilizes cutting means (OGINO SEISAKUSHO CO., LTD. manufacture, name of product " SUPER CUTTER PN1-
600 ") laminate is cut.Adhering agent layer after visually cutting really cuts face (length: 100mm), is commented according to following benchmark
Valence epithelium intensity.The results are shown in Table 2.
Zero: the defect on section without adhering agent layer (epithelium intensity is high)
×: there is the defect of adhering agent layer on section (epithelium intensity is low)
[test example 8] (evaluation of segment difference tracing ability)
Glass plate (NSG PRECISION manufacture, name of product " CORNING Glass EAGLE XG ", long 90mm ×
Wide 50mm × thickness 0.5mm) surface, with ultra-violet solidified ink (TEIKOKU PRINTING INKS MFG.CO., LTD.
Manufacture, name of product " POS-911SUMI ") with frame-shaped (external form: long 90mm × wide 50mm, thick 5mm) progress silk-screen printing, make it
Coating thickness be 5 μm, 10 μm, 15 μm with any of 20 μm.Then, ultraviolet light (80W/cm is irradiated2, metal halide lamp 2
It is a, the high 15cm of lamp, belt speed 10~15m/ minutes), make the above-mentioned ultraviolet hardening ink cured printed, production has by printing
Brush bring segment difference (height of segment difference: 5 μm, 10 μm, 15 μm with any of 20 μm) band segment difference glass plate.
From light exfoliated stripping film is peeled in embodiment and comparative example on obtained adhesive sheet off, by the adhering agent layer of exposing
It is pasted on polyethylene terephthalate film (TOYOBO CO., LTD. manufacture, name of product " PET with adhesive layer
A4300 ", thickness: 100 μm).Then, it peels off and re-releases type stripping film, expose adhering agent layer.Then, using plastic packaging machine
(FUJIPLA INC. manufacture, name of product " LPD3214 "), in a manner of the printing surface entire surface of adhering agent layer covering frame-shaped,
Above-mentioned laminate layers are pressed in each band segment difference glass plate, as sample for evaluation.
After the sample for evaluation of acquisition to be carried out to high pressure sterilization processing in 30 minutes under conditions of 50 DEG C, 0.5Mpa, place
24 hours in normal pressure, 23 DEG C, 50%RH.Then, in 85 DEG C, 85%RH it is durable under the conditions of take care of (durable survey in 72 hours
Examination), segment difference tracing ability is evaluated later.Segment difference tracing ability, by being carried out using whether adhering agent layer is fully filled with printing segment difference
Judgement, when gap or bubble etc. are observed in the interface for printing segment difference and adhering agent layer, printing segment difference can not be followed by being judged as.?
This, segment difference tracing ability is evaluated in such a way that the segment difference as shown in following formula follows rate (%).The results are shown in Table 2.
Segment difference follows rate (%)={ (after durable test, maintain the height of the state being filled and the segment difference of tight or bubble
Spend (μm))/(thickness of adhering agent layer: 50 μm) } × 100
[table 1]
[table 2]
Can clearly it find out from table 2, obtained adhering agent layer has excellent segment difference tracing ability and high skin in embodiment
Film-strength.
Industrial applicibility
Adhesive sheet of the invention can be suitable for for example showing the stickup of module with the protection board with segment difference.
Description of symbols
1 ... adhesive sheet;11 ... adhering agent layers;12a, 12b ... stripping film;2 ... display bodies;21 ... first display body constituting portion
Part;22 ... second display body component parts;3 ... printing layers.
Claims (9)
1. a kind of adhesive sheet, there is the adhering agent layer and two panels stripping film formed by sticker, the adhering agent layer with institute
The mode that the release surface of two panels stripping film is in contact is stated to be clamped by the stripping film, which is characterized in that
The adhering agent layer, which is used to paste, at least in the face for the side that is stuck there is a display body component parts of segment difference to show with another
Show body component parts,
By forming adherence composition heat cross-linking and active energy line curing, which contains the sticker
Have: containing as the monomeric unit for constituting polymer, (methyl) acrylate polymer A of the monomer containing reactive functional groups,
More than two degrees of functionality active energy ray-curable ingredient B and thermally crosslinkable crosslinking agent C;
The content of the active energy ray-curable ingredient B in the adherence composition, for the gelling for making the sticker
Part G1 and the adherence composition heat that the active energy ray-curable ingredient B will be removed from the adherence composition
The gel fraction G2 of sticker made of crosslinking substantially the same amount;Also,
When being formed with a thickness of 600 μm, the adhering agent layer that width is 10mm, in the environment of 23 DEG C, 50%RH, it is with measured length
20mm, tensile speed are that maximum stress when being extended to elongation at break in 200mm/ minutes is 2.8N or more.
2. adhesive sheet according to claim 1, which is characterized in that the gel fraction G1 is 40~80%.
3. adhesive sheet according to claim 1, which is characterized in that formed with a thickness of 600 μm, the adhering agent layer that width is 10mm
When, it in the environment of 23 DEG C, 50%RH with measured length is 20mm, tensile speed is elongation at break when stretching for 200mm/ minutes
It is 1000% or more.
4. adhesive sheet according to claim 1 again, which is characterized in that (methyl) the acrylate polymer A's divides equally
Son amount is 200,000~1,000,000.
5. adhesive sheet according to claim 1, which is characterized in that (methyl) the acrylate polymer A contains 5~30
The monomer containing reactive functional groups as the monomeric unit for constituting the polymer of quality %.
6. adhesive sheet according to claim 1, which is characterized in that
The reactive functional groups of the monomer containing reactive functional groups be carboxyl and/or hydroxyl,
The crosslinking agent C is isocyanates crosslinking agent and/or epoxies crosslinking agent.
7. adhesive sheet according to claim 1, which is characterized in that the adhering agent layer with a thickness of 10~400 μm.
8. a kind of display body, which is included
At least the side that is stuck face have segment difference a display body component parts,
Another display body component parts and
The adhering agent layer that the one display body component parts and another display body component parts are mutually pasted, feature exist
In,
The adhering agent layer is the adhering agent layer of adhesive sheet described in any one of claim 1 to 7.
9. the display body according to claim 8, which is characterized in that the segment difference, vertical view are seen as frame-shaped.
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PCT/JP2014/078270 WO2016063405A1 (en) | 2014-10-23 | 2014-10-23 | Adhesive, adhesive sheet, and display element |
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CN107077801B true CN107077801B (en) | 2019-10-15 |
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JP (1) | JP6251293B6 (en) |
KR (1) | KR20170072198A (en) |
CN (1) | CN107077801B (en) |
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JP6676501B2 (en) * | 2016-08-19 | 2020-04-08 | リンテック株式会社 | Adhesive sheet, display body and method for producing them |
JP6820705B2 (en) * | 2016-09-16 | 2021-01-27 | リンテック株式会社 | Adhesive sheets, display bodies and their manufacturing methods |
JP6895266B2 (en) * | 2017-02-09 | 2021-06-30 | リンテック株式会社 | Adhesive sheet |
JP7170387B2 (en) * | 2017-08-21 | 2022-11-14 | リンテック株式会社 | Adhesive sheet and display |
JP2019044024A (en) * | 2017-08-30 | 2019-03-22 | リンテック株式会社 | Adhesive sheet, display body and method for manufacturing display body |
TWI708685B (en) * | 2019-02-20 | 2020-11-01 | 住華科技股份有限公司 | Manufacturing process of laminated film and laminated film made thereby |
WO2023189284A1 (en) * | 2022-03-31 | 2023-10-05 | 王子ホールディングス株式会社 | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
WO2024106519A1 (en) * | 2022-11-18 | 2024-05-23 | 日東電工株式会社 | Adhesive sheet, optical laminate, method for manufacturing optical laminate, and optical device |
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CN103302952A (en) * | 2012-03-12 | 2013-09-18 | 日东电工株式会社 | Production method of flat panel display |
CN103361004A (en) * | 2012-03-28 | 2013-10-23 | 琳得科株式会社 | Adhesive composition, adhesive and adhesive sheet |
JP2014196452A (en) * | 2013-03-29 | 2014-10-16 | リンテック株式会社 | Active energy ray-curable pressure-sensitive adhesive, pressure-sensitive adhesive sheet, and laminate |
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JP5514817B2 (en) * | 2009-05-26 | 2014-06-04 | 三菱樹脂株式会社 | Adhesive material with removability |
JP5552338B2 (en) * | 2010-03-12 | 2014-07-16 | リンテック株式会社 | Adhesive composition, adhesive and adhesive sheet |
JP6030316B2 (en) * | 2012-03-07 | 2016-11-24 | 三菱樹脂株式会社 | Transparent double-sided pressure-sensitive adhesive sheet for image display device, method for producing component for image display device, and image display device |
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2014
- 2014-10-23 KR KR1020177009888A patent/KR20170072198A/en not_active IP Right Cessation
- 2014-10-23 WO PCT/JP2014/078270 patent/WO2016063405A1/en active Application Filing
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CN103302952A (en) * | 2012-03-12 | 2013-09-18 | 日东电工株式会社 | Production method of flat panel display |
CN103361004A (en) * | 2012-03-28 | 2013-10-23 | 琳得科株式会社 | Adhesive composition, adhesive and adhesive sheet |
JP2014196452A (en) * | 2013-03-29 | 2014-10-16 | リンテック株式会社 | Active energy ray-curable pressure-sensitive adhesive, pressure-sensitive adhesive sheet, and laminate |
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TW201623521A (en) | 2016-07-01 |
TWI677546B (en) | 2019-11-21 |
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JP6251293B6 (en) | 2018-06-27 |
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KR20170072198A (en) | 2017-06-26 |
WO2016063405A1 (en) | 2016-04-28 |
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