CN107077801A

CN107077801A - Sticker, adhesive sheet and display body

Info

Publication number: CN107077801A
Application number: CN201480082732.8A
Authority: CN
Inventors: 荒井隆行; 高桥洋; 高桥洋一; 所司悟
Original assignee: Lintec Corp
Current assignee: Lintec Corp
Priority date: 2014-10-23
Filing date: 2014-10-23
Publication date: 2017-08-18
Anticipated expiration: 2034-10-23
Also published as: KR20170072198A; TWI677546B; JP6251293B6; TW201623521A; JPWO2016063405A1; CN107077801B; JP6251293B2; WO2016063405A1

Abstract

A kind of sticker, it is used to paste a display body component parts and another display body component parts at least in the face for the side that is stuck with segment difference, and sticker is by the way that adherence composition heat cross-linking and active energy line curing are formed, and the adherence composition contains：The monomeric unit of polymer, (methyl) acrylate polymer (A) of the monomer containing reactive functional groups, active energy ray-curable compositions (B) more than two degrees of functionality, heat cross-linking crosslinking agent (C) are constituted containing being used as；The content of composition (B) is the gel fraction (G1) for making the sticker, the amount substantially the same with the gel fraction (G2) of the sticker of the adherence composition heat cross-linking by composition (B) is removed from adherence composition in adherence composition；Also, formed thickness be 600 μm, a width of 10mm adhering agent layer when, under 23 DEG C, 50%RH environment, by 20mm of measured length, draw speed be maximum stress when being extended to elongation at break for 200mm/ minutes for more than 2.8N.

Description

Sticker, adhesive sheet and display body

Technical field

It is used to pasting the sticker of display body component parts and adhesive sheet the present invention relates to a kind of and uses the adhesive sheet Adhering agent layer obtained by display body.

Background technology

The various mobile electron machines such as recent mobile phone and tablet PC terminating machine, all carry with Liquid crystal module, light Diode (LED component), organic electroluminescent LED (organic EL) component etc. show the display body (display that module is used Device).

In the display, it will usually install protection panels, protection panels and display body in display body module table surface side Space is provided between module, even if allowing protection panels by outer force deformation, the protection panels of deformation will not also touch display module.

If however, there is the space, even air layer is present, then in the presence of the refractive index because of protection panels and air layer The light reflection loss that difference and the refringence of air layer and display module are caused is big, the problem of display image quality is reduced.

Therefore, it is proposed to by filling protection panels and the space of display body intermodule with sticker, improve display and draw The motion of matter.But in the display body module side of protection panels, the printing layer of border shape can turn into segment difference and exist.If adhering agent layer The segment difference is not followed, then segment difference periphery has adhering agent layer and floated, thus produce the reflection loss of light.Therefore, the sticker Layer requires segment difference tracing ability.

To solve the problem, Patent Document 1 discloses a kind of adhering agent layer its as being filled in protection panels and aobvious Show the adhering agent layer in space between module, in the environment of 25 DEG C, 1Hz, storage modulus (G ') is 1.0 × 10⁵Below Pa, and glue Solidifying part is more than 40%.

Prior art literature

Patent document

Patent document 1：Japanese Patent Publication 2010-97070 publications

The content of the invention

The technical problem to be solved in the present invention

In patent document 1, when adhering agent layer is placed in normal temperature, storage modulus is low, therefore must improve segment difference tracing ability.In addition, As other methods, considering have by reducing the crosslinking degree of the sticker of heat cross-linking type i.e. gel fraction, and improve segment difference Tracing ability.If but reduction storage modulus or gel fraction, the epithelium intensity decreases of adhering agent layer, processability variation.For example, viscous When piece punch process, sticker can be attached to knife face, the problems such as producing some defect of adhering agent layer.

The present invention in view of above-mentioned present situation and complete, it is therefore intended that provide that a kind of segment difference tracing ability is excellent, show high epithelium The sticker of intensity and adhesive sheet 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, and the sticker, which is used to paste, at least to be glued The face of patch side has a kind of display body component parts and another display body component parts of segment difference, it is characterised in that

The sticker is by the way that adherence composition heat cross-linking and active energy line curing are formed, the adherence composition Contain：Contain (methyl) acrylate polymer for being used as composition the monomeric unit of polymer, the monomer containing reactive functional groups (A), active energy ray-curable compositions (B) and thermally crosslinkable crosslinking agent (C) more than two degrees of functionality；

The content of the active energy ray-curable composition (B) in the adherence composition, to make the sticker Gel fraction (G1), with the adhesion of the active energy ray-curable composition (B) will be removed from the adherence composition The gel fraction (G2) of the sticker of property composition heat cross-linking is essentially identical amount；Also,

When forming thickness for 600 μm, a width of 10mm adhering agent layer, in the environment of 23 DEG C, 50%RH, with measured length It it is 200mm/ minutes for 20mm, draw speed, maximum stress when being extended to elongation at break is more than 2.8N (invention 1).

Sticker involved by foregoing invention (invention 1), by meeting above-mentioned condition, with excellent segment difference tracing ability, 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), to form thickness be 600 μm, a width of 10mm adhering agent layer when, 23 DEG C, In the environment of 50%RH by 20mm of measured length, draw speed be 200mm/ minutes stretching when elongation at break be preferably More than 1000% (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) 5~30 mass % monomer containing the reactive functional groups (hair as the monomeric unit for constituting the polymer 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) is isocyanates crosslinking agent and/or epoxies crosslinking agent (invention 6).

Second, the present invention provides a kind of adhesive sheet, and the adhesive sheet has by gluing that the sticker (invention 1~6) is 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), 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).

3rd, the present invention provides a kind of display body, and the display body has：

At least have in the face for the side that is stuck 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 Levy and be,

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

Sticker involved in the present invention and the segment difference tracing ability of the adhering agent layer of adhesive sheet are excellent, and show high epithelium Intensity.In the display body obtained from using such adhesive sheet, in the case of having segment difference in stickup surface side, adhering agent layer can be chased after With the segment difference, after durable condition, it is not easy to produce space or bubble between the segment difference and sticker, adhesion can be maintained Oxidant layer fills up the state of the segment difference.

Brief description of the drawings

Fig. 1 is the profile of the adhesive sheet involved by one embodiment of the present invention.

Fig. 2 is the profile of the layered product involved by one embodiment of the present invention.

Embodiment

Hereinafter, embodiments of the present invention are illustrated.

[sticker]

Sticker involved by present embodiment, is a display at least in the face for the side that is stuck for pasting with segment difference The sticker of body component parts and another display body component parts.Display body is described with display body component parts below.

The sticker of present embodiment is by the way that adherence composition (hereinafter sometimes referred to " adherence composition P ") heat is handed over Connection and active energy line curing are formed, and the adherence composition contains：, containing as constitute polymer it is monomeric unit, contain Active energy ray-curable composition more than (methyl) acrylate polymer (A) of reactive functional groups monomer, two degrees of functionality And thermally crosslinkable crosslinking agent (C) (B).It is assumed that in the sticker, (methyl) acrylate polymer (A) is by handing over Join agent (C) and be crosslinked, form space network, active energy ray-curable composition (B) mutually polymerize, be wound in above-mentioned vertical Body network structure.The structure is referred to as " structure X " sometimes below.In addition, in this manual, so-called (methyl) acrylic acid is Refer to acrylic acid and both methacrylic acids.Other similar terms are also identical.In addition, also including " copolymer " in " polymer " Concept.

The content of active energy ray-curable composition (B) in above-mentioned adherence composition P, to make involved by present embodiment And sticker gel fraction (G1), with active energy ray-curable composition (B) will be removed from above-mentioned adherence composition P Adherence composition heat cross-linking after sticker (hereinafter sometimes referred to " sticker H ") gel fraction (G2) substantially Identical amount.In addition, so-called herein " practically identical ", the gel fraction rate of change for referring to following presentation is less than 15% Level.

Gel fraction rate of change, the gel fraction of the sticker of present embodiment is set into G1 (%), will be from adherence The sticker H of the adherence composition heat cross-linking of active energy ray-curable composition (B) gelling portion is removed in composition P When being divided into G2 (%), represented by following formula.

Gel fraction rate of change (%)={ (G1-G2)/G2 } × 100

For the sticker involved by present embodiment, gel fraction rate of change is preferably 0~15%, and particularly preferably 0 ~10%, more preferably 0~4%.In addition, the assay method of gel fraction is identical with shown in test example below.

In addition, the sticker involved by present embodiment, forms thickness for 600 μm, the feelings of a width of 10mm adhering agent layer Under condition, in the environment of 23 DEG C, 50%RH, when being stretched to elongation at break within 200mm/ minutes with measured length 20mm, draw speed, Maximum stress must be more than 2.8N.Thus, the problems such as starved (paste and owe け) of adhering agent layer when can prevent from cutting can be obtained Epithelium intensity.From the point of view of same insight, above-mentioned maximum stress is preferably more than 3N, particularly preferably more than 4N.On the other hand, though The upper limit of right above-mentioned maximum stress is not particularly limited, but segment difference is followed from the viewpoint of rate is deteriorated, preferably 7N with Under, particularly preferably below 6N.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 making active energy ray-curable composition (B) that adherence composition P contains ormal weight.

In sticker involved by present embodiment, thus it is speculated that by making to contain active energy ray-curable composition with above-mentioned amount (B) adherence composition P heat cross-linkings and active energy line curing, be thus formed in (methyl) acrylate polymer (A) with In the space network of crosslinking agent (C) formation, with degree of the gel fraction essentially without change, the work having polymerize is wound with The structure X of property energy line curability composition (B).By structure X, the sticker involved by present embodiment plays excellent answer Power slackness, segment difference tracing ability also becomes excellent.Therefore, in the display body that will at least there is segment difference in the face for the side being stuck When component parts is pasted with another display body component parts, the sticker involved by present embodiment can follow the section well Difference, after defined durable condition, is not easy to produce space or bubble, adhering agent layer can be tieed up between the segment difference and sticker 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 said structure X, high epithelium intensity is presented in the sticker involved by present embodiment, thus, for example, adhesive sheet is rushed During pressure processing, the problems such as sticker is attached to blade and occurs a part of defect of adhering agent layer can be suppressed.

(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, react 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 Single group body, preferably including intramolecular, there is the monomer (hydroxyl monomer) of hydroxyl, intramolecular to have the monomer of carboxyl (containing carboxyl Monomer), intramolecular there is monomer (emulsion stability) of amino etc..Wherein, preferably with isocyanates crosslinking agent or epoxies Reactive excellent the hydroxyl monomer and carboxyl group-containing monomer of crosslinking agent.

As hydroxyl monomer, for example, it can include：(methyl) acrylic acid 2- hydroxyl ethyl esters, (methyl) acrylic acid 2- hydroxypropyls Ester, (methyl) acrylic acid 3- hydroxypropyl acrylates, (methyl) acrylic acid 2- hydroxy butyl esters, (methyl) acrylic acid 3- hydroxy butyl esters, (methyl) propylene (methyl) acrylic acid hydroxy alkyl ester of sour 4- hydroxy butyl esters 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 esters Or (methyl) acrylic acid 4- hydroxy butyl esters.They may be used alone, two or more kinds can also be used in combination.

As carboxyl group-containing monomer, for example, it can include：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 2 kinds with On be applied in combination.

As emulsion stability, for example, it can include：(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 comprises 5~30 mass %, particularly preferably contains 7~25 mass %, enters One step preferably comprises 10~20 mass % monomer containing reactive functional groups as the monomeric unit for constituting the polymer.Containing anti- If more than the mass % of content 5 of answering property monomer, then can ensure that crosslinking points, said structure X is formed well.In addition, If the content of the monomer containing reactive functional groups is below 30 mass %, required adherence can be readily available.

(methyl) acrylate polymer (A) contains contains hydroxyl as the monomer containing reactive functional groups for constituting the polymer In the case of base monomer, its 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) is preferably comprised as monomeric unit, alkyl the carbon for constituting the polymer Atomicity is 1~20 (methyl) alkyl acrylate.Thus, resulting sticker can show good adherence.This Outside, hard monomer described later is removed from (methyl) alkyl acrylate.

(methyl) alkyl acrylate for being 1~20 as the carbon number of alkyl, for example, can include：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 adherence is more improved, preferably the carbon number of alkyl is 1~8 (first Base) acrylate, particularly preferred (methyl) n-butyl acrylate and (methyl) 2-EHA.They can individually make With, can also two or more be applied in combination.

(methyl) acrylate polymer (A) preferably comprise 40~95 mass %, particularly preferably containing 50~93 mass %, Further preferably the carbon number of 55~90 mass % alkyl as the monomeric unit for constituting the polymer is 1~20 (methyl) alkyl acrylate.

Here, in display body, when implementing hot and humid condition, bubble can be produced near segment difference sometimes or from conduct The plastic plates of protection panels produces exhaust, so that the problem of bubbling such as producing bubble, float, peel off.On this basis, (methyl) Acrylate polymer (A) preferably comprises glass transition temperature polymer monomer unit, as homopolymer as composition Spend the hard monomer of (Tg) more than 70 DEG C.As the monomeric unit for constituting (methyl) acrylate polymer (A), by containing upper Hard monomer is stated, the cohesive force of resulting sticker is improved, and blister resistance is more preferable in display body.Particularly, as 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) is (for example：Tg is preferably less than -30 DEG C, particularly preferably less than -60 DEG C of monomer) make In the case of for main component, because with 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, particularly preferably 80~180 DEG C.In addition, As the monomer containing reactive functional groups in (methyl) acrylate polymer (A), during using carboxyl group-containing monomer, pass through the list Body, can obtain a certain degree of cohesive force.Therefore, in this case, in most cases without using above-mentioned hard monomer.

As above-mentioned hard monomer, for example, it can include：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), DMAA (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, from prevent for adherence with the transparency wait other characteristics negative effect and further hair From the viewpoint of the performance for waving hard monomer, more preferably methyl methacrylate, isobornyl acrylate and acryloyl morpholine；From Further from the viewpoint of the reduction of reduction 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 more than 10 mass %, energy Enough expect the improvement of blister resistance brought by the monomeric unit.On the other hand, by making above-mentioned hard monomer be 45 matter Below % content is measured, then can prevent the relative of other monomers unit in (methyl) acrylate polymer (A) in addition to this its Deficiency, makes the adherence and segment difference tracing ability of resulting sticker excellent.

(methyl) acrylate polymer (A), can also contain as the monomeric unit for constituting the polymer as needed Other monomers.As other monomers, for the effect of without prejudice to monomer containing reactive functional groups, preferably without with reactivity Functional group monomer.As such other monomers, for example, it can include：(methyl) methoxyethyl acrylate, (methyl) Ethoxyethyl acrylate etc. (methyl) alkoxyalkyl acrylate；(methyl) cyclohexyl acrylate etc. has aliphatic ring (methyl) acrylate；(methyl) acrylic acid N, N- dimethylamino ethyl ester, (methyl) acrylic acid N, N- dimethylamino propyl ester etc. have There is (methyl) acrylate of the tertiary amino of non-crosslinked property；Vinyl acetate, styrene etc..They can be used alone, and also may be used 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, more preferably 400,000~700,000.In addition, the weight average molecular weight in this specification is to utilize gel permeation chromatography (GPC) what is determined is converted into the value of polystyrene standard.

By making the weight average molecular weight of (methyl) acrylate polymer (A) be in as described above in relatively low scope, energy Access the more excellent sticker of segment difference tracing ability.(methyl) acrylate polymer (A) if weight average molecular weight more than 100 Ten thousand, cause segment difference tracing ability to be deteriorated sometimes.On the other hand, (methyl) acrylate polymer (A) if weight average molecular weight it is small In 200,000, then the durability of sticker is caused to be deteriorated sometimes.

, can also 2 in addition, in adherence composition P, (methyl) acrylate polymer (A) can be used alone one kind Combination of the above is planted to use.

(2) active energy ray-curable composition (B)

By make adherence composition P with above-mentioned addition contain more than two degrees of functionality active energy ray-curable into Divide (B), so that sticker obtained from adherence composition P is solidified has excellent segment difference tracing ability, have simultaneously There is high epithelium intensity.

Active energy ray-curable composition (B), as long as the effect of the without prejudice to present invention and be photograph by active energy ray The composition of row solidification is injected, is just not particularly limited, is monomer, oligomer or polymer, or their mixing Thing.Wherein, preferably include：It is less than 1000 with the molecular weight of the excellent compatibility of (methyl) acrylate polymer (A) etc. Polyfunctional acrylic ester class monomer.

It is less than 1000 polyfunctional acrylic ester class monomer as molecular weight, for example, can preferably includes：1,4- fourths two Alcohol two (methyl) acrylate, 1,6-HD 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, (first of allylation cyclohexyl two Base) acrylate, ethoxylated bisphenol a diacrylate, double [4- (2- acryloyloxyethoxies) 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, the hydroxyl of epoxy pronane modification three Methylpropane three (methyl) acrylate, three (acryloyl-oxyethyl) isocyanuric acid esters, 6-caprolactone are modified three (2- (methyl) Acryloyl-oxyethyl) the three-functionality-degree acrylic ester monomer such as isocyanuric acid ester；Two glycerine four (methyl) acrylate, season penta The tetra functional acrylic ester monomers such as tetrol four (methyl) acrylate；Propionic acid is modified dipentaerythritol five (methyl) acrylic acid The degree of functionality acrylic ester monomer of ester etc. five；Dipentaerythritol six (methyl) acrylate, caprolactone modification dipentaerythritol six Degree of functionality acrylic ester monomer of (methyl) acrylate etc. six etc..They can be used alone one kind, can also two or more group Conjunction is used.

It is used as active energy ray-curable composition (B), it is possible to use the esters of acrylic acid of active energy ray-curable is oligomeric Thing.The weight average molecular weight of the acrylate quasi-oligomer is preferably less than 50,000.It is used as such acrylate quasi-oligomer Example, can include：Polyester acrylic esters, Epoxy Acrylates, urethane acrylate class, polyether acrylate Class, polybutadiene acrylic acid esters, silicon acrylate etc..

The weight average molecular weight of aforesaid propylene acid esters quasi-oligomer is preferably 50, less than 000, particularly preferably 500~50, 000, more preferably 3,000~40,000.These acrylate quasi-oligomers can be used alone one kind, can also combine Two or more is used.

In addition, as active energy ray-curable composition (B), can also use and imported in side chain with (methyl) propylene 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, with being somebody's turn to do The part of the cross-linking functional group of copolymer is reacted and obtained.

The weight average molecular weight of aforesaid propylene esters of gallic acid polymer adduct is preferably 50,000~900,000 or so, particularly preferably 100000~500,000 or so.

Active energy ray-curable composition (B), can be oligomeric from above-mentioned polyfunctional acrylic ester class monomer, esters of acrylic acid Thing can be combined with selecting one kind to use in acrylic polymer adduct, also it is two or more use, also can be combined using removing Active energy ray-curable composition beyond this.

Active energy ray-curable composition (B) in adherence composition P though content as described above, but specifically, from Obtain from the viewpoint of appropriate epithelium intensity, relative to (methyl) acrylate polymer (A) of 100 mass parts, be preferably More than 0.1 mass parts, more than particularly preferably 0.5 mass parts, more than more preferably 1 mass parts.On the other hand, from this reality Apply the gel fraction (G1) of the sticker of mode and to removing active energy ray-curable composition (B) from adherence composition P The adherence composition sticker H that carries out 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 composition (B), relative to (methyl) acrylate of 100 mass parts It is optimal below particularly preferably 2.5 mass parts below more preferably 3 mass parts below polymer (A), preferably 4 mass parts Elect as less than 2.0 mass parts.

(3) crosslinking agent (C)

Adherence composition is by the way that containing thermally crosslinkable crosslinking agent (C), (methyl) acrylate is crosslinked by heating Polymer (A), forms space network, the cohesive force of the sticker obtained by improving, and assigns the sticker durability.

As above-mentioned crosslinking agent (C), as long as the reactive functional that can have with (methyl) acrylate polymer (A) Group is reacted, for example, can include：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 When the reactive functional groups that ester polymer (A) has are hydroxyl, the reactive excellent isocyanates with hydroxyl is preferably used Class crosslinking agent；When the reactive functional groups that (methyl) acrylate polymer (A) has are carboxyl, preferably use and carboxyl The excellent epoxies crosslinking agent of reactivity.In addition, crosslinking agent (C) can be used alone one kind, can also combine two or more makes With.

Isocyanates crosslinking agent at least contains polyisocyanate compounds.As polyisocyanate compounds, it can enumerate Go out for example：The fragrance adoption isocyanide such as toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, XDI Acid esters；The aliphatic polymeric isocyanates such as hexamethylene diisocyanate, IPDI, hydrogenated methylene diphenyld two are different The ester ring type PIC such as cyanate；And the biuret body of these polyisocyanate compounds, isocyanuric acid ester body, Yi Jizuo To be anti-with the active hydrogen-contg compound of the low molecule amount such as ethylene glycol, propane diols, neopentyl glycol, trimethylolpropane, castor oil Answer adduct of thing etc..Wherein, from the viewpoint of the reactivity with hydroxyl, the fragrant adoption that preferably trimethylolpropane is modified Isocyanates, the benzene two that the toluene di-isocyanate(TDI) and trimethylolpropane that particularly preferred trimethylolpropane is modified are modified is sub- Methyl diisocyanate.

As epoxies crosslinking agent, it can include 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, relative to (methyl) acrylic ester polymerization of 100 mass parts Thing (A), preferably 0.001~2 mass parts, particularly preferably 0.01~1 mass parts, more preferably 0.02~0.3 mass Part.When the content of crosslinking agent (C) is more than 0.001 mass parts, durability can be assigned to resulting sticker and improve effect；Hand over When joining the content of agent (C) for below 2 mass parts, the degree appropriateness of crosslinking can be made, the sticker obtained by can ensuring 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, For example：Silane coupler, Photoepolymerizationinitiater initiater, antistatic additive, tackifier, antioxidant, ultra-violet absorber, light stabilizer, Softening agent, filler, refractive index adjusters etc..

Be the organo-silicon compound that intramolecular at least has 1 alkoxysilane group as silane coupler, preferably with The good silane coupler of the compatibility of (methyl) acrylate polymer (A).In addition, when sticker is used for optical applications, it is excellent Silane coupler of the choosing with translucency.

As the silane coupler, it can include：Vinyltrimethoxy silane, VTES, methyl The silicon compound containing polymerism unsaturated group such as acryloxypropyl trimethoxy silane；3- glycidol ethers epoxide third Base trimethoxy silane, 2- (3,4- expoxycyclohexyls) ethyl trimethoxy silane etc. have the silicon compound of epoxy construction； 3-mercaptopropyi trimethoxy silane, 3- Mercaptopropyltriethoxysilanes, 3- mercaptopropyi dimethoxymethylsilanes etc. contain The silicon compound of sulfydryl；3- TSL 8330s, N- (2- amino-ethyls) -3- TSL 8330s, The silicon compounds containing amino such as N- (2- amino-ethyls) -3- amino propyl methyl dimethoxysilanes；3- r-chloropropyl trimethoxyls Silane；3- NCO propyl-triethoxysilicanes；Or at least one of these silane couplers and methyl triethoxy The contracting of the silicon compound containing alkyl such as silane, ethyl triethoxysilane, MTMS, ethyl trimethoxy silane Compound etc..These silane couplers can be used alone one kind, can also two or more be applied in combination.

The addition of silane coupler, relative to (methyl) acrylate polymer (A) of 100 mass parts, be preferably 0.01~1.0 mass parts, particularly preferably 0.05~0.5 mass parts.

In addition, in the case of using ultraviolet 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) solidifies, and the exposure of polymerizing curable time and active energy ray can be also reduced in addition.

As such Photoepolymerizationinitiater initiater, it can include：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 acetophenones, 2- hydroxy-2-methyls -1- phenyl -propyl- 1- ketone, 1- hydroxycyclohexylphenyls Ketone, 2- methyl isophthalic acids-[4- (methyl mercapto) phenyl] -2- morpholinyls -propyl- 1- ketone, 4- (2- hydroxyl-oxethyls) phenyl -2- (hydroxyl -2- Propyl group) ketone, benzophenone, to phenyl benzophenone, 4,4'- diethylaminos benzophenone, dichloro benzophenone, 2- methyl anthracenes Quinone, 2- EAQs, 2- tert-butyl groups anthraquinone, 2- amino anthraquinones, 2- methyl thioxanthones, 2- ethyls thioxanthones, CTX, 2, 4- dimethyl thioxanthones, 2,4- diethyl thioxanthones, benzyl dimethyl ketal, acetophenone dimethyl ketal, to dimethylamino Benzoic ether, oligomeric [2- hydroxy-2-methyls -1 [4- (1- methyl ethylenes) phenyl] acetone], 2,4,6- trimethylbenzoyls 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 composition (B) of 100 mass parts, preferably with 2~15 mass Part, particularly preferably used with the amount of the scope of 4~12 mass parts.

(5) manufacture of adherence composition

Adherence composition P, can be by manufacturing (methyl) acrylate polymer (A), then by resulting (methyl) Acrylate polymer (A), mix with active energy ray-curable composition (B) and crosslinking agent (C), and be added as needed on It is prepared by additive.

(methyl) acrylate polymer (A), can will constitute the list of polymer by using common radical polymerization Body mixture polymerize to prepare.The polymerization of (methyl) acrylate polymer (A), polymerization initiator can be used as needed, led to Cross solution polymerization process and carry out.As polymer solvent, it can include：Ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, Acetone, hexane, MEK etc., two or more can be also used side by side.

As polymerization initiator, it can include：Azo compound, organic peroxide etc., also can side by side using 2 kinds with On.As azo compound, it can include：2,2'- azodiisobutyronitriles, 2,2'- azos two (2- methylbutyronitriles), 1,1'- Double (2, the 4- dimethyl -4- methoxies of azo two (hexamethylene -1- nitriles), 2,2'- azos two (2,4- methyl pentane nitrile), 2,2'- azos Base valeronitrile), dimethyl 2,2'- azos double (2 Methylpropionic acid ester), 4,4'- azos two (4- cyanopentanoic acids), 2,2'- azos two (2- hydroxymethyls propionitrile), 2,2'- azos two [2- (2- imidazoline -2- bases) propane] etc..

As organic peroxide, it can enumerate：Benzoyl peroxide, t-butyl perbenzoate, cumyl hydroperoxide, mistake Aoxidize two diisopropyl carbonates, diη-propyl peroxy dicarbonate, two (2- ethoxyethyl groups) peroxy dicarbonates, tertiary fourth Base new decanoate ester peroxide, t-butylperoxy pivarate, (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, can adjust resulting polymer Weight average molecular weight.

If obtaining (methyl) acrylate polymer (A), by the solution of (methyl) acrylate polymer (A) Active energy ray-curable composition (B), crosslinking agent (C) and additive as needed are added, and is sufficiently mixed, is adhered Property composition P.

(6) manufacture of sticker

By after the adherence composition P by more than is coated on desired object, carrying out heat cross-linking, and pass through work The irradiation of property energy line is solidified (active energy line curing), so as to obtain the sticker involved by present embodiment.

Adherence composition P heat cross-linking, can be carried out by heating.The heating can also be in coating adhesion Property composition P after drying process in carry out simultaneously.The heating-up temperature of heating, preferably 50~150 DEG C, particularly preferably For 70~120 DEG C.In addition, the heat time is preferably 10 seconds~10 minutes, particularly preferably 50 seconds~2 minutes.

Here, so-called active energy ray, refers to there is the active-energy of the quanta of energy in electromagnetic wave or charged particle beam Line, specifically, can include ultraviolet or electron beam etc..In active energy ray, particularly preferred maneuverable ultraviolet.

Ultraviolet irradiation can be carried out using high-pressure sodium lamp, Fusion H lamps, xenon lamp etc., and ultraviolet irradiation amount is excellent It is 50~1000mW/cm to select illumination²Left 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) reacts with crosslinking agent (C), is formed Cross-linked structure, i.e. space network.If in addition, irradiating active energy ray, active energy line curing to adherence composition P Property composition (B) polymerization, solidified while being wound in above-mentioned space network.Involved by present embodiment obtained by so And sticker, its segment difference tracing ability is good, and high epithelium intensity is presented.

In addition, when manufacturing the sticker of present embodiment, active energy ray being irradiated after being heated, also may be used Both processing are carried out simultaneously.Additionally, it is preferred that after a heating treatment or after irradiation active energy ray, in normal temperature (for example：23℃、 The curing period of setting 1~2 week or so under 50%RH).

(7) gel fraction

The gel fraction (G1) of sticker involved by present embodiment is preferably 40~80%, particularly preferably 45~ 70%, more preferably 50~65%.If gel fraction (G1) is more than 40%, the epithelium of sticker can be ensured well Intensity.If in addition, gel fraction (G1) is less than 80%, the segment difference tracing ability of sticker can be ensured well.

(8) elongation at break

Sticker involved by present embodiment, in the case of being made 600 μm of thickness, width 10mm adhering agent layer, preferably In 23 DEG C, 50%RH environment, elongation at break when being extended using length 20mm, draw speed 200mm/ minutes as 1000% with On, particularly preferably 1100~4000%, more preferably 1200~2500%.In addition, the specific method of the stretching experiment, As shown in test example below.

Sticker involved by present embodiment, by by described adherence composition P heat cross-linkings and active energy ray Curability is formed, to reach above-mentioned elongation at break.By making 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 by present embodiment, it is preferably more than 20% to follow rate (%) with the segment difference shown in following formula, Particularly preferably 25~80%, more 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 by present embodiment, it is solid by described adherence composition P heat cross-linkings and active energy ray Change, can reach that big segment difference follows rate as described above.

[adhesive sheet]

As shown in figure 1, the adhesive sheet 1 involved by present embodiment, by two panels stripping film 12a, 12b, and with two panels The mode of stripping film 12a, 12b release surface contact is constituted by the two panels stripping film 12a, 12b adhering agent layer 11 clamped.This Outside, the release surface of the stripping film in this specification, refers to there is the face of fissility in stripping film, release-treated face and Though not release-treated but with fissility face is all included.

(1) adhering agent layer

The adhering agent layer 11 of adhesive sheet 1 is formed by described sticker, i.e., by by adherence composition P heat cross-linkings with activity The sticker of energy line curing is formed.

The thickness (value determined 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 individual layer, also can laminated multi-layer and formed.

If the thickness of adhering agent layer 11 is less than 10 μm, sufficient segment difference tracing ability can not be obtained sometimes.On the other hand, if The thickness of adhering agent layer 11 is less than 1000 μm, then processability is good.

(2) stripping film

As stripping film 12a, 12b, it can include：Polyethylene film, polypropylene screen, polybutene film, polybutadiene film, poly- first It is base amylene film, polychloroethylene film, vinyl chloride copolymer film, polyethylene terephthalate film, PEN film, poly- Butylene terephthalate film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethene-(methyl) acrylic acid are common Polymers film, ethene-(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.

Preferred pair above-mentioned stripping film 12a, 12b release surface (face particularly contacted with adhering agent layer 11) are implemented at stripping Reason.As the remover for being used for lift-off processing, it can include：Alcohol acids, silicone, fluorine class, unsaturated polyester (UP) class, polyolefin The remover of class, wax class.In addition, in stripping film 12a, 12b, a stripping film preferably is set into the big re-release type of peeling force Stripping film, the small light exfoliated stripping film of peeling force is set to by another stripping film.

Although being not particularly limited for stripping film 12a, 12b thickness, generally 20~150 μm or so.

(3) manufacture of adhesive sheet

As a Production Example of adhesive sheet 1, in the release surface of a stripping film 12a (or 12b), above-mentioned adhesion is coated with Property composition P coating fluid, then coating layer is heated, while by adherence composition P heat cross-linkings, irradiation activity Energy line, solidifies adherence composition P, and forms adhering agent layer 11.In overlapping another on thus formed adhering agent layer 11 The release surface of one stripping film 12b (or 12a), as adhesive sheet 1., also can be in addition, the irradiation of above-mentioned active energy ray Carry out heat cross-linking to adherence composition P coating layer, and on the coating layer overlapping another stripping film 12b (or 12a) stripping Carried out from after face.

As another Production Example of adhesive sheet 1, in being coated with above-mentioned adherence composition in stripping film 12a release surface P coating fluid, heats to coating layer, while by adherence composition P heat cross-linkings, irradiates active energy ray, makes Adherence composition P solidifies, and forms the first adhering agent layer.In addition, in being coated with above-mentioned adhesion in another stripping film 12b release surface Property composition P coating fluid, coating layer is heated, while by adherence composition P heat cross-linkings, irradiation activity Energy line, solidifies adherence composition P, forms the second adhering agent layer.Then, the stripping film with the first adhering agent layer is made 12a, the stripping film 12b with carrying the second adhering agent layer, paste in the way of two adhering agent layers are in contact with each other, as adhesion Piece 1.Alternatively, it is also possible to the stage before by each coating layer heat cross-linking, it is in contact with each other, unify the active energy of irradiation afterwards Line is measured, and adhesive sheet 1 is obtained, rather than acquisition adhesive sheet 1 after the first adhering agent layer and the second adhering agent layer are formed respectively.

As the method for the coating fluid for being coated with above-mentioned adherence composition P, for example, it can utilize rod coating method, scraper for coating Method, roller rubbing method, plate rubbing method, die coating methods, gravure coating method etc..For the heating for the adherence composition P being coated with The condition of processing is as described above.

In adhesive sheet 1 more than, because the segment difference tracing ability of adhering agent layer 11 is excellent, therefore, tool segment difference is pasted on After display body component parts, even in defined durable condition, be also not easy between the segment difference and adhering agent layer 11 produce Raw space or bubble, adhering agent layer 11 can fill up the segment difference.Further, since the epithelium intensity of adhering agent layer 11 is high, and therefore, example Such as, when carrying out punch process to adhesive sheet 1, sticker can be suppressed and be attached to blade and cause a part for adhering agent layer 11 to be owed The generation for the problems such as lacking.

(4) haze value

Mist degree (Haze) value of adhering agent layer 11 involved by present embodiment is (according to JIS K7136：2000 are determined Value) it is preferably less than 3%, particularly preferably less than 2%, more preferably less than 1%.If haze value is less than 3%, thoroughly Bright property is very high, is suitable for optical applications.

(5) adhesion strength

The adhesive sheet 1 of present embodiment, in order to also play good segment difference tracing ability, adhesion strength after durable condition (according to JIS Z0237:2009 values determined) it is preferably more than 5N/25mm, more preferably more than 10N/25mm, particularly preferably For more than 25N/25mm.In addition, from the viewpoint of the re-workability of adhesive sheet 1 is assigned, above-mentioned bonding force is preferably 50N/25mm Hereinafter, more preferably below 40N/25mm, particularly preferably below 35N/25mm.In addition, the test method of adhesion strength is detailed Situation, as described in test example.

[display body]

As shown in Fig. 2 the display body 2 involved by present embodiment, by including：At least there is section in the face for the side that is stuck First display body component parts 21 (a display body component parts) of difference, and (another display body of the second display body component parts 22 Component parts), and between the first display body component parts 21 and the second display body component parts 22, for incite somebody to action both The adhering agent layer 11 pasted each other and be configured.In the display body 2 involved by present embodiment, the first display body component parts 21, there is segment difference in the face of the side of adhering agent layer 11, specifically, with the segment difference caused by printing layer 3.

As display body 2, it can include：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, is preferably by the layered product including both in addition to glass plate, plastic plate Etc. the protection board of composition.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 shows module (for example：Liquid crystal (LCD) module, light emitting diode (LED) module, organic electroluminescent (organic EL) module etc.) or one part is (for example：The optical components such as polarizer).

As above-mentioned glass plate, it is not particularly limited, can includes：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.

As above-mentioned plastic plate, it is not particularly limited, can enumerates：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, the single or double in above-mentioned glass plate or plastic plate can be provided with various functions layers (nesa coating, metal Layer, silicon dioxide layer, hard conating, antiglare layer etc.), also can laminated optical member.In addition, nesa coating also can quilt with metal level Patterning.

As above-mentioned optical component, it can include：Polarizer (polarizing coating), polaroid, polarizer (phase retardation film), regard Angle compensation film, brightness enhancement film, contrast enhancing film, liquid crystalline polymer film, diffusion barrier, hard coating film, Transflective film etc..

The material of printing layer 3 is constituted, is not particularly limited, the known material of usable printing.The thickness of printing layer 3 Degree, i.e. the highly preferred of segment difference is 3~45 μm, particularly preferably 5~35 μm, more 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 constituted with the first display body The corresponding size of 21 and second display body component parts of part 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 be also blocked, and adhering agent layer 11 is partly cut with a stripping film 12a.This When, because the epithelium intensity of adhering agent layer 11 is high, therefore, it can restrain and occur adhering agent layer 11 because sticker adheres to blade The problem of a part of defect.

Then, after a stripping film 12a of adhesive sheet 1 is peeled off, the adhering agent layer 11 exposed of adhesive sheet 1 is pasted on the The face for the side that the printing layer 3 of one display body component parts 21 is present.Afterwards, peeled off from the adhering agent layer 11 of adhesive sheet 1 another Individual stripping film 12b, the adhering agent layer 11 exposed of adhesive sheet 1 and the second display body component parts 22 are pasted.

In above-mentioned operation, when pasting 11 and first display body component parts 21 of adhering agent layer, due to the section of adhering agent layer 11 Poor tracing ability is good, therefore, after defined durable condition, is not easy to because of segment difference formed by printing layer 3 and adhesion Space is produced between oxidant layer 11, adhering agent layer 11 can fill up the segment difference.

Embodiments described above, is to be recorded to be readily appreciated that the present invention, and be not in order to limit the present invention And record.Therefore, each element disclosed in above-mentioned embodiment, is also including all of term technical scope of the invention Design alteration or the meaning of equivalent.

For example, it is also possible to any one in omitting stripping film 12a, 12b of adhesive sheet 1.In addition, the first display body is constituted Part 21, can have the segment difference in addition to printing layer 3, can also not have segment difference.Further, can also not only the first display body Component parts 21, and the second display body component parts 22 also has segment difference in the side of adhering agent layer 11.

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

Make the mass parts of n-butyl acrylate 90 and the mass parts copolymerization of acrylic acid 10, prepare (methyl) acrylate polymer (A) result for the molecular weight for being somebody's turn to do (methyl) acrylate polymer (A), weight average molecular weight (Mw), are determined using method described later For 400,000.

2. the preparation of adherence composition

The mass parts of (methyl) acrylate polymer (A) 100 obtained in above-mentioned operation (1) (are converted into solid constituent Value；It is same as below), be used as active energy ray-curable composition (B) three (acrylyl oxy-ethyl) isocyanuric acid esters (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. manufactures, Name of product " TETRAD-C ", solid component concentration：100 mass %) 0.05 mass parts and as silane coupler 3- shrink Glycerin ether epoxide propyl trimethoxy silicane (SHIN-ETSU CHEMICAL CO., LTD. manufacture, name of product " KBM-403 ") 0.2 mass parts are mixed, then the 1- hydroxyl rings for being used as Photoepolymerizationinitiater initiater are added using the quality of the 10 mass % equivalent to (B) composition Hexyl phenyl ketone (BASF AG manufactures, name of product " IRGACURE184 "), is diluted after being sufficiently stirred for MEK, so that To coating solution of the solid component concentration for 37 mass % adherence composition.

Here, the mixed proportion of the adherence composition is as shown in table 1.In addition, the feelings in detail such as code name described 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 composition]

M-315：Three (acryloyl-oxyethyl) isocyanuric acid esters (TOAGOSEI CO., LTD. manufactures, name of product " M- 315”)

A-400：Polyethyleneglycol diacrylate (SHIN-NAKAMURA CHEMICAL CO., LTD. manufactures, name of product " A-400 ", the molecular weight of polyethylene glycol：400)

A-TMM-3：Pentaerythritol triacrylate (SHIN-NAKAMURA CHEMICAL CO., LTD. manufactures, ProductName Claim " A-TMM-3 ")

A-DPH：Dipentaerythritol acrylate (SHIN-NAKAMURA CHEMICAL CO., LTD. manufactures, ProductName Claim " A-DPH ")

[crosslinking agent]

Epoxy -1：(N, the N'- diglycidyl aminomethyl) hexamethylenes of 1,3- bis- (MITSUBISH GAS CHEMICAL COMPANY, INC. are manufactured, name of product " TETRAD-C ")

Epoxy -2：N, N, N', N'- four glycidyl group-m-xylene diamine (MITSUBISH GAS CHEMICAL COMPANY, INC. are manufactured, name of product " TETRAD-X ")

Isocyanates：Toluene di-isocyanate(TDI) (the SOKEN CHEMICAL＆ENGINEERING that trimethylolpropane is modified CO., LTD. is manufactured, name of product " L-45 ")

3. the manufacture of adhesive sheet

Silanes remover progress lift-off processing, formation re-release type are utilized to the one side of polyethylene terephthalate film Stripping film (LINTEC CORPORATION manufacture, name of product " SP-PET752150 "), using scraping on its lift-off processing face The coating solution of adherence composition obtained by the coating of knife coating machine.In addition, heating 2 points at 100 DEG C to coating layer Zhong Hou, under it is following under conditions of irradiation ultraviolet radiation, it is 25 μm of the first adhering agent layer to be consequently formed thickness.

[ultraviolet irradiation condition]

Light source：High-pressure sodium lamp

Light quantity：500mJ/cm²

Illumination：200mW/cm²

In addition, UV illumination-quantometer " UVPF-36 " that illumination is manufactured with light quantity according to EYE GRAPHICSCO., LTD. Confirmed.

Similarly, the one side of polyethylene terephthalate film is peeled off using silanes remover, forms light stripping Release stripping film (LINTEC CORPORATION are manufactured, name of product " SP-PET382120 ") is sharp on its lift-off processing face The coating solution of adherence composition obtained by being coated with knife type coater.In addition, heating to coating layer at 100 DEG C After 2 minutes, as described above, irradiation ultraviolet radiation is consequently formed the second adhering agent layer that thickness is 25 μm.

Then, by the re-release type stripping film with the first adhering agent layer of above-mentioned middle acquisition and in above-mentioned middle acquisition Light exfoliated stripping film with the second adhering agent layer, is pasted in the way of two adhering agent layers are in contact with each other, and is made by weight Exfoliated stripping film/adhering agent layer (thickness：50 μm) adhesive sheet of the structure formation of/light exfoliated stripping film.In addition, sticker The thickness of layer, is that, according to JIS K7130, using constant pressure thickness measuring instrument, (TECLOCK CORPORATION are manufactured, name of product " PG-02 ") value that is determined.

[embodiment 2~17, comparative example 1~4]

Ratio, (methyl) acrylate polymer except each monomer will (methyl) acrylate polymer (A) constituted (A) weight average molecular weight, the species of active energy ray-curable composition (B) and addition, the species of crosslinking agent (C) and addition Beyond the addition of amount and silane coupler is changed 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 to utilize gel permeation chromatography (GPC), determine under the following conditions The weight average molecular weight for being converted into polystyrene of (GPC measure).

＜ condition determinations ＞

GPC determines device：TOSOH CORPORATION are manufactured, HLC-8020

GPC posts (pass through) according to following order：TOSOH CORPORATION are manufactured

TSK guard column HXL-H

TSK gel GMHXL(×2)

TSK gel G2000HXL

Determine solvent：Tetrahydrofuran

Determine temperature：40℃

[test example 1] (measure of adhesion strength)

Light exfoliated stripping film is peeled on adhesive sheet obtained in from embodiment and comparative example, by the adhering agent layer exposed Being pasted on the polyethylene terephthalate film with adhesive layer, (TOYOBO CO., LTD. manufactures, PET A4300 are thick Degree：100 μm) adhesive layer.The layered product is cut into wide 25mm, length 100mm size, as sample.From the sample On peel re-release type stripping film, the adhering agent layer exposed be pasted on soda-lime glass (NIPPON SHEET GLASS CO., LTD. manufacture).

Afterwards, after being placed 24 hours under conditions of normal pressure, 23 DEG C, 50%RH, with JIS Z0237:On the basis of 2009, Under conditions of peeling rate 300mm/min, 180 ° of peel angle, using measurer for pulling force (ORIENTEC CO., LTD. manufacture, Name of product " TENSILON ") test adhesion strength (N/25mm).As a result it is as shown in table 2.

[test example 2] (measure of haze value)

On the adhering agent layer of resulting adhesive sheet in embodiment and comparative example, according to JIS K7361-1：1997 are Benchmark, is surveyed using haze meter (NIPPON DENSHOKU INDUSTRIES CO., LTD. manufactures, name of product " NDH-2000 ") Determine haze value (%).As a result it is as shown in table 2.

[test example 3] (measure of gel fraction)

Resulting adhesive sheet in embodiment and comparative example is cut into 80mm × 80mm size, the adhering agent layer bag In the net (size of mesh 200) for overlaying on polyester, it is placed in precision balance and determines its quality；By subtracting the single matter of above-mentioned net Amount, can calculate the quality of only sticker.Quality now is denoted as M1.

Then, by the above-mentioned sticker being covered by polyester ester net, it is soaked under room temperature (23 DEG C) in ethyl acetate 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 determined using precision balance, by subtracting the single quality of above-mentioned net, The quality of only sticker can be calculated.Quality now is denoted as M2.Gel fraction (G1；%) represented with (M2/M1) × 100.Knot Fruit is as shown in table 2.

[test example 4] (measure of gel fraction rate of change)

In embodiment and comparative example, in addition to no addition active energy ray-curable composition (B), with above-mentioned phase Same method manufacture adherence composition.Using the adherence composition, in addition to not carrying out ultraviolet treatment with irradiation, with Adhesive sheet is made in above-mentioned identical method.On the adhering agent layer of the adhesive sheet obtained, using with the identical method of test example 3 Determine gel fraction (G2；%).When being denoted as G2 by the gel fraction, the gel fraction measured in test example 3 is denoted as into G1, finally Go out the gel fraction rate of change (%) shown in following formula.As a result it is as shown in table 2.

Gel fraction rate of change (%)={ (G1-G2)/G2 } × 100

[test example 5] (tension test)

Embodiment and the adhering agent layer stacking of adhesive sheet resulting in comparative example is several layers of, its gross thickness is turned into 600 μ After m, wide 10mm × length 75mm sample is cut into.Using sample measurement site as width 10mm × length 20mm (draw direction) side Formula, measurer for pulling force (ORIENTEC CO., LTD. manufacture, name of product " TENSILON ") is placed in by above-mentioned sample, 23 DEG C, In the environment of 50%RH, using the measurer for pulling force, minute it is allowed to extend by 200mm/ of draw speed, determines elongation at break (%).In addition, untill sample is stretched into elongation at break, determining maximum stress (N).As a result it is as shown in table 2.

[test example 6] (evaluation of blister resistance)

The polyethylene terephthalate film of the nesa coating formed by tin indium oxide (ITO) is provided with one side (OIKE＆CO., LTD. are manufactured, ito film, thickness：125 μm) nesa coating, with by makrolon (PC) plate (MITSUBISH GAS CHEMICAL COMPANY, INC. manufactures, name of product " IUPIRONSHEET MR58 ", thickness：1mm) or poly- methyl Acrylic panel (MITSUBISH GAS CHEMICAL COMPANY, the INC. manufactures, ProductName of methyl acrylate (PMMA) formation Claim " IUPIRONSHEET MR200 ", thickness：1mm), clamping embodiment and the sticker of adhesive sheet resulting in comparative example Layer, obtains layered product.

By the layered product of acquisition under conditions of 50 DEG C, 0.5Mpa, carry out after the processing of 30 minutes autoclavings, 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.Visually confirm afterwards Whether adhering agent layer has bubble, floats or peel off, according to following benchmark evaluation blister resistance.As a result it is as shown in table 2.

The completely no bubbles of ◎ ..., float and peeling phenomenon.

Zero ... only produces a diameter of below 0.1mm bubble.

× ... produce diameter and exceed 0.1mm bubble, float 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 resulting in comparative example, turn into its gross thickness 1mm, utilizes cutting means (OGINO SEISAKUSHO CO., LTD. manufactures, name of product " SUPER CUTTER PN1- 600 ") laminate is cut.Adhering agent layer after visually cutting really cuts face (length：100mm), commented according to following benchmark Valency epithelium intensity.As a result it is as shown in table 2.

○：Defect on tangent plane without adhering agent layer (epithelium intensity is high)

×：There is the defect (epithelium low intensity) of adhering agent layer on tangent plane

[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) silk-screen printing is carried out, make it Coating thickness be 5 μm, 10 μm, 15 μm with any one in 20 μm.Then, irradiation ultraviolet radiation (80W/cm², metal halide lamp 2 It is individual, the high 15cm of lamp, belt speed 10~15m/ minutes), make the above-mentioned ultraviolet hardening ink cured printed, making has by printing Segment difference (the height of segment difference that brush is come：5 μm, 10 μm, 15 μm with any one in 20 μm) band segment difference glass plate.

Light exfoliated stripping film is peeled on adhesive sheet obtained by from embodiment and comparative example off, by the adhering agent layer exposed It is pasted on polyethylene terephthalate film (TOYOBO CO., LTD. manufactures, name of product " PET with adhesive layer A4300 ", thickness：100μm).Then, peel re-release type stripping film off, expose adhering agent layer.Then, using plastic packaging machine (FUJIPLA INC. are manufactured, name of product " LPD3214 "), in the way of the printing surface entire surface that adhering agent layer covers frame-shaped, Above-mentioned laminate layers are pressed in each band segment difference glass plate, as sample for evaluation.

The sample for evaluation of acquisition is carried out under conditions of 50 DEG C, 0.5Mpa after autoclaving processing in 30 minutes, placed 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 72 hours (it is durable survey Examination), segment difference tracing ability is evaluated afterwards.Segment difference tracing ability, is carried out by using whether adhering agent layer is fully filled with printing segment difference Judge, when observing gap or bubble etc. at the interface for printing segment difference and adhering agent layer, be judged as that printing segment difference can not be followed. This, segment difference tracing ability is evaluated in the way of following rate (%) by the segment difference shown in following formula.As a result it is as shown in table 2.

Segment difference follows rate (%)={ (after durable test, maintain the height of the state that is filled and the segment difference of tight or bubble Spend (μm))/(thickness of adhering agent layer：50μm)}×100

[table 1]

[table 2]

Can clearly it find out from table 2, resulting adhering agent layer has excellent segment difference tracing ability and high skin in embodiment Film-strength.

Industrial applicibility

The adhesive sheet of the present invention can be applied to for example show the stickup of module and the protection board with segment difference.

Description of reference numerals

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

1. a kind of sticker, the sticker is used to paste a display body component parts at least in the face for the side that is stuck with segment difference With another display body component parts, it is characterised in that

The sticker is by the way that adherence composition heat cross-linking and active energy line curing are formed, and the adherence composition contains Have：Contain (methyl) acrylate polymer for being used as composition the monomeric unit of polymer, the monomer containing reactive functional groups (A), active energy ray-curable compositions (B) and thermally crosslinkable crosslinking agent (C) more than two degrees of functionality；

The content of the active energy ray-curable composition (B) in the adherence composition, to make the glue of the sticker Solidifying partly (G1), with the adherence group of the active energy ray-curable composition (B) will be removed from the adherence composition Substantially the same amount of the gel fraction (G2) of the sticker of compound heat cross-linking；Also,

Formed thickness be 600 μm, a width of 10mm adhering agent layer when, in the environment of 23 DEG C, 50%RH, using measured length as 20mm, draw speed are that maximum stress when being extended to elongation at break in 200mm/ minutes is more than 2.8N.

2. sticker according to claim 1, it is characterised in that the gel fraction (G1) is 40~80%.

3. sticker according to claim 1 or 2, it is characterised in that it is 600 μm, a width of 10mm adhesion to form thickness During oxidant layer, in the environment of 23 DEG C, 50%RH by 20mm of measured length, draw speed be 200mm/ minutes stretching when fracture Degree of stretching is more than 1000%.

4. sticker as claimed in any of claims 1 to 3, it is characterised in that (methyl) acrylate gathers The weight average molecular weight of compound (A) is 200,000~1,000,000.

5. sticker as claimed in any of claims 1 to 4, it is characterised in that (methyl) acrylate gathers Compound (A) is containing 5~30 mass % as constituting monomer containing reactive functional groups described in the monomeric unit of the polymer.

6. sticker as claimed in any of claims 1 to 5, it is characterised 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. a kind of adhesive sheet, the adhesive sheet has the sticker formed as the sticker described in any one in claim 1 to 6 Layer.

8. adhesive sheet according to claim 7, it is characterised in that the thickness of the adhering agent layer is 10~400 μm.

9. the adhesive sheet according to claim 7 or 8, it is characterised in that

The adhesive sheet has two panels stripping film；

The adhering agent layer, in the way of the release surface with the two panels stripping film is in contact, is clamped by the stripping film.

10. a kind of display body, the display body has：

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, its feature exists In,

The adhering agent layer is the adhering agent layer of the adhesive sheet described in any one in claim 7 to 9.

11. the display body according to claim 10, it is characterised in that the segment difference, vertical view is seen as frame-shaped.