CN107709493A

CN107709493A - Light-cured type bonding sheet, bonding sheet and image display device

Info

Publication number: CN107709493A
Application number: CN201680032296.2A
Authority: CN
Inventors: 新美嘉穗儿; 山本亮太; 内田贵久; 稻永诚
Original assignee: Mitsubishi Kasei Corp
Current assignee: Mitsubishi Kasei Corp
Priority date: 2015-06-02
Filing date: 2016-06-01
Publication date: 2018-02-16
Anticipated expiration: 2036-06-01
Also published as: KR20200019792A; WO2016194957A1; CN111732904A; TWI792195B; TW201716536A; TW202126775A; CN107709493B; TWI726883B; KR102080224B1; TW202024272A; TWI792369B; CN108977113A; CN108977113B; KR20180015716A; TWI728711B; TW202024273A; TW202136462A

Abstract

A kind of bonding sheet is provided, the difference of height portion of binding face can be followed so as to be filled into each corner, even if also not reduced through prolonged light irradiation bonding reliability, can easily carry out fitting operation.Therefore a kind of bonding sheet is proposed, it is characterized in that, it is the bonding sheet before the photocuring formed by the resin combination containing (methyl) acrylic copolymer (A), crosslinking agent (B) and Photoepolymerizationinitiater initiater (C), it has photo-curable, and possesses the characteristic of following (1) and (2)：(1) shape can be kept at 0~40 DEG C, and shows self adhesion；(2) at 70~100 DEG C, viscosity is shown as 100~3000Pas.

Description

Light-cured type bonding sheet, bonding sheet and image display device

Technical field

The present invention relates to the light-cured type bonding sheet before photocuring and the bonding sheet for forming its photocuring.Specifically relate to And the image of computer, mobile terminal (PDA), game machine, TV (TV), auto-navigation system, touch panel, handwriting pad or the like Display device and the bonding sheet that can be suitably used as its member of formation.

Background technology

In recent years, in order to improve the visibility of image display device, following operation has been carried out：By liquid crystal display (LCD), The image display panel of plasma scope (PDP) or electroluminescent display (ELD) etc. be configured at its front-surface side (depending on Recognize side) protection panels, the space bonding sheet between touch panel component, the filling such as liquid adhesive, come suppress incident light, Reflection of the emergent light from display image in air-layer interface.

Method as the space between such filling device used for image display member of formation with adhesive, it is known that will wrap After liquid adhering resin composition containing uv curing resin is filled in the space, irradiates ultraviolet and make its solidification Method (patent document 1).

In addition, it is also known that the method that the space between device used for image display member of formation is filled with bonding sheet.It is such as special Disclosed in sharp document 2：As the figure possessed in the structure of at least unilateral stacking image display device member of formation of bonding sheet As the manufacture method of display device composition layered product, the bonding sheet being once crosslinked with ultraviolet is conformed into image and shown After showing device member of formation, make the side of its secondary solidification to bonding sheet irradiation ultraviolet across image display device member of formation Method.

In addition, Patent Document 3 discloses used using weight average molecular weight as 20,000~100,000 polyurethane (methyl) propylene Acid esters is the piece of the heat molten type adhesive composition of main component, the loss angle tangent at 25 DEG C less than 1.

And then Patent Document 4 discloses a kind of adhesive phase for the fitting for being suitable for touch panel, it includes crosslinking Agent and (methyl) acrylic monomer and the monomer copolymerization of specific macromonomer with cross-linking functional group will be contained Obtained from (methyl) acrylic polymer.

Prior art literature

Patent document

Patent document 1：No. 2010/027041 publication of International Publication

Patent document 2：No. 2012/032995 publication of International Publication

Patent document 3：No. 2010/038366 publication of International Publication

Patent document 4：Japanese Unexamined Patent Publication 2013-18227 publications

Patent document 5：Japanese Unexamined Patent Publication 2012-184423 publications

The content of the invention

Problems to be solved by the invention

Centered on mobile phone, mobile terminal etc., in the field of image display device, on thinning, the basis of high-precision densification Upper constantly to promote the variation designed, new problem is also producing therewith.For example, generally printed in the peripheral part of surface protection panel The shielding portion of black brushed with frame-shaped.Therefore, possesses the bonding sheet of the member of formation of such Printing Department for fitting, it is desirable to can Printing difference of height is followed so as to fill to the printing difference of height tracing ability in each corner.

In addition, the use range of the image display device such as touch panel is more and more wider, therewith together, to being shown for image Even if device composition is not also reduced viscous with bonding sheet requirement long-time performance in the light such as illumination, sunshine of layered product Connect reliability.

The present invention the 1st purpose be to provide a kind of new bonding sheet, its before photocuring in the state of can follow patch The difference of height portion in conjunction face so as to fill to each corner, even and if after photocuring in the state of glued through prolonged light irradiation Connecing reliability does not also reduce, therefore can easily carry out fitting operation.

The present invention the 2nd purpose be to provide a kind of new bonding sheet, it in binding face even to having Printing Department Situation about being bonded etc. the device used for image display member of formation in light tight portion and transmittance section can also be obtained to difference of height portion Deng tracing ability, surface, even if will not also be produced in light tight portion strain, deformation, and can with high cohesion will Adherend is bonded securely between each other, even and if then can cause in hot and humid inferior extreme environment, the bonding exposed Face is not also tacky.

The present invention the 3rd purpose be to provide a kind of bonding sheet, its be Photocrosslinkable bonding sheet, even if before photo-crosslinking Also there is cohesive, the situation overflowed, collapsed so as to adhesive resin composition in the absence of jointing material excess flow during fitting, And then sufficient hardness can be obtained after photo-crosslinking.

The solution used to solve the problem

The present invention proposes a kind of bonding sheet to reach the 1st purpose, it is characterised in that it is by containing above-mentioned (methyl) It is viscous before the photocuring that the resin combination of acrylic copolymer (A), crosslinking agent (B) and Photoepolymerizationinitiater initiater (C) is formed Piece is closed, it has photo-curable, and possesses the characteristic of following (1) and (2)：

(1) shape can be kept at 0~40 DEG C, and shows self adhesion；

(2) at 70~100 DEG C, viscosity is shown as 100~3000Pas.

The above-mentioned bonding sheet that the present invention proposes to reach the 1st purpose can under 0~40 DEG C of room temperature state i.e. normality To keep sheet, and tack can be shown, therefore be easily processed, and such as attach when positioning easily carry out, Ke Yixiao Rate carries out fitting operation well.In addition, viscosity turns into 100~3000Pas when reaching 70~100 DEG C, hot melt is shown, because This jog that can follow such as printing difference of height carrys out filling adhesive.And then high cohesion is showed after photocuring, example Excellent resistance to foaminess can also be such as played after prolonged light irradiation, even if through prolonged light irradiation bonding reliability It will not reduce.Therefore, light-cured type bonding sheet proposed by the present invention be suitable for computer, mobile terminal (PDA), game it is mechanical, electrical Depending on the member of formation of (TV), auto-navigation system, touch panel, handwriting pad or the like image display device.

The present invention proposes a kind of bonding sheet to reach the 2nd purpose, it is characterised in that it is to contain (methyl) acrylic acid Analog copolymer (A) and the bonding sheet formed by photocuring, it is more than 40% to have piece portion of the gel fraction less than 1% and gel fraction Piece portion.

The above-mentioned bonding sheet that the present invention proposes to reach the 2nd purpose can be obtained by piece portion of the gel fraction less than 1% To the tracing ability to difference of height portion etc., surface, strain, the deformation in piece can be relaxed, on the other hand, passes through gel fraction It for more than 40% piece portion, can not only make it that adhesive surface is not tacky, can also make adherend firm between each other with high cohesion Admittedly be bonded.

Thus, for example, even to having the image in the light tight portions and transmittance section such as Printing Department to show dress in binding face Situation about being bonded with member of formation is put, tracing ability, table to printing difference of height portion can also be integrally obtained as bonding sheet Face flatness, even if will not also be produced in light tight portion strain, deformation, and then, can be made with high cohesion adherend mutually it Between be bonded securely.In addition, it is hard portion by the adhesive surface for making to expose, even if can cause in hot and humid inferior extreme ring Under border, the adhesive surface exposed is not also tacky.

The present invention proposes a kind of bonding sheet to reach the 3rd purpose, it is characterised in that it is by containing (methyl) acrylic acid The mass parts of analog copolymer (A) 100, the mass parts of crosslinking agent (B) 0.5~20 and the mass parts of Photoepolymerizationinitiater initiater (C) 0.1~5 Resin combination is formed, the ratio between stretch modulus (X2) after stretch modulus (X1) of the bonding sheet before photo-crosslinking and photo-crosslinking (X1/X2) it is more than 3.

The above-mentioned bonding sheet that is itd is proposed to reach the 3rd purpose of the present invention has the stretch modulus (X1) before and after photo-crosslinking Significant difference feature such greatly, even if also having cohesive before photo-crosslinking, jointing material excess flow is not present in fitting The dynamic situation overflowed, collapsed so as to adhesive resin composition, and then sufficient hardness can be obtained after photo-crosslinking.

Brief description of the drawings

Fig. 1 is the top perspective view of one for showing the bonding sheet of the present invention.

Fig. 2 is the top perspective view of another for showing the bonding sheet of the present invention.

Fig. 3 is the top perspective view for the another example for showing the bonding sheet of the present invention.

Fig. 4 is the figure of one of the bonding laminate for the bonding sheet for showing to possess shown in Fig. 3 (B), and (A) is its vertical view Stereogram, (B) are sectional view.

Fig. 5 is the top perspective view for the another example for showing the bonding sheet of the present invention.

Embodiment

One of embodiments of the present invention is described in detail below.In addition, the invention is not restricted to following implementations Mode.

[this bonding sheet 1]

The bonding sheet of one (be referred to as " this bonding sheet 1 ") of embodiments of the present invention is characterised by, its be by containing The resin combination of (methyl) acrylic copolymer (1-A), crosslinking agent (1-B) and Photoepolymerizationinitiater initiater (1-C) (is referred to as " this adhesive composition 1 ") formed photocuring before bonding sheet, it has photo-curable, and possesses following (1) and (2) Characteristic：

(1) shape can be kept at 0~40 DEG C, and shows self adhesion；

(2) at 70~100 DEG C, viscosity is shown as 100~3000Pas.

Here, " bonding sheet before photocuring " as long as the bonding sheet with photo-curable, be not limited to completely The not bonding sheet Jing Guo photocuring process.That is, the bonding sheet of photocuring process and the further photocuring of energy is for example, have passed through, As long as the effect of the present invention can be reached, then it is also contained in the present invention.

This bonding sheet 1 before photocuring in the state of possess the characteristic of above-mentioned (1) and (2), therefore can be at 0~40 DEG C Room temperature state, sheet is in other words kept under normal conditions, and possess tack, the property of bonding force can be played under original state Matter.And then the hot melt of melting or even flowing can be shown during heating, play excellent cohesive force after photocuring, such as through Resistance to foaminess is shown after prolonged light irradiation.

This bonding sheet 1 have (1) before photocuring in the state of, sheet can be kept under 0~40 DEG C of room temperature state, And feature as display tack.

Like this in room temperature state, when can keep sheet under normal conditions, easily handled, and be bonded the production of component Rate is especially excellent.And then when showing tack under normal conditions, such as attach when positioning easily carry out, fitting operation very just Profit.

In order to obtain such characteristic, such as this can be manufactured by adhesive composition described later (1-I) or (1-II) Bonding sheet 1.In addition, it is also not necessarily limited to this.

(180 ° of peeling forces under 23 DEG C of 40%RH)

This bonding sheet 1 can have the feature of following (6).I.e. (6) are crimped on soda-lime glass, in 23 DEG C of 40%RH Under, with 180 ° of peel angle, peeling rate 60mm/ minutes by this bonding sheet 1 from foregoing soda-lime glass peel off when to glass 180 ° of peeling forces can be more than 3N/cm.It is more than 3N/cm by making 180 ° of peeling forces at 23 DEG C, has under normal temperature The appropriate adhesiveness of adherend, fitting operability is excellent, therefore preferably.

From the point of view, 180 ° of peeling forces under 23 DEG C of 40%RH of this bonding sheet 1 are preferably more than 3N/cm, Wherein preferred below 20N/cm, wherein particularly preferred more than 4N/cm or below 15N/cm.

In this bonding sheet 1, in order to adjust 180 ° of peeling forces under 23 DEG C of 40%RH, such as combined by adhesive described later Thing (1-I) or (1-II) manufacture this bonding sheet 1, and then adjust crosslinking agent, the species of Photoepolymerizationinitiater initiater, ratio of components, or adjustment The light irradiation condition after heat/pressure condition, fitting during fitting.In addition, it is also not necessarily limited to such method.

This bonding sheet 1 has (2) before photocuring, and viscosity is changed into 100~3000Pas when being heated to 70~100 DEG C, shows Show feature as mobility.

When this bonding sheet 1 possesses such hot melt, its softening or even liquidation are made by heating, printing can be followed The jogs such as difference of height carry out filling adhesive, therefore can not produce the ground such as foaming and be filled.

In order to obtain such characteristic, such as can be originally viscous by adhesive composition described later (1-I) or (1-II) manufacture Close piece 1.In addition, it is also not necessarily limited to this.

The viscosity when being heated to 70~100 DEG C of this bonding sheet 1 is changed into 100~3000Pas, wherein preferably becoming More than 150Pas or below 2700Pas, wherein preferably becoming more than 200Pas or below 2500Pas.

(180 ° of peeling forces under 80 DEG C of 10%RH)

This bonding sheet 1 can have the feature of following (7).I.e. (7) are crimped on soda-lime glass, in 80 DEG C of 10%RH Under, using 180 ° of peel angle, peeling rate 60mm/ minutes by this bonding sheet 1 from foregoing soda-lime glass peel off when separation mode as Cohesional failure, 180 ° of peeling forces to glass can be below 1N/cm.

When 180 ° of peeling forces at 80 DEG C are below 1N/cm, the high wettability to adherend can be obtained, therefore preferably.

From the point of view, 180 ° of peeling forces under 80 DEG C of 10%RH of this bonding sheet 1 are preferably below 1N/cm, Wherein preferred below 0.8N/cm, wherein particularly preferred below 0.5N/cm.

In this bonding sheet 1, in order to adjust 180 ° of peeling forces under 80 DEG C of 10%RH, such as combined by adhesive described later Thing (1-I) or (1-II) manufacture this bonding sheet 1, and then adjust crosslinking agent, the species of Photoepolymerizationinitiater initiater, ratio of components, or The light irradiation condition after heat/pressure condition, fitting during adjustment fitting.In addition, it is also not necessarily limited to such method.

This bonding sheet 1 can carry out photocuring, and after having (3) photocuring, the viscosity at 70~100 DEG C is changed into 3000~ Feature as 50000Pas.

For this bonding sheet 1, after photocuring, from the viewpoint of high cohesion is obtained, the viscosity at 70~100 DEG C is excellent Choosing is changed into 3000~50000Pas, wherein more than 3500Pas or below 48000Pas is preferably become, wherein further Preferably become more than 4000Pas or below 45000Pas.

(180 ° of peeling forces under 23 DEG C of 40%RH after photocuring)

This bonding sheet 1 can have the feature of following (4) after photocuring.I.e. (4) are for being crimped on soda-lime glass simultaneously Carry out light irradiation so that its solidification photocuring after bonding sheet, under 23 DEG C of 40%RH, with 180 ° of peel angle, peel off speed Degree 60mm/ minutes by bonding sheet from foregoing soda-lime glass peel off when 180 ° of peeling forces to glass can be more than 3N/cm.

When 180 ° of peeling forces at 23 DEG C after photocuring are more than 3N/cm, adherend can be made mutual securely Bonding, therefore preferably.

From the point of view, 180 ° of peeling forces at 23 DEG C after the photocuring of this bonding sheet 1 be preferably 3N/cm with On, wherein it is preferred that more than 4N/cm, wherein particularly preferred more than 5N/cm or below 30N/cm.

(180 ° of peeling forces under 80 DEG C of 10%RH after photocuring)

This bonding sheet 1 can have the feature of following (5) after photocuring.I.e. (5) are for being crimped on soda-lime glass simultaneously Carry out light irradiation so that its solidification photocuring after bonding sheet, under 80 DEG C of 10%RH, with 180 ° of peel angle, peel off speed Degree 60mm/ minutes by bonding sheet from the soda-lime glass peel off when 180 ° of peeling forces to glass can be more than 3N/cm.

When 180 ° of peeling forces at 80 DEG C after photocuring are more than 3N/cm, the resistance to foaminess under hot environment is excellent, because This is preferred.

From the point of view, 180 ° of peeling forces at 80 DEG C after the photocuring of this bonding sheet 1 be preferably 3N/cm with On, wherein preferably more than 4N/cm, wherein especially preferably more than 5N/cm or below 20N/cm.

In this bonding sheet 1, in order to adjust 180 ° of peeling forces at 23 DEG C after photocuring or 80 DEG C, such as by described later viscous Mixture composite (1-I) or (1-II) manufacture this bonding sheet 1, and then adjust crosslinking agent, the species of Photoepolymerizationinitiater initiater, composition Than, or heat/pressure condition during adjustment fitting, the light irradiation condition after fitting.In addition, it is also not necessarily limited to such side Method.

For this bonding sheet after photocuring 1, the xenon arc lamp-based light resistance as defined in JIS K7350-2 (ISO4892-2) Exhaust yield after testing machine 24 hours light irradiations of progress is by hexadecane conversion preferably more than 40000ppm.

When exhaust yield is scaled more than 40000ppm by hexadecane, the viscosity of bonding sheet, the wetability to adherend Improve, therefore preferably.

Therefore, from the point of view, in this bonding sheet 1, above-mentioned exhaust yield is preferably by hexadecane conversion More than 40000ppm, wherein preferably more than 45000ppm, wherein especially preferably more than 50000ppm.

It should be noted that in this bonding sheet 1, in order that above-mentioned exhaust yield is in above range, such as by aftermentioned Adhesive composition (1-I) or (1-II) manufacture this bonding sheet 1.In addition, it is also not necessarily limited to this.

This bonding sheet 1 after photocuring preferably shows a diameter of below 5mm of bubble in following resistance to foaminess experiment Resistance to foaminess.

Resistance to foaminess experiment：Between two glass plates that cornerwise length is more than 5 inches and thickness is below 1mm Clamp bonding sheet and make layered product, according to JIS K7350-2 (ISO4892-2), carried out with xenon arc lamp-based light fastness test machine During 24 hours light irradiations, the diameter of caused bubble in bonding sheet is determined.

It is feature as 3000~50000Pas that this bonding sheet 1, which has the viscosity after photocuring at 70~100 DEG C, Therefore such resistance to foaminess can be shown after photocuring.Therefore, even if can play through prolonged light irradiation, reliability The property not reduced, even if such as can be obtained for a long time exposed to illumination, sunshine etc. for various image display devices Under light, bonding reliability that performance does not also reduce.

As suitable one of this adhesive composition 1 used in the making of this bonding sheet 1, can enumerate containing by Possess macromonomer as branch composition graft copolymer form acrylic copolymer (1-A1), crosslinking agent (1-B1) with And the adhesive composition (1-I) of Photoepolymerizationinitiater initiater (1-C1).

In addition, another example as this adhesive composition 1, can be enumerated containing (methyl) acrylic copolymer (1- A2), the adhesive composition (1-II) of crosslinking agent (1-B2) and Photoepolymerizationinitiater initiater (1-C2), (methyl) acrylic compounds Copolymer (1-A2) be make by glass transition temperature (Tg) less than 0 DEG C monomer a1, glass transition temperature (Tg) be 0 DEG C with Upper and monomer a2 less than 80 DEG C and monomer a3 that glass transition temperature (Tg) is more than 80 DEG C are with a1：a2：A3=10~ 40：90~35：The copolymer that 0~25 mol ratio copolymerization forms, and weight average molecular weight is 50000~400000.

In addition, it is not limited to adhesive composition (1-I) or (1-II) for forming the adhesive composition of this bonding sheet 1.

It should be noted that number-average molecular weight and weight average molecular weight are used using using gel permeation chromatography (GPC) Scaled value of the polystyrene as standard substance.

During by the adhesive composition (1-I) prepared with known method or (1-II) to manufacture this bonding sheet 1, Ke Yi Room temperature state lower retention tab shape and display tack, have the hot melt for melting or even flowing during heating under non cross-linked state, And then excellent cohesive force can be played after photocuring with photocuring.

As adhesive composition (1-I), it can enumerate to contain and be total to by possessing macromonomer as the grafting of branch composition The adhesive combination for acrylic copolymer (1-A1), crosslinking agent (1-B1) and the Photoepolymerizationinitiater initiater (1-C1) that polymers is formed Thing.

(acrylic copolymer (1-A1))

Based on polymer acrylic copolymer (1-A1) to possess grafting of the macromonomer as branch composition Copolymer.

(trunk composition)

The trunk composition of foregoing acrylic copolymer (1-A1) is preferably by containing the repetition from (methyl) acrylate The copolymer composition of unit is formed.

Form the copolymer of the trunk composition of the acrylic copolymer (1-A1) glass transition temperature be preferably- 70~0 DEG C.

Now, the glass transition temperature for forming the copolymer composition of trunk composition refers to, is only total to composition acrylic compounds The glass transition temperature of polymer obtained from the monomer component copolymerization of the trunk composition of polymers (1-A1).Specifically, it is Refer to the glass transition temperature and composition according to the polymer obtained by the homopolymer of each composition of the copolymer, pass through Fox The value that formula calculates.

It should be noted that Fox formulas refer to the calculated value obtained by following formula, polymer handbook can be used Value described in (PolymerHandBook, J.Brandrup, Interscience, 1989) is obtained.

1/ (273+Tg)=Σ (Wi/ (273+Tgi))

[in formula, Wi represents monomer i percentage by weight, and Tgi represents the Tg (DEG C) of monomer i homopolymer.]

Form the glass transition temperature meeting of the copolymer composition of the trunk composition of foregoing acrylic copolymer (1-A1) Influence the wetting of the flexibility, adhesive composition (1-I) of the adhesive composition (1-I) under room temperature state to adherend Property, i.e. cementability, therefore, in order to obtain adhesive composition (1-I) cementability (viscosity) appropriate under room temperature state, the glass Glass transition temperature is preferably -80 DEG C~0 DEG C, wherein it is preferred that more than -75 DEG C or less than -5 DEG C, wherein particularly preferably -70 DEG C Above or less than -10 DEG C.

Wherein, can also be by adjusting molecular weight even if the glass transition temperature of the copolymer composition is mutually synthermal To adjust viscoplasticity.Such as by reducing the molecular weight of copolymer composition, its more softness can be made.

(methyl) acrylate monomer that trunk composition as foregoing acrylic copolymer (1-A1) contains, such as can To enumerate：(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) isoamyl acrylate, (methyl) acrylic acid peopentyl ester, (methyl) Hexyl 2-propenoate, (first Base) cyclohexyl acrylate, (methyl) heptylacrylate, 2-EHA, n-octyl, Isooctyl acrylate monomer, (methyl) acrylic acid nonyl ester, the different nonyl ester of (methyl) acrylic acid, (methyl) t-butylcyclohexyl ester, (methyl) acrylic acid last of the ten Heavenly stems Ester, (methyl) isodecyl acrylate, (methyl) acrylic acid hendecane base ester, (methyl) lauryl acrylate, (methyl) acrylic acid Cetyl, (methyl) stearyl acrylate ester, the different stearyl ester of (methyl) acrylic acid, (methyl) acrylic acid behenyl ester, (methyl) propylene Sour isobornyl thiocyanoacetate, (methyl) acrylic acid 2- phenoxy ethyls, acrylic acid 3,5,5- 3-methyl cyclohexanols ester, p- cumyl phenols EO are modified (methyl) acrylate, the ring pentyl ester of (methyl) acrylic acid two, (methyl) acrylic acid dicyclopentenyl ester, the ring penta of (methyl) acrylic acid two Alkenyl epoxide ethyl ester, (methyl) benzyl acrylate etc..(methyl) propylene for possessing hydrophilic group, organo-functional group etc. can also be used Hydroxyl (the first such as sour hydroxyl ethyl ester, (methyl) hydroxypropyl acrylate, (methyl) hy-droxybutyl, (methyl) glycerol acrylate Base) acrylate, (methyl) acrylic acid, 2- (methyl) acryloyl-oxyethyls hexahydrophthalic acid, 2- (methyl) acryloyl Epoxide propyl group hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyls phthalic acid, 2- (methyl) acryloxy third Base phthalic acid, 2- (methyl) acryloyl-oxyethyls maleic acid, 2- (methyl) acryloxypropyls maleic acid, 2- (first Base) acryloyl-oxyethyl butanedioic acid, 2- (methyl) acryloxypropyls butanedioic acid, crotonic acid, fumaric acid, maleic acid, clothing The monomers containing anhydride group such as carboxyl group-containing monomer, maleic anhydride, the itaconic anhydrides such as health acid, monomethyl maleate, monomethyl itaconate, (methyl) glycidyl acrylate, α-ethylacrylate ethylene oxidic ester, (methyl) acrylic acid 3,4- epoxy butyl esters etc. contain ring Epoxide monomer, (methyl) dimethylaminoethyl acrylate, (methyl) diethylaminoethyl acrylate etc. contain amino (methyl) propylene Acid esters system monomer, (methyl) acrylamide, the N- tert-butyl groups (methyl) acrylamide, N- methylols (methyl) acrylamide, N- first Epoxide methyl (methyl) acrylamide, N- butoxymethyls (methyl) acrylamide, DAAM, maleic amide, horse It is single to carry out the heterocycle systems such as the monomer containing amide groups such as acid imide, vinyl pyrrolidone, vinylpyridine, vinyl carbazole alkalescence Body, etc..

Alternatively, it is also possible to suitably using can with aforesaid propylene acrylic monomer, methacrylic monomer be copolymerized styrene, T-butyl styrene, α-methylstyrene, vinyltoluene, acrylonitrile, methacrylonitrile, vinylacetate, propionate, The various vinyl monomers such as alkyl vinyl ether, hydroxyalkyl vinylether, alkyl vinyl monomers.

In addition, the trunk composition of acrylic copolymer (1-A1) preferably comprises hydrophobic (methyl) acrylate monomer With hydrophilic (methyl) acrylate monomer as Component units.

When the trunk composition of acrylic copolymer (1-A1) is only made up of hydrophobic monomer, discovery has inclining for damp and hot albefaction To, therefore hydrophilic monomer is also preferably imported in trunk composition to prevent damp and hot albefaction.

Specifically, the trunk composition as aforesaid propylene acid copolymer (1-A1), can enumerate hydrophobic (first Base) acrylate monomer and the end of hydrophilic (methyl) acrylate monomer and macromonomer polymerizable functional group without Copolymer composition obtained from rule copolymerization.

Here, as above-mentioned hydrophobic (methyl) acrylate monomer, Arrcostab (its preferably without polar group In do not include methyl acrylate), such as can enumerate：(methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) Sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) isoamyl acrylate, (methyl) third Olefin(e) acid peopentyl ester, (methyl) Hexyl 2-propenoate, (methyl) cyclohexyl acrylate, (methyl) heptylacrylate, acrylic acid 2- ethyls Own ester, n-octyl, Isooctyl acrylate monomer, (methyl) acrylic acid nonyl ester, the different nonyl ester of (methyl) acrylic acid, (methyl) propylene Sour t-butyl cyclohexyl methacrylate, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) acrylic acid hendecane base ester, (first Base) lauryl acrylate, (methyl) acrylic acid cetyl, (methyl) stearyl acrylate ester, the different stearyl ester of (methyl) acrylic acid, (methyl) acrylic acid behenyl ester, (methyl) isobornyl acrylate, (methyl) cyclohexyl acrylate, the ring penta of (methyl) acrylic acid two Alkenyl epoxide ethyl ester, methyl methacrylate.

In addition, as hydrophobic vinyl monomer, such as can enumerate：Vinylacetate, styrene, tert-butyl benzene second Alkene, α-methylstyrene, vinyltoluene, alkyl vinyl monomers etc..

As above-mentioned hydrophilic (methyl) acrylate monomer, preferably methyl acrylate, the ester with polar group, example It can such as enumerate：Methyl acrylate, (methyl) acrylic acid, (methyl) tetrahydrofurfuryl acrylate, (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate, (methyl) glycerol acrylate etc. hydroxyl (methyl) propylene Acid esters, (methyl) acrylic acid, 2- (methyl) acryloyl-oxyethyls hexahydrophthalic acid, 2- (methyl) acryloxypropyl Hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyls phthalic acid, 2- (methyl) acryloxypropyl neighbour benzene two Formic acid, 2- (methyl) acryloyl-oxyethyls maleic acid, 2- (methyl) acryloxypropyls maleic acid, 2- (methyl) acryloyl Epoxide ethylsuccinic acid, 2- (methyl) acryloxypropyls butanedioic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, Malaysia The monomers containing anhydride group such as the carboxyl group-containing monomers such as sour mono-methyl, monomethyl itaconate, maleic anhydride, itaconic anhydride, (methyl) propylene Acid glycidyl ester, α-ethylacrylate ethylene oxidic ester, (methyl) acrylic acid 3,4- epoxy butyl esters etc. are containing epoxy based monomers, first Epoxide polyethylene glycol (methyl) acrylate etc. alkoxy polyalkyleneglycol (methyl) acrylate, N, N- dimethyl allene acyls Amine, hydroxyethyl acrylamide etc..

(branch composition：Macromonomer)

For acrylic copolymer (1-A1), as the branch composition of graft copolymer, preferably macromonomer is imported simultaneously Contain the repeat unit from macromonomer.

Macromonomer refers to there is the polymerizable functional group of end and the high polymer monomer of HMW framework ingredient.

The glass transition temperature (Tg) of macromonomer, which is preferably above, forms aforesaid propylene acid copolymer (1-A1) The glass transition temperature of copolymer composition.

Specifically, the glass transition temperature (Tg) of macromonomer can influence adhesive composition (1-I) heating Melting temperature (hot melting temperature), therefore the glass transition temperature (Tg) of macromonomer is preferably 30 DEG C~120 DEG C, wherein excellent More than 40 DEG C or less than 110 DEG C are selected, wherein further preferred more than 50 DEG C or less than 100 DEG C.

For such glass transition temperature (Tg) when, by adjusting molecular weight, excellent processability, keeping can be kept Stability, and can be adjusted to nearby to heat at 80 DEG C.

The glass transition temperature of macromonomer refers to the macromonomer glass transition temperature of itself, Ke Yitong Differential scanning calorimeter (DSC) is crossed to determine (programming rate：5 DEG C/min, Tg is determined according to the flex point of needle position misalignment).

In addition, under room temperature state, branch composition adsorbs between each other, can maintain to have carried out thing as adhesive composition The state of crosslinking is managed, moreover, by being heated to appropriate temperature, the physical crosslinking can be caused to release and obtain mobility, For this it is also preferred that the molecular weight of adjustment macromonomer, content.

From the point of view, with the mass % of 5 mass %~30 ratio preferably in acrylic copolymer (1-A1) Containing macromonomer, wherein it is preferred that more than 6 mass % or below 25 mass %, wherein it is preferred that more than 8 mass % or 20 Below quality %.

In addition, the number-average molecular weight of macromonomer is preferably 500 less than 8000, wherein preferably more than 800 Or less than 7500, wherein preferably more than 1000 or less than 7000.

Macromonomer can be suitably using conventionally fabricated material (such as the macromolecular list that East Asia Synesis Company manufactures Body etc.).

The HMW framework ingredient of macromonomer is preferably by acrylic polymer or ethylene-based polymer.

As the HMW framework ingredient of foregoing macromonomer, such as can enumerate：(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (first Base) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) Isoamyl acrylate, (methyl) acrylic acid peopentyl ester, (methyl) Hexyl 2-propenoate, (methyl) cyclohexyl acrylate, (methyl) third Olefin(e) acid heptyl ester, 2-EHA, n-octyl, Isooctyl acrylate monomer, (methyl) acrylic acid nonyl ester, (methyl) third The different nonyl ester of olefin(e) acid, (methyl) t-butylcyclohexyl ester, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (first Base) acrylic acid hendecane base ester, (methyl) lauryl acrylate, (methyl) acrylic acid cetyl, (methyl) stearyl acrylate ester, The different stearyl ester of (methyl) acrylic acid, (methyl) acrylic acid behenyl ester, (methyl) isobornyl acrylate, (methyl) acrylic acid 2- benzene Epoxide ethyl ester, acrylic acid 3,5,5- 3-methyl cyclohexanols ester, p- cumyl phenols EO are modified (methyl) acrylate, (methyl) acrylic acid Two ring pentyl esters, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid dicyclopentenyl epoxide ethyl ester, (methyl) acrylic acid benzyl Ester, (methyl) hydroxyalkyl acrylates, (methyl) acrylic acid, (methyl) glycidyl acrylate, (methyl) acrylamide, N, N- dimethyl (methyl) acrylamide, (methyl) acrylonitrile, (methyl) alkoxyalkyl acrylate, alkoxypolyalkylene (methyl) acrylate monomer, styrene, t-butyl styrene, α-methylstyrene, the ethene such as glycol (methyl) acrylate The various vinyl monomers such as base toluene, alkyl vinyl monomers, vinylacetate, alkyl vinyl ether, hydroxyalkyl vinylether, These can be used alone or are used in combination of two or more.

As the end polymeric functional group of foregoing macromonomer, such as methylacryloyl, acryloyl can be enumerated Base, vinyl etc..

(crosslinking agent (1-B1))

As crosslinking agent (1-B1), such as can suitably select with the epoxy radicals of more than 2, NCO, oxa- The crosslinking agent of the crosslinkable groups such as cyclobutane base, silanol group, (methyl) acryloyl group.Wherein, in reactivity, obtained solidification The aspect of the intensity of thing, preferably with more than 2 (methyl) acryloyl groups, wherein preferably with more than 3 (methyl) acryloyls Multifunctional (methyl) acrylate of base；(methyl) acrylate with epoxy radicals, NCO etc..

After the fitting integration of image display device member of formation, by making crosslinking agent (1-B1) be handed in jointing material Connection, the piece lose hot melt, the substitute is the high cohesion shown under hot environment, can obtain excellent resistance to foaming Reliability.

As such (methyl) acrylate, such as can enumerate：1,4- butanediols two (methyl) acrylate, new penta Glycol two (methyl) acrylate, glycerine two (methyl) acrylate, glycerine glycidol ether two (methyl) acrylate, 1,6- Hexylene glycol two (methyl) acrylate, 1,9- nonanediols two (methyl) acrylate, Tricyclodecane Dimethanol two (methyl) propylene More ethyoxyl two (methyl) acrylate of acid esters, bisphenol-A, more alkoxy two (methyl) acrylate of bisphenol-A, the more alcoxyls of Bisphenol F Base two (methyl) acrylate, PAG two (methyl) acrylate, trimethylolpropane tris epoxide ethyl (methyl) Acrylate, 6-caprolactone are modified three (2- ethoxys) isocyanuric acid ester three (methyl) acrylate, pentaerythrite three (methyl) Acrylate, pentaerythritol propoxylate three (methyl) acrylate, ethoxylation pentaerythrite three (methyl) acrylate, season Penta tetrol four (methyl) acrylate, pentaerythritol propoxylate four (methyl) acrylate, (first of ethoxylation pentaerythrite four Base) acrylate, dipentaerythritol six (methyl) acrylate, polyethylene glycol two (methyl) acrylate, three (acryloxies Ethyl) isocyanuric acid ester, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, two seasons penta 4 Alcohol five (methyl) acrylate, tripentaerythritol six (methyl) acrylate, tripentaerythritol five (methyl) acrylate, hydroxyl Pivalic acid neopentyl glycol two (methyl) acrylate, 3-hydroxypivalic acid neopentyl glycol 6-caprolactone addition product two (methyl) third Olefin(e) acid ester, trimethylolpropane tris (methyl) acrylate, oxyalkylated trihydroxy methyl-propane three (methyl) acrylate, double three The ultraviolet hardening polyfunctional monomer classes such as hydroxymethyl-propane four (methyl) acrylate；And polyester (methyl) acrylate, The multifunctional acrylic compounds such as epoxy (methyl) acrylate, polyurethane (methyl) acrylate, polyethers (methyl) acrylate are low Polymers class, isocyanates (methyl) acrylate, 1,1- (double (methyl) acryloyloxymethyls) ethyl isocyanate, 2- (2- (methyl) acryloyl-oxyethyl epoxide) ethyl isocyanate, (methyl) glycidyl acrylate, (methyl) acrylic acid hydroxyl second Ester glycidol ether, (methyl) hydroxypropyl acrylate glycidol ether, (methyl) hy-droxybutyl glycidol ether etc..

In enumerating above, from the viewpoint of improving the adaptation to adherend, suppressing the effect of damp and hot albefaction, preferably Polyfunctional monomer or oligomer containing hydroxyl isopolarity functional group.

Wherein, preferably using multifunctional (methyl) acrylate with hydroxyl or carboxyl.

Therefore, from the viewpoint of damp and hot albefaction is prevented, as foregoing acrylic copolymer (1-A1), i.e. graft copolymerization The trunk composition of thing, hydrophobic acrylate monomer and hydrophilic acrylate monomer are preferably comprised, and then, as crosslinking Agent (1-B), preferably using multifunctional (methyl) acrylate with hydroxyl.

The content of crosslinking agent (1-B1) is had no particular limits.As benchmark, relative to acrylic copolymer (1- A1) 100 mass parts are 0.5~20 mass parts, wherein it is preferred that more than 1 mass parts or below 15 mass parts, wherein it is preferred that 2 mass Ratio more than part or below 10 mass parts.

By containing crosslinking agent (1-B1) within the above range, the shape of this bonding sheet 1 under non cross-linked state can be taken into account The resistance to foaming reliability in jointing material after shape stability and crosslinking.Furthermore, it is contemplated that the balance with other element, can also Beyond the scope.

(Photoepolymerizationinitiater initiater (1-C1))

Photoepolymerizationinitiater initiater (1-C1) is that the reaction in the cross-linking reaction as foregoing crosslinking agent (1-B1) triggers auxiliary agent And play the material of function.

Photoepolymerizationinitiater initiater can suitably use presently known material.Wherein, from the easy of the control of cross-linking reaction From the viewpoint of degree, the Photoepolymerizationinitiater initiater sensed to below wavelength 380nm ultraviolet is preferable.

On the other hand, the light that the Photoepolymerizationinitiater initiater sensed to the light of wavelength ratio wavelength 380nm length is sensed is easy The depths of this bonding sheet 1 is reached, is preferable in this respect.

Photoepolymerizationinitiater initiater is roughly divided into two classes according to the difference of free radical generation mechanism：Optical polymerism initiator itself Singly-bound fracture, decompose so as to may result from the cracking type Photoepolymerizationinitiater initiater by base；And in light activated initiator and system Hydrogen donor form excitation state complex compound, the hydrogen-abstraction Photoepolymerizationinitiater initiater of the hydrogen migration of hydrogen donor can be made.

When cracking type Photoepolymerizationinitiater initiater among these produces free radical by light irradiation, decompose and formed other Compound, the function as reaction initiator is lost once being excited.Therefore, the jointing material after cross-linking reaction terminates In be not re-used as spike and remain, in the absence of the possibility of the light deterioration caused to jointing material outside expected etc., therefore preferably.

On the other hand, the Photoepolymerizationinitiater initiater of hydrogen-abstraction is irradiated by ultraviolet isoreactivity energy-ray and free radical life occurs Into during reaction, the analyte as cracking type Photoepolymerizationinitiater initiater will not be produced, thus reaction terminate after be not easy to turn into and wave Composition is sent out, is useful from the infringement aspect to adherend can be reduced.

As preceding cleavage type light trigger, such as can enumerate：2,2- dimethoxy -1,2- diphenylethane -1- ketone, 1- hydroxycyclohexylphenylketones, 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone, 1- (4- (2- hydroxyl-oxethyls) phenyl) -2- Hydroxy-2-methyl -1- propane -1- ketone, 2- hydroxyls -1- [4- { 4- (2- hydroxy-2-methyls-propiono) benzyl } phenyl] -2- first Base-propane -1- ketone, oligomeric (2- hydroxy-2-methyls -1- (4- (1- methyl ethylenes) phenyl) acetone), phenylacetaldehyde acid methyl esters, 2- Benzyl -2- dimethylaminos -1- (4- morpholinyl phenyls) butane -1- ketone, 2- methyl isophthalic acids-[4- (methyl mercapto) phenyl] -2- morpholine propanes - 1- ketone, 2- (dimethylamino) -2- [(4- aminomethyl phenyls) methyl] -1- [4- (4- morpholinyls) phenyl] -1- butanone, double (2,4,6- Trimethylbenzoyl)-phenyl phosphine oxide, 2,4,6- trimethylbenzoyls diphenyl phosphine oxide, these derivative etc..

As foregoing hydrogen-capture-type light initiator, such as can enumerate：Benzophenone, 4- methyl-benzophenones, 2,4,6- tri- Methyl benzophenone, 4- phenyl benzophenones, 3,3'- dimethyl -4- methoxy benzophenones, 4- (methyl) acryloxy two Benzophenone, 2- methyl benzoylbenzoates, methyl benzoylformate, double (2- phenyl -2- Oxoacetic Acids) epoxides double ethene, 4- (decyl of five oxos of 1,3- acryloyls -1,4,7,10,13- three) benzophenone, thioxanthones, CTX, 3- methyl thioxanthones, 2,4- dimethyl thioxanthones, 2-methylanthraquinone, 2- EAQs, 2- tert-butyl groups anthraquinone, 2- amino anthraquinones, its derivative etc..

In addition, as Photoepolymerizationinitiater initiater, cited material is not limited to.It can be gathered using above-named cracking type light Close initiator and hydrogen-abstraction Photoepolymerizationinitiater initiater any of, can also be applied in combination two or more.

The content of Photoepolymerizationinitiater initiater (1-C1) is had no particular limits.As benchmark, to be total to relative to acrylic compounds The mass parts of polymers (1-A1) 100 are 0.1~10 mass parts, wherein more than 0.5 mass parts or below 5 mass parts, wherein 1 mass It is preferable that ratio more than part or below 3 mass parts, which contains,.

It is above range by making the content of Photoepolymerizationinitiater initiater (1-C1), can obtains to active energy beam appropriateness Reaction sensitivity.

(other compositions)

For adhesive composition (1-I), as composition other than the above, adhesive combination can be mixed in containing generally matching somebody with somebody The known composition of thing.For example, it can suitably contain tackifying resin, antioxidant, light stabilizer, metal passivation as needed The various additions such as agent, age resister, hygroscopic agent, polymerization inhibitor, ultra-violet absorber, antirust agent, silane coupler, inorganic particle Agent.

In addition, it can suitably contain catalysts (tertiary amine based compound, quaternary ammonium based compound, laurate as needed Tin compound etc.).

As adhesive composition (1-II), can enumerate containing (methyl) acrylic copolymer (1-A2), crosslinking agent (1-B2) and Photoepolymerizationinitiater initiater (1-C2) adhesive composition, (methyl) acrylic copolymer (1-A2) are contained It it is 0 DEG C less than 80 DEG C of list by monomer a1 of the glass transition temperature (Tg) less than 0 DEG C, glass transition temperature (Tg) Body a2 and glass transition temperature (Tg) are more than 80 DEG C of monomer a3 with a1：a2：A3=10~40：90~35：0~25 Mol ratio copolymerization obtained from, (methyl) acrylate copolymer or ethylene copolymer of weight average molecular weight 50000~400000.

((methyl) acrylic copolymer (1-A2))

Based on polymer (methyl) acrylic copolymer (1-A2) be preferably (methyl) acrylate copolymer Or ethylene copolymer.

For above-mentioned (methyl) acrylate copolymer or ethylene copolymer, from the shape retention taken into account in room temperature state From the viewpoint of hot melt, weight average molecular weight is preferably 50000~500000, wherein preferably more than 60000 or Less than 450000, wherein more preferably more than 70000 or less than 400000.

For acrylate based copolymer, by suitably selecting to be used to prepare its used acrylic monomer, methyl Species, composition ratio and then polymerizing condition of acrylic monomer etc., it can suitably adjust glass transition temperature (Tg), divide The physical property such as son amount.

Now, the acrylic monomer as composition acrylate copolymer, such as acrylic acid 2- ethyl hexyls can be enumerated Ester, n-octyl, Isooctyl acrylate monomer, n-butyl acrylate, ethyl acrylate etc. are used as main material.

In addition to these, can also be by with various functional groups according to assigning cohesive force, assigning the purpose of polarity (methyl) acrylic monomer is copolymerized with aforesaid propylene acrylic monomer.

As (methyl) acrylic monomer with the functional group, such as methyl methacrylate, propylene can be enumerated Sour methyl esters, hydroxy-ethyl acrylate, acrylic acid, glycidyl acrylate, N- substituted acrylamides, acrylonitrile, methacrylonitrile, The fluorine-containing Arrcostab of acrylic acid, containing organic silyl acrylate etc..

On the other hand, as ethylene copolymer, can enumerate that also suitable polymerization has can be with aforesaid propylene acrylic monomer, methyl The vinylacetate of acrylic monomer copolymerization, alkyl vinyl ether, the various vinyl monomers such as hydroxyalkyl vinylether and obtain The ethylene copolymer arrived.

It is preferably that glass transition temperature (Tg) is low as (methyl) acrylic copolymer (1-A2) of this bonding sheet 1 Monomer a1, glass transition temperature (Tg) in 0 DEG C are 0 DEG C less than 80 DEG C of monomer a2 and glass transition temperature (Tg) it is more than 80 DEG C of monomer a3 with a1：a2：A3=10~40：90~35：(methyl) that 0~25 mol ratio copolymerization forms Acrylate copolymer or ethylene copolymer.

Now, (homopolymerization when monomer a1, a2 and a3 each glass transition temperature (Tg) refers to make polymer by the monomer Materialization) each glass transition temperature (Tg).

The monomer a1 for example preferably has (methyl) acrylate monomer of following alkyl structure：The alkyl structure is The alkyl structure of side chain with carbon number more than 4.

Now, the side chain of carbon number more than 4 can be made up of straight chain, can also be made up of the carbochain being branched.

More particularly, for aforementioned monomer a1, it is however preferred to have (methyl) third of the straight chained alkyl structure of carbon number 4~10 Olefin(e) acid ester monomer or with carbon number 6~18 branched chain alkyl moiety (methyl) acrylate monomer.

Here, as " (methyl) acrylate monomer with the straight chained alkyl structure of carbon number 4~10 ", can enumerate： The positive nonyl ester of n-butyl acrylate, the just own ester of acrylic acid, n-octyl, acrylic acid, the positive last of the ten Heavenly stems ester of acrylic acid etc..

On the other hand, as " (methyl) acrylate monomer with the branched chain alkyl moiety of carbon number 6~18 ", Ke Yiju Go out：2-EHA, 2-Ethylhexyl Methacrylate, the own ester of acrylic acid 2- methyl, Isooctyl acrylate monomer, acrylic acid Different nonyl ester, isodecyl acrylate, isodecyl methacrylate etc..

(methyl) acrylate monomer below 4 of the preferred carbon numbers of aforementioned monomer the a2, (first in side chain with cyclic skeleton Base) vinyl monomer below 4 of acrylate monomer, carbon number or there is the vinyl monomer of cyclic skeleton in side chain.

Wherein, the carbon number of the above-mentioned particularly preferred side chains of monomer a2 is less than 4 vinyl monomer.

Here, as " (methyl) acrylate monomer of carbon number below 4 ", can enumerate：Methyl acrylate, metering system Acetoacetic ester, n-propyl, n propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, methacrylic acid N-butyl, tert-butyl acrylate, isobutyl acrylate, Isobutyl methacrylate etc..

As " there is (methyl) acrylate monomer of cyclic skeleton in side chain ", can enumerate：Isobornyl acrylate, Cyclohexyl acrylate, cyclohexyl methacrylate, 1,4 cyclohexane dimethanol mono acrylic ester, tetrahydrofurfuryl methacrylate, Benzyl acrylate, benzyl methacrylate, acrylate, phenoxyethyl methacrylate, acrylic acid 2- hydroxyls- 3- phenoxy-propyls, 3,3,5- cyclonols acrylate, cyclic trimethylolpropane dimethoxym ethane acrylate, 4- ethoxies Base cumyl phenol acrylate, acrylic acid dicyclopentenyl epoxide ethyl ester, methacrylic acid dicyclopentenyl epoxide ethyl ester, third Olefin(e) acid dicyclopentenyl ester etc..

As " vinyl monomer of the carbon number below 4 ", can enumerate：Vinylacetate, propionate, butyric acid ethene Ester, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether, IVE etc..

As " there is the vinyl monomer of cyclic skeleton in side chain ", can enumerate：Styrene, cyclohexyl vinyl ether, Norborny vinyl ethers, norbornene vinyl ethers etc..Wherein, the carbon number of particularly preferred side chain is less than 4 ethene system The carbon number of monomer or side chain is less than 4 acrylate monomer.

(methyl) acrylate monomer or there is ring-type in side chain that the carbon number of the preferred side chains of aforementioned monomer a3 is less than 1 (methyl) acrylate monomer of skeleton.

Here, as " carbon number of side chain is less than 1 (methyl) acrylate monomer ", can enumerate：Methacrylic acid Methyl esters, acrylic acid, methacrylic acid etc..

As " there is (methyl) acrylate monomer of cyclic skeleton in side chain ", can enumerate：The different ice of methacrylic acid Piece ester, methacrylic acid 3,3,5- 3-methyl cyclohexanols ester, acrylic acid bicyclopentyl ester, methacrylic acid bicyclopentyl ester, methyl Acrylic acid dicyclopentenyl base ester etc..

(methyl) acrylic copolymer (1-A2) contains monomer a1 and monomer a2 and monomer a3 with a1：a2：A3=10 ~40：90~35：When (methyl) acrylate copolymer or ethylene copolymer that 0~25 mol ratio copolymerization forms, it can incite somebody to action Tan δ peak is adjusted to 0~20 DEG C, can in the normal state, i.e., the shape in room temperature state lower retention tab shape.Furthermore, it is possible to Show to be adhered to the property (be referred to as " viscosity ") of adherend in a short time by slight power.In addition, it is heated to heat-fusible Temperature when, become to show mobility, the difference of height portion that can follow binding face is filled to each corner.

Therefore, from the point of view, (methyl) acrylate for forming (methyl) acrylic copolymer (1-A2) is common The mol ratio of monomer a1 and monomer a2 and monomer a3 in polymers or ethylene copolymer is preferably a1：a2：A3=10~40：90~ 35：0~25, wherein preferably 13~40：87~35：0~23, wherein preferably 15~40：85~38：2~20.

In addition, from viewpoint similar to the above, (methyl) acrylic acid of (methyl) acrylic copolymer (1-A2) The mol ratio of monomer a1 and monomer a2 and monomer a3 in ester copolymer or ethylene copolymer is preferably a2>a1>a3.

(crosslinking agent (1-B2))

By making crosslinking agent (1-B2) be crosslinked in this bonding sheet 1, this bonding sheet 1 can be shown in high temperature environments High cohesion, obtain excellent resistance to foaming reliability.

As such crosslinking agent (1-B2), for example, can suitably select have more than 2 epoxy radicals, NCO, The crosslinking agent of the crosslinkable groups such as oxetanyl, silanol group, (methyl) acryloyl group.Wherein, in reactivity, obtain The aspect of the intensity of solidfied material, preferably with more than 2 (methyl) acryloyl groups, wherein preferably with more than 3 (methyl) third Multifunctional (methyl) acrylate of enoyl-；(methyl) acrylate with epoxy radicals, NCO etc..

As such (methyl) acrylate, such as can enumerate：1,4- butanediols two (methyl) acrylate, glycerine Two (methyl) acrylate, 1,6-HD two (methyl) acrylate, 1,9- nonanediols two (methyl) acrylate, the three ring last of the ten Heavenly stems More ethyoxyl two (methyl) acrylate of alkane dimethanol two (methyl) acrylate, bisphenol-A, the more propoxyl group two (methyl) of bisphenol-A More ethyoxyl two (methyl) acrylate of acrylate, Bisphenol F, ethylene glycol two (methyl) acrylate, trimethylolpropane tris Epoxide ethyl (methyl) acrylate, 6-caprolactone are modified three (2- ethoxys) isocyanuric acid ester three (methyl) acrylate, season Penta tetrol three (methyl) acrylate, pentaerythritol propoxylate three (methyl) acrylate, (first of ethoxylation pentaerythrite three Base) acrylate, pentaerythrite four (methyl) acrylate, pentaerythritol propoxylate four (methyl) acrylate, ethyoxyl Change pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, polyethylene glycol two (methyl) acrylic acid Ester, three (acryloyl-oxyethyl) isocyanuric acid esters, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) third Olefin(e) acid ester, dipentaerythritol five (methyl) acrylate, tripentaerythritol six (methyl) acrylate, (first of tripentaerythritol five Base) acrylate, 3-hydroxypivalic acid neopentyl glycol two (methyl) acrylate, the 6-caprolactone of 3-hydroxypivalic acid neopentyl glycol add Into two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, the more (first of ethyoxyl three of trimethylolpropane of thing Base) ultraviolet hardening such as acrylate, double trimethylolpropane four (methyl) acrylate polyfunctional monomer class；It is and poly- Ester (methyl) acrylate, epoxy (methyl) acrylate, carbamate (methyl) acrylate, polyethers (methyl) acrylic acid The oligomeric species of the multifunctional acrylic compounds such as ester, isocyanates (methyl) acrylate, 1,1- (double (methyl) acryloxy first Base) ethyl isocyanate, 2- (2- (methyl) acryloyl-oxyethyls epoxide) ethyl isocyanate, (methyl) acrylic acid shrink it is sweet Grease, (methyl) hydroxy-ethyl acrylate glycidol ether, (methyl) hydroxypropyl acrylate glycidol ether, (methyl) acrylic acid hydroxyl Butyl ester glycidol ether etc..

In enumerating above, the viewpoint of the adaptation of adherend, heat resistance, the effect for suppressing damp and hot albefaction is gone out from improving Hair, preferably comprise the polyfunctional monomer or oligomer of polar functional group.Wherein, preferably using more with isocyanuric acid ring skeleton Function (methyl) acrylate.

The content of crosslinking agent (1-B2) is had no particular limits.As benchmark, relative to (methyl) acrylic copolymer The mass parts of thing (1-A2) 100 are 0.5~20 mass parts, wherein preferably more than 1 mass parts or below 15 mass parts, it is wherein preferred Ratio more than 2 mass parts or below 10 mass parts.

By containing crosslinking agent (1-B2) within the above range, the shape of this bonding sheet 1 under non cross-linked state can be taken into account The resistance to foaming reliability in bonding sheet after shape stability and crosslinking.Furthermore, it is contemplated that the balance with other element, can also surpass Go out the scope.

(Photoepolymerizationinitiater initiater (1-C2))

Photoepolymerizationinitiater initiater (1-C2) is that the reaction in the cross-linking reaction as foregoing crosslinking agent (1-B2) triggers auxiliary agent And the material of function is played, it can suitably use the material in the related record of foregoing Photoepolymerizationinitiater initiater (1-C1).

The content of Photoepolymerizationinitiater initiater (1-C2) is had no particular limits.As benchmark, with relative to (methyl) propylene The mass parts of acid copolymer (1-A2) 100 are 0.1~10 mass parts, wherein more than 0.5 mass parts or below 5 mass parts, its In ratio more than 1 mass parts or below 3 mass parts to contain be preferable.

It is above range by making the content of Photoepolymerizationinitiater initiater (1-C2), can obtains to active energy beam appropriateness Reaction sensitivity.

(other compositions)

For adhesive composition (1-II), as composition other than the above, adhesive group can be mixed in containing generally matching somebody with somebody The known composition of compound.For example, it can suitably contain tackifying resin, antioxidant, light stabilizer, metal passivation as needed The various additions such as agent, age resister, hygroscopic agent, polymerization inhibitor, ultra-violet absorber, antirust agent, silane coupler, inorganic particle Agent.

This bonding sheet 1 can be the piece formed by individual layer or the multilayer tablet for being laminated more than 2 layers.

In the case of bonding sheet of this bonding sheet 1 for multilayer, possess the adhesive layer formed by this adhesive composition 1 and (claim Make " this adhesive layer 1 "), such as in the case of the bonding sheet that formation possesses intermediate layer and the such stacking of outermost layer is formed, It is preferred that its outermost layer is formed by this adhesive composition 1, wherein it is preferred that being formed by adhesive composition (1-I) (1-II).

In addition, this bonding sheet 1 can possess this adhesive layer 1 that will be formed by this adhesive composition 1 and formed be stripped The piece that is formed obtained from film or possess on adherend, for example in aftermentioned such device used for image display The piece formed is formed obtained from above-mentioned adhesive layer 1 on member of formation.In addition, for example can be to possess to be formed on base material State the bonding sheet with base material that is formed obtained from this adhesive layer 1 or without base material without base material bonding sheet.Enter And can be double-sided adhesive sheet of the upper and lower both sides with this adhesive layer 1 or only in upper and lower single-face side with this bonding The one side bonding sheet of layer 1.

From the viewpoint of the thinning without prejudice to image display device, the thickness preferably at most caliper portion of this bonding sheet 1 Thickness be less than 250 μm.In other words, this bonding sheet 1 both can be that in uniform thickness or local thickness are different Uneven piece, in the case of being piece in uneven thickness, the thickness of preferred thickness the best part is less than 250 μm.

In addition, from the viewpoint of without prejudice to the closing force with adherend, impact absorbency, preferably at most caliper portion Thickness is more than 5 μm, more preferably more than 10 μm, more preferably more than 15 μm.

This bonding sheet 1 can both use under original form, can also use in such a way.In addition, to this bonding The Application way of piece 1 does not limit.

This bonding sheet 1 for example can be to possess the composition formed in the one side of this bonding sheet 1 or two-sided stacking mould release film Bonding laminate form and provide.

Clip this bonding sheet 1 alternatively, it is also possible to make and will be laminated between 2 device used for image display member of formation With layered product, (hereinafter referred to as " this image display device forms and uses layered product 1 " the image display device composition of composition.) and provide.

This image display device composition can for example make by the following method of layered product 1：By device used for image display Member of formation and other device used for image display member of formation clip above-mentioned bonding sheet 1 and are laminated, and show across the former image Showing device member of formation carries out light irradiation to described bonding sheet 1 so that the bonding sheet photocuring.

One as this image display device composition with layered product 1, it can enumerate：Possesses protection panels/this bonding sheet The layered product of the composition of 1/ light polarizing film, and such as touch panel of image display panel/this bonding sheet 1/, image display panel/ The protection panels of this bonding sheet 1/, the touch panel of image display panel/this bonding sheet 1//protection panels of this bonding sheet 1/, light polarizing film/ The configuration examples such as the touch panel of this bonding sheet 1/, the touch panel of light polarizing film/this bonding sheet 1//protection panels of this bonding sheet 1/.

For protection panels and image display panel, group can enter to touch in protection panels or image display panel itself Panel sensors.

Can using this bonding sheet 1 or this image display device composition with layered product come form image display device (with It is referred to as " this image display device 1 " down.).

One of the preferable preparation method of this image display device 1 is illustrated.

First, above-mentioned bonding sheet 1 is heated so that its hot melt, clips above-mentioned bonding sheet 1 and be laminated image display dress Put with member of formation and another device used for image display member of formation.In this stage, this bonding sheet 1 is moderately soft, therefore Keeping stability can be maintained and fully follow difference of height.

Next, irradiate the light such as ultraviolet from the outside of device used for image display member of formation.So, can be crosslinked Reaction is so that its photocuring, it is possible to achieve excellent peel resistance and resistance to foaminess.

As foregoing 2 device used for image display member of formation, such as can enumerate：Computer, mobile terminal (PDA), trip The composition of the image display device such as gaming machine, TV (TV), auto-navigation system, touch panel, handwriting pad etc., LCD, PDP or EL Component.More specifically, such as can enumerate：What touch panel, image display panel, surface protection panel and light polarizing film formed Any of group or the layered product formed by two or more combinations.

[this bonding sheet 2]

The bonding sheet of one of the other embodiment of the present invention (is referred to as " this bonding sheet 2 ".) it is following bonding sheet：Contain There are polymer based on (methyl) acrylic copolymer (A) and the bonding sheet formed by part photocuring, bonding sheet is appointed The piece portion that meaning part has piece portion (be referred to as " soft part ") of the gel fraction less than 1% and gel fraction is more than 40% (is referred to as " hard Portion ").

As the assay method of gel fraction, it can enumerate and be extracted using solvent.Specifically, bonding sheet is being formed In the case that polymer is uncrosslinked, the solvent (good solvent) of the Selective dissolution polymer, then, bonding sheet is entered using the solvent Row extraction.Solvent during as extraction, such as can enumerate：Vinylacetate, acetone, toluene, dimethylbenzene, lower alcohol, tetrahydrochysene Furans etc..

Temperature, time during extraction can arbitrarily be set.After carrying out extracting operation, recovery fails to be dissolved in the solvent Composition (swelling composition) and after drying, determines its weight fraction.As specific extracting process, can enumerate：Soxhlet Method described in extraction, embodiment described later etc..

It should be noted that in the case of gel fraction height, for extraction after can bonding sheet suitably be crushed.

In the expression picture such as mobile phone, using layered polarization film etc. in liquid crystal panel displays (LCD), Clip adhesive thereon again so piece come plastic laminate protection panels composition, the periphery at the back side of the protection panels Portion is generally attached to the light tight portion such as Printing Department.

Such protection panels for being attached to Printing Department are fitted in into other images such as touch panel clipping bonding sheet In the case of display device member of formation, the bonding sheet can follow printing difference of height and fill to each corner, and bonding sheet If surface is unsmooth, strain, deformation can be produced when fitting image shows member of formation in bonding sheet, is turned into because showing inequality The reason for visibility reduces, therefore, flexibility is required for the bonding sheet.Moreover, also exist because printing difference of height etc. causes Bonding sheet content be also easy to produce strain, deformation as problem.

On the other hand, it is desirable to also not tacky in hot and humid inferior extreme environment, the adhesive surface exposed.Moreover, Also require to clip the high cohesion for not being peeling, foaming in the bonding sheet after bonding sheet is bonded image display device member of formation Power.

Therefore, the present invention wants to provide a kind of new bonding sheet 2, and it is for example even fitted in has print in binding face In the case of the device used for image display member of formation of the light tight portion such as brush portion and transmittance section, it can also obtain to difference of height portion etc. Tracing ability, surface, even if will not also be produced in light tight portion strain, deformation, furthermore, it is possible to high cohesion make by Viscous thing is bonded securely between each other, and then, it can cause in hot and humid inferior extreme environment, the adhesive surface exposed is not yet It is tacky.

This bonding sheet 2 is less than 1% soft part by gel fraction, can obtain the tracing ability to difference of height portion etc., surface Flatness, the strain in piece of can relaxing, deformation on the other hand, not only can be with by the hard portion that gel fraction is more than 40% Make adhesive surface not tacky, adherend can also be made to be bonded securely between each other with high cohesion.

Show thus, for example, even fitting in the image that there is the light tight portions and transmittance section such as Printing Department in binding face In the case of showing device member of formation, it is flat that bonding sheet can also integrally obtain the tracing ability to printing difference of height portion, surface Property, even if strain, deformation will not be also produced in light tight portion, and then, adherend can be made firm between each other with high cohesion Ground is bonded.In addition, be hard portion by the adhesive surface for making to expose, even if can cause in hot and humid inferior extreme environment, The adhesive surface exposed is not also tacky.

This bonding sheet 2 can be such as Fig. 1 or as shown in Fig. 2 to have foregoing soft part and hard in the piece surface of bonding sheet The form in matter portion, furthermore it is also possible to as shown in Fig. 3 (A) (B) or Fig. 5, have for the end face portion at least side of bonding sheet The form of foregoing hard portion.Now, the piece surface of bonding sheet can be that soft part can also be hard portion.In addition, such as Fig. 5 institutes Show there can be the form of the hard portion for the end face portion at least side for being rolled into the bonding sheet of web-like.

" base polymer " in the present invention refers to, forms the tree of the main component for the adhesive composition for forming each layer Fat.The specific content of base polymer is not limited, as benchmark, refers to be wrapped in the adhesive composition for forming each layer Accounted in the resin contained more than 50 mass %, wherein more than 80 mass %, wherein more than 90 mass % (including 100 mass %) tree Fat.It should be noted that when base polymer is two or more situation, their total amount is equivalent to foregoing content.

Go out to the tracing ability in difference of height portion, surface and then the strain in piece of can relaxing, the viewpoint of deformation Hair, the gel fraction of above-mentioned soft part are preferably shorter than 1%, wherein preferably shorter than 0.8%, wherein being particularly preferably less than 0.5%.

On the other hand, even if from high cohesion is played so as to improving cementability, be glued in hot and humid inferior extreme environment Conjunction face also it is not tacky so from the viewpoint of, the gel fraction of above-mentioned hard portion is preferably more than 40%, wherein it is preferred that more than 45%, Wherein particularly preferred more than 50%.

In addition, the glass transition temperature (Tg [S]) of the above-mentioned soft part determined using differential scanning calorimeter (DSC) For -70~-10 DEG C when, in normal temperature region have appropriateness flexibility and tack, therefore the Tg of soft part be preferably -70 ~-10 DEG C, wherein be preferably more than -65 DEG C or less than -15 DEG C, wherein be especially preferably more than -60 DEG C or -20 DEG C with Under.

On the other hand, the glass transition temperature (Tg of the above-mentioned hard portion determined using differential scanning calorimeter (DSC) [H]) when being -60~+10 DEG C, high cohesion can be obtained, therefore the Tg of hard portion is preferably -60~+20 DEG C, wherein it is preferred that For more than -55 DEG C or less than+15 DEG C, wherein being especially preferably more than -50 DEG C or less than+10 DEG C.

In addition, the difference of the glass transition temperature (Tg [S]) of soft part and the glass transition temperature (Tg [H]) of hard portion When (Tg [H]-Tg [S]) is more than 3 DEG C, flexibility and cohesive force the two opposite characteristics, knot can be taken into account with higher level To the tracing ability of sticky surface and the excellent resistance to foaming reliability being made after layered product when fruit can take into account fitting, thus it is excellent Choosing.Therefore, the difference (Tg of the glass transition temperature (Tg [S]) of soft part and the glass transition temperature (Tg [H]) of hard portion [H]-Tg [S]) it is preferably more than 3 DEG C, wherein preferably more than 5 DEG C, wherein especially preferably more than 7 DEG C.

(the ASKER hardness of soft part)

By make the soft part in this bonding sheet 2 ASKER hardness (c) be more than 10, can obtain to processing of cutting, Appropriate hardness for the easy degree of curling, therefore preferably.In addition, by making the ASKER hardness (c) be less than 60, can be with Appropriate flexibility and the adhesiveness to adherend are obtained, therefore preferably.

From the point of view, the ASKER hardness (c) of the soft part in this bonding sheet 2 be preferably 10 less than 60, Wherein preferably more than 15 or less than 55, wherein especially preferably more than 20 or less than 50.

(the ASKER hardness of hard portion)

It is more than 40 by making the ASKER hardness (d) of the hard portion in this bonding sheet 2, high cohesion can be obtained, can be with Obtain shape stability, the resistance to layered product excellent in reliability that foams.In addition, by making foregoing ASKER hardness (d) be less than 90, can To obtain becoming crisp, excellent impact resistance layered product, therefore preferably.

From the point of view, the ASKER hardness (d) of the hard portion in this bonding sheet 2 be preferably 40 less than 90, It is preferably wherein more than 43 or less than 88, wherein especially preferably more than 45 or less than 85.

And then in this bonding sheet 2, by making foregoing (d)-(c) be more than 20, sticky surface is chased after when can take into account fitting Excellent resistance to foaming reliability casual and being made after layered product, therefore preferably.

From the point of view, in this bonding sheet 2, the ASKER hardness (c) of soft part and the ASKER hardness (d) of hard portion Difference ((d)-(c)) be preferably more than 20, wherein preferably more than 20 or less than 80, wherein particularly preferred more than 25 or 75 Below.

In this bonding sheet 2, in order to adjust the ASKER hardness (d) of the ASKER hardness (c) of soft part and hard portion, in group The ratio of components of crosslinking agent, Photoepolymerizationinitiater initiater is adjusted into, preparation method, or adjustment is to the light irradiation amount of adhesive composition Can.In addition, it is also not necessarily limited to such method.

(180 ° of peeling forces of soft part)

It is more than 3N/cm by making 180 ° of peeling forces of the soft part in this bonding sheet 2, has to the adherend under normal temperature Appropriate adhesiveness, fitting operability is excellent, therefore preferably.

From the point of view, 180 ° of peeling forces of the soft part in this bonding sheet 2 are preferably more than 3N/cm, wherein excellent Below 20N/cm is elected as, wherein especially preferably more than 4N/cm or below 15N/cm.

(180 ° of peeling forces of hard portion)

Be more than 5N/cm by 180 ° of peeling forces of the hard portion in this bonding sheet 2, can obtain excellent resistance to foaming/ Fissility, therefore preferably.

From the point of view, 180 ° of peeling forces of the hard portion in this bonding sheet 2 are preferably more than 5N/cm, wherein excellent Below 25N/cm is elected as, wherein especially preferably more than 6N/cm or below 20N/cm.

In this bonding sheet 2, in order to adjust the 180 of soft part and hard portion ° of peeling forces, crosslinking is adjusted in composition, preparation method Agent, the species of Photoepolymerizationinitiater initiater, ratio of components, or heat/pressure condition during adjustment fitting, the light irradiation condition after fitting .In addition, it is also not necessarily limited to such method.

(40 DEG C of confining forces of soft part)

, can be with by making confining force of the soft part in this bonding sheet 2 at 40 DEG C of temperature be less than 10mm for deflected length Obtain excellent processability, keeping stability.

From the point of view, confining force of the soft part in this bonding sheet 2 at 40 DEG C of temperature is preferably deflected length Less than 10mm, wherein preferably shorter than 8mm, wherein even more preferably below 5mm.

(70 DEG C of confining forces of soft part)

In addition, for the confining force under the temperature 70 C of the soft part in this bonding sheet 2, face is attached when less than 10 minutes Skew and counterweight be when dropping, excellent adaptation, concavo-convex absorbability when can obtain fitting to adherend, therefore preferably.

From the point of view, for the confining force under the temperature 70 C of the soft part in this bonding sheet 2, preferably less than At 10 minutes attach face skew and counterweight drops, wherein further preferably when less than 8 minutes attach face skew and counterweight drops, Attaching face is offset wherein further preferably when less than 6 minutes and counterweight drops.

(40 DEG C of hard portion or 70 DEG C of confining forces)

The confining force of hard portion in this bonding sheet 2 at 40 DEG C and 70 DEG C of temperature preferably offsets length and is less than 1mm, More preferably less than 0.7mm, even more preferably below 0.5mm.

It is above range by making confining force of the hard portion in this bonding sheet 2 at 40 DEG C and 70 DEG C of temperature, can be with Obtain shape stability, the resistance to foaming reliability under high cohesion, hygrothermal environment.

This bonding sheet 2 can make as follows.

(1) for photo curable bonding sheet, the structure that will not be passed through with light tight component, the light used in photocuring When part masking will turn into position and the irradiation light of soft part, the part being coated to light tight component can turn into soft part, not have The part that is coated to by light tight component, that is, the part of light is irradiated hard portion can be turned into by photocuring.

(2) in addition, end face portion irradiation light to bonding sheet, to the part beyond the end face portion not irradiation light when, can make The end face portion turns into hard portion and other parts is turned into soft part.

For example, to the end face portion of bonding sheet, (can be configured using by the surface of piece and the back side along direction vertically Setting) from above-below direction irradiation light vertically or horizontally or sideling, furthermore it is possible on the surface of bonding sheet and One or both sides in the back side are layered in the piece that the light used in photocuring will not pass through in advance, from vertically or horizontally Or above-below direction irradiation light sideling.Like this irradiation light when, the end face portion photocuring of bonding sheet can be made.Now, as Will not pass through described of the light used in photocuring, it is particularly suitable to be led to using such as the inferior light used in photocuring The release sheet crossed：Based on polyethylene terephthalate the release sheet of polymer, used in poly terephthalic acid second Ultra-violet absorber is mixed into terephthalate films, polyolefin film or the demoulding of the film of ultra-violet absorber is coated with surface Piece etc..

It should be noted that during irradiation light, end face portion and its periphery can turn into hard portion.

(3) in addition, making the bonding sheet each with desired gel fraction respectively in advance, will the two integration can also be Soft part and hard portion are formed in bonding sheet.

This bonding sheet 2 can use bonding sheet X as following and form its local photocuring.It is in addition, unlimited In forming this bonding sheet 2 using following bonding sheet X.

From can before photocuring in the state of show hot melt from the viewpoint of, the gel before bonding sheet X photocuring Rate (a) is less than 1%, wherein preferably shorter than 0.8%, wherein being particularly preferably less than 0.5%.

In addition, from high cohesion can be obtained after photocuring, the viewpoint of the resistance to foaming reliability under hygrothermal environment is obtained Set out, the gel fraction (b) after bonding sheet X photocuring is preferably more than 40%, wherein preferably more than 45% or 95% with Under, wherein especially preferably more than 50% or less than 90%.

In order to the gel fraction (b) after the gel fraction (a) and photocuring before photocuring is adjusted to as described above, composition, Crosslinking agent, the ratio of components of Photoepolymerizationinitiater initiater, or temperature, irradiate light quantity during adjustment processing are adjusted in preparation method.In addition, It is also not necessarily limited to such method.

Resin combination (hereinafter referred to as " this adhesive composition to above-mentioned bonding sheet X can be suitably used to form 2”.) illustrate.In addition, this is only one, however it is not limited to this.

As this adhesive composition 2, preferably Photocurable pressure-sensitive adhesive composition.Wherein, preferably (methyl) is contained The resin combination of acrylic copolymer (2-A), crosslinking agent (2-B) and Photoepolymerizationinitiater initiater (2-C).

As long as in addition, can as described above cause attach after gel fraction it is different according to the position in bonding sheet, Just the composition of the adhesive composition for forming this bonding sheet 2 is not limited.

Here, this bonding sheet 2 especially preferably can keep sheet under normal conditions, when having heating under non cross-linked state Melting or even the hot melt of flowing, and with the bonding sheet for the photo-curable that can carry out photocuring.

When can keep sheet under normal conditions, compared with liquid adhesive, it is easily processed and liquid filling body can be saved Operation, productivity ratio are especially excellent.

And then possess appropriate cohesive in normality, i.e. near room temperature, can be by slight power in a short time When being adhered to the property (being referred to as " viscosity ") of adherend, positioning when easily being attached, operability is excellent, therefore preferably normal State, possesses viscosity near room temperature, the more preferably relatively low temperature province at -5 DEG C~20 DEG C also possesses viscosity.

In addition, when possessing heating during the hot melt of melting or even flowing, it is set to soften or even flow by being heated Change, the jogs such as printing difference of height can be followed filling adhesive, therefore the ground such as foaming can not be produced and be filled.

And then when there is photo-curable, by finally making its photocuring, it can be bonded securely.

Sheet can be kept under normal conditions like this in order to make, and melted or even flowed when there is heating under non cross-linked state Dynamic hot melt, and during the bonding sheet for the bonding sheet, for example, individual layer that can carry out photocuring, by the adhesive next illustrated Composition (2-I) or (2-II) make the bonding sheet of individual layer.On the other hand, in the case of the bonding sheet of multilayer, example It can such as enumerate：Will be by adhesive composition (2-I) or (2-II) adhesive layer formed and by other adhesive composition shapes Into bonding layer stackup obtain 2 kinds 2 layers composition；Middle resin layer is clipped on surface and back side configuration by adhesive composition The 2 kinds of 3 layers of compositions for the adhesive layer that (2-I) or (2-II) is formed；It will be formed successively by adhesive composition (2-I) or (2-II) Adhesive layer and the intermediate layer formed by middle resin combination and by bonding layer stackup that other adhesive compositions are formed and Into 3 kinds 3 layers composition etc..

In addition, it is not limited to adhesive composition (2-I) or (2-II) for forming the adhesive composition of this bonding sheet 2.

As adhesive composition (2-I), it can enumerate to contain and be total to by possessing macromonomer as the grafting of branch composition The resin combination of acrylic copolymer (2-A1), crosslinking agent (2-B1) and Photoepolymerizationinitiater initiater (2-C1) that polymers is formed Thing.

(acrylic copolymer (2-A1))

Based on polymer acrylic copolymer (2-A1) to possess grafting of the macromonomer as branch composition Copolymer.

(trunk composition)

The trunk composition of foregoing acrylic copolymer (2-A1) is preferably by containing the repetition from (methyl) acrylate The copolymer composition of unit is formed.

Form the copolymer of the trunk composition of the acrylic copolymer (2-A1) glass transition temperature be preferably- 70~0 DEG C.

Now, the glass transition temperature for forming the copolymer composition of trunk composition refers to only form acrylic copolymer The glass transition temperature of polymer obtained from the monomer component copolymerization of the trunk composition of thing (2-A1).Specifically refer to, The glass transition temperature and composition of the polymer obtained according to the homopolymer by each composition of the copolymer, are calculated by Fox The value that formula calculates.

1/ (273+Tg)=Σ (Wi/ (273+Tgi))

Form the glass transition temperature meeting of the copolymer composition of the trunk composition of foregoing acrylic copolymer (2-A1) Influence the flexibility of adhesive composition (2-I) under room temperature state, adhesive composition (2-I) to the wetability of adherend, That is cementability, therefore, in order to obtain adhesive composition (2-I) cementability (viscosity) appropriate under room temperature state, the glass It is preferably -70 DEG C~0 DEG C to change transition temperature, wherein being preferably more than -65 DEG C or less than -5 DEG C, wherein being especially preferably -60 More than DEG C or less than -10 DEG C.

Even if, can also be by adjusting molecular weight in addition, the glass transition temperature of the copolymer composition is mutually synthermal To adjust viscoplasticity.For example, by reducing the molecular weight of copolymer composition, its more softness can be made.

(methyl) acrylate monomer that trunk composition as foregoing acrylic copolymer (2-A1) contains, such as can To enumerate：(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) isoamyl acrylate, (methyl) acrylic acid peopentyl ester, (methyl) Hexyl 2-propenoate, (first Base) cyclohexyl acrylate, (methyl) heptylacrylate, 2-EHA, n-octyl, Isooctyl acrylate monomer, (methyl) acrylic acid nonyl ester, the different nonyl ester of (methyl) acrylic acid, (methyl) t-butylcyclohexyl ester, (methyl) acrylic acid last of the ten Heavenly stems Ester, (methyl) isodecyl acrylate, (methyl) acrylic acid hendecane base ester, (methyl) lauryl acrylate, (methyl) acrylic acid Cetyl, (methyl) stearyl acrylate ester, the different stearyl ester of (methyl) acrylic acid, (methyl) acrylic acid behenyl ester, (methyl) propylene Sour isobornyl thiocyanoacetate, (methyl) acrylic acid 2- phenoxy ethyls, acrylic acid 3,5,5- 3-methyl cyclohexanols ester, p- cumyl phenols EO are modified (methyl) acrylate, the ring pentyl ester of (methyl) acrylic acid two, (methyl) acrylic acid dicyclopentenyl ester, the ring penta of (methyl) acrylic acid two Alkenyl epoxide ethyl ester, (methyl) benzyl acrylate etc..(methyl) propylene for possessing hydrophilic group, organo-functional group etc. can also be used Hydroxyl (the first such as sour hydroxyl ethyl ester, (methyl) hydroxypropyl acrylate, (methyl) hy-droxybutyl, (methyl) glycerol acrylate Base) acrylate, (methyl) acrylic acid, 2- (methyl) acryloyl-oxyethyls hexahydrophthalic acid, 2- (methyl) acryloyl Epoxide propyl group hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyls phthalic acid, 2- (methyl) acryloxy third Base phthalic acid, 2- (methyl) acryloyl-oxyethyls maleic acid, 2- (methyl) acryloxypropyls maleic acid, 2- (first Base) acryloyl-oxyethyl butanedioic acid, 2- (methyl) acryloxypropyls butanedioic acid, crotonic acid, fumaric acid, maleic acid, clothing The monomers containing anhydride group such as carboxyl group-containing monomer, maleic anhydride, the itaconic anhydrides such as health acid, monomethyl maleate, monomethyl itaconate, (methyl) glycidyl acrylate, α-ethylacrylate ethylene oxidic ester, (methyl) acrylic acid 3,4- epoxy butyl esters etc. contain ring Epoxide monomer, (methyl) dimethylaminoethyl acrylate, (methyl) diethylaminoethyl acrylate etc. contain amino (methyl) propylene Acid esters system monomer, (methyl) acrylamide, the N- tert-butyl groups (methyl) acrylamide, N- methylols (methyl) acrylamide, N- first Epoxide methyl (methyl) acrylamide, N- butoxymethyls (methyl) acrylamide, DAAM, maleic amide, horse Carry out the heterocycle system alkalescence of the monomer containing amide groups such as acid imide, vinyl pyrrolidone, vinylpyridine, vinyl carbazole etc. Monomer etc..

In addition, the trunk composition of acrylic copolymer (2-A1) preferably comprises hydrophobic (methyl) acrylate monomer With hydrophilic (methyl) acrylate monomer as Component units.

When the trunk composition of acrylic copolymer (2-A1) is only made up of hydrophobic monomer, inclining for damp and hot albefaction is found To, therefore hydrophilic monomer is also preferably imported in trunk composition to prevent damp and hot albefaction.

Specifically, the trunk composition as aforesaid propylene acid copolymer (2-A1), can enumerate hydrophobic (first Base) acrylate monomer and the end of hydrophilic (methyl) acrylate monomer and macromonomer polymerizable functional group without Copolymer composition obtained from rule copolymerization.

Here, as above-mentioned hydrophobic (methyl) acrylate monomer, the preferably Arrcostab without polar group (not including methyl acrylate wherein), such as can enumerate：(methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (first Base) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) isoamyl acrylate, (methyl) Acrylic acid peopentyl ester, (methyl) Hexyl 2-propenoate, (methyl) cyclohexyl acrylate, (methyl) heptylacrylate, acrylic acid 2- second The own ester of base, n-octyl, Isooctyl acrylate monomer, (methyl) acrylic acid nonyl ester, the different nonyl ester of (methyl) acrylic acid, (methyl) third Olefin(e) acid t-butyl cyclohexyl methacrylate, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) acrylic acid hendecane base ester, (methyl) lauryl acrylate, (methyl) acrylic acid cetyl, (methyl) stearyl acrylate ester, the different tristearin of (methyl) acrylic acid Ester, (methyl) acrylic acid behenyl ester, (methyl) isobornyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid two Cyclopentenyl epoxide ethyl ester, methyl methacrylate.

As above-mentioned hydrophilic (methyl) acrylate monomer, preferably methyl acrylate, there is the ester of polar group, Such as it can enumerate：Methyl acrylate, (methyl) acrylic acid, (methyl) tetrahydrofurfuryl acrylate, (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate, (methyl) glycerol acrylate etc. hydroxyl (methyl) propylene Acid esters, (methyl) acrylic acid, 2- (methyl) acryloyl-oxyethyls hexahydrophthalic acid, 2- (methyl) acryloxypropyl Hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyls phthalic acid, 2- (methyl) acryloxypropyl neighbour benzene two Formic acid, 2- (methyl) acryloyl-oxyethyls maleic acid, 2- (methyl) acryloxypropyls maleic acid, 2- (methyl) acryloyl Epoxide ethylsuccinic acid, 2- (methyl) acryloxypropyls butanedioic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, Malaysia The monomers containing anhydride group such as the carboxyl group-containing monomers such as sour mono-methyl, monomethyl itaconate, maleic anhydride, itaconic anhydride, (methyl) propylene Acid glycidyl ester, α-ethylacrylate ethylene oxidic ester, (methyl) acrylic acid 3,4- epoxy butyl esters etc. are containing epoxy based monomers, first Alkoxy polyalkyleneglycol (methyl) acrylate, N of epoxide polyethylene glycol (methyl) acrylate etc., N- dimethyl allenes Acid amides, hydroxyethyl acrylamide etc..

(branch composition：Macromonomer)

For acrylic copolymer (2-A1), as the branch composition of graft copolymer, preferably macromonomer is imported simultaneously Contain the repeat unit from macromonomer.

The glass transition temperature (Tg) of macromonomer, which is preferably above, forms aforesaid propylene acid copolymer (2-A1) The glass transition temperature of copolymer composition.

Specifically, the glass transition temperature (Tg) of macromonomer can influence adhesive composition (2-I) heating Melting temperature (hot melting temperature), therefore the glass transition temperature (Tg) of macromonomer is preferably 30 DEG C~120 DEG C, wherein excellent More than 40 DEG C or less than 110 DEG C are elected as, wherein more preferably more than 50 DEG C or less than 100 DEG C.

For such glass transition temperature (Tg) when, by adjusting the processability, keeping that molecular weight can keep excellent Stability, and can be adjusted to nearby to heat at 80 DEG C.

The glass transition temperature of macromonomer refers to the macromonomer glass transition temperature of itself, Ke Yiyong Differential scanning calorimeter (DSC) determines.(programming rate：5 DEG C/min, Tg is determined according to the flex point of needle position misalignment)

In addition, under room temperature state, branch composition adsorbs between each other, can maintain to have carried out thing as adhesive composition The state of crosslinking is managed, moreover, by being heated to appropriate temperature, the physical crosslinking can be caused to release and obtain mobility, Therefore, it is preferred that the molecular weight of adjustment macromonomer, content.

From the point of view, with the mass % of 5 mass %~30 ratio preferably in acrylic copolymer (2-A1) Containing macromonomer, wherein it is preferred that more than 6 mass % or below 25 mass %, wherein it is preferred that more than 8 mass % or 20 Below quality %.

For macromonomer, conventionally fabricated material (such as the macromolecular list that East Asia Synesis Company manufactures can be used Body etc.).

As the HMW framework ingredient of foregoing macromonomer, such as can enumerate：(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (first Base) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) Isoamyl acrylate, (methyl) acrylic acid peopentyl ester, (methyl) Hexyl 2-propenoate, (methyl) cyclohexyl acrylate, (methyl) third Olefin(e) acid heptyl ester, 2-EHA, n-octyl, Isooctyl acrylate monomer, (methyl) acrylic acid nonyl ester, (methyl) third The different nonyl ester of olefin(e) acid, (methyl) t-butylcyclohexyl ester, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (first Base) acrylic acid hendecane base ester, (methyl) lauryl acrylate, (methyl) acrylic acid cetyl, (methyl) stearyl acrylate ester, The different stearyl ester of (methyl) acrylic acid, (methyl) acrylic acid behenyl ester, (methyl) isobornyl acrylate, (methyl) acrylic acid 2- benzene Epoxide ethyl ester, acrylic acid 3,5,5- 3-methyl cyclohexanols ester, p- cumyl phenols EO are modified (methyl) acrylate, (methyl) acrylic acid Two ring pentyl esters, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid dicyclopentenyl epoxide ethyl ester, (methyl) acrylic acid benzyl Ester, (methyl) hydroxyalkyl acrylates, (methyl) acrylic acid, (methyl) glycidyl acrylate, (methyl) acrylamide, N, N- dimethyl (methyl) acrylamide, (methyl) acrylonitrile, (methyl) alkoxyalkyl acrylate, the poly- alkane glycol of alkoxy (methyl) acrylate etc. (methyl) acrylate monomer, styrene, t-butyl styrene, α-methylstyrene, vinyl first Various vinyl monomers such as benzene, alkyl vinyl monomers, vinylacetate, alkyl vinyl ether, hydroxyalkyl vinylether etc., this It can be used alone or be used in combination of two or more.

(crosslinking agent (2-B1))

As crosslinking agent (2-B1), such as can suitably select with the epoxy radicals of more than 2, NCO, oxa- The crosslinking agent of the crosslinkable groups such as cyclobutane base, silanol group, (methyl) acryloyl group.Wherein, in reactivity, obtained solidification The aspect of the intensity of thing, preferably with more than 2 (methyl) acryloyl groups, wherein preferably with more than 3 (methyl) acryloyls Multifunctional (methyl) acrylate of base, there is epoxy radicals, NCO, (methyl) acrylate of silanol group.

After the fitting integration of image display device member of formation, by making crosslinking agent (2-B1) be handed in jointing material Connection, the piece lose hot melt, the substitute is the high cohesion shown under hot environment, can obtain excellent resistance to foaming Reliability.

As such (methyl) acrylate, such as can enumerate：1,4- butanediols two (methyl) acrylate, new penta Glycol two (methyl) acrylate, glycerine two (methyl) acrylate, glycerine glycidol ether two (methyl) acrylate, 1,6- Hexylene glycol two (methyl) acrylate, 1,9- nonanediols two (methyl) acrylate, Tricyclodecane Dimethanol two (methyl) propylene More ethyoxyl two (methyl) acrylate of acid esters, bisphenol-A, more alkoxy two (methyl) acrylate of bisphenol-A, the more alcoxyls of Bisphenol F Base two (methyl) acrylate, PAG two (methyl) acrylate, trimethylolpropane tris epoxide ethyl (methyl) Acrylate, 6-caprolactone are modified three (2- ethoxys) isocyanuric acid ester three (methyl) acrylate, pentaerythrite three (methyl) Acrylate, pentaerythritol propoxylate three (methyl) acrylate, ethoxylation pentaerythrite three (methyl) acrylate, season Penta tetrol four (methyl) acrylate, pentaerythritol propoxylate four (methyl) acrylate, (first of ethoxylation pentaerythrite four Base) acrylate, dipentaerythritol six (methyl) acrylate, polyethylene glycol two (methyl) acrylate, three (acryloxies Ethyl) isocyanuric acid ester, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, two seasons penta 4 Alcohol five (methyl) acrylate, tripentaerythritol six (methyl) acrylate, tripentaerythritol five (methyl) acrylate, hydroxyl Pivalic acid neopentyl glycol two (methyl) acrylate, 3-hydroxypivalic acid neopentyl glycol 6-caprolactone addition product two (methyl) third Olefin(e) acid ester, trimethylolpropane tris (methyl) acrylate, oxyalkylated trihydroxy methyl-propane three (methyl) acrylate, double three The ultraviolet hardening polyfunctional monomer classes such as hydroxymethyl-propane four (methyl) acrylate；And polyester (methyl) acrylate, The multifunctional acrylic compounds such as epoxy (methyl) acrylate, polyurethane (methyl) acrylate, polyethers (methyl) acrylate are low Polymers class, isocyanates (methyl) acrylate, 1,1- (double (methyl) acryloyloxymethyls) ethyl isocyanate, 2- (2- (methyl) acryloyl-oxyethyl epoxide) ethyl isocyanate, (methyl) glycidyl acrylate, hydroxy-ethyl acrylate shrink Glycerin ether, (methyl) hydroxypropyl acrylate glycidol ether, (methyl) hydroxy butyl acrylate glycidol ether etc..

In enumerating above, from the viewpoint of the adaptation to adherend, the wet effect for suppressing hot albefaction is improved, preferably Polyfunctional monomer or oligomer containing hydroxyl isopolarity functional group.

Therefore, from the viewpoint of damp and hot albefaction is prevented, as foregoing acrylic copolymer (2-A1), i.e. graft copolymerization The trunk composition of thing, hydrophobic acrylate monomer and hydrophilic acrylate monomer are preferably comprised, and then, as crosslinking Agent (2-B), preferably using multifunctional (methyl) acrylate with hydroxyl.

The content of crosslinking agent (2-B1) is had no particular limits.As benchmark, relative to acrylic copolymer (2- A1) 100 mass parts are 0.5~20 mass parts, wherein it is preferred that more than 1 mass parts or below 15 mass parts, wherein it is preferred that 2 mass Ratio more than part or below 10 mass parts.

By containing crosslinking agent (2-B1) within the above range, the shape of this bonding sheet 2 under non cross-linked state can be taken into account The resistance to foaming reliability in jointing material after shape stability and crosslinking.Furthermore, it is contemplated that the balance with other element, can also Beyond the scope.

(Photoepolymerizationinitiater initiater (2-C1))

Photoepolymerizationinitiater initiater (2-C1) is to trigger auxiliary agent as the reaction in the cross-linking reaction of foregoing crosslinking agent (2-B1) And play the material of function.

On the other hand, the light that the Photoepolymerizationinitiater initiater sensed to the light of wavelength ratio wavelength 380nm length is sensed is easy The depths of this bonding sheet 2 is reached, is preferable in this respect.

When cracking type Photoepolymerizationinitiater initiater among these produces free radical by irradiation light, decompose and formed other Compound, the function as reaction initiator is lost once being excited.Therefore, the jointing material after cross-linking reaction terminates In be not re-used as spike and remain, in the absence of causing the possibility that exceeds expected light deterioration etc. to jointing material, therefore excellent Choosing.

The content of Photoepolymerizationinitiater initiater (2-C1) is had no particular limits.As benchmark, to be total to relative to acrylic compounds The mass parts of polymers (2-A1) 100 are 0.1~10 mass parts, wherein more than 0.5 mass parts or below 5 mass parts, wherein 1 mass It is preferable that ratio more than part or below 3 mass parts, which contains,.

It is above range by making the content of Photoepolymerizationinitiater initiater (2-C1), can obtains to active energy beam appropriateness Reaction sensitivity.

(other compositions)

For adhesive composition (2-I), as composition other than the above, adhesive combination can be mixed in containing generally matching somebody with somebody The known composition of thing.For example, it can suitably contain tackifying resin, antioxidant, light stabilizer, metal passivation as needed The various additions such as agent, age resister, hygroscopic agent, polymerization inhibitor, ultra-violet absorber, antirust agent, silane coupler, inorganic particle Agent.

As adhesive composition (2-II), can enumerate containing (methyl) acrylic copolymer (2-A2), crosslinking agent (2-B2) and Photoepolymerizationinitiater initiater (2-C2) resin combination, wherein (methyl) acrylic copolymer (2-A2) contains Have monomer a of the glass transition temperature (Tg) less than 0 DEG C, glass transition temperature (Tg) for 0 DEG C less than 80 DEG C Monomer b and glass transition temperature (Tg) are more than 80 DEG C of monomer c with a：b：C=10~40：90~35：0~25 mole Than obtained from copolymerization, (methyl) acrylate copolymer or ethylene copolymer of weight average molecular weight 50000~400000.

((methyl) acrylic copolymer (2-A2))

Based on polymer (methyl) acrylic copolymer (2-A2) be preferably (methyl) acrylate copolymer Or ethylene copolymer.

For above-mentioned (methyl) acrylate copolymer or ethylene copolymer, from the shape retention taken into account in room temperature state From the viewpoint of hot melt, weight average molecular weight is preferably 50000~400000, wherein preferably more than 60000 or Less than 350000, wherein more preferably more than 70000 or less than 300000.

As (methyl) acrylic copolymer (2-A2) of this bonding sheet 2, preferably by glass transition temperature (Tg) Monomer a, glass transition temperature (Tg) less than 0 DEG C are 0 DEG C less than 80 DEG C of monomer b and glass transition temperature (Tg) it is more than 80 DEG C of monomer c with a：b：C=10~40：90~35：(methyl) propylene that 0~25 mol ratio copolymerization forms Acid ester copolymer or ethylene copolymer.

Now, (homopolymer when monomer a, b and c each glass transition temperature (Tg) refers to make polymer by the monomer Change) each glass transition temperature (Tg).

The monomer a for example preferably has (methyl) acrylate monomer of following alkyl structure：The alkyl structure is The alkyl structure of side chain with carbon number more than 4.

More specifically, aforementioned monomer a is preferably (methyl) acrylate of the straight chained alkyl structure with carbon number 4~10 Monomer or with carbon number 6~18 branched chain alkyl moiety (methyl) acrylate monomer.

(methyl) acrylate monomer below 4 of the preferred carbon numbers of aforementioned monomer b, (methyl) in side chain with cyclic skeleton Vinyl monomer below 4 of acrylate monomer, carbon number has the vinyl monomer of cyclic skeleton in side chain.

Wherein, the carbon number of the above-mentioned particularly preferred side chains of monomer b is less than 4 vinyl monomer.

(methyl) acrylate monomer or there is ring-type bone in side chain that the carbon number of the preferred side chains of aforementioned monomer c is less than 1 (methyl) acrylate monomer of frame.

(methyl) acrylic copolymer (2-A2) is included monomer a and monomer b and monomer c with a：b：C=10~40：90 ~35：, can be by Tan δ peak when (methyl) acrylate copolymer or ethylene copolymer that 0~25 mol ratio copolymerization forms Adjust to 0~20 DEG C, under usual state, i.e. room temperature state, the shape of sheet can be kept.Furthermore, it is possible to show peelable From degree cementability (be referred to as " viscosity ").In addition, when being heated to heat-fusible temperature, become to show mobility, can be with The difference of height portion for following binding face is filled to each corner.

Therefore, from the point of view, (methyl) acrylate for forming (methyl) acrylic copolymer (2-A2) is common The mol ratio of monomer a, monomer b and monomer c in polymers or ethylene copolymer are a：b：C=10~40：90~35：0~25, its In be preferably 13~40：87~35：0~23, wherein preferably 15~40：85~38：2~20.

In addition, from viewpoint similar to the above, (methyl) third of composition (methyl) acrylic copolymer (2-A2) The mol ratio of monomer a, monomer b and monomer c in olefin(e) acid ester copolymer or ethylene copolymer are preferably b>a>c.

(crosslinking agent (2-B2))

By making crosslinking agent (2-B2) be crosslinked in this bonding sheet 2, this bonding sheet 2 can be shown in high temperature environments High cohesion, obtain excellent resistance to foaming reliability.

As such crosslinking agent (2-B2), for example, can suitably select have more than 2 epoxy radicals, NCO, The crosslinking agent of the crosslinkable groups such as oxetanyl, silanol group, (methyl) acryloyl group.Wherein, in reactivity, obtain The aspect of the intensity of solidfied material, preferably with more than 2 (methyl) acryloyl groups, wherein preferably with more than 3 (methyl) third Multifunctional (methyl) acrylate of enoyl-, there is epoxy radicals, NCO, (methyl) acrylate of silanol group.

As such (methyl) acrylate, such as can enumerate：1,4- butanediols two (methyl) acrylate, glycerine Two (methyl) acrylate, 1,6-HD two (methyl) acrylate, 1,9- nonanediols two (methyl) acrylate, the three ring last of the ten Heavenly stems More ethyoxyl two (methyl) acrylate of alkane dimethanol two (methyl) acrylate, bisphenol-A, the more propoxyl group two (methyl) of bisphenol-A More ethyoxyl two (methyl) acrylate of acrylate, Bisphenol F, ethylene glycol two (methyl) acrylate, trimethylolpropane tris Epoxide ethyl (methyl) acrylate, 6-caprolactone are modified three (2- ethoxys) isocyanuric acid ester three (methyl) acrylate, season Penta tetrol three (methyl) acrylate, pentaerythritol propoxylate three (methyl) acrylate, (first of ethoxylation pentaerythrite three Base) acrylate, pentaerythrite four (methyl) acrylate, pentaerythritol propoxylate four (methyl) acrylate, ethyoxyl Change pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, polyethylene glycol two (methyl) acrylic acid Ester, three (acryloyl-oxyethyl) isocyanuric acid esters, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) third Olefin(e) acid ester, dipentaerythritol five (methyl) acrylate, tripentaerythritol six (methyl) acrylate, (first of tripentaerythritol five Base) acrylate, 3-hydroxypivalic acid neopentyl glycol two (methyl) acrylate, the 6-caprolactone of 3-hydroxypivalic acid neopentyl glycol add Into two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, the more (first of ethyoxyl three of trimethylolpropane of thing Base) ultraviolet hardening such as acrylate, double trimethylolpropane four (methyl) acrylate polyfunctional monomer class；It is and poly- Ester (methyl) acrylate, epoxy (methyl) acrylate, carbamate (methyl) acrylate, polyethers (methyl) acrylic acid The oligomeric species of the multifunctional acrylic compounds such as ester, isocyanates (methyl) acrylate, 1,1- (double (methyl) acryloxy first Base) ethyl isocyanate, 2- (2- (methyl) acryloyl-oxyethyls epoxide) ethyl isocyanate, (methyl) acrylic acid shrink it is sweet Grease, hydroxy-ethyl acrylate glycidol ether, (methyl) hydroxypropyl acrylate glycidol ether, the contracting of (methyl) hy-droxybutyl Water glycerin ether.

The content of crosslinking agent (2-B2) is had no particular limits.As benchmark, relative to (methyl) acrylic copolymer The mass parts of thing (2-A2) 100 are 0.5~20 mass parts, wherein preferably more than 1 mass parts or below 15 mass parts, it is wherein preferred Ratio more than 2 mass parts or below 10 mass parts.

By containing crosslinking agent (2-B2) within the above range, the shape of this bonding sheet 2 under non cross-linked state can be taken into account The resistance to foaming reliability in bonding sheet after shape stability and crosslinking.Furthermore, it is contemplated that the balance with other element, can also surpass Go out the scope.

(Photoepolymerizationinitiater initiater (2-C2))

Photoepolymerizationinitiater initiater (2-C2) is to trigger auxiliary agent as the reaction in the cross-linking reaction of foregoing crosslinking agent (2-B2) And the material of function is played, it can suitably use the material in the related record of foregoing Photoepolymerizationinitiater initiater (2-C1).

The content of Photoepolymerizationinitiater initiater (2-C2) is had no particular limits.As benchmark, with relative to (methyl) propylene The mass parts of acid copolymer (2-A2) 100 are 0.1~10 mass parts, wherein more than 0.5 mass parts or below 5 mass parts, its In ratio more than 1 mass parts or below 3 mass parts to contain be preferable.

It is above range by making the content of Photoepolymerizationinitiater initiater (2-C2), can obtains to active energy beam appropriateness Reaction sensitivity.

(other compositions)

For adhesive composition (2-II), as composition other than the above, adhesive group can be mixed in containing generally matching somebody with somebody The known composition of compound.For example, it can suitably contain tackifying resin, antioxidant, light stabilizer, metal passivation as needed The various additions such as agent, age resister, hygroscopic agent, polymerization inhibitor, ultra-violet absorber, antirust agent, silane coupler, inorganic particle Agent.

Method on making bonding sheet X, can be enumerated：Adhesive composition (the 2- that will be prepared by known method I), (2-II) is dissolved in the solution coating process of solvent and coating, the adhesive composition is heated to the hot melt painting for melting and coating Cover method etc..As long as just being had no particular limits in addition, target bonding sheet can be obtained, known method can be used to make.

It should be noted that for above-mentioned adhesive composition (2-I), (2-II), it is configured to below 50 μm of thickness During film product, from the easiness aspect of thickness control, it is preferred to use solution coating process.On the other hand, it is configured to thickness During the bonding sheet that more than 50 μm of degree, from the easy degree of environmental pollution, thick film shaping, it is preferred to use hot melt cladding process.

This bonding sheet 2 can be the piece formed by individual layer or the multilayer tablet for being laminated more than 2 layers.

In the case of transparent double face jointing material of this bonding sheet 2 for multilayer, form as stacking, can specifically lift Go out：2 kinds 2 layers obtained from this adhesive composition 2 and the stacking of other adhesive resin compositions are formed, clips intermediary tree Lipid layer be configured with surface and the back side this adhesive composition 22 kinds 3 layers form, in order by this adhesive composition 2, in Between resin combination and other adhesive resin compositions be laminated 3 kinds 3 layers composition etc..Wherein, outermost layer is preferably made Formed by this adhesive composition 2, adhesive composition as escribed above (2-I) (2-II).

Furthermore it is possible to by this adhesive composition 2 and other adhesive resin compositions respectively in the different demouldings Slabbing is shaped on film or even image display device member of formation, two adhesive surfaces are laminated so as to obtain this bonding sheet 2, separately Outside, this adhesive composition 2, middle resin combination and adhesive resin composition can also be coextruded so as to obtain successively 2 kinds 3 layers this bonding sheet 2, alternatively, it is also possible to be laminated at the surface of middle resin layer, the back side this adhesive composition 2 or other Adhesive resin composition so as to obtaining this bonding sheet 2.

In addition, for example, it may be possessing the adhesive layer formed by this adhesive composition 2 on base material (is referred to as " this bonding Layer 2 ") the bonding sheet with base material or without base material without base material bonding sheet.And then can have in upper and lower both sides The double-sided adhesive sheet of standby foregoing adhesive layer 2, only can also possess the one side bonding of foregoing adhesive layer 2 in upper and lower single-face side Piece.

From the viewpoint of the thinning without prejudice to image display device, the thickness preferably at most caliper portion of this bonding sheet 2 Thickness be less than 250 μm.In other words, this bonding sheet 2 both can be that in uniform thickness or local thickness are different Uneven piece, in the case of being piece in uneven thickness, the thickness of preferred thickness the best part is less than 250 μm.

This bonding sheet 2 can both use under original form, can also use in such a way.In addition, to this bonding The Application way of piece 2 does not limit.

(bonding laminate 2)

This bonding sheet 2 for example can be to possess the composition formed in the one side of this bonding sheet 2 or two-sided stacking mould release film Bonding laminate 2 form and provide.

Now, this bonding sheet 2 can be to have foregoing soft part and hard in piece surface such as Fig. 1 or as shown in Figure 2 The form in matter portion, alternatively, it is also possible to be before the end face portion of at least side of bonding sheet has shown in (A) (B) such as Fig. 3 State the form of hard portion.At this point it is possible to it is that the part that the whole face of the end face portion is foregoing hard portion or the end face portion is Foregoing hard portion.In addition, there can be hard portions in end face and face.

As shown in Fig. 4 (A) (B), when the end face portion of this bonding sheet 2 is the form of hard portion, such as even in high temperature height Wet inferior extreme environment, the end face portion exposed is not also tacky, therefore can suitably take care of.

(this image display device forms and uses layered product 2)

In the case that this bonding sheet 2 has above-mentioned soft part and above-mentioned hard portion in piece surface, for example, can make simultaneously The figure for possessing and the composition that this bonding sheet 2 is laminated being clipped between 2 device used for image display member of formation is provided As display device is formed, with layered product, (hereinafter referred to as " this image display device forms and uses layered product 2 ".).

This image display device composition can for example make as follows of layered product 2：Clipping above-mentioned bonding sheet X will be in binding face Device used for image display member of formation and other device used for image display member of formation layers with light tight portion and transmittance section It is folded, light irradiation is carried out to aforementioned adhesion piece X across the former image display device member of formation, consolidates the bonding sheet local light Change.

One as this image display device composition with layered product 2, it can enumerate：Include protection panels/this bonding sheet The layered product of the composition of 2/ light polarizing film, and such as touch panel of image display panel/this bonding sheet 2/, image display panel/ The protection panels of this bonding sheet 2/, the touch panel of image display panel/this bonding sheet 2//protection panels of this bonding sheet 2/, light polarizing film/ The configuration examples such as the touch panel of this bonding sheet 2/, the touch panel of light polarizing film/this bonding sheet 2//protection panels of this bonding sheet 2/.

(this image display device 2)

Using this bonding sheet 2 or above-mentioned image display device composition image display device can be formed with layered product (hereinafter referred to as " this image display device 2 ".).

That is, this image display device 2 is configured to following image display device：It is at least to possess facing 2 Device used for image display member of formation, the device used for image display member of formation of at least one binding face have light tight portion and The image display device of transmittance section, it is characterised in that it is bonded between possessing foregoing 2 device used for image display member of formation The composition that forms of piece filling, the gel fraction of position contact with foregoing transmittance section of aforementioned adhesion piece be more than 40% and with it is preceding The gel fraction for stating the position of light tight portion's contact is less than 1%.

Above-mentioned image display device is formed with layered product 2 and this image display device 2, will have picture in binding face Around Printing Department grade part (being referred to as " light tight portion " in the present invention) that the light of wavelength necessary to photocuring is not through with And the device used for image display for the part (being referred to as " transmittance section " in the present invention) that the light of wavelength necessary to photocuring passes through is formed When component is bonded with other device used for image display member of formation, by the gel for the position for making to contact with foregoing light tight portion Rate is less than 1%, and the gel fraction of position for making contact with foregoing transmittance section is more than 40%, can make because being oppressed by light tight portion and It the stress relaxation being subject to, can make to diminish caused by the part, and with high cohesion adherend can also be made mutual It is bonded securely.

It should be noted that the gel fraction of the position contacted with light tight portion is particularly preferably less than 1%, wherein further excellent Choosing is less than 0.8%.

On the other hand, the gel fraction of the position contacted with transmittance section is especially preferably more than 40%, wherein further preferably For more than 45%.

One of the preferable preparation method of this image display device 2 is illustrated.

First, above-mentioned bonding sheet X is heated and makes its hot melt, the image of Printing Department (1) will be had by clipping above-mentioned bonding sheet X Display device member of formation 1 and device used for image display member of formation 3 are laminated.In this stage, bonding sheet X appropriateness it is soft It is soft, therefore keeping stability can be maintained and fully follow difference of height.

Next, irradiate the light such as ultraviolet from the outside of device used for image display member of formation 1.So, Printing Department (1) hides It is opacus, therefore light will not reach the part contacted with Printing Department (1), or the light reached is significantly limited, on the other hand, light fills Ground is divided to reach the part contacted with not possessing the transmittance section of Printing Department (1) (3), the cross-linking reaction of the part can be carried out so as to light Solidification, it is possible to achieve excellent peel resistance and resistance to foaminess.

(bonding sheet volume)

The form that this bonding sheet 2 can be rolled into a roll as shown in Figure 5.Such as can be by bonding sheet X rolleds After shape, light irradiation is only carried out to its end face to be made its photocuring and makes, and end face has been carried out the sheet of photocuring Bonding sheet 2 is rolled into a roll and made.In any case, as long as the end face of the bonding sheet for the form being rolled into a roll turns into photocuring portion, Even if then for example in hot and humid inferior extreme environment, the volume end face exposed also will not be tacky, therefore can suitably take care of.

The double-sided adhesive sheet (hereinafter referred to as " this bonding sheet 3 ") of the others one of embodiments of the present invention be by containing The mass parts of (methyl) acrylic copolymer (3-A) 100, the mass parts of crosslinking agent (3-B) 0.5~20 and Photoepolymerizationinitiater initiater Adhesive resin composition (hereinafter referred to as " this adhesive resin composition 3 " of (3-C) 0.1~5 mass parts.) formed it is two-sided Bonding sheet, it is characterised in that for stretch modulus, the stretch modulus (X before photo-crosslinking₁) with photo-crosslinking after stretch modulus (X₂) The ratio between (X₁/X₂) it is more than 3.

In the field of image display device centered on mobile phone, mobile terminal etc., on thinning, the basis of high-precision densification On, the variation of design is constantly promoting, and new problem is also producing therewith.For example, lead in the peripheral part of surface protection panel Often it is printed with the shielding portion of the black of frame-shaped.Therefore, for the bonding for being bonded the member of formation for possessing such Printing Department Piece, it is desirable to printing difference of height can be followed so as to fill to the printing difference of height tracing ability in each corner.Now, it is viscous before photo-crosslinking Conjunction property (viscosity) is without in the case of, and fitting operation is not easy to carry out.

Therefore the present invention will provide this bonding sheet 3, and it is the bonding sheet of Photocrosslinkable, even if also having before photo-crosslinking It is adhesive, be not in the situation that jointing material excess flow is overflowed, collapsed so as to adhesive resin composition during fitting, enter And sufficient hardness can be obtained after photo-crosslinking.

This bonding sheet 3 has the stretch modulus (X before and after photo-crosslinking₁) significant difference feature such greatly, even if in light Also there is cohesive before crosslinking, is not in jointing material excess flow during fitting so as to adhesive resin composition spilling, collapse Sunken situation, and then sufficient hardness can be obtained after photo-crosslinking.

This adhesive resin composition 3 is as described above, to contain (methyl) acrylic copolymer (3-A), crosslinking agent (3- B) and Photoepolymerizationinitiater initiater (3-C) resin combination.

<(methyl) acrylic copolymer (3-A)>

Based on polymer (methyl) acrylic copolymer (3-A) be preferably possess macromonomer as branch into The graft copolymer (3-A1) divided.

Here, " base polymer " refers to the resin for forming the main component of this adhesive resin composition 3.It is poly- to basis The specific content of compound does not limit, as benchmark, to account for 50 matter of the resin that this adhesive resin composition 3 is included Measure more than %, wherein more than 80 mass %, wherein more than 90 mass % (including 100 mass %) resin.It should be noted that In the case where base polymer is two or more, their total amount is equivalent to foregoing content.

(trunk composition)

The trunk composition of foregoing graft copolymers (3-A1) is preferably by containing the repeat unit from (methyl) acrylate Copolymer composition form.

The glass transition temperature of the copolymer of the trunk composition of composition foregoing graft copolymers (3-A1) preferably -70~ 0℃。

Now, the glass transition temperature for forming the copolymer composition of trunk composition refers to, will only form graft copolymer The glass transition temperature of polymer obtained from the monomer component copolymerization of the trunk composition of (3-A1).Specifically refer to, root The glass transition temperature and composition of the polymer obtained according to the homopolymer by each composition of the copolymer, pass through Fox formulas The value calculated.

1/ (273+Tg)=Σ (Wi/ (273+Tgi))

Forming the glass transition temperature of the copolymer composition of the trunk composition of foregoing graft copolymers (3-A1) influences room The flexibility of this adhesive resin composition 3 under temperature state, this adhesive resin composition 3 to the wetability of adherend, i.e. Cementability, therefore, in order to obtain the cementability appropriate under room temperature state of this adhesive resin composition 3 (viscosity), the glass It is preferably -70 DEG C~0 DEG C to change transition temperature, wherein being preferably more than -65 DEG C or less than -5 DEG C, wherein being especially preferably -60 More than DEG C or less than -10 DEG C.

Even if, can also be by adjusting molecular weight in addition, the glass transition temperature of the copolymer composition is mutually synthermal Adjust viscoplasticity.For example, by reducing the molecular weight of copolymer composition, its more softness can be made.

(methyl) acrylate monomer that trunk composition as foregoing graft copolymers (3-A1) contains, such as can lift Go out：2-EHA, n-octyl, Isooctyl acrylate monomer, n-butyl acrylate, ethyl acrylate, methyl-prop E pioic acid methyl ester, methyl acrylate etc..Can also wherein using the hydroxy-ethyl acrylate for possessing hydrophilic group, organo-functional group etc., Hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, acrylic acid, methacrylic acid, acrylic acid shrink sweet Grease, acrylamide, N, N- DMAAs, acrylonitrile, methacrylonitrile etc..

Alternatively, it is also possible to suitably using the acetic acid second that can be copolymerized with aforesaid propylene acrylic monomer, methacrylic monomer The various vinyl monomers such as alkene ester, alkyl vinyl ether, hydroxyalkyl vinylether.

In addition, the trunk composition of graft copolymer (3-A1) preferably comprises hydrophobic (methyl) acrylate monomer and parent Water-based (methyl) acrylate monomer is as Component units.

When the trunk composition of graft copolymer (3-A1) is only made up of hydrophobic monomer, the tendency of damp and hot albefaction is found, because This preferably also imports hydrophilic monomer to prevent damp and hot albefaction in trunk composition.

Specifically, the trunk composition as above-mentioned graft copolymer (3-A1), can enumerate hydrophobic (methyl) third The polymerizable functional group of olefin(e) acid ester monomer and the end of hydrophilic (methyl) acrylate monomer and macromonomer is randomly common Copolymer composition obtained from poly-.

Here, as above-mentioned hydrophobic (methyl) acrylate monomer, the preferably Arrcostab without polar group (not including methyl acrylate wherein), such as can enumerate：(methyl) n-butyl acrylate, (methyl) the just own ester of acrylic acid, (first Base) n-octyl, the positive nonyl ester of (methyl) acrylic acid, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid, (methyl) 2-EHA, The own ester of (methyl) acrylic acid 2- methyl, (methyl) Isooctyl acrylate monomer, the different nonyl ester of (methyl) acrylic acid, (methyl) Isodecyl Ester, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) tert-butyl acrylate, (methyl) isobutyl acrylate, (methyl) isobornyl acrylate, (methyl) cyclohexyl acrylate, the ring penta of (methyl) acrylic acid two Alkenyl epoxide ethyl ester, methyl methacrylate, vinylacetate etc..

As above-mentioned hydrophilic (methyl) acrylate monomer, preferably methyl acrylate, there is the ester of polar group, Such as it can enumerate：Methyl acrylate, (methyl) acrylic acid, (methyl) tetrahydrofurfuryl acrylate, (methyl) acrylic acid 2- hydroxyls Ethyl ester, methoxy poly (ethylene glycol) (methyl) acrylate, 2- (methyl) acryloyl-oxyethyls butanedioic acid, 2- (methyl) acryloyl Epoxide ethyl phthalic acid, 2- (methyl) acryloxypropyls hexahydrophthalic acid, N, N- DMAAs, hydroxyl Ethyl acrylamide etc..

(branch composition：Macromonomer)

As the branch composition of graft copolymer (3-A1), macromonomer is preferably imported, containing from macromonomer Repeat unit.

The glass transition temperature (Tg) of macromonomer is preferably above the copolymerization for forming above-mentioned graft copolymer (3-A1) The glass transition temperature of thing composition.

Specifically, the glass transition temperature (Tg) of macromonomer influences the heating of this adhesive resin composition 3 Melting temperature (hot melting temperature), the glass transition temperature (Tg) of macromonomer is preferably 30 DEG C~120 DEG C, wherein being preferably More than 40 DEG C or less than 110 DEG C, wherein more preferably more than 50 DEG C or less than 100 DEG C.

In addition, under room temperature state, branch composition can adsorb between each other, can be tieed up as this adhesive resin composition 3 The state being physical crosslinking is held, moreover, by being heated to appropriate temperature, said physical crosslinking can be caused to release and obtain Mobility is obtained, is this it is also preferred that molecular weight, the content of adjustment macromonomer.

From the point of view, contained preferably in graft copolymer (3-A1) with the mass % of 5 mass %~30 ratio Macromonomer, wherein it is preferred that more than 6 mass % or below 25 mass %, wherein it is preferred that more than 8 mass % or 20 matter Measure below %.

Macromonomer can use conventionally fabricated material (such as macromonomer of East Asia Synesis Company manufacture etc.).

As the HMW framework ingredient of foregoing macromonomer, such as can enumerate：Polystyrene, styrene and third The copolymer of alkene nitrile, poly- (t-butyl styrene), poly- (α-methylstyrene), polyvinyl-toluene, polymethyl methacrylate Deng.

(physical property of (methyl) acrylic copolymer (3-A))

Complex viscosity of foregoing (methyl) acrylic copolymer (3-A) under 130 DEG C of temperature, frequency 0.02Hz be preferably 100~800Pas, more preferably 150~700Pas, more preferably 170~600Pas.

Complex viscosity at 130 DEG C of the temperature of foregoing (methyl) acrylic copolymer (3-A) influences to make the transparent double face The mobility of adhesive resin composition when jointing material is heated and used, therefore the complex viscosity is 100~800Pas When, there can be excellent hot melt adaptability.

In order to which the complex viscosity of foregoing (methyl) acrylic copolymer (3-A) is adjusted to aforementioned range, such as can be with The glass transition temperature for enumerating the copolymer composition of the trunk composition to forming graft copolymer (3-A1) is adjusted.Can be with It is preferred that enumerate adjust to -70 DEG C~0 DEG C, wherein adjust to more than -65 DEG C or less than -5 DEG C, wherein especially adjust to - The molecular weight of the copolymer composition is adjusted while more than 60 DEG C or less than -10 DEG C, so as to adjust viscoelastic side Method.In addition, it is also not necessarily limited to this method.

As crosslinking agent (3-B), such as can suitably select with the epoxy radicals of more than 2, NCO, oxa- ring The crosslinking agent of the crosslinkable groups such as butane group, silanol group, (methyl) acryloyl group.Wherein, in reactivity, obtained solidfied material Intensity aspect, preferably with more than 2 (methyl) acryloyl groups, wherein preferably with more than 3 (methyl) acryloyl Multifunctional (methyl) acrylate of base, there is epoxy radicals, NCO, (methyl) acrylate of silanol group.

As such multifunctional (methyl) acrylate, such as can enumerate：1,4- butanediols two (methyl) acrylic acid Ester, glycerine two (methyl) acrylate, glycerine glycidol ether two (methyl) acrylate, 1,6-HD two (methyl) propylene Acid esters, 1,9- nonanediols two (methyl) acrylate, Tricyclodecane Dimethanol two (methyl) acrylate, the more ethyoxyls of bisphenol-A More propoxyl group two (methyl) acrylate of two (methyl) acrylate, bisphenol-A, more ethyoxyl two (methyl) acrylate of Bisphenol F, Ethylene glycol two (methyl) acrylate, trimethylolpropane tris epoxide ethyl (methyl) acrylate, 6-caprolactone are modified three (2- Ethoxy) isocyanuric acid ester three (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythritol propoxylate three (methyl) acrylate, ethoxylation pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, the third oxygen Base pentaerythrite four (methyl) acrylate, ethoxylation pentaerythrite four (methyl) acrylate, (first of dipentaerythritol six Base) acrylate, polyethylene glycol two (methyl) acrylate, three (acryloyl-oxyethyl) isocyanuric acid esters, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, three seasons penta 4 Alcohol six (methyl) acrylate, tripentaerythritol five (methyl) acrylate, 3-hydroxypivalic acid neopentyl glycol two (methyl) propylene Acid esters, two (methyl) acrylate of 6-caprolactone addition product of 3-hydroxypivalic acid neopentyl glycol, trimethylolpropane tris (first Base) acrylate, more ethyoxyl three (methyl) acrylate of trimethylolpropane, double trimethylolpropane four (methyl) acrylic acid The polyfunctional monomer class of the ultraviolet hardenings such as ester；And polyester (methyl) acrylate, epoxy (methyl) acrylate, amino The oligomeric species of multifunctional acrylic compounds, the isocyanates (first such as formic acid esters (methyl) acrylate, polyethers (methyl) acrylate Base) acrylate, 1,1- (double (methyl) acryloyloxymethyls) ethyl isocyanate, 2- (2- (methyl) acryloxy second Base epoxide) ethyl isocyanate, (methyl) glycidyl acrylate, hydroxy-ethyl acrylate glycidol ether, (methyl) propylene Sour hydroxypropyl acrylate glycidol ether, (methyl) hydroxy butyl acrylate glycidol ether.

Wherein, preferably using multifunctional (methyl) acrylate with hydroxyl.

Therefore, from the viewpoint of damp and hot albefaction is prevented, as the trunk composition of foregoing graft copolymers (3-A1), preferably Containing hydrophobic acrylate monomer and hydrophilic acrylate monomer, and then, as crosslinking agent (3-B), preferably use Multifunctional (methyl) acrylate with hydroxyl.

For crosslinking agent (3-B) content, preferably with relative to the mass parts of (methyl) acrylic copolymer (3-A) 100 Ratio for 0.5~20 mass parts contains, wherein preferably more than 1 mass parts or below 15 mass parts, wherein further excellent Elect the ratio more than 2 mass parts or below 10 mass parts as.

By containing crosslinking agent (3-B) within the above range, the shape of this bonding sheet 3 under non cross-linked state can be taken into account The resistance to foaming reliability in jointing material after stability and crosslinking.Furthermore, it is contemplated that the balance with other element, can also surpass Go out the scope.

Photoepolymerizationinitiater initiater (3-C) be as in the cross-linking reaction of foregoing crosslinking agent (3-B) reaction initiation auxiliary agent and Play the material of function.

On the other hand, the Photoepolymerizationinitiater initiater that senses of light of wavelength ratio wavelength 380nm length is sensed, light it is easy The depths of this bonding sheet 3 is reached, is preferable in this respect.

When cracking type Photoepolymerizationinitiater initiater among these produces free radical by irradiation light, decompose to form otherization Compound, the function as reaction initiator is lost once being excited.Therefore, in the jointing material after cross-linking reaction terminates It is not re-used as spike and remains, in the absence of the possibility of the light deterioration caused to jointing material outside expected etc., therefore preferably.

For Photoepolymerizationinitiater initiater (3-C) content, preferably with relative to (methyl) acrylic copolymer (3-A) 100 Mass parts contain for the ratios of 0.1~5 mass parts, wherein it is preferred that with more than 0.5 mass parts or below 3 mass parts, wherein enter One step is preferably contained with ratios more than 1 mass parts.

It is above range by the content of Photoepolymerizationinitiater initiater (3-C), can obtains to the anti-of active energy beam appropriateness Answer sensitivity.

For this adhesive resin composition 3, as composition other than the above, can contain common with being mixed in bonding The known composition of agent resin combination.For example, can suitably contain as needed tackifying resin, antioxidant, light stabilizer, Matal deactivator, age resister, hygroscopic agent, polymerization inhibitor, ultra-violet absorber, antirust agent, silane coupler, inorganic particle etc. are each Kind additive.

This bonding sheet 3 can be following bonding sheet：Sheet can be kept under normal conditions, and there is heating under non cross-linked state When melt or even the hot melt of flowing, and with the photo-curable of photocuring can be carried out.

When can keep sheet under normal conditions, compared with liquid adhesive, it is easily processed and liquid filling body can be saved Operation, productivity ratio are especially excellent.Now, in normality, i.e. near room temperature so that possess appropriate cohesive, can show it is logical When crossing slight power and being adhered to the property (be referred to as " viscosity ") of adherend in a short time, positioning during attaching is easily carried out, behaviour The property made is excellent, therefore possesses viscosity preferably in normality, i.e. near room temperature, more preferably -5 DEG C~20 DEG C of relatively low humidity province Domain also possesses viscosity.By using above-mentioned graft copolymer (3-A1) as (methyl) acrylic copolymer (3-A), can obtain To such viscosity.

In addition, when possessing heating during the hot melt of melting or even flowing, its softening or even liquidation are made by heating, can With with following the jogs such as printing difference of height filling adhesive, therefore the ground such as foaming can not be produced and be filled.

And then when there is photo-curable, by finally carrying out photocuring, it can be bonded securely.

As described above, sheet can be kept under normal conditions in order to make, it is with melting when heating under non cross-linked state , can be by above-mentioned bonding to the hot melt of flowing, and during the bonding sheet for the bonding sheet, for example, individual layer that can carry out photocuring Agent resin combination 3 makes the bonding sheet of individual layer.On the other hand, in the case of the bonding sheet of multilayer, such as can enumerate：Will The adhesive layer that is formed by this adhesive resin composition 3 and by bonding layer stackup that other adhesive resin compositions are formed and Into 2 kinds 2 layers form, clip middle resin layer be configured with surface and the back side formed by this adhesive resin composition 3 it is viscous Close layer 2 kinds 3 layers are formed, in order by the adhesive layer formed by this adhesive resin composition 3, by middle resin combination shape Into be laminated 3 kinds 3 layers of intermediate layer and the adhesive layer that is formed by other adhesive resin compositions form.

In addition, it is not limited to this adhesive resin composition 3 for forming the adhesive resin composition of this bonding sheet 3.

(gel fraction)

From can before photocuring in the state of show hot melt from the viewpoint of, this bonding sheet 3 is solidifying before photocuring Glue rate (a) is less than 5%, wherein preferably less than 4%, wherein especially preferably less than 2%.

In addition, high cohesion can be obtained after photocuring, the viewpoint that obtains the resistance to foaming reliability under hygrothermal environment goes out Hair, gel fraction (b) of this bonding sheet 3 after photocuring is preferably more than 50%, wherein preferably more than 60% or 90% with Under, wherein especially preferably more than 65% or less than 80%.

In order to adjust the gel fraction (b) after gel fraction (a) and photocuring before photocuring as described above, such as using Adjusted while possessing graft copolymer (A1) of the macromonomer as branch composition as (methyl) acrylic copolymer (3-A) Temperature, light irradiation amount when whole crosslinking agent, the ratio of components of Photoepolymerizationinitiater initiater or adjustment processing.In addition, it is also not necessarily limited to Such method.

(stretch modulus)

On this bonding sheet 3, the stretch modulus (X before photo-crosslinking₁) with photo-crosslinking after stretch modulus (X₂) the ratio between (X₁/ X₂) be more than 3 when, good difference of height absorbability, resistance to foaming reliability can be obtained.

From the point of view, the stretch modulus (X before photo-crosslinking₁) with photo-crosslinking after stretch modulus (X₂) the ratio between (X₁/ X₂) be preferably more than 3, wherein preferably more than 5 or less than 30, wherein be further preferably more than 10 or 27 with Under.

Stretch modulus (X before photo-crosslinking₁) it is preferably more than 0.01MPa and below 0.2MPa, wherein being more preferably More than 0.05MPa or below 0.1MPa.

On the other hand, the stretch modulus (X after photo-crosslinking₂) it is preferably more than 0.8MPa and below 2.0MPa, wherein entering one Step is preferably more than 1.0MPa or below 1.8MPa.

(stretching maximum stress (Y))

On this bonding sheet 3, the stretching maximum stress (Y before photo-crosslinking₁) with photo-crosslinking after stretching maximum stress (Y₂) it Than (Y₁/Y₂) be more than 5 and less than 20 when, good difference of height absorbability, resistance to foaming reliability can be obtained.

From the point of view, the stretching maximum stress (Y before the photo-crosslinking of this bonding sheet 3₁) with photo-crosslinking after stretching Maximum stress (Y₂) the ratio between (Y₁/Y₂) it is preferably more than 5 and less than 20, wherein more preferably more than 8 or less than 15.

Stretching maximum stress (Y before photo-crosslinking₁) be preferably more than 0.5N and below 5N, wherein especially preferably 0.8N with Upper or below 2N.

On the other hand, the stretching maximum stress (Y after photo-crosslinking₂) it is preferably more than 7N and below 15N, wherein particularly preferably For more than 9N or below 12N.

(tensile break stress (Z))

On this bonding sheet 3, the tensile break stress (Z before photo-crosslinking₁) with photo-crosslinking after tensile break stress (Z₂) it Than (Z₁/Z₂) be more than 10 and less than 50 when, good difference of height absorbability, resistance to foaming reliability can be obtained.

From the point of view, the tensile break stress (Z before the photo-crosslinking of this bonding sheet 3₁) with photo-crosslinking after stretching Fracture strength (Z₂) the ratio between (Z₁/Z₂) it is preferably more than 10 and less than 50, wherein especially preferably more than 15 or less than 40.

Tensile break stress (Z before photo-crosslinking₁) be preferably more than 0.1N and below 2N, wherein especially preferably 0.2N with Upper or below 0.6N.

On the other hand, the tensile break stress (Z after photo-crosslinking₂) it is preferably more than 7N and below 16N, wherein particularly preferably For more than 9N or below 12N.

In this bonding sheet 3, in order to which stretch modulus, stretching maximum stress and tensile break stress are adjusted to above range, Such as the graft copolymer (3-A1) for possessing macromonomer as branch composition is being used as (methyl) acrylic copolymer Species, the number of the macromonomer are adjusted while (3-A).In addition, it is also not necessarily limited to this method.

As (methyl) acrylic copolymer (3-A), using possessing graft copolymerization of the macromonomer as branch composition During thing (3-A1), sheet can be also kept in the normal state, can be by heating performance mobility and meeting that difference of height is followed Property, curing reaction can be carried out so as to obtain excellent bonding reliability by ultraviolet-crosslinkable.

This bonding sheet 3 can be the piece formed by individual layer or the multilayer tablet for being laminated more than 2 layers.

In the case of transparent double face jointing material of this bonding sheet 3 for multilayer, the preferred situation of outermost layer and above-mentioned individual layer Similarly have concavo-convex tracing ability and resistance to foaming reliability concurrently, therefore preferably shaped with above-mentioned adhesive resin composition 3.

On the other hand, bonding of the intermediate layer to image display device member of formation is not contributed, and is not damaged it is therefore preferable that having The evil transparency and do not hinder the translucency of the degree of outermost 2 curing reactions, and with improving cutting and treatability Property.

For the species for the base polymer for forming intermediate layer, as long as just there is no particular limitation for transparent resin.Formed The base polymer in intermediate layer can be and outermost base polymer identical resin, or different resins.Its In, from the transparent easy degree for ensuring, making and then prevent from the viewpoint of being laminated the refraction of the light at interface, preferably make With with outermost base polymer identical acrylic resin.

For intermediate layer and other resin beds, be able to can also not have with active energy ray-curable.Such as can Formed, can also be formed in a manner of Yin Re solidifies by a manner of being solidified by ultraviolet-crosslinkable.Alternatively, it is also possible to The mode for specially not carrying out solidify afterwards is formed.Additionally, it is contemplated that during with outermost adaptation, preferably in a manner of carrying out solidify afterwards Formed, particularly preferably formed in a manner of carrying out ultraviolet-crosslinkable.

Now, cross-linked evocating agent containing quantitative change it is more when, light transmittance reduces, therefore preferably with the cross-linked evocating agent in intermediate layer The containing ratio lower than the containing ratio in outer layer contains ultraviolet-crosslinkable agent.

In the case of transparent double face jointing material of this bonding sheet 3 for multilayer, form as stacking, can specifically lift Go out：During 2 kinds 2 layers obtained from this adhesive resin composition 3 and the stacking of other adhesive resin compositions are formed, are clipped Between resin bed be configured with surface and the back side this adhesive resin composition 32 kinds 3 layers form, this adhesive is set in order 3 kinds of 3 layers of compositions that oil/fat composition 3, middle resin combination and other adhesive resin compositions are laminated etc..

Furthermore it is possible to by this adhesive resin composition 3 and other adhesive resin compositions respectively different Slabbing is shaped on mould release film or even image display device member of formation, two adhesive surfaces are laminated and obtain this bonding sheet 3；Separately Outside, can also in order by this adhesive resin composition 3, middle resin combination and adhesive resin composition be coextruded and Obtain 2 kinds 3 layers this bonding sheet 3；Alternatively, it is also possible to fold this adhesive resin group on the surface of middle resin layer and back side surface layer Compound 3 or other adhesive resin compositions and obtain this bonding sheet 3.

In addition, for example can be to possess the gluing with base material for being formed obtained from above-mentioned adhesive layer 3 and being formed on base material Close piece or without base material without base material bonding sheet.And then can be pair in upper and lower both sides with this adhesive layer 3 Face bonding sheet or the one side bonding sheet only in upper and lower single-face side with this adhesive layer 3.

From the viewpoint of viewpoint as the thinning without prejudice to image display device and difference of height absorbability are such, this is viscous The thickness for closing piece 3 is that gross thickness is preferably 50 μm~1mm, wherein more preferably more than 75 μm or less than 500 μm.

When the gross thickness of this bonding sheet 3 is more than 50 μm, it can realize and the bumps such as height printing difference of height are followed, be During below 1mm, the requirement of thinning can be met.

And then the printing height of the shielding layer of the periphery from than conventional image display device is high, specifically 80 μm From the viewpoint of the difference of height of left and right can also fill, the gross thickness of this bonding sheet 3 is preferably more than 75 μm, especially further preferably For more than 100 μm.On the other hand, it is preferably less than 500 μm, especially further excellent from the viewpoint of the requirement of thinning is met Elect less than 350 μm as.

In the case of being formed for multilayer, the ratio of the thickness in each outermost thickness and intermediate layer is 1：1~1：20, wherein Especially it is more preferably 1：2~1：10.

When the thickness in intermediate layer is above range, the thickness contribution of the bonding material layer in layered product will not be excessive, also not Meeting is excessively soft and make it that the operability related to cutting, handling is deteriorated, thus preferably.

In addition, when outermost layer is above range, it will not to be deteriorated to the tracing ability in concavo-convex, bending face, can maintain Bonding force, wetability to adherend, thus preferably.

Additionally, it is preferred that the thickness of the maximum gauge part of this bonding sheet 3 is less than 250 μm.In other words, this bonding sheet 3 had been both Can be in uniform thickness or the different uneven piece of local thickness, in the case of being piece in uneven thickness, The thickness of preferred thickness the best part is less than 250 μm.

This bonding sheet 3 can both use under original form, can also use in such a way.In addition, to this bonding The Application way of piece 3 does not limit.

(bonding laminate)

This bonding sheet 3 for example can be to possess the composition formed in the one side of this bonding sheet 3 or two-sided stacking mould release film Bonding laminate and provide.

(this image display device forms and uses layered product 3)

As one of the purposes of this bonding sheet 3, it can make and possess between 2 device used for image display member of formation Clip image display device composition layered product (hereinafter referred to as " this image display for the composition that this bonding sheet 3 is laminated Device forms and uses layered product 3 ".).

For this image display device composition layered product 3, such as following image display device composition layer can be enumerated Stack：It is to possess 2 at least facing device used for image display member of formation, and the device used for image display of at least one Member of formation has the image display device composition layered product in light tight portion and transmittance section in binding face, and possesses foregoing 2 The composition filled between device used for image display member of formation by this bonding sheet 3, wherein, possess and shown across earlier figures picture Device carries out light irradiation so that the composition that the bonding sheet part photocuring forms with member of formation to aforementioned adhesion piece.

At this point it is possible to the gel fraction for making the position contacted with foregoing transmittance section of aforementioned adhesion piece is more than 50%, and it is preceding The gel fraction for stating the position contacted with light tight portion is less than 5%.

Here, as above-mentioned device used for image display member of formation, can enumerate by touch panel, image display panel, Any number of or layered product that is formed by two or more combinations in surface protection panel and the group of light polarizing film composition.

One as this image display device composition with layered product 3, it can enumerate：Possesses protection panels/this bonding sheet The layered product of the composition of 3/ light polarizing film, and such as touch panel of image display panel/this bonding sheet 3/, image display panel/ The protection panels of this bonding sheet 3/, the touch panel of image display panel/this bonding sheet 3//protection panels of this bonding sheet 3/, light polarizing film/ The configuration examples such as the touch panel of this bonding sheet 3/, the touch panel of light polarizing film/this bonding sheet 3//protection panels of this bonding sheet 3/.

This image display device composition can be manufactured with layered product 3 by the process of for example following (1)~(3).

In addition, the manufacture method of this image display device composition layered product 3 at least possesses the work of following (1)~(3) Sequence, therefore other processes can be added, or other processes are inserted between each operation.

Prepared by process (1) contains (methyl) acrylic copolymer (3-A), crosslinking agent (B) and Photoepolymerizationinitiater initiater (C) Adhesive resin composition, the sheet of single or multiple lift is shaped as using the adhesive resin composition, it is viscous so as to make this Close piece 3.

Process (2) clips this bonding sheet 3 and attaches 2 image display device member of formation and be laminated.

Process (3) irradiates active-energy from the outside of the image display device member of formation of at least one to this bonding sheet 3 Ray, it is crosslinked this bonding sheet 3, so as to which 2 image display device member of formation be bonded.

(process (1))

In process (1), this adhesive resin composition 3 is prepared with known method, is shaped as possessing by the adhesive The sheet for adhesive layer, single or multiple lift the non cross-linked state that resin combination is formed, so as to make this bonding sheet 3.

This adhesive resin composition 3 is shaped to the method for slabbing can arbitrarily use presently known method.

At this point it is possible to this adhesive resin composition 3 is shaped as to the sheet of single or multiple lift on mould release film, to make Make the transparent double face jointing material for possessing the single or multiple lift of adhesive layer.

Furthermore it is possible to this adhesive resin composition 3 is shaped as individual layer or more on image display device member of formation The sheet of layer, it is produced on the transparent double face bonding material for the single or multiple lift for possessing adhesive layer on the image display device member of formation Material.

(process (2))

In process (2), foregoing bonding sheet 3 can be clipped and attach 2 image display device member of formation so as to be laminated.

Now, when the base polymer as this bonding sheet 3 uses above-mentioned graft copolymer (A1), in usual state, i.e. Under room temperature state, interior coalescence formation manages cross-linked structure to the macromonomer between each other, and it is excellent can to assign this bonding sheet 3 Keeping stability, processing of cutting.

In addition, complex viscosity of (methyl) acrylic copolymer (3-A) under 130 DEG C of temperature, frequency 0.02Hz is 100 During~800Pas, in fitting as hot melt piece and in use, excellent operability can be possessed.

So, in process (2), this bonding sheet 3 can be clipped and attach 2 image display device member of formation so as to layer It is folded.When operating like this, it can obtain only by the way that this bonding sheet 3 is pressed against into the viscous of the degree that just can be simply bonded on adherend Conjunction property, therefore, the positioning for attaching jointing material is easily carried out, very convenient in operation.

In addition, for this bonding sheet 3, from shape retention it is excellent, arbitrary shape aspect can be processed into advance, Can according to the size for the image display device member of formation to be laminated and advance this bonding sheet 3 to being shaped on mould release film Cut.

For cutting method now, common is to utilize the punching press of Thomson cutter, utilize super cutter (super Cutter), the cutting of laser, the more preferably demoulding to surface and back side any one party in a manner of mould release film is easily peeled off are thin Film carries out hemisect and remains into frame-shaped.

In process (2), this bonding sheet 3, i.e. transparent double face jointing material are also non cross-linked state.

(process (3))

In process (3), from the outside of the image display device member of formation of at least one to the foregoing viscous of this bonding sheet 3 Layer irradiation active energy beam is closed, is crosslinked the adhesive layer, makes 2 image display device member of formation bondings, so as to make Make this image display device composition layered product 3.

This bonding sheet 3 contains crosslinking agent (B) and Photoepolymerizationinitiater initiater (C), therefore to the aforementioned adhesion layer of this bonding sheet 3 Irradiation active energy beam can be crosslinked the adhesive layer and solidify, can be by 2 image display device member of formation securely Attach.

Now, as active energy beam, the triggering such as heat ray, X ray, electron beam, ultraviolet, visible ray can be irradiated The energy-ray of polymerization initiator.Wherein, the infringement from suppression to image display device member of formation, the easy journey of reaction controlling From the viewpoint of degree, ultraviolet, the ultraviolet especially below wavelength 380nm are preferably irradiated.

Ultraviolet irradiation condition is had no particular limits.For example, it is preferable to reach the accumulation of the ultraviolet of jointing material Light quantity is 500~5000mJ/cm at wavelength 365nm²Mode be irradiated.This be in order at holding operability and fully The viewpoint for carrying out cross-linking reaction.

In addition, irradiation ultraviolet when across image display device component parts can cover above-mentioned wavelength light situation Under, preferably with across part correspondingly, the energy that jointing material absorbed suitably is adjusted according to the species of polymerization initiator and penetrated The species of line.

(other processes)

Between foregoing sequence (2) and foregoing sequence (3), the sandwich heating obtained to foregoing sequence (2) may be inserted into So that the process of the adhesive layer heating melting of transparent double face jointing material.I.e., it is possible to the sandwich attached in process (2) is entered Row heating causes the adhesive layer heating melting (hot melt) of this bonding sheet 3.

For this bonding sheet 3, during heating, the mutual foregoing cohesion of macromonomer is untied, so as to be physical crosslinking knot Structure releases, and can show high fluidity.Therefore, in the case where adhesive surface has printing difference of height etc. concavo-convex, 2 images are shown When showing device member of formation is laminated, by being heated and being made it to flow (hot melt) to this bonding sheet 3, the bumps of jointing material chase after It is casual, the wetability of adherend is improved, residual strain and component can not be made to be more firmly integrated between each other.

Now, being preferably heated to 60~100 DEG C makes its hot melt.For more than 60 DEG C when, can fully assign jointing material Mobility, fully adhesive resin composition can be filled to jog.On the other hand, be less than 100 DEG C when, not only It can suppress to cause pyrolytic damage to the image display device member of formation as adherend, be also prevented from jointing material excess flow The spilling of adhesive resin composition, the generation collapsed caused by dynamic.

From such a viewpoint, hot melting temperature is preferably 60~100 DEG C, wherein more preferably more than 62 DEG C or Less than 95 DEG C, wherein being more than 65 DEG C or less than 90 DEG C.

(this image display device 3)

Using this bonding sheet 3 or above-mentioned image display device composition image display device can be formed with layered product (hereinafter referred to as " this image display device 3 ".).

Such as it can enumerate：This image display device 3 is to possess 2 at least facing device used for image display to form structure Part, and the device used for image display member of formation of at least one shows dress in the image that binding face has light tight portion and transmittance section Put, it possesses the composition formed between foregoing 2 device used for image display member of formation by bonding sheet filling.At this point it is possible to make The gel fraction of the position contacted with foregoing transmittance section of aforementioned adhesion piece is more than 50%, and the foregoing position contacted with light tight portion The gel fraction put is less than 5%.

Above-mentioned image display device is formed with layered product 3 and this image display device 3, will have picture in binding face Around Printing Department grade part (being referred to as in the present invention in " light tight portion ") that the light of the wavelength needed for photocuring is not through with And the device used for image display of the part (being referred to as in the present invention " transmittance section ") of the light transmission of the wavelength needed for photocuring is formed Component is bonded with other device used for image display member of formation, by the gel fraction for the position for making to contact with foregoing light tight portion Less than 1%, the gel fraction of position for making to contact with foregoing transmittance section is more than 40%, can make because oppressed by light tight portion and by It the stress relaxation arrived, can make to diminish caused by the part, and can make adherend firm between each other with high cohesion Ground is bonded.

One of the concrete example of the preferable preparation method of this image display device 3 is illustrated.

First, this bonding sheet 3 is heated so that it is heated, clipping above-mentioned bonding sheet 3 will be with Printing Department i.e. Device used for image display member of formation and device used for image display the member of formation stacking in light tight portion.In this stage, this is viscous The softness of the appropriateness of piece 3 is closed, therefore keeping stability can be maintained and fully follow difference of height.

Next, irradiate the light such as ultraviolet from the outside of device used for image display member of formation.So, Printing Department covers Light, therefore light will not reach the part contacted with Printing Department, or the light reached is significantly limited, on the other hand, light is fully The part that is contacted with without the transmittance section of Printing Department is reached, the cross-linking reaction of the part can carry out so that its photocuring, can To realize excellent peel resistance and resistance to foaminess.

As foregoing 2 device used for image display member of formation, such as can enumerate：Computer, mobile terminal (PDA), trip The composition of the image display device such as gaming machine, TV (TV), auto-navigation system, touch panel, handwriting pad etc., LCD, PDP or EL Component.More specifically, such as can enumerate：By touch panel, image display panel, surface protection panel and polarizing film group Into group in any number of or layered product that is formed by two or more combinations.

[explanations of words and phrases etc.]

In general " piece " refers to thin, its thickness relative to the smaller flat system of length and width in JIS definition Product；In general " film " refers to that thickness is extremely small compared with length and width, and maximum gauge is arbitrarily defined thin and flat Product, generally provide (JIS JISK6900) as rolls.But the boundary of piece and film is not fixed, this The necessity for distinguishing both not on word in invention, therefore, in the present invention, the situation for being referred to as " film " also includes " piece ", Referred to as the situation of " piece " also includes " film ".

In addition, the situation that " panel " is expressed as image display panel, protection panels etc. includes tabular, piece and thin Film or these layered product.

In this specification, it is recited as that " X~Y " (X, Y are arbitrary numeral) situation is in the case where being not particularly limited The implication of " more than X and below Y " is included, also comprising " preferably greater than X " or " preferably smaller than Y " implication.

In addition, the situation of " more than X " (X be arbitrary numeral) is recited as in the case where being not particularly limited comprising " excellent Implication of the choosing more than X ", the situation of " below Y " (Y is arbitrary numeral) is recited as, is included in the case where being not particularly limited " preferably smaller than Y " implication.

Embodiment

Hereinafter, it is described in more detail by embodiment.In addition, the present invention is not by these any restrictions.

[embodiment 1-1]

Will be big as (methyl) acrylic copolymer (1-A), number-average molecular weight 2400 polymethyl methacrylate Molecule monomer (Tg：105 DEG C) 15 mass parts (18mol%) and butyl acrylate (Tg：- 55 DEG C) 81 mass parts (75mol%) and Acrylic acid (Tg：106 DEG C) acrylic copolymer (1-A-1) (Weight-average molecular obtained from 4 mass parts (7mol%) random copolymerization Amount：23 ten thousand) 1kg, as crosslinking agent (1-B), glycerine dimethacrylate (Japan Oil Co manufacture, ProductName：GMR) (1-B-1) 75g and 2,4,6- tri-methyl benzophenones as Photoepolymerizationinitiater initiater (1-C) are mixed with 4- methyl benzophenones (LAMBERTI GROUP are manufactured compound, ProductName：ESACURE TZT) (1-C-1) 15g uniformly mixes, make adhesive combination Thing 1-1.

With two mould release films, (Mitsubishi's resin is public for i.e. release-treated two pet films Department manufacture " DIAFOIL MRV-V06 ", Resins Corporation of 100 μm/Mitsubishi of thickness manufacture " 75 μm of DIAFOIL MRQ ", thickness) Foregoing 1-1 is clipped, figuration slabbing, making bonding sheet 1-1 are (thick in a manner of thickness reaches 150 μm using laminating machine 150 μm of degree).

Implement at the peripheral part of 238mm × 182mm × thickness 0.8mm glass (long side 20mm, short brink 17mm) thick The printing for being not through ultraviolet light of 60 μm of degree, prepare the glass with printing difference of height that non-printing portion is 198mm × 148mm Plate.

The mould release film of a bonding sheet 1-1 side is peeled off, roller fits in 150mm × 200mm thickness 1mm sodium calcium glass Glass.

Then, peel off remaining mould release film, with printing difference of height glass plate printing surface, with the 4 of adhesive surface While the mode for being erected on printing difference of height (absolute pressure 5kPa, 80 DEG C of temperature, is pressed after carrying out compacting crimping with vacuum molding machine Pressing pressure 0.04MPa), implement autoclave process (80 DEG C, gauge pressure 0.2MPa, 20 minutes) so as to complete to attach.Printed from implementing The glass side of brush, reach 2000mJ/cm to reach bonding sheet 1-1 wavelength 365nm ultraviolet²Mode shone with high-pressure sodium lamp Ultraviolet is penetrated, solidifies bonding sheet 1-1, so as to make layered product 1-1.

[embodiment 1-2]

Relative to as (methyl) acrylic copolymer (1-A), 2-EHA (Tg：- 70 DEG C) 55 matter Measure part (36mol%) and vinylacetate (Tg：32 DEG C) 40 mass parts (56mol%) and acrylic acid (Tg：106 DEG C) 5 mass parts Acrylic copolymer (1-A-2) (weight average molecular weight obtained from (8mol%) random copolymerization：17 ten thousand) 1kg, uniformly mixing are made For crosslinking agent (1-B), ε caprolactone modification isocyanuric acid triacrylates (1-B-2) (manufacture of chemical company of Xin Zhong villages, product Name：A9300-1CL) 75g and as Photoepolymerizationinitiater initiater (1-C), ESACURE KTO46 (1-C-2) (LAMBERTI GROUP is manufactured) 5g, make adhesive composition 1-2.

By foregoing 1-2 in the same manner as embodiment 1-1 figuration slabbing, make bonding sheet 1-2 (150 μm of thickness).

In addition to using bonding sheet 1-2, layered product 1-2 is made in the same manner as embodiment 1-1.

[embodiment 1-3]

Will be big as (methyl) acrylic copolymer (1-A), number-average molecular weight 1400 polymethyl methacrylate Molecule monomer (Tg：105 DEG C) 10 mass parts (17mol%) and 2-EHA (Tg：- 70 DEG C) 90 mass parts Acrylic copolymer (1-A-3) (weight average molecular weight obtained from (83mol%) random copolymerization：23 ten thousand) 1kg, as crosslinking agent (1-B), pentaerythritol propoxylate triacrylate (manufacture of chemical company of Xin Zhong villages, ProductName：ATM-4PL)(1-B-3) 50g and 4- methyl benzophenones (1-C-3) 15g as Photoepolymerizationinitiater initiater (1-C) are uniformly mixed, and make adhesive combination Thing 1-3.

By foregoing 1-3 in the same manner as embodiment 1-1 figuration slabbing, make bonding sheet 1-3 (150 μm of thickness).

In addition to using bonding sheet 1-3, layered product 1-3 is made in the same manner as embodiment 1-1.

[embodiment 1-4]

Will be big as (methyl) acrylic copolymer (1-A), number-average molecular weight 2400 polymethyl methacrylate Molecule monomer (Tg：105 DEG C) 12 mass parts (19mol%) and 2-EHA (Tg：- 70 DEG C) 85 mass parts (74mol%) and acrylic acid (Tg：106 DEG C) acrylic copolymer (1-A- obtained from 3 mass parts (7mol%) random copolymerization 4) (weight average molecular weight：8 ten thousand) 1kg, as crosslinking agent (1-B), glycerine dimethacrylate (Japan Oil Co manufacture, ProductName：GMR) (1-B-1) 90g and ESACURE KTO46 (1-C-2) (LAMBERTI as Photoepolymerizationinitiater initiater (1-C) GROUP is manufactured) 5g uniformly mixes, make adhesive composition 1-4.

By foregoing 1-4 in the same manner as embodiment 1-1 figuration slabbing, make bonding sheet 1-4 (150 μm of thickness).

In addition to using bonding sheet 1-4, layered product 1-4 is made in the same manner as embodiment 1-1.

[comparative example 1-1]

Layered product 5 is made as follows in a manner of equivalent to the embodiment of No. 2012/032995 publication of International Publication.

As (methyl) acrylic copolymer (1-A), 2-EHA (Tg：- 70 DEG C) 75 mass parts (57mol%) and vinylacetate (Tg：32 DEG C) 20 mass parts (33mol%) and acrylic acid (Tg：106 DEG C) 5 mass parts Mixing addition is as crosslinking agent (1-B) in acrylic copolymer (1-A-5) 1kg obtained from (10mol%) random copolymerization Trimethylolpropane trimethacrylate (1-B-4) the 200g and 4- methyl benzophenones (1-C- as Photoepolymerizationinitiater initiater (1-C) 3) 10g, so as to prepare intermediate layer resin combination.With two release-treated pet films (PANAC CORPORATION are manufactured, NP75Z01,75 μm/TOYOBO of thickness CO., LTD. manufactures, 38 μm of E7006, thickness) folder Foregoing intermediate layer resin combination is held, the figuration slabbing in a manner of thickness reaches 80 μm, makes intermediate layer with piece (α).

Then, it is used as Photoepolymerizationinitiater initiater (1-C) relative to foregoing acrylic copolymer (1-A-5) 1kg, addition mixing 4- methyl benzophenones (1-C-3) 20g, prepare adhesive linkage resin combination.

With two mould release films, (Mitsubishi's resin is public for i.e. release-treated two pet films Department's manufacture " DIAFOIL MRA ", 75 μm/TOYOBO of thickness CO., " E7006 ", 38 μm of the thickness of LTD. manufactures) clamping is foregoing Adhesive linkage resin combination, the figuration slabbing in a manner of thickness reaches 35 μm, adhesive linkage is made with resin sheet (β).

And then with release-treated two pet films (Resins Corporation of Mitsubishi manufactures, DIAFOIL MRF, 75 μm/TOYOBO of thickness CO., LTD. manufactures, 38 μm of E7006, thickness) clamping adhesive linkage resin combination Thing, the figuration slabbing in a manner of thickness reaches 35 μm, adhesive linkage is made with resin sheet (β ').

Successively peel off remove the intermediate layer both sides of piece (α) PET film, and peel off adhesive linkage resin sheet (β) and The PET film of the side of (β '), the adhesive surface exposed is fitted in two surfaces of intermediate layer piece (α) successively, make by (β)/ 3 layers of bonding sheet that (α)/(β ') is formed.

PET film across the surface for residuing in (β) and (β '), 1000mJ/ is reached with wavelength 365nm accumulated light cm²Mode high voltage mercury lamp radiation ultraviolet, (α), (β) and (β ') is carried out ultraviolet-crosslinkable, it is (thick to make bonding sheet 1-5 150 μm of degree).

In addition to using bonding sheet 1-5, layered product 1-5 is made in the same manner as embodiment 1-1.

[comparative example 1-2]

Relative to (comprehensive as (methyl) acrylic copolymer (1-A), commercially available acrylic adhesives (1-A-6) KCC is ground to manufacture, and trade name " SK-DYNE 1882 ") 1kg, it is (comprehensive to grind chemistry uniformly to mix isocyanates system curing agent Co., Ltd. manufactures, trade name " L-45 ") (Soken Chemical ＆ Engineering Co., Ltd. manufactures, trade name " E- for 1.85g and epoxy curing agent 5XM ") 0.5g, prepare adhesive composition 1-6.

In 50 μm of mould release film, i.e. release-treated polyethylene terephthalate film (Mitsubishi's resin of thickness " MRF75 " of company's manufacture：75 μm of thickness) stripping surface, be coated with aforementioned combinatorial in a manner of dried thickness reaches 75 μm Thing 1-6, solvent seasoning is made by heating, makes the bonding sheet of 75 μm of thickness.

And then in mould release film, i.e. release-treated polyethylene terephthalate film (Resins Corporation of Mitsubishi system Make " 100 μm of DIAFOIL MRV-V06 ", thickness) stripping surface, be coated with a manner of dried thickness reaches 75 μm foregoing Composition 1-6, solvent seasoning is made by heating, makes the bonding sheet of 75 μm of thickness.

For two bonding sheets of making, respective adhesive surface is attached and conserved 1 week, so as to make bonding sheet 1- 6 (150 μm of thickness).

The mould release film of a bonding sheet 1-6 side is peeled off, roller fits in 150mm × 200mm thickness 1mm sodium calcium glass Glass.

Then, remaining mould release film is peeled off, with printing difference of height glass plate printing surface, with adhesive surface The mode that 4 sides are erected on printing difference of height carries out (absolute pressure 5kPa, temperature 80 after compacting crimping using vacuum molding machine DEG C, pressing pressure 0.04MPa), implement autoclave process (80 DEG C, gauge pressure 0.2MPa, 20 minutes) so as to complete to attach, make layer Stack 1-6.

[comparative example 1-3]

It is following to make layered product 1-7 in a manner of the embodiment equivalent to No. WO2010038366.

Making will be as phenoxy resin (1-A-7) (InChem of the replacement of (methyl) acrylic copolymer (1-A) Holdings, Inc. are manufactured, and ten thousand) 650g, the replacement as crosslinking agent (1-B) have a carbonic ester for PKHH, weight average molecular weight 5.2 Skeleton urethane acrylate (1-B-4) (Negami Chemical Ind Co., Ltd. manufacture, UN5500, weight average molecular weight 6.7 ten thousand) 1kg, 1- cyclohexyl-phenyl ketones (1-C-4) (BASF AG manufactures, Irgacure184) 43g as Photoepolymerizationinitiater initiater (1-C) is uniform The adhesive composition 1-7 being obtained by mixing.

By foregoing 1-7 in the same manner as embodiment 1-1 figuration slabbing, make bonding sheet 1-7 (150 μm of thickness).

The mould release film of a bonding sheet 1-7 side is peeled off, roller fits in 150mm × 200mm thickness when heating for 80 DEG C 1mm soda-lime glass.

Then, peel off remaining mould release film, with printing difference of height glass plate printing surface, with the 4 of adhesive surface While be erected on printing difference of height mode carry out compacting crimping with vacuum molding machine after (absolute pressure 5kPa, temperature 80 DEG C, layer Pressure pressure 0.04MPa), implement autoclave process (80 DEG C, gauge pressure 0.2MPa, 20 minutes) so as to complete to attach.Printed from implementing The glass side of brush, reach 2000mJ/cm to reach the wavelength 365nm of bonding sheet ultraviolet²Mode high voltage mercury lamp radiation Ultraviolet, solidify bonding sheet 1-7, make layered product 1-7.

[evaluation]

The bonding sheet and layered product made to embodiment and comparative example, is carried out as follows evaluation.

(viscosimetric analysis)

Respectively using bonding sheet 1-1~1-7 that multiple make in embodiment and comparative example, reach 1mm~2mm's with thickness The mode of thickness is laminated, and makes the circular piece for striking out diameter 20mm.

Using rheometer (" MARS " that Eko Instruments Trading manufactures), in bonding fixture：Φ 25mm parallel-plates, answer Become：0.5%th, frequency：1Hz, programming rate：It is viscous before the photocuring at determining from 70 DEG C to 120 DEG C under conditions of 3 DEG C/min Close the complex viscosity of piece.

For 1-1~1-5 and 1-7, reach 2000mJ/cm using high-pressure sodium lamp, with 365nm accumulated light²Mode, Ultraviolet is irradiated to bonding sheet across pet film, solidifies bonding sheet.By the bonding sheet after solidification It is laminated in a manner of thickness reaches 1mm~2mm, makes the circular piece for striking out diameter 20mm.

Using rheometer (" MARS " that Eko Instruments Trading manufactures), in bonding fixture：Φ 25mm parallel-plates, answer Become：0.5%th, frequency：1Hz, programming rate：It is viscous after the photocuring at determining from 70 DEG C to 120 DEG C under conditions of 3 DEG C/min Close the complex viscosity of piece.

(bonding force after solidification)

The mould release film of the bonding sheet 1-1~1-7 made in embodiment and comparative example a side is peeled off, is bonded conduct 50 μm of the PET film (Resins Corporation of Mitsubishi manufacture, 50 μm of DIAFOIL T100, thickness) of backing film is so as to preparing to be laminated Product.

After above-mentioned stacking product are cut into length 150mm, width 10mm, peel off remaining mould release film and will expose Adhesive surface with 2kg roller back and forth 1 time and roll-in is connected to soda-lime glass.To fitting product implement autoclave process (80 DEG C, gauge pressure 0.2MPa, 20 minutes) so as to complete attaching after, 2000mJ/cm is reached with 365nm accumulated light²Mode irradiate it is ultraviolet Line conserves 15 hours so that bonding sheet solidification, and peeling force measure sample is made.

Measure by above-mentioned peeling force determination sample in the environment of 23 DEG C of 40%RH and 80 DEG C of 10%RH with 180 ° of peel angle, The peeling force (N/cm) to glass when peeling rate 60mm/ minutes peel off, obtain the bonding force after solidification.

(solidification front attachment power)

The mould release film of the bonding sheet 1-1~1-7 made in embodiment and comparative example a side is peeled off, is bonded conduct 50 μm of the PET film (Resins Corporation of Mitsubishi manufactures, 50 μm of DIAFOIL T100, thickness) of backing film, so as to prepare to be laminated Product.

After above-mentioned stacking product are cut into length 150mm, width 10mm, peel off remaining mould release film and will expose Adhesive surface on soda-lime glass with 2kg roller back and forth 1 time and roll-in connects aforementioned adhesion piece.

Measure by the bonding force determination sample in the environment of 23 DEG C of 40%RH and 80 DEG C of 10%RH with 180 ° of peel angle, stripping The peeling force (N/cm) to glass when being peeled off from speed 60mm/ minutes, obtain the bonding force before solidification.

It should be noted that on the separation mode under 80 DEG C of 10%RH environment during stripping, in table when being cohesional failure Described in be " CF ", when being interface peel be " AF " described in table.

(transparency)

The mould release film of the bonding sheet 1-1~1-7 made in embodiment and comparative example a side is peeled off, by what is exposed Adhesive surface roller is fitted in after two soda-lime glass (82mm × 53mm × 0.5mm is thick), implements autoclave process (80 DEG C, gauge pressure 0.2MPa, 20 minutes) so as to completing to attach, make optical assessment layered product.

For foregoing layered product, using haze meter (Japanese electricity Se industrial groups manufacture, NDH5000), according to JIS K7136 Obtain haze value and obtain total light transmittance (%) according to JIS K7361-1.

(fitting operability)

In the making of above-mentioned optical assessment layered product, it is fitted in what is made in embodiment and comparative example on soda-lime glass During piece, roller fitting will be carried out in the environment of 23 DEG C 40% and is determined as " zero so as to the closely sealed situation for being fixed on glass plate (excellent) "；Can not be closely sealed in the environment of 23 DEG C 40% by glass plate and piece, need situation about heating to be determined as when roller is bonded " × (is bad) ".

(exhaust gas analysis)

According to the present invention, the exhaust after light irradiation refers to the exhaust detected using following analysis methods.

(exhaust production method)

To the bonding sheet 1-1~1-5 and 1-7 made in embodiment and comparative example, using high-pressure sodium lamp, with 365nm's Accumulated light reaches 2000mJ/cm²Mode, across pet film to bonding sheet irradiate ultraviolet, Make equivalent to the bonding sheet after photocuring.Bonding sheet after photocuring is cut into 1cm × 3cm, loads 20ml bottle In (vial bottle) and seal.The bottle is loaded into xenon UV irradiation units (SUNTEST CPS：Toyo Seiki system), in illumination 765W/m², implement the UV treatment with irradiation of 24 hours under temperature 60 C.

Comparative example 1-2 bonding sheet 1-6 is cut into 1cm × 3cm, loads 20ml bottle and sealing.This is small bottled Enter xenon UV irradiation units (SUNTEST CPS：Toyo Seiki system), in illumination 765W/m², implement the UV of 24 hours under temperature 60 C Treatment with irradiation.

(exhaust gas analysis method)

Caused gas can use the gas phase color with head-space sampler in the resin combination handled as described above through UV Analytic approach (HS-GC) is composed to determine.

(1) collection of gas is analyzed

The gas as caused by following conditional capture above-mentioned bonding sheet.

1.HS injectors：TuboMatrix40 (manufacture of PerkinElmer companies)

2. heating-up temperature：80℃

3. the heat time：30 minutes

4. sampling probe temperature：110℃

5. transmission line temperature：170℃

6. injection length：0.1 point

7. column pressure：16.0psi

(2) GC is analyzed

With GC (PerkinElmer Co., Ltd. manufactures：Clarus580) gas caused by analysis, the exhaust that will be detected Yield is quantified with hexadecane conversion.

(concavo-convex absorbability)

Layered product 1-1~1-7 that visually observation embodiment and comparative example make, jointing material near difference of height will printed Do not follow and remain alveolate situation and be determined as " × (bad) "；It will be confirmed near difference of height from the residual of bonding sheet The uneven situation of strain is stayed to be determined as " △ "；Situation about by bubble-free, being smoothly bonded is determined as " zero (excellent) ".

(resistance to foaming reliability)

Xenon UV irradiation units (SUNTEST CPS will be loaded in layered product 1-1~1-7 of embodiment and comparative example making： Toyo Seiki system), observe in illumination 765W/m², implement outward appearance after 24 hours UV treatment with irradiation under temperature 60 C.

The situation that more than diameter 5mm bubble is generated in bonding sheet is determined as " × (bad) "；It will confirm that diameter The situation of below 5mm bubble is determined as " △ (general) "；" zero will be determined as without the situation of change without foaming, outward appearance (excellent) ".

[table 1]

Numeral in ※ tables represents mass parts.

[table 2]

(research)

For embodiment 1-1~1-4 make bonding sheet, before photocuring at a high temperature of separation mode be cohesional failure This point understands that not only the wetability to sticky surface is excellent, excellent to the tracing ability of male and fomale(M＆F), and the bonding force after photocuring Also it is high.Therefore, the bonding sheet made using embodiment 1-1~1-4, even if the long-time ultraviolet irradiation under high-temperature is so Harsh environmental test under it is also not peeling-off, foaming, deformation, the layered product with high reliability can be obtained.

In addition, the bonding sheet that embodiment 1-1~1-4 makes can keep shape at 0~40 DEG C, and show autoadhesion Property.

Comparative example 1-1 bonding sheet is partial cross-linked and adhesive resin composition due to being irradiated by ultraviolet, as light State after solidification, thus with printing difference of height it is glass laminated when, printing difference of height near confirm because of bonding sheet The inequality brought of residual strain, be bonded poor appearance.In addition, bonding force after its once again photocuring is low, cohesive force is poor, therefore Foaming is confirmed in ultraviolet radiation test, fitting reliability is also poor.

Stage of the cross-linking reaction of comparative example 1-2 adhesive resin composition before being bonded to component is over, So even irradiation ultraviolet, viscosity, bonding force are also without changing.In addition, with printing difference of height it is glass laminated When, as a result there is some adhesive not to be filled up completely near the corner that printing difference of height interlocks and remain bubble.In addition, with The strain of jointing material near difference of height is starting point, and the growth of bubble is confirmed in ultraviolet radiation test.

Comparative example 1-3 is not use (methyl) acrylic copolymer as main component, but has been used in room temperature Region possesses the heat molten type adhesive sheet of adhesive resin composition rigid to a certain degree.

Bonding force before the photocuring of comparative example 1-3 piece is low, be will also realize that from this point, the bonding sheet phase with embodiment Than the viscosity under near room temperature is very low, and the self adhesion at 0~40 DEG C is insufficient.Comparative example 1-3 bonding sheet is in fitting Just need to preheat adherend since the stage of positioning, with only pressing can normal temperature attach bonding sheet compared with, exist The inconvenience of complex operation.

[embodiment 2-1]

Will as (methyl) acrylic copolymer (2-A), by polymethyl methacrylate (Tg：105 DEG C) form The mass parts of macromonomer 15 (18mol%) and butyl acrylate (Tg of number-average molecular weight 2900：- 55 DEG C) 81 mass parts (75mol%) and acrylic acid (Tg：106 DEG C) acrylic graft copolymers obtained from 4 mass parts (7mol%) random copolymerization (2-A-1) (weight average molecular weight：23 ten thousand) 1kg, the glycerine dimethacrylate (Japan Oil Co as crosslinking agent (2-B) Manufacture, ProductName：GMR) (2-B-1) 90g and 2,4,6- tri-methyl benzophenones and 4- as Photoepolymerizationinitiater initiater (2-C) (LAMBERTI GROUP are manufactured the mixture of methyl benzophenone, ProductName：ESACURETZT) (2-C-1) 15g is uniformly mixed, Make adhesive resin composition 2-1.

With release-treated polyethylene terephthalate film Y, (Resins Corporation of Mitsubishi manufactures, DIAFOIL MRV- 100 μm of V06, thickness, be referred to as " mould release film Y ") and release-treated polyethylene terephthalate film Z (Mitsubishi trees Fat company manufactures, 75 μm of DIAFOIL MRQ, thickness, be referred to as " mould release film Z ") clamping foregoing 2-1, use laminating machine The figuration slabbing in a manner of thickness reaches 150 μm, make bonding sheet X1 (150 μm of thickness).

Will be in the single-sided lamination double faced adhesive tape of black patch (LSL-8, INOAC Corporation are manufactured, light penetration 0%) Band and cut into 50mm × 100mm piece conform to the side for being layered in aforementioned adhesion piece X1 mould release film Z surface, so as to Light tight portion is formed, is produced on the bonding laminate in piece surface with transmittance section and light tight portion.

Next, from the black patch side of the bonding laminate so made, using high-pressure sodium lamp with the tired of wavelength 365nm Product light quantity reaches 2000mJ/cm²Mode irradiate ultraviolet and solidify the transmittance section of bonding laminate, make have it is soft Portion and the bonding sheet 2-1 of hard portion.(reference picture 2)

Here, soft part refers to by the position of the bonding sheet of black patch masking；Hard portion refers to not covered by black patch Bonding sheet position.

[embodiment 2-2]

Relative to as (methyl) acrylic copolymer (2-A), 2-EHA (Tg：- 70 DEG C) 55 matter Measure part (36mol%) and vinylacetate (Tg：32 DEG C) 40 mass parts (56mol%) and acrylic acid (Tg：106 DEG C) 5 mass parts Acrylic copolymer (2-A-2) (weight average molecular weight obtained from (8mol%) random copolymerization：17 ten thousand) 1kg, uniformly mixing are made Mixture (the 2- of isocyanuric acid EO modified diacrylates and isocyanuric acid EO modified triacrylates for crosslinking agent (2-B) B-2) (East Asia Synesis Company manufactures, ProductName：Aronix M313) 70g and as Photoepolymerizationinitiater initiater (2-C) ESACURE KTO46 (2-C-2) (LAMBERTI GROUP manufactures) 5g, make adhesive resin composition 2-2.

Foregoing 2-2 is clamped with above-mentioned mould release film Y, Z, is assigned using laminating machine in a manner of thickness reaches 150 μm Sheet is formed, makes bonding sheet X2 (150 μm of thickness).

Except using in addition to bonding sheet X2, making bonding laminate in the same manner as embodiment 2-1, so with embodiment 2- 1 similarly makes the bonding sheet 2-2 with soft part and hard portion.

[embodiment 2-3]

Will be big as (methyl) acrylic copolymer (2-A), number-average molecular weight 1400 polymethyl methacrylate Molecule monomer (Tg：105 DEG C) 10 mass parts (17mol%) and 2-EHA (Tg：- 70 DEG C) 90 mass parts Acrylic graft copolymers (2-A-3) (weight average molecular weight obtained from (83mol%) random copolymerization：23 ten thousand) 1kg, as friendship Join tristane dimethylacrylate (manufacture of KCC of Xin Zhong villages, the ProductName of agent (2-B)：DCP)(2-B-3) 50g and 2,4,6- tri-methyl benzophenones and the mixture of 4- methyl benzophenones as Photoepolymerizationinitiater initiater (2-C) (LAMBERTI GROUP are manufactured, ProductName：ESACURE TZT) (2-C-1) 15g uniformly mixes, make adhesive resin composition 2-3。

Foregoing 2-3 is clamped with above-mentioned mould release film Y, Z, is assigned using laminating machine in a manner of thickness reaches 150 μm Sheet is formed, makes bonding sheet X3 (150 μm of thickness).

Except using in addition to bonding sheet X3, making bonding laminate in the same manner as embodiment 2-1, so with embodiment 2- 1 similarly makes the bonding sheet 2-3 with soft part and hard portion.

[embodiment 2-4]

Will be big as (methyl) acrylic copolymer (2-A), number-average molecular weight 2400 polymethyl methacrylate Molecule monomer (Tg：105 DEG C) 12 mass parts (19mol%) and 2-EHA (Tg：- 70 DEG C) 85 mass parts (74mol%) and acrylic acid (Tg：106 DEG C) acrylic graft copolymers obtained from 3 mass parts (7mol%) random copolymerization (2-A-4) (weight average molecular weight：8 ten thousand) 1kg, glycerine dimethacrylate (Japan Oil Co's systems as crosslinking agent (2-B) Make, ProductName：GMR) (2-B-1) 90g and 2,4,6- tri-methyl benzophenones and 4- first as Photoepolymerizationinitiater initiater (2-C) (LAMBERTI GROUP are manufactured the mixture of base benzophenone, ProductName：ESACURETZT) (2-C-1) 15g is uniformly mixed, system Make adhesive resin composition 2-4.

Foregoing 2-4 is clamped with above-mentioned mould release film Y, Z, is assigned using laminating machine in a manner of thickness reaches 150 μm Sheet is formed, makes bonding sheet X4 (150 μm of thickness).

Except using in addition to bonding sheet X4, making bonding laminate in the same manner as embodiment 2-1, so with embodiment 2- 1 similarly makes the bonding sheet 2-4 with soft part and hard portion.

[embodiment 2-5]

Acrylic copolymer (2-A-1) (weight average molecular weight that embodiment 2-1 is used：23 ten thousand) 1kg, as crosslinking agent Trimethylolpropane trimethacrylate (2-B-4) 70g of (2-B) and the 2,4,6- front threes as Photoepolymerizationinitiater initiater (2-C) Mixture (LAMBERTI GROUP manufactures, the ProductName of base benzophenone and 4- methyl benzophenones：ESACURE TZT)(2- C-1) 8g is uniformly mixed, and makes adhesive resin composition 2-5.

Adhesive resin composition 2-5 is diluted to the solution of solid component concentration 40% with ethyl acetate, at stripped place (Resins Corporation of Mitsubishi manufactures the pet film Y of reason, 100 μm of DIAFOILMRV-V06, thickness, is referred to as " mould release film Y ") lift-off processing face, after being coated with previous solu in a manner of dried thickness reaches 25 μm and drying, Coated adhesive surface be coated to release-treated polyethylene terephthalate film Z (Resins Corporation of Mitsubishi manufactures, 75 μm of DIAFOIL MRQ, thickness, be referred to as " mould release film Z "), make bonding sheet X5 (25 μm of thickness).

Except using in addition to bonding sheet X5, making bonding laminate in the same manner as embodiment 2-1, so with embodiment 2- 1 similarly makes the bonding sheet 2-5 with soft part and hard portion.

[comparative example 2-1]

In 2-EHA (Tg：- 70 DEG C) 75 mass parts (57mol%) and vinylacetate (Tg：32℃)20 Mass parts (33mol%) and acrylic acid (Tg：106 DEG C) obtained (methyl) acrylic compounds of 5 mass parts (10mol%) random copolymerization Mixing addition trimethylolpropane trimethacrylate (2-B-4) 200g and 4- methyl benzophenones in copolymer (2-A-5) 1kg (2-C-3) 10g is so as to preparing intermediate layer resin combination.

With release-treated two pet films (PANACCORPORATION is manufactured, NP75Z01,75 μm/TOYOBO of thickness CO., LTD. manufactures, 38 μm of E7006, thickness) the foregoing intermediate layer resin combination of clamping Thing, the figuration slabbing in a manner of thickness reaches 80 μm, intermediate layer is made with piece (α).

Then, it is used as Photoepolymerizationinitiater initiater (2-C) relative to foregoing acrylic copolymer (2-A-5) 1kg addition mixing , 4- methyl benzophenones (2-C-3) 20g, prepare adhesive layer resin combination.

With two release-treated pet films, (Resins Corporation of Mitsubishi manufactures, DIAFOIL MRA, 75 μm/TOYOBO of thickness CO., LTD. manufactures, 38 μm of E7006, thickness) clamping aforementioned adhesion layer resin combination, with Thickness reaches 35 μm of mode figuration slabbing, makes adhesive layer with resin sheet (β).

On the other hand, with release-treated two pet films (Resins Corporation of Mitsubishi manufactures, DIAFOIL MRF, 75 μm/TOYOBO of thickness CO., LTD. manufactures, 38 μm of E7006, thickness) clamping adhesive layer resin combination Thing, the figuration slabbing in a manner of thickness reaches 35 μm, adhesive layer is made with resin sheet (β ').

Successively peel off remove the intermediate layer both sides of piece (α) PET film, and peel off adhesive layer resin sheet (β) and The PET film of the side of (β '), the adhesive surface exposed is fitted in two surfaces of intermediate layer piece (α) successively, make by (β)/ 3 layers of bonding sheet that (α)/(β ') is formed.

PET film across the surface for residuing in (β) and (β '), 1000mJ/ is reached with wavelength 365nm accumulated light cm²Mode high voltage mercury lamp radiation ultraviolet, to (α), (β) and (β ') carry out ultraviolet-crosslinkable, make bonding sheet X6 (thickness 150μm)。

Will be in the single-sided lamination double faced adhesive tape of black patch (LSL-8, INOAC Corporation are manufactured, light penetration 0%) Band and cut into 50mm × 100mm piece fit in aforementioned adhesion piece X6 side release-treated poly terephthalic acid second The surface of terephthalate films (Resins Corporation of Mitsubishi manufactures, DIAFOIL MRF), so as to form light tight portion, is produced on piece surface The interior bonding laminate with transmittance section and light tight portion.

Next, from the black patch side of the bonding laminate so made, using high-pressure sodium lamp, with wavelength 365nm's Accumulated light reaches 2000mJ/cm²Mode irradiate ultraviolet and the bonding material at pair position contacted with the transmittance section of layered product Expect further irradiation light, make bonding sheet 2-6.

[comparative example 2-2]

Make phenoxy resin (2-A-6) (InChem Holdings, Inc. manufactures, PKHH, weight average molecular weight 5.2 Ten thousand) 650g, as the replacement of crosslinking agent (2-B) the urethane acrylate (2-B-4) with carbonic ester skeleton it is (on root industrial Co., Ltd. manufactures, UN5500, weight average molecular weight 6.7 ten thousand) 1kg, the 1- cyclohexyl-phenyl ketones as Photoepolymerizationinitiater initiater (2-C) The adhesive resin composition 2-7 that (2-C-4) (BASF AG manufactures, Irgacure184) 43g is obtained by uniformly mixingg.

With two release-treated pet films, (Resins Corporation of Mitsubishi manufactures, DIAFOIL MRV-V06, the manufacture of Resins Corporation of 100 μm/Mitsubishi of thickness, 75 μm of DIAFOIL MRQ, thickness) clamping foregoing 2-7, make With laminating machine in a manner of thickness reaches 150 μm figuration slabbing, make bonding sheet X7 (150 μm of thickness).

Will be in the single-sided lamination double faced adhesive tape of black patch (LSL-8, INOAC Corporation are manufactured, light penetration 0%) Band and cut into 50mm × 100mm piece fit in aforementioned adhesion piece X7 side release-treated poly terephthalic acid second The surface of terephthalate films (Resins Corporation of Mitsubishi manufactures, DIAFOIL MRQ) is produced in piece surface so as to form light tight portion Bonding laminate with transmittance section and light tight portion.

Next, from the black patch side of the bonding laminate so made, using high-pressure sodium lamp, with wavelength 365nm's Accumulated light reaches 2000mJ/cm²Mode irradiate ultraviolet so that bonding laminate transmittance section solidification, make bonding Piece 2-7.

[comparative example 2-3]

Relative to commercially available acrylic adhesives (2-A-7), (Soken Chemical ＆ Engineering Co., Ltd. manufactures, trade name " SK-DYNE 1882 ") 1kg, uniformly mix isocyanates system curing agent (Soken Chemical ＆ Engineering Co., Ltd. manufactures, trade name " L-45 ") 1.85g and Epoxy curing agent (Soken Chemical ＆ Engineering Co., Ltd. manufactures, trade name " E-5XM ") 0.5g, so as to prepare adhesive resin composition 2- 6。

In 50 μm of release-treated polyethylene terephthalate film (trade name " MRF75 " of thickness：Mitsubishi tree Fat company manufacture) stripping surface, be coated with foregoing 2-6 in a manner of dried thickness reaches 75 μm, by heating make Solvent seasoning, make the bonding sheet of 75 μm of thickness.

And then (Resins Corporation of Mitsubishi manufactures, DIAFOIL in release-treated polyethylene terephthalate film 100 μm of MRV-V06, thickness) stripping surface, be coated with foregoing 2-6 in a manner of dried thickness reaches 75 μm, pass through Heating makes solvent seasoning, makes the bonding sheet of 75 μm of thickness.

For two bonding sheets of making, respective adhesive surface is attached and conserves one week and reacts curing agent, is made Bonding sheet 2-8 (150 μm of thickness).

[evaluation]

The following various physics values for determining and evaluating the bonding sheet 2-1~2-8 made in embodiment and comparative example.

(gel fraction)

To be taken respectively from the bonding sheet 2-1~2-7 made in embodiment and comparative example the position contacted with transmittance section, I.e. hard portion and do not contacted with transmittance section position, i.e. the sample of soft part, carry out following measure.

For comparative example 2-3 bonding sheet 2-8, following measure is carried out to any part.

1) adhesive composition (W1) is weighed, is wrapped in the SUS nets (W0) of 200 mesh of weight are measured in advance.

2) above-mentioned SUS nets are immersed in 100mL ethyl acetate 24 hours.

3) SUS nets are taken out, are dried 4 hours half at 75 DEG C.

4) dried weight (W2) is obtained, the gel fraction of adhesive composition is determined by following formula.

Gel fraction (%)=100 × (W2-W0)/W1

(glass transition temperature (Tg))

The Differential Scanning Calorimetry measure device (DSC-8500) manufactured using PerkinElmer Co., Ltd.s, according to JIS K-7121 (ISO3146) carries out heating measure for 5 DEG C/min with programming rate, according to obtained Thermogram, obtains bonding sheet 2-1 ~2-7 the position contacted with transmittance section, i.e. hard portion and the respective vitrifying of the position not contacted with transmittance section, i.e. soft part Transition temperature (Tg).

For comparative example 2-3 bonding sheet 2-8, same measure is carried out to arbitrary position.

(ASKER hardness)

It is the position not contacted with transmittance section for bonding sheet 2-1~2-7 for being made in embodiment and comparative example, i.e. soft Matter portion, the stripping film of stripping film, the adhesive surface exposed is overlapped successively, the layer in a manner of in the range of gross thickness is 5mm~7mm Fold multiple bonding sheets.It is possible thereby to reduce the influence of the hardness of the platform of carrying measure sample, can compare/to determine material peculiar Identation hardness.And then the adhesive surface exposed of the bonding sheet to stacking, by the scleroscopic front end terminals of ASKER C2L to carry Lotus 1kg is pressed to vertical lower with the speed of 3mm/ minutes, determines the C2ASKER hardness (c) of soft part.

For the bonding sheet 2-1~2-7 made in embodiment and comparative example the position contacted with transmittance section, i.e. hard Portion, also the laminate adhesive piece in a manner of reaching in the range of 5mm~7mm, the C2ASKER for determining hard portion are hard as described above Spend (d).

To the bonding sheet 2-8 made in comparative example 2-3, same measure is carried out to any part.

(180 ° of peeling forces of soft part)

By the bonding sheet 2-1~2-7 made in embodiment and comparative example the position not contacted with transmittance section, i.e. soft part Cut out, then peel off the mould release film of a side, be bonded 50 μm of PET film (Resins Corporation of the Mitsubishi system as backing film Make, 50 μm of DIAFOIL T100, thickness) so as to preparing stacking product.

Measure by the bonding force determination sample in the environment of 23 DEG C of 40%RH with 180 ° of peel angle, peeling rate 60mm/ The peeling force (N/cm) to glass when minute peeling off, obtains position, i.e. 180 ° of soft part not contact with transmittance section and peels off Power.

(180 ° of peeling forces of hard portion)

Bonding sheet X1~7 of state before the light irradiation made for embodiment 2-2-1~4 and comparative example 2-1,2-2, will The mould release film of one side is peeled off, and is bonded 50 μm of PET film (manufacture of Resins Corporation of Mitsubishi, DIAFOIL as backing film T100,50 μm), so as to prepare stacking product.

After above-mentioned stacking product are cut into length 150mm, width 10mm, peel off remaining mould release film and will expose With 2kg roller, 1 ground roll is crimped on soda-lime glass to adhesive surface back and forth.To fitting product implement autoclave process (80 DEG C, gauge pressure 0.2MPa, 20 minutes) so as to complete attaching after, 2000mJ/cm is reached with 365nm accumulated light²Mode irradiate it is ultraviolet Line conserves 15 hours so that bonding sheet solidification, obtains peeling force measure sample.

Measure by above-mentioned peeling force determination sample in the environment of 23 DEG C of 40%RH with 180 ° of peel angle, peeling rate The peeling force (N/cm) to glass when 60mm/ minutes peel off, obtain the position contacted with transmittance section, i.e. 180 ° of hard portion strippings From power.

For the bonding sheet 2-8 made in comparative example 2-3, bonding sheet is cut out in any part, then with the 180 of soft part The order of DEG C peeling force is similarly measured.

(confining force of soft part)

By the bonding sheet 2-1~2-7 made in embodiment and comparative example the position not contacted with transmittance section, i.e. soft Portion cuts into 50mm × 100mm, and then, the stripping film of one side is peeled off, with the one side of the bonding sheet and gathering for lining Ethylene glycol terephthalate film (38 μm of thickness) overlapping mode is attached with hand roller, is cut into width 25mm × length Spend 100mm strip and obtain test film.

Next, the stripping film of residual is peeled off, to vertically disposed SUS plates (thickness 120mm, 5mm × 1.5mm), with The overlapping mode of length that test film only has 20mm is attached with hand roller.Now, the attaching face of transparent double face bonding sheet and SUS plates Product is 25mm × 20mm.

Thereafter, after test film is conserved 15 minutes in the environment of 40 DEG C and 70 DEG C, on test film vertically After hanging 4.9N counterweight and standing 30 minutes, the length (mm) that the sticking position of SUS and test film is offset downwards is determined. For the skew of attaching face and counterweight in the case of of dropping, measure counterweight drops the required time.

It should be noted that comparative example 2-2 bonding sheet 2-7 does not have tack, therefore, the examination of SUS plates will be laminated in Test piece to preheat 5 minutes at 80 DEG C, make to carry out confining force measure again after it is closely sealed with adherend.

(confining force of hard portion)

Bonding sheet X1~7 of state before the light irradiation made for embodiment 2-2-1~5 and comparative example 2-1,2-2, with Confining force measure before photocuring similarly makes the layered product of SUS and test film, afterwards, to reach the wavelength of bonding sheet 365nm ultraviolet reaches 2000mJ/cm²Mode, while with quantometer (USHIO INC. are manufactured, UNIMETERUIT250/ inspection Survey device：UVD-C365 accumulated light) is confirmed, while using high-pressure mercury from the pet film side for lining Light irradiation ultraviolet, make the bonding sheet equivalent to the position contacted with transmittance section, i.e. hard portion.

Thereafter, after test film is conserved 15 minutes in the environment of 40 DEG C and 70 DEG C, on test film vertically After hanging 4.9N counterweight and standing 30 minutes, the length (mm) that the sticking position of SUS and test film is offset downwards is determined.

Substantially motionless for test film, deflected length is less than 0.1mm situation, be designated as in table 3 "<0.1mm”.

For the bonding sheet 2-8 made in comparative example 2-3, bonding sheet is cut out in any part, afterwards, the guarantor with soft part Holding force measure order is similarly measured.

(transparency)

For the bonding sheet 2-1~2-7 made in embodiment and comparative example the position contacted with transmittance section, i.e. hard Portion, the mould release film of a side is peeled off, the adhesive surface roller exposed is fitted in into two soda-lime glass (82mm × 53mm × 0.5mm It is thick) after, implement autoclave process (80 DEG C, gauge pressure 0.2MPa, 20 minutes) so as to complete to attach, make optical assessment and be laminated Body.

For the bonding sheet 2-8 made in comparative example 2-3, sample is similarly made to any part.

(concavo-convex absorbability)

Bonding sheet X1~4 of state before the light irradiation that embodiment 2-1~2-4 and comparative example 2-1,2-2 are made, 6,7 50mm × 80mm is cut into, for the adhesive surface peeled off the mould release film of a side and exposed, 3mm implements thickness in peripheral part The printing surface of the soda-lime glass (82mm × 53mm × 0.5mm is thick) of 80 μm of printing, it is high to be erected on printing with 4 sides of jointing material Low poor mode carries out compacting crimping (absolute pressure 5kPa, 80 DEG C of temperature, pressing pressure 0.04MPa) using vacuum molding machine. Then remaining mould release film is peeled off, compacting fitting ZEONOR films (ZEON CORPORATION are manufactured, 100 μ m-thicks) it Afterwards, autoclave process (80 DEG C, gauge pressure 0.2MPa, 20 minutes) is implemented so as to complete to attach.From the soda-lime glass for implementing printing Side, reach 2000mJ/cm to reach piece X wavelength 365nm ultraviolet²Mode high voltage mercury lamp radiation ultraviolet, make with Do not implement the opening portion of printing, i.e. the piece at the position of transmittance section contact solidifies, making evaluation layered product 2-1~2-6.

The bonding sheet X5 made for embodiment 2-5, the print thickness using the soda-lime glass for implementing printing are 15 μm Glass, similarly make evaluation layered product 2-7.

The bonding sheet 2-8 made for comparative example 2-3, using bonding sheet 2-7, implement by with foregoing same sequentially built The soda-lime glass of printing is with after the layered product of ZEONOR films (ZEON CORPORATION are manufactured, 100 μ m-thicks), implementing high Pressure kettle processing (80 DEG C, gauge pressure 0.2MPa, 20 minutes) makes evaluation layered product 2-8 so as to complete to attach.

Layered product 2-1~2-8 that visually observation makes, jointing material it will not follow and remain near printing difference of height Alveolate situation is determined as "×"；It will confirm that because film is in the feelings that difference of height is bent around, concavo-convex uneven caused by deformation Condition is determined as " △ "；Situation about by bubble-free, being smoothly bonded is determined as "○".

(resistance to foaming reliability)

The constant temperature that the evaluation made in the evaluation of concavo-convex absorbability is put into 85 DEG C of 85%RH with layered product 2-1~2-8 is permanent Wet sump, observe the outward appearance after maintenance in 100 hours.The situation that bubble is produced in bonding sheet is determined as "×"；Outward appearance is not had The situation of change is determined as "○".

[table 3]

[table 4]

(research)

For the bonding sheet made in embodiment 2-1~2-5, the gel fraction of soft part is less than 1%, therefore can be because heating table Existing high fluidity.Therefore, its melting is made by carrying out heating in fitting, it is not only excellent to the tracing ability of male and fomale(M＆F), and i.e. Just a side of adherend is low rigid material as film, and bending will not be also produced near difference of height, can be obtained smooth Layered product.And then the gel fraction of hard portion is more than 40%, so even under hot and humid inferior harsh environmental test Also show high cohesion, will not it is peeling-off, foaming, deformation, the layered product with high reliability can be obtained.

For comparative example 2-1 bonding sheet, being irradiated by ultraviolet, adhesive resin composition is partial cross-linked, therefore with When glass and film with printing difference of height are laminated, the bumps brought by printing difference of height are transferred to film side, can not obtain Smooth layered product.In addition, the strain of the jointing material near using difference of height is confirmed as starting point and under high temperature and humidity test Foaming, keeping stability are poor.

Comparative example 2-2 does not use (methyl) acrylic copolymer, is to have used to possess to a certain degree in room temperature region The heat molten type bonding sheet of rigid adhesive resin composition.

For comparative example 2-2 piece, compared with the bonding sheet of embodiment, the viscosity under near room temperature is very low.With print When the glass of brush difference of height is laminated with piece, mobility during heating is low, therefore is somewhat led in one side transferred with by printing difference of height The bumps of cause, as a result compared with the bonding sheet of embodiment, the flatness of layered product is poor.In addition, according in light tight position The high this point of ASKER hardness is understood, high in the rigidity of fitting operation time slice, without tack, therefore in fitting from positioning Stage start just to need to preheat adherend, with only by pressing can normal temperature attach bonding sheet compared with, behaviour be present Make problem as complexity.

For comparative example 2-3, the cross-linking reaction of bonding sheet 2-7 adhesive resin composition is over, therefore is bonded In the absence of the soft part that gel fraction is less than 1% in piece, not only in film side transferred with concavo-convex as caused by printing difference of height, nothing Method obtains smooth layered product, and result has some adhesive not fill out completely near the corner that printing difference of height interlocks Fill and remain bubble.

The result of the test that the result of embodiment more than and up to the present the present inventor are carried out is, it can be said that use Possess gel fraction less than 1% soft part and gel fraction be more than 40% hard portion and comprising (methyl) acrylic copolymer Photo-curable transparent double face bonding sheet when, can in the same manner as embodiment by 2 image display device member of formation suitably Bonding.

In addition, it can be said that the gel fraction of the soft part in bonding sheet surface is preferably shorter than 1%, the gel fraction of hard portion is preferred For more than 40%.

In addition we know, the glass transition temperature (actual measurement Tg) of the soft part in bonding sheet surface is preferably -70~-10 DEG C, the glass transition temperature of hard portion (actual measurement Tg) is -60~+20 DEG C, the glass transition temperature (Tg [H]) of hard portion with The difference (Tg [H]-Tg [S]) of the glass transition temperature (Tg [S]) of soft part is preferably more than 3 DEG C.

[embodiment 2-6]

For the bonding sheet X1 made in embodiment 2-1, by the laminates of width 150mm, length 100m strip with Initial coiling tension 70N, the condition of taper ratio 20% are batched in the plastics core of 6 inches of diameter, make bonding sheet volume.

In the end face portion that the piece of making is rolled up, using high-pressure sodium lamp, 500mJ/cm is reached with wavelength 365nm accumulated light² Mode carry out light irradiation and make end face portion photocuring, obtain the bonding sheet volume for possessing hard portion in end face portion.

[comparative example 2-4]

In addition to no irradiation light, bonding sheet volume is made in the same manner as embodiment 2-6.

Rolled up and in end face for the only comparative example 2-4 of soft part bonding sheet so make, without hard portion The bonding sheet that portion has the embodiment 2-6 of hard portion is rolled up, and after 40 DEG C of 90%RH constant temperature and humidity cabinet is taken care of 2 weeks, is visually seen Examine the end face portion of bonding sheet volume.

The bonding sheet volume for possessing the embodiment 2-5 of hard portion in end face portion overflows in the absence of from the glue of end face portion, the volume of piece Extract operation is good, and relatively, the end face portion of the bonding sheet volume for the comparative example 2-4 being only made up of soft part causes to hold because glue overflows Face is tacky, and as a result taking-up activities are brought with obstruction.

[embodiment 3-1]

As (methyl) acrylic copolymer (3-A), polymethyl methacrylate macromonomer (Tg is used：105 DEG C, number-average molecular weight 2400) 15 mass parts (18mol%) and butyl acrylate (Tg：- 55 DEG C) 81 mass parts (75mol%) With acrylic acid (Tg：106 DEG C) graft copolymer (3-A1) obtained from 4 mass parts (7mol%) random copolymerization.

In the graft copolymer (3-A1), the glass transition temperature for forming the copolymer of trunk composition is -60 DEG C, divided greatly Content in the graft copolymer (3-A1) of sub- monomer is 15 mass %, and the complex viscosity under 130 DEG C of temperature, frequency 0.02Hz is 260Pa·s。

Using graft copolymer (3-A1) 1kg, glycerine dimethacrylate (the day oil strain formula as crosslinking agent (3-B) Commercial firm manufactures, ProductName：GMR) 90g and 2,4,6- tri-methyl benzophenones and 4- first as Photoepolymerizationinitiater initiater (3-C) (LAMBERTI GROUP are manufactured the mixture of base benzophenone, ProductName：ESACURE TZT) 15g uniformly mixes, make bonding Agent resin combination 3-1.

With two mould release films, (Mitsubishi's resin is public for i.e. release-treated two pet films Department manufacture " DIAFOIL MRV-V06 ", Resins Corporation of 100 μm/Mitsubishi of thickness manufacture " 75 μm of DIAFOIL MRQ ", thickness) Aforementioned binder resin composition 3-1 is clamped, figuration slabbing, making are viscous in a manner of thickness reaches 150 μm using laminating machine Close piece 3-1 (150 μm of thickness).

[embodiment 3-2]

Except as crosslinking agent (3-B), using glycerine dimethacrylate, (chemical industrial company of Xin Zhong villages manufactures, product Name：NK ESTER 701) beyond (3-B-1) 90g, adhesive resin composition 3-2 is made in the same manner as embodiment 3-1.

Using aforementioned binder resin composition 3-2, the bonding sheet 3-2 (μ of thickness 150 are made in the same manner as embodiment 3-1 m)。

[embodiment 3-3]

Will be with embodiment 3-1 identicals graft copolymer (3-A1) 1kg, the glycerine dimethyl propylene as crosslinking agent (3-B) (Japan Oil Co manufactures olefin(e) acid ester, ProductName：GMR) 90g and the 2,4,6- trimethyls as Photoepolymerizationinitiater initiater (3-C) (LAMBERTI GROUP are manufactured the mixture of benzophenone and 4- methyl benzophenones, ProductName：ESACURE TZT) 15g and (Ciba Japan are manufactured UV stable agent, ProductName：TIN123) 50g is uniformly mixed, and makes adhesive resin composition 3-3。

And then using adhesive resin composition 3-3, bonding sheet 3-3 (thickness 150 is made in the same manner as embodiment 3-1 μm)。

[embodiment 3-4]

As (methyl) acrylic copolymer (3-A), polymethyl methacrylate macromonomer (Tg is used：105 DEG C, number-average molecular weight 2500) 10 mass parts (12mol%) and butyl acrylate (Tg：- 55 DEG C) 88 mass parts (84mol%) With acrylic acid (Tg：106 DEG C) graft copolymer (3-A2) obtained from 2 mass parts (7mol%) random copolymerization.

In the graft copolymer (3-A2), the glass transition temperature for forming the copolymer of trunk composition is -60 DEG C, divided greatly Content in the graft copolymer (3-A2) of sub- monomer is 10 mass %, and the complex viscosity under 130 DEG C of temperature, frequency 0.02Hz is 240Pa·s。

Using graft copolymer (3-A2) 1kg, as crosslinking agent (3-B) trimethylolpropane trimethacrylate (in new Chemical industrial company of village manufactures, ProductName：CLM400) 50g and the 2,4,6- trimethyls two as Photoepolymerizationinitiater initiater (3-C) (LAMBERTI GROUP are manufactured the mixture of Benzophenone and 4- methyl benzophenones, ProductName：ESACURE TZT) 15g, make Adhesive resin composition 3-4.

And then using adhesive resin composition 3-4, bonding sheet 3-4 (thickness 150 is made in the same manner as embodiment 3-1 μm)。

[embodiment 3-5]

As (methyl) acrylic copolymer (3-A), polymethyl methacrylate macromonomer (Tg is used：105 DEG C, number-average molecular weight 2500) 8 mass parts (10mol%) and butyl acrylate (Tg：- 55 DEG C) 89 mass parts (85mol%) and Acrylic acid (Tg：106 DEG C) graft copolymer (3-A3) obtained from 3 mass parts (5mol%) random copolymerization.

In the graft copolymer (3-A3), the glass transition temperature for forming the copolymer of trunk composition is -40 DEG C, divided greatly Content in the graft copolymer (3-A3) of sub- monomer is 8 mass %, and the complex viscosity under 130 DEG C of temperature, frequency 0.02Hz is 220Pa·s。

Using graft copolymer (3-A3) 1kg, glycerine dimethacrylate (the day oil strain formula as crosslinking agent (3-B) Commercial firm manufactures, ProductName：GMR) 90g and 2,4,6- tri-methyl benzophenones and 4- first as Photoepolymerizationinitiater initiater (3-C) (LAMBERTI GROUP are manufactured the mixture of base benzophenone, ProductName：ESACURE TZT) 15g uniformly mixes, make bonding Agent resin combination 3-5.

And then using adhesive resin composition 3-5, bonding sheet 3-5 (thickness 150 is made in the same manner as embodiment 3-1 μm)。

[comparative example 3-1]

Make the embodiment equivalent to No. 2012/032995 publication of International Publication.

That is, as (methyl) acrylic copolymer (3-A), 2-EHA (Tg：- 70 DEG C) 75 mass Part (57mol%) and vinylacetate (Tg：32 DEG C) 20 mass parts (33mol%) and acrylic acid (Tg：106 DEG C) 5 mass parts In acrylic copolymer (3-A-5) 1kg obtained from (10mol%) random copolymerization, mixing addition is as crosslinking agent (3-B) Trimethylolpropane trimethacrylate (3-B-4) the 200g and 4- methyl benzophenones (3-C- as Photoepolymerizationinitiater initiater (3-C) 3) 10g, so as to prepare intermediate layer resin combination.

With release-treated two pet films (PANACCORPORATION is manufactured, NP75Z01,75 μm/TOYOBO of thickness CO., LTD. manufactures, 38 μm of E7006, thickness) the intermediate layer resin combination is clamped, The figuration slabbing in a manner of thickness reaches 80 μm, intermediate layer is made with piece (α).

Then, it is used as Photoepolymerizationinitiater initiater (3-C) relative to foregoing acrylic copolymer (3-A-5) 1kg, addition mixing 4- methyl benzophenones (3-C-3) 20g, prepare adhesive linkage resin combination.

The PET film for removing the intermediate layer both sides of piece (α) is peeled off successively, and by adhesive linkage resin sheet (β) and (β ') The PET film of side peel off, the adhesive surface exposed is fitted in two surfaces of intermediate layer piece (α) successively, make by (β)/ 3 layers of bonding sheet that (α)/(β ') is formed.

PET film across the surface for residuing in (β) and (β '), 1000mJ/ is reached with wavelength 365nm accumulated light cm²Mode high voltage mercury lamp radiation ultraviolet, ultraviolet-crosslinkable is carried out to (α), (β) and (β '), it is (thick to make bonding sheet 3-6 150 μm of degree).

[comparative example 3-2]

Bonding sheet is made according to WO2010/038366 embodiment 6.

That is, making will be as the phenoxy resin (InChem of the replacement of (methyl) acrylic copolymer (3-A) Holdings, Inc. are manufactured, and ten thousand) 650g, the replacement as crosslinking agent (3-B) have a carbonic ester for PKHH, weight average molecular weight 5.2 Skeleton urethane acrylate (Negami Chemical Ind Co., Ltd. manufactures, UN5500, weight average molecular weight 6.7 ten thousand) 1kg, gather as light Close initiator (3-C), 1- cyclohexyl-phenyl ketones (BASF AG manufacture, Irgacure184) 43g be obtained by uniformly mixingg it is viscous Mixture resin combination 3-7.

For foregoing 3-7, bonding sheet 3-7 (150 μm of thickness) is made with the method same with embodiment 3-1.

[evaluation]

(stretch modulus, fracture strength, elongation at break)

Bonding sheet 3-1~3-7 is cut into width 20mm, obtains the stretching test measurement sample before photo-crosslinking.

After bonding sheet 3-1~3-7 is cut into width 20mm, 2000mJ/cm is reached with 365nm accumulated light²'s Mode, solidify bonding sheet using high voltage mercury lamp radiation ultraviolet from demoulding PET sides, it is small that 15 are conserved under 23 DEG C of 50%RH When, obtain the stretching test measurement sample after photo-crosslinking.

Above-mentioned stretching test measurement sample is determined in the environment of 23 DEG C of 50%RH, is stretched with test speed 300mm/ minutes When stretch modulus, tensile break strength, tension fracture elongation rate.

It should be noted that the displacement of the condition determination of stretch modulus is 30~50mm.

(gel fraction)

The position contacted with transmittance section, i.e. to being taken respectively from the bonding sheet 3-1~3-7 made in embodiment and comparative example The sample of hard portion and the position not contacted with transmittance section, i.e. soft part, carries out following measure.

1) adhesive resin composition (W1) is weighed, is wrapped in the SUS nets (W0) of 200 mesh of weight are measured in advance.

2) above-mentioned SUS nets are impregnated 24 hours in 100mL ethyl acetate.

3) SUS nets are taken out, are dried 4 hours half at 75 DEG C.

4) dried weight (W2) is obtained, the gel fraction of adhesive resin composition is determined by following formula.

Gel fraction (%)=100 × (W2-W0)/W1

(operability (keeping property))

Bonding sheet 3-1~the 3-7 for cutting into 50mm × 50mm square is clipped in 100mm × 100mm square and thickness 2mm Between two glass plates, so as to make layered product.500g counterweight is placed in the top of layered product, is placed in the environment of 60 DEG C After 24 hours, visually observe whether adhesive overflows from layered product.

The layered product of making is visually observed, the situation that adhesive is integrally overflowed is determined as "×"；By adhesive Situation about only being overflowed in corner is determined as " △ "；Adhesive is determined as "○" without situation about overflowing.

(difference of height absorbability)

Bonding sheet 3-1~3-6 of state before the light irradiation that embodiment 3-1~3-5 and comparative example 3-1 is made is cut into 50mm × 80mm, for the adhesive surface peeled off the mould release film of a side and exposed, in peripheral part, 3mm implements 80 μm of thickness The printing surface of the soda-lime glass (82mm × 53mm × 0.5mm is thick) of printing, printing difference of height is erected on 4 sides of jointing material Mode carries out compacting crimping (absolute pressure 5kPa, 80 DEG C of temperature, pressing pressure 0.04MPa) using vacuum molding machine.Then, will Remaining mould release film is peeled off, and after lamination joint ZEONOR films (ZEON CORPORATION are manufactured, 100 μ m-thicks), is implemented Autoclave process (80 DEG C, gauge pressure 0.2MPa, 20 minutes) is so as to completing to attach.

Next, from the soda-lime glass side for implementing printing, reached with reaching piece X wavelength 365nm ultraviolet 2000mJ/cm²Mode high voltage mercury lamp radiation ultraviolet, make with without implement printing opening portion, i.e. transmittance section contact The piece solidification at position, makes evaluation layered product 3-1~3-6.

The bonding sheet 3-7 made for comparative example 3-2, using bonding sheet 3-7, implement by with foregoing same sequentially built The soda-lime glass of printing is with after the layered product of ZEONOR films (ZEON CORPORATION are manufactured, 100 μ m-thicks), implementing high Pressure kettle processing (80 DEG C, gauge pressure 0.2MPa, 20 minutes) makes evaluation layered product 3-7 so as to complete to attach.

Layered product 3-1~3-7 that visually observation makes, jointing material it will not follow and remain near printing difference of height Alveolate situation is determined as "×"；Will confirm that because film difference of height is bent around, deformation and caused by it is concavo-convex uneven Situation is determined as " △ "；Situation about by bubble-free, being smoothly bonded is determined as "○".

[table 5]

The bonding sheet made for embodiment 3-1~3-5, there is big change in tensile properties before and after photocuring.Due to Have characteristics that, the bonding sheet for confirming embodiment 3-1~3-5 making there can be excellent difference of height before photocuring Absorbability, on the other hand, there can be excellent resistance to foaminess after photocuring.

On the other hand, in a comparative example, the change of the tensile properties before and after photocuring is insufficient, therefore in comparative example In 3-1, the change after photo-crosslinking is insufficient, thus obtain be poor reliability piece, in comparative example 3-2, what is obtained is light The piece of operability (keeping property) difference before crosslinking.

Claims

1. a kind of bonding sheet, it is characterised in that it is by containing (methyl) acrylic copolymer (A), crosslinking agent (B) and light Bonding sheet before the photocuring that the resin combination of polymerization initiator (C) is formed, it has photo-curable, and possesses following (1) and (2) characteristic：

(1) shape can be kept at 0~40 DEG C, and shows self adhesion；

(2) at 70~100 DEG C, viscosity is shown as 100~3000Pas.

2. bonding sheet according to claim 1, it is characterised in that (methyl) acrylic copolymer (A) is to possess Graft copolymer of the macromonomer as branch composition.

3. bonding sheet according to claim 1, it is characterised in that (methyl) acrylic copolymer (A) is glass Change transition temperature (Tg) less than 0 DEG C monomer a1, glass transition temperature (Tg) be 0 DEG C less than 80 DEG C monomer a2, And the monomer a3 that glass transition temperature (Tg) is more than 80 DEG C is with a1：a2：A3=10~40：90~35：0~25 mole Formed than copolymerization, and weight average molecular weight is 50000~400000.

4. the bonding sheet according to any one of claims 1 to 3, it is characterised in that also have after photocuring following (3) characteristic：

Viscosity at (3) 70~100 DEG C is 3000~50000Pas.

5. a kind of bonding sheet, it is characterised in that it is viscous to be formed containing (methyl) acrylic copolymer (A) and by photocuring Close piece, have gel fraction less than 1% piece portion and gel fraction be more than 40% piece portion.

6. bonding sheet according to claim 5, wherein, piece portion of the gel fraction less than 1% utilizes differential scanning amount The glass transition temperature (Tg [H]) of heat meter (DSC) measure is -70~-10 DEG C, and gel fraction is the utilization in more than 40% piece portion The glass transition temperature (Tg [S]) of differential scanning calorimetry (DSC) (DSC) measure is -60~+20 DEG C, and gel fraction is more than 40% The difference (Tg [H]-Tg [S]) of the glass transition temperature in piece portion of the glass transition temperature and gel fraction in piece portion less than 1% is 3 More than DEG C.

7. the bonding sheet according to claim 5 or 6, its be the piece formed by resin combination is subjected to part photocuring and Into, the resin combination contains (methyl) acrylic copolymer (A), crosslinking agent (B) and Photoepolymerizationinitiater initiater (C).

8. the bonding sheet according to any one of claim 5~7, it is characterised in that (methyl) acrylic compounds are common Polymers (A) is to possess graft copolymer of the macromonomer as branch composition.

9. the bonding sheet according to any one of claim 5~8, it is characterised in that (methyl) acrylic compounds are common Monomer a1, the glass transition temperature (Tg) that polymers (A) is glass transition temperature (Tg) less than 0 DEG C be 0 DEG C less than 80 DEG C of monomer a2 and glass transition temperature (Tg) is more than 80 DEG C of monomer a3 with a1：a2：A3=10~40：90~ 35：What 0~25 mol ratio copolymerization formed, and weight average molecular weight is 50000~400000.

10. the bonding sheet according to any one of claim 5~9, it is characterised in that in the piece surface of bonding sheet, With gel fraction less than 1% piece portion and gel fraction be more than 40% piece portion.

11. a kind of bonding sheet, it is characterised in that it is by containing the mass parts of (methyl) acrylic copolymer (A) 100, crosslinking agent (B) resin combination of 0.5~20 mass parts and the mass parts of Photoepolymerizationinitiater initiater (C) 0.1~5 is formed,

Stretch modulus (X1) of the bonding sheet before photo-crosslinking is 3 with the ratio between the stretch modulus (X2) after photo-crosslinking (X1/X2) More than.

12. bonding sheet according to claim 11, it is characterised in that (methyl) acrylic copolymer (A) is tool Standby graft copolymer of the macromonomer as branch composition, contains the macromonomer with 5~30 mass % ratio.

13. one kind bonding laminate, it possesses the bonding sheet and mould release film described in any one of claim 1~12 The composition being laminated.

14. a kind of image display device composition layered product, it possesses following composition：Formed in 2 device used for image display The bonding sheet described in any one of claim 1~12 is clamped between component and is laminated.

15. image display device composition layered product according to claim 14, it is characterised in that described image display dress It is any of group that touch panel, image display panel, surface protection panel and light polarizing film form to put with member of formation Or the layered product formed by two or more combinations.

16. a kind of image display device, it is the image display device composition layered product described in usage right requirement 14 or 15 Form.