CN105969262A

CN105969262A - Adhesive composition, adhesive layer, and optical member with adhesive layer

Info

Publication number: CN105969262A
Application number: CN201610139922.XA
Authority: CN
Inventors: 郑景文; 郑宰旭; 森冈公平
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2015-03-11
Filing date: 2016-03-11
Publication date: 2016-09-28
Anticipated expiration: 2036-03-11
Also published as: TWI784925B; TW202300617A; CN105969262B; TW201641650A; KR20160110901A; JP6758869B2; JP2016169383A; KR102542169B1

Abstract

The invention provides an adhesive composition, an adhesive layer having same, and an optical member with the adhesive layer; the adhesive composition comprises the following ingredients by weight parts: 100 parts of (methyl) acrylic acid series resin (A), wherein the resin A takes 3.5 weight% and has the forming unit of (methyl) acrylic acid monomer from hydroxyl, and the glass-transition temperature is below-25 DEG C; Aromatic isocyanate cross-linking agent (B) 0.3-1 weight part; a compound (C) comprising either organic salt (C-1) or alkylene oxygroup compound (C-2) or both, wherein if the organic salt is contained, the content will be 0.0001-5 weight part, and if the alkylene oxygroup compound (C-2) is contained, the content will be 0.1-5 weight part.

Description

Adhesive composition, adhesive phase and the optical component of band adhesive phase

Technical field

The present invention relates to adhesive composition, the adhesive phase comprising this adhesive composition and possess The optical component of this adhesive phase.

Background technology

Polarization plates at the one or both sides stacking laminating protecting film of polaroid is at liquid crystal display Image display devices such as device, organic electroluminescent (organic EL) display device, the most in recent years The portable phone that comes, smart mobile phone, panel type terminal etc various mobile devices in widely used Optical component.The optical component of polarization plates etc fits in other component (examples by adhesive phase mostly Such as optical components such as the liquid crystal cells in liquid crystal indicator) use (referring for example to Japanese Unexamined Patent Publication 2010-229321 publication).It is thus possible, for instance polarization plates is in most cases with in one face On be previously provided with the form with the polarization plates of adhesive phase of adhesive phase and commercially circulate.

Summary of the invention

Require durable for adhesive composition used in the adhesive phase of optical component laminating Property.That is, fit in optical component and be assembled into the adhesive phase of graphical representation device etc. and be sometimes placed Under high temperature or hot and humid environment or be placed on high temperature and low temperature repeatedly in the environment of, to viscous Even if mixture layer requires the most also can suppress along with the change in size of adjacent optical component Issuable unfavorable condition.As this unfavorable condition, including: at adhesive phase and its light adjacent Learn component interface on float or peel off, the foaming of adhesive phase.

But, when conventional adhesive composition fits in optical component with the form of adhesive phase Durability is the most insufficient, is even across electricity on the surface of the optical component of adhesive phase of will fitting The surface activations such as dizzy process process in the case of being not easy to the surface effectively activated, and durability is outstanding It is insufficient.

Even if the surface that it is an object of the invention to provide optical component is to process through surface activation It is not easy to the surface effectively activated, fits in durability during this surface with the form of adhesive phase The best adhesive composition, the adhesive phase comprising this adhesive composition and possess this glue The optical component of the band adhesive phase of mixture layer.

The present invention provides adhesive composition, adhesive phase and the light of band adhesive phase shown below Learn component.

[1] a kind of adhesive composition, it contains:

Containing Component units and its content from (methyl) acrylic monomer with hydroxyl is Below 3.5 weight % and (methyl) acrylic acid series tree that glass transition temperature is less than-25 DEG C Fat (A) 100 weight portion；

Aromatic isocyanate system cross-linking agent (B) 0.3～1 weight portion；With

Selected from acylate (C-1) and comprise alkylidene epoxide compound (C-2) at least 1 Plant compound (C),

When containing above-mentioned acylate (C-1), its content is relative to above-mentioned (methyl) acrylic acid Be resin (A) 100 weight portion be 0.0001～5 weight portions,

When containing above-mentioned compound (C-2) comprising alkylidene epoxide, its content is relative to above-mentioned (methyl) acrylic resin (A) 100 weight portion is 0.1～5 weight portions.

[2] according to adhesive composition described in [1], wherein, above-mentioned alkylidene epoxide is comprised Compound (C-2) for comprise at least 1 double bond and at least 1 alkylenedioxy group in intramolecular Compound.

[3] according to the adhesive composition described in [1] or [2], wherein, above-mentioned from having The content of the Component units of (methyl) acrylic monomer of hydroxyl is more than 0.5 weight %.

[4] according to adhesive composition according to any one of [1]～[3], its possibly together with from Sub-property compound (D).

[5] according to the adhesive composition according to any one of [1]～[4], it is possibly together with silicon Hydride compounds (E).

[6] according to the adhesive composition according to any one of [1]～[5], will be by ring-type Above-mentioned adhesive composition is shaped and by the bonding of stratiform with stratiform on the film that polyolefin-based resins is formed After agent compositions is taken care of 24 hours in the environment of temperature 23 DEG C with the state being laminated in alkali-free glass plate Peeling force when this alkali-free glass plate is peeled off is set to P (CO) 23, and

The combination of above-mentioned binding agent will be shaped with stratiform on the film by cyclic polyolefin hydrocarbon system resin formation Thing and by the adhesive composition of stratiform to be laminated in the state of alkali-free glass plate at temperature 50 C When under environment, after keeping 48 hours, peeling force when this alkali-free glass plate is peeled off is set to P (CO) 50,

The ratio (P (CO) 50/P (CO) 23) of above-mentioned P (CO) 50 and above-mentioned P (CO) 23 is more than 3.2.

[7] according to adhesive composition according to any one of [1]～[5], wherein, will be Formed by (methyl) acrylic resin and shape above-mentioned adhesive composition and by layer with stratiform on film The adhesive composition of shape is to be laminated in state keeping in the environment of temperature 23 DEG C of alkali-free glass plate After 24 hours, the peeling force when this alkali-free glass plate is peeled off is set to P (AC) 23, and

Above-mentioned binding agent group will be shaped with stratiform on the film formed by (methyl) acrylic resin Compound and by the adhesive composition of stratiform to be laminated in the state of alkali-free glass plate at temperature 50 C In the environment of after keeping 48 hours peeling force when this alkali-free glass plate is peeled off be set to P (AC) 50 Time,

The ratio (P (AC) 50/P (AC) 23) of above-mentioned P (AC) 50 and above-mentioned P (AC) 23 is more than 3.2.

[8] according to the adhesive composition according to any one of [1]～[7], it contains above-mentioned Acylate (C-1) and the above-mentioned compound (C-2) comprising alkylidene epoxide,

The content of above-mentioned acylate (C-1) is relative to above-mentioned (methyl) acrylic resin (A) 100 weight portions are 0.0001～0.1 weight portion,

The content of the above-mentioned compound (C-2) comprising alkylidene epoxide is relative to above-mentioned (methyl) Acrylic resin (A) 100 weight portion is 0.1～5 weight portions.

[9] a kind of adhesive phase, it comprises the binding agent group according to any one of [1]～[8] Compound.

[10] optical component of a kind of band adhesive phase, it comprises optical component and is laminated thereon The adhesive phase described in [9].

[11] according to the optical component of the band adhesive phase described in [10], wherein, stacking is above-mentioned viscous The surface of the above-mentioned optical component of the mixture layer contact angle rate of change when carrying out sided corona treatment is 40% Below.

[12] according to the optical component of the band adhesive phase described in [11], wherein, above-mentioned optics structure Part comprises polaroid and the protecting film being laminated thereon,

Above-mentioned surface is the surface of said protection film.

[13] according to the optical component of the band adhesive phase described in [11] or [12], wherein, on Stating surface is the surface through sided corona treatment.

[14] according to the optical component of the band adhesive phase according to any one of [10]～[13], It also comprises the glass substrate being layered on above-mentioned adhesive phase.

[15] optics of a kind of band adhesive phase, it is to have resin molding and be laminated in this tree The optical component of the band adhesive phase of the adhesive phase at least one face of adipose membrane,

Above-mentioned adhesive phase comprises the adhesive composition according to any one of [1]～[8],

The optics of this band adhesive phase is being laminated in alkali-free glass in order to above-mentioned adhesive phase The state of plate is stripping when this alkali-free glass plate is peeled off after keeping 24 hours in the environment of temperature 23 DEG C From power be set to P23 and

The optics of this band adhesive phase is laminated in alkali-free glass plate in order to above-mentioned adhesive phase State stripping when this alkali-free glass plate is peeled off after keeping 48 hours in the environment of temperature 50 C When power is set to P50,

The ratio (P50/P23) of above-mentioned P50 and above-mentioned P23 is more than 3.2.

According to the present invention it is possible to provide the good adhesive composition of durability, comprise this binding agent The adhesive phase of compositions and possess the optical component of band adhesive phase of this adhesive phase.

Accompanying drawing explanation

Fig. 1 is the schematic sectional view of an example of the optical component of the band adhesive phase representing the present invention.

Fig. 2 is the schematic sectional view of another example of the optical component of the band adhesive phase representing the present invention.

Fig. 3 is the schematic sectional of another example again of the optical component of the band adhesive phase representing the present invention Figure.

Fig. 4 is the schematic sectional of yet another example of the optical component of the band adhesive phase representing the present invention Figure.

Detailed description of the invention

(1) (methyl) acrylic resin (A)

(methyl) acrylic resin (A) is for containing from (methyl) acrylic acid with hydroxyl It is the polymer of the Component units of monomer, is preferably in addition to this Component units possibly together with from following formula (I) Component units of (methyl) acrylate shown in is as the polymer of main constituent.In this theory In bright book, " (methyl) acrylic acid " refers to acrylic acid and/or methacrylic acid, is denoted as (methyl) " (methyl) " during acrylate etc. is also identical implication.

[changing 1]

In above-mentioned formula (I), R¹Represent hydrogen atom or methyl, R²Expression can be by carbon number 1～10 The alkyl of the substituted carbon number of alkoxyl 1～14 or can be replaced by the alkoxyl of carbon number 1～10 The aralkyl of carbon number 7～21.R²The carbon number that preferably can be replaced by the alkoxyl of carbon number 1～10 The alkyl of 1～14.

As (methyl) acrylate shown in formula (I), (methyl) acrylic acid alkyl can be enumerated Ester, its concrete example includes: (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) N-propyl, (methyl) n-butyl acrylate, (methyl) n-octyl, (methyl) The moieties of lauryl acrylate etc is (methyl) alkyl acrylate of straight-chain；(methyl) Isopropyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) 2-EHA, (first Base) (methyl) alkyl acrylate etc. that moieties is branched of Isooctyl acrylate monomer etc. The carbon number of the moieties in (methyl) alkyl acrylate is preferably 1～8, more preferably 1～6.

At R²For alkyl after being replaced by alkoxyl time, R²For the formula (I) during alkoxyalkyl The concrete example of shown (methyl) acrylate includes (methyl) acrylic acid 2-methoxy acrylate, (first Base) ethioxy methyl ester etc..The carbon number of the alkyl in above-mentioned alkoxyalkyl is preferably 1～8, More preferably 1～6.The carbon number of the alkoxyl in above-mentioned alkoxyalkyl is preferably 1～8, more preferably It is 1～4.At R²For (methyl) acrylic acid shown in the formula (I) during the aralkyl of carbon number 7～21 The concrete example of ester includes (methyl) benzyl acrylate etc..The carbon number of above-mentioned aralkyl is preferably 7～11.

(methyl) acrylate shown in formula (I) can be used alone a kind, it is also possible to and with 2 More than Zhong.Wherein, (methyl) acrylate preferably comprises (methyl) alkyl acrylate, more excellent Choosing comprises alkyl acrylate, further preferably comprises n-butyl acrylate.(methyl) acrylic acid series Resin (A) preferably comprise in constituting its whole Component units more than 50 weight % from third The Component units of olefin(e) acid N-butyl.It is of course also possible to go back and with except it in addition to n-butyl acrylate (methyl) acrylate shown in formula (I) in addition.

Content from the Component units of (methyl) acrylate shown in formula (I) is constituting (first Base) acrylic resin (A) whole Component units in usually more than 60 weight % and not enough 100 weight %, preferably 70～99.9 weight %, more preferably 80～99.6 weight %.

(methyl) acrylic resin (A) is containing from (methyl) acrylic acid series with hydroxyl The Component units of monomer.Containing this Component units improve adhesive phase and optical component adaptation, It is favourable in the durability of adhesive phase.(methyl) acrylic monomer with hydroxyl is preferably There is (methyl) acrylate of hydroxyl.There is the concrete example bag of (methyl) acrylate of hydroxyl Include: (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) third Olefin(e) acid 4-hydroxybutyl, (methyl) acrylic acid 2-(2-hydroxyl-oxethyl) ethyl ester, (methyl) propylene (methyl) acrylic acid hydroxyl Arrcostab of acid 2-or 3-chlorine-2-hydroxyl propyl ester etc；Diethyl two The polyfunctional alcohol of alcohol list (methyl) acrylate etc and (methyl) acrylic acid partial esterification thing etc.. From adhesive phase and the adaptation of optical component, the sight of the durability (especially thermostability) of adhesive phase Point sets out, and the monomer with hydroxyl preferably has (methyl) acrylate of hydroxyl, is more preferably (methyl) acrylic acid hydroxyl Arrcostab.Alkane in (methyl) acrylic acid hydroxyl Arrcostab The carbon number of base section is preferably 1～8, more preferably 1～6.

Content from the Component units of (methyl) acrylic monomer with hydroxyl is constituting (first Base) acrylic resin (A) whole Component units in be below 3.5 weight %, be preferably 3 Below weight %, it is more preferably below below 2.5 weight %, more preferably 2 weight %.If From the content of Component units of (methyl) acrylic monomer with hydroxyl more than 3.5 weight %, Then the durability of adhesive phase, especially thermostability are not enough.On the other hand, from (the first with hydroxyl Base) content of Component units of acrylic monomer is usually more than 0.1 weight %, is preferably 0.2 More than weight %, more than more preferably 0.5 weight %.If from (methyl) propylene with hydroxyl Acid be the content of the Component units of monomer less than 0.1 weight %, then adhesive phase and optical component is close Conjunction property, the deficiency such as durability of adhesive phase.

(methyl) acrylic resin (A) can be containing from except (methyl) third with hydroxyl Other beyond olefin(e) acid system monomer have the Component units of the monomer of polar functional group.This has polarity official The monomer that can roll into a ball preferably has (methyl) acrylic monomer of polar functional group.As this monomer The polar functional group being had, can enumerate carboxyl (free carboxy), amino, heterocyclic radical (such as ring Epoxide) etc..

The concrete example of other monomers with polar functional group includes: (methyl) acrylic acid, β-carboxyl The monomer with carboxyl of ethyl (methyl) acrylate etc；Acryloyl morpholine, vinyl are own Lactams, NVP, vinylpyridine, (methyl) acrylic acid tetrahydro furfuryl ester, Caprolactone modification acrylic acid tetrahydro furfuryl ester, (methyl) acrylic acid 3,4-epoxycyclohexanecarboxylate, (first Base) glycidyl acrylate, the monomer with heterocyclic radical of DHF etc；(methyl) Acrylate, (methyl) acrylic acid N, N-dimethylaminoethyl, (methyl) acrylic acid two The monomer etc. with the amino different from heterocycle of methylamino propyl ester etc.Other have polar functional group Monomer can be used alone only a kind, it is also possible to and use two or more.

In addition to (methyl) acrylic monomer with hydroxyl, also and with other, there is polar functional group Monomer, especially there is (methyl) acrylic monomer of carboxyl improving adhesive phase and optics structure The adaptation of part, adhesive phase durability (especially thermostability) on be favourable.

There is the monomer of polar functional group from other, preferably there is (methyl) acrylic acid of carboxyl Be monomer Component units content constitute (methyl) acrylic resin (A) whole constitute Unit is preferably below below 5 weight %, more preferably 4 weight %.If there is pole from other More than 5 weight %, then there is the durable of adhesive phase in the content of the Component units of the monomer of property functional group Property, tendency that especially thermostability is not enough.On the other hand, from other, there is the monomer of polar functional group The content of Component units in the case of containing it usually more than 0.1 weight %, be preferably 0.2 More than weight %, more than more preferably 0.3 weight %.If there is the list of polar functional group from other The content of the Component units of body less than 0.1 weight %, then is difficult to confirm its using effect.Come self-contained There is (methyl) acrylic monomer structure at interior all monomers with polar functional group of hydroxyl Become unit in the whole Component units constituting (methyl) acrylic resin (A) usually 0.1～ 8.5 weight %, preferably 0.2～7 weight %.

(methyl) acrylic resin (A) can comprise to come comfortable intramolecular further and have 1 The monomer of alkene double bond and at least 1 aromatic rings (wherein, does not includes being equivalent to above-mentioned formula (I) Shown monomer or the monomer of the above-mentioned monomer with polar functional group.) Component units.As suitable The example closed, can enumerate (methyl) acrylic monomer with aromatic rings.At this, there is aromatic rings (methyl) acrylic monomer in also comprise neopentyl glycol benzoate (methyl) acrylate etc., The tool of (methyl) acrylate containing Phenoxyethyl shown in particularly preferred following formula (II) etc There is (methyl) acrylate of aromatic yloxy yl alkyl.(methyl) acrylate containing Phenoxyethyl Only can be used alone Deng the monomer in intramolecular with 1 alkene double bond and at least 1 aromatic rings 1 kind, it is also possible to and use two or more.

[changing 2]

In above-mentioned formula (II), R³Representing hydrogen atom or methyl, n represents the integer of 1～8, R⁴Table Show hydrogen atom, alkyl, aralkyl or aryl.At R⁴In the case of alkyl, its carbon number can be 1～about 9, at R⁴In the case of aralkyl, its carbon number can be 7～about 11, it addition, At R⁴In the case of aryl, its carbon number can be 6～about 10.

As composition R in formula (II)⁴The alkyl of carbon number 1～9, can enumerate methyl, butyl, Nonyls etc., as the aralkyl of carbon number 7～11, can enumerate benzyl, phenethyl, menaphthyl etc., make For the aryl of carbon number 6～10, phenyl, tolyl, naphthyl etc. can be enumerated.

The concrete example of (methyl) acrylate containing Phenoxyethyl shown in formula (II) includes (first Base) acrylic acid 2-phenoxy ethyl, (methyl) acrylic acid 2-(2-phenoxy group) ethyl ester, (methyl) acrylate of ethylene-oxide-modified nonyl phenol, (methyl) acrylic acid 2-(adjacent phenyl Phenoxy group) ethyl ester etc..Wherein, (methyl) acrylate containing Phenoxyethyl preferably comprises (first Base) acrylic acid 2-phenoxy ethyl, (methyl) acrylic acid 2-(adjacent phenylphenoxy) ethyl ester and/ Or (methyl) acrylic acid 2-(2-phenoxy group) ethyl ester.

Content from the Component units of the monomer with aromatic rings is constituting (methyl) acrylic acid series Whole Component units of resin (A) are usually 0～20 weight % (such as 6～12 weight %). But, in order to make the glass transition temperature of (methyl) acrylic resin (A) be rule described later Determine scope, it is sometimes preferred to without the Component units from the monomer with aromatic rings.

(methyl) acrylic resin (A) can be containing from except formula described above (I) institute (methyl) acrylic monomer of showing, there is the monomer of polar functional group and there is the monomer of aromatic rings Monomer in addition is (following, also referred to as " other monomers ".) Component units.Other monomers concrete Example includes coming that comfortable intramolecular has (methyl) acrylic monomer that ester ring type constructs and (preferably dividing Have in son ester ring type structure (methyl) acrylate) Component units, from polystyrene list The Component units of body, from ethylene base system monomer Component units, carry out comfortable intramolecular there is multiple (first Base) acryloyl group monomer Component units, from the composition list of (methyl) acrylamide compound Unit etc..Other monomers can be used alone only a kind, it is also possible to and use two or more.

Ester ring type in intramolecular has (methyl) acrylate of ester ring type structure is configured to carbon Number is usually the cycloalkane structure of more than 5, preferably 5～about 7.There is (the first of ester ring type structure Base) concrete example of acrylate includes (methyl) isobornyl acrylate, (methyl) acrylic acid ring Own ester, (methyl) acrylic acid bicyclopentyl ester, (methyl) acrylic acid cyclo-dodecyl ester, (methyl) Acrylic methyl cyclohexyl, (methyl) acrylic acid 3-methyl cyclohexanol ester, (methyl) acrylic acid tert-butyl group Cyclohexyl, (methyl) acrylate base phenyl ester, α-ethoxy-c olefin(e) acid cyclohexyl etc..

The concrete example of styrenic monomers includes: styrene；Methyl styrene, dimethyl styrene, Trimethyl styrene, ethyl styrene, diethyl, triethylbenzene ethylene, propylstyrene, The ring-alkylated styrenes of butylstyrene, hexyl benzene ethylene, heptyl benzene ethylene, octyl styrene etc； The halogeno-benzene second of fluorobenzene ethylene, chlorostyrene, bromstyrol, Dowspray 9, iodobenzene ethylene etc Alkene；Nitrostyrolene, acetylbenzene ethylene, methoxy styrene, divinylbenzene etc..

The concrete example of ethylene base system monomer includes: vinyl acetate, propionate, butanoic acid ethylene The fatty acid vinyl ester of ester, 2 ethyl hexanoic acid vinyl acetate, vinyl laurate etc；Vinyl chloride, bromine The vinyl halides of ethylene etc；The meta-halo ethylene of vinylidene chloride etc；Vinylpyridine, ethylene The nitrogenous aromatic vinyl of base ketopyrrolidine, VCz etc；Butadiene, isoprene, chlorine The conjugate diene monomer of butadiene etc；Acrylonitrile, methacrylonitrile etc..

The concrete example of the monomer having multiple (methyl) acryloyl group in intramolecular includes BDO Two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, 1,9-nonanediol two (first Base) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylic acid Ester, TEG two (methyl) acrylate, tripropylene glycol two (methyl) acrylate etc There is the monomer of 2 (methyl) acryloyl groups in intramolecular；Trimethylolpropane tris (methyl) third The monomer etc. in intramolecular with 3 (methyl) acryloyl groups of olefin(e) acid ester etc.

The concrete example of (methyl) acrylamide compound include N-methylol (methyl) acrylamide, N-(2-hydroxyethyl) (methyl) acrylamide, N-(3-hydroxypropyl) (methyl) acrylamide, N-(4-hydroxybutyl) (methyl) acrylamide, N-(5-Hydroxy pentyl) (methyl) acrylamide, N-(6-hydroxyl hexyl) (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N- Diethyl (methyl) acrylamide, N-isopropyl (methyl) acrylamide, N-(3-dimethylamino Propyl group) (methyl) acrylamide, N-(1,1-dimethyl-3-oxo butyl) (methyl) acrylamide, N-(2-(2-oxo-1-imidazolinyl) ethyl) (methyl) acrylamide, 2-Acryloyl amino -2-methyl isophthalic acid-propane sulfonic acid, N-(methoxy) acrylamide, N-(ethoxyl methyl) (methyl) Acrylamide, N-(propoxy methyl) (methyl) acrylamide, N-(1-methylethoxy ylmethyl) (methyl) acrylamide, N-(1-methyl propoxy methyl) (methyl) acrylamide, N-(2- Methyl propoxy methyl) (methyl) acrylamide (another name: N-(isobutoxymethyl) (methyl) Acrylamide), N-(butoxymethyl) (methyl) acrylamide, N-(1,1-dimethylethyloxy Methyl) (methyl) acrylamide, N-(2-methoxy ethyl) (methyl) acrylamide, N-(2- Ethoxyethyl group) (methyl) acrylamide, N-(2-Among) (methyl) acrylamide, N-(2-(1-methyl ethoxy) ethyl) (methyl) acrylamide, N-(2-(1-methyl-prop epoxide) Ethyl) (methyl) acrylamide, N-(2-(2-methyl-prop epoxide) ethyl) (methyl) acryloyl Amine (another name: N-(2-isobutoxyethy) (methyl) acrylamide), N-(2-butoxyethyl group) (methyl) acrylamide, N-(2-(1,1-dimethylethyloxy) ethyl) (methyl) acrylamide Deng.Wherein, N-(methoxy) acrylamide, N-(ethoxyl methyl) third are preferably used Acrylamide, N-(propoxy methyl) acrylamide, N-(butoxymethyl) acrylamide, N- (2-methyl propoxy methyl) acrylamide.

(methyl) acrylic resin (A) in constituting its whole Component units generally with 0～ The ratio of 20 weight %, preferably 0～10 weight % contains the Component units from other monomers.

Adhesive composition can belong to (methyl) acrylic resin (A) containing two or more (methyl) acrylic resin.It addition, adhesive composition can contain and (methyl) acrylic acid It is different other (methyl) acrylic resins of resin (A).Other (methyl) acrylic acid seriess The example of resin is for having the Component units from (methyl) acrylic monomer shown in formula (I) And not there is (methyl) acrylic resin of polar functional group.Wherein, adhesive composition preferably contains There is (methyl) acrylic resin (A) as main constituent, (methyl) acrylic resin (A) Content be preferably in the summation of all of (methyl) acrylic resin more than 60 weight %, It is more preferably more than more than 80 weight %, more preferably 90 weight %.

(methyl) acrylic resin (A) utilizes the glass that differential scanning calorimetry (DSC) (DSC) measures Glass transition temperature (Tg) is less than-25 DEG C, is preferably less than-30 DEG C.It is-25 DEG C according to containing Tg The adhesive composition of the present invention of following (methyl) acrylic resin (A), can improve Adhesive phase and the adaptation of optical component, the durability of adhesive phase.From the viewpoint of durability, The Tg of (methyl) acrylic resin (A) usually more than-55 DEG C, preferably more than-50 DEG C.

It addition, according to the basis containing (methyl) acrylic resin (A) that Tg is less than-25 DEG C The adhesive composition of invention, it is possible to realize the shortening of the curing time of adhesive phase.I.e., usually Make cross-linking reaction carry out to obtain the operability of appropriateness, the degree of processability and (viscous to adhesive phase Mixture sheet) carry out maintenance, result: according to the adhesive composition of the present invention, can shorten fully to enter The curing time of the adhesive phase needed for row cross-linking reaction.

(methyl) acrylic resin (A) standard polyphenyl based on gel permeation chromatography (GPC) The weight average molecular weight (Mw) of ethylene conversion is preferably in the scope of 500,000～2,000,000, more preferably locates In the scope of 600,000～1,800,000.If Mw is more than 500,000, then the bonding under hot and humid environment Oxidant layer improves with the adaptation of optical component, is between adhesive phase and optical component generation floating The tendency that the probability rise, peeled off reduces, and the tendency that the re-workability being in adhesive phase improves. If it addition, Mw is less than 2,000,000, even if then adhesive phase being fitted in the optical component time The size learning component changes, and adhesive phase is the most easily followed this change in size and changed, because of This is favourable at the aspect of adhesive phase with the adaptation of optical component, the durability of adhesive phase. During it addition, the optical component of band adhesive phase is applied to liquid crystal display device according to above-mentioned tracing ability, There is no difference between brightness and the brightness of central part of the circumference of liquid crystal cells, there is leakage white (white け), the tendency that irregular colour is suppressed.Weight average molecular weight (Mw) and number-average molecular weight (Mn) The molecular weight distribution shown in ratio (Mw/Mn) be usually 2～about 10, be preferably 3～7.

(methyl) acrylic resin (A), can any other (methyl) acrylic acid It is that resin such as can utilize solution polymerization process, mass polymerization, suspension polymerization, emulsion polymerization Manufacture Deng known method.The manufacture of (methyl) acrylic resin generally use polymerization cause Agent.Total amount 100 relative to the whole monomers used in the manufacture of (methyl) acrylic resin Weight portion, uses the polymerization initiator about 0.001～5 weight portions.It addition, (methyl) acrylic acid It is that resin can also utilize the method so that such as ultraviolet isoreactivity energy-ray carries out being polymerized to manufacture.

As polymerization initiator, use thermal polymerization, Photoepolymerizationinitiater initiater etc..Gather as light Close initiator, such as 4-(2-hydroxyl-oxethyl) phenyl (2-hydroxyl-2-propyl group) ketone etc. can be enumerated. As thermal polymerization, such as 2 can be enumerated, 2 '-azodiisobutyronitrile, 2, double (the 2-methyl of 2 '-azo Butyronitrile), 1,1 '-azo double (hexamethylene-1-formonitrile HCN), 2,2 '-azo double (2,4-methyl pentane nitrile), 2,2 '-azo double (2,4-dimethyl-4-methoxyl-valeronitrile), dimethyl-2, double (the 2-methyl-prop of 2 '-azo Acid esters), 2, the Azo of 2 '-azo double (2-hydroxymethyl propionitrile) etc；The peroxidating moon Osmanthus acyl, tert-butyl hydroperoxide, benzoyl peroxide, tert butyl peroxy benzoate, peroxidating Hydrogen isopropylbenzene, di-isopropyl peroxydicarbonate, dipropyl peroxydicarbonate, peroxidating neodecanoic acid The tert-butyl ester, the peroxidating pivalic acid tert-butyl ester, peroxidating (3,5,5-trimethyl acetyl) etc organic Peroxide；The inorganic peroxide etc. of potassium peroxydisulfate, Ammonium persulfate., hydrogen peroxide etc.It addition, And the oxidoreduction series initiators having used peroxide and reducing agent etc. can also be as polymerization initiator Use.

As the manufacture method of (methyl) acrylic resin, in method illustrated above preferably Solution polymerization process.One example of solution polymerization process is to mix, the monomer used and organic solvent at nitrogen Under atmosphere, add thermal polymerization, stir 3～15 about 40～90 DEG C, preferably about 60～80 DEG C About hour.In order to control reaction, can by monomer, thermal polymerization in polymerization continuously or Add with having a rest, or add to be dissolved in the state of organic solvent.As organic solvent, it is possible to use Such as: toluene, dimethylbenzene etc aromatic hydrocarbon；The esters of ethyl acetate, butyl acetate etc； The aliphatic alcohols of propanol, isopropanol etc；The ketone of acetone, butanone, methyl iso-butyl ketone (MIBK) etc Class etc..

(2) aromatic isocyanate system cross-linking agent (B)

Adhesive composition is possibly together with aromatic isocyanate system cross-linking agent (B).Aromatic series Carbimide. Ester system cross-linking agent (B) is for have aromatic rings and to have the change of more than 2 NCOs in intramolecular Compound.By using aromatic isocyanate based compound (B) as cross-linking agent, can improve viscous Mixture layer and the adaptation of optical component, the durability of adhesive phase.

The concrete example of aromatic isocyanate system cross-linking agent (B) is toluene di-isocyanate(TDI), chlorobenzene two Isocyanates, methyl diphenylene diisocyanate, XDI, polymethylene polyphenyl base Isocyanates, naphthalene diisocyanate etc..It addition, aromatic isocyanate system cross-linking agent (B) includes Polyol compound adduct (the adduction of such as trimethylolpropane of these isocyanate compounds Thing), isocyanuric acid carboxylate, biuret type compound and with polyether polyol, polyester polyols The additive reaction such as alcohol, acrylic polyol, polybutadiene polyol, polyisoprene polyol and obtain The derivant of isocyanate compound etc. of carbamate prepolymer type.Aromatic isocyanate system Cross-linking agent (B) can be used alone only a kind, it is also possible to and use two or more.

In aromatic isocyanate system cross-linking agent (B), it is being effectively improved adhesive phase and optics The adaptation of component, the aspect of durability of adhesive phase, it may be preferred to use and combine on aromatic rings The aromatic isocyanate system cross-linking agent of NCO.Aromatic rings combines the virtue of NCO The concrete example of isocyanates system of fragrant race cross-linking agent include toluene di-isocyanate(TDI), chlorophenylene diisocyanates, Methyl diphenylene diisocyanate, polymethylene polyphenyl isocyanate, naphthalene diisocyanate etc..

The content of aromatic isocyanate system cross-linking agent (B) is relative to (methyl) acrylic resin (A) 100 weight portions are 0.3～1 weight portion, are preferably 0.35～0.9 weight portion.If aromatic series The content of isocyanates system cross-linking agent (B) is less than 0.3 weight portion, then even from laminating adhesive The material on surface of the optical component of layer and apply sufficient curing time, adhesive phase and optical component Adaptation the most insufficient.It addition, according to the material on the surface of the optical component of laminate adhesive oxidant layer Difference, durability when adhesive phase fits in optical component reduces.If aromatic isocyanate system The content of cross-linking agent (B) is more than 1 weight portion, even if then applying sufficient curing time, binding agent Layer is the most insufficient with the adaptation of optical component.It addition, when adhesive phase is fitted in optical component Durability, especially thermostability reduce.

(3) compound (C)

Adhesive composition is possibly together with selected from acylate (C-1) and the chemical combination that comprises alkylidene epoxide At least one compound (C) in thing (C-2).According to the present invention's containing compound (C) Adhesive composition, can improve adhesive phase and the adaptation of optical component and by adhesive phase Durability when fitting in optical component, especially thermostability.It addition, be capable of supporting of adhesive phase Protect the shortening of time.Adhesive composition can contain only acylate (C-1), it is also possible to contains only Comprise the compound (C-2) of alkylidene epoxide, it is also possible to containing both.

Acylate (C-1) is preferably by having salt that the organic acid of carboxylic acid terminal formed, i.e. with alkali Organic carboxylate.In the case of using organic carboxylate as acylate (C-1), carboxylate radical The counter cation of anion is preferably the counter cation of below trivalent.Acylate (C-1) can Only to use a kind, it is also possible to and use two or more.

As above-mentioned counter cation, metal ion, ammonium ion can be enumerated, there is hetero ring type structure The cation etc. made.The preference of metal ion includes alkali metal ion and alkaline-earth metal ions.Have The preference of the cation of hetero ring type structure includes pyrrolin ion, imidazol ion, triazole (triazolium) ion, pyrrolidinium ions, pyridinium ion and piperidines ion.

As the carboxylate anion of acylate (C-1), can enumerate such as: formate ion, Acetate ion, propionate ion, enanthic acid radical ion, caprylate ion, laurate ion etc Straight chain saturated alkyl carboxylic acid ion；The straight chain unsaturation alkane of (methyl) acrylic acid, oleic acid etc Yl carboxylic acid radical ion；The aromatic carboxylic acid radical ion of benzoic acid, cinnamic acid etc；The tool of nicotinic acid etc There is the carboxylic acid ion that hetero ring type constructs；The dicarboxylic acids of succinic acid, fumaric acid, phthalic acid etc Radical ion；The carboxylic with oxygen ethylidene skeleton of 2-(2-ethyoxyl) ethoxy carboxylate radical ion etc Acid radical anion etc..

The content of acylate (C-1) is relative to (methyl) acrylic resin (A) 100 weight Part is 0.0001～5 weight portions, is preferably 0.0005～5 weight portions, is more preferably 0.0007～3 Weight portion, more preferably 0.001～1 weight portion, particularly preferably 0.0015～0.5 weight portion. If the content in the range of Gai, then adhesive phase and optical component adaptation and by adhesive phase Durability when fitting in optical component is good, furthermore it is possible to obtain being capable of supporting of adhesive phase Protect the adhesive composition of the shortening of time.

The compound (C-2) comprising alkylidene epoxide is preferably and comprises at least 1 double bond in intramolecular The compound of at least 1 alkylidene epoxide.Alkylidene epoxide is preferably with alkylenedioxy group (-O- Alkylidene-O-) form be contained in compound (C-2).The preference of above-mentioned double bond is (methyl) Double bond contained in acryloyl group.The compound (C-2) comprising alkylidene epoxide can only use 1 Kind, it is also possible to and use two or more.According to by containing the compound (C-2) comprising alkylidene epoxide Adhesive composition formed adhesive phase, it is also possible to inhibition layer is laminated on the stripping of adhesive layer surface Film is heated relative to the peeling force of adhesive phase and strengthens.

From adhesive phase and the adaptation of optical component and adhesive phase is fitted in optical component Time the viewpoint such as durability set out, the preference of above-mentioned alkylenedioxy group is the alkylene of carbon number 1～4 The alkylenedioxy group of the straight or branched of base two epoxide, more preferably carbon number 1～3, the most excellent Elect ethylene epoxide (-O-C as₂H₄-O-).It is explained, is not the alkylene of alkylenedioxy group Too, alkylidene epoxide is preferably the alkylidene epoxide of carbon number 1～4, more excellent to the example of base epoxide Elect the alkylidene epoxide of the straight or branched of carbon number 1～3, more preferably ethyleneoxy group as (-O-C₂H₄-)。

From adhesive phase and the adaptation of optical component and adhesive phase is fitted in optical component Time the viewpoint such as durability set out, compound (C-2) preferably comprises containing following formula (C-2a) institute The compound (C-2a) of (methyl) acryloyl group shown, more preferably it is made up of compound (C-2a). In formula, h represents the integer of 1～6, Q¹Represent hydrogen atom or methyl, Q⁰Represent that there is at least 1 The group of the h valency of alkylenedioxy group.Compound (C-2) can comprise compound of more than two kinds (C-2a).H is preferably the integer of 1～3.

[changing 3]

Q⁰The group of the shown h valency with at least 1 alkylenedioxy group can be to have at least 1 The alkyl of the h valency of individual alkylenedioxy group, it is however preferred to have at least 1 ethylene epoxide 1～ The alkyl of trivalent.As this alkyl, following Q can be enumerated⁰¹、Q⁰²、Q⁰³And Q⁰⁴Shown base Group.

[changing 4]

[changing 5]

Q⁰¹In, Q²Expression can by carbon number 1～3 alkoxyl replace carbon number 1～4 alkyl, Aryl or aralkyl, L represents singly-bound or the alkylidene of carbon number 1～4, i represent 1～50 (such as 1～ 30) integer.Can be as Q²The carbon number of aryl be preferably 6～20, the carbon number of aralkyl preferred It is 7～20.Q⁰²In, j represents the integer of 1～40 (such as 1～30).Q⁰³In, y and z divides Represent the integer of 1～40 (such as 1～30) the most independently, y+z can be 1～40 (such as 1～ 30) integer.Q⁰⁴In, e, f and g separately represent 1～20 (such as 1～10) Integer, e+f+g can be the integer of 1～30 (such as 1～25).

As the compound (C-2a) being preferably used, the change shown in following formula (C-2a-1) can be enumerated Compound (C-2a-1).Compound (C-2) can comprise compound of more than two kinds (C-2a-1). Compound (C-2a-1) is the Q in above-mentioned formula (C-2a)⁰For Q⁰¹Compound.Q in formula¹、 L、i、Q²Represent implication same as described above.In compound (C-2a-1), L is preferably singly-bound, I is preferably the integer of 7～35, the integer of more preferably 9～25.Q²It is preferably carbon number 1～3 Alkyl or the aryl of carbon number 6～20, as Q²Concrete example, can illustrate methyl, ethyl, positive third Base, isopropyl, phenyl, xenyl.

[changing 6]

As the concrete example of compound (C-2a-1), Q can be enumerated¹、L、i、Q²Such as table 1 below Shown compound.

[table 1]

Other examples of the compound (C-2a) being preferably used are the Q in above-mentioned formula (C-2a)⁰For Q⁰⁴ Compound.Now, the h in above-mentioned formula (C-2a) is 3.Compound (C-2) can comprise 2 Plant above Q⁰For Q⁰⁴Compound.Q⁰⁴In, e+f+g is preferably the integer of 5～25.

Other examples of the compound (C-2a) being preferably used are the Q in above-mentioned formula (C-2a)⁰For Q⁰³ Compound.Now, the h in above-mentioned formula (C-2a) is 2.Compound (C-2) can comprise 2 Plant above Q⁰For Q⁰³Compound.Q⁰³In, y+z is preferably the integer of 5～25.

The content of compound (C-2) is relative to (methyl) acrylic resin (A) 100 weight portion It is 0.1～5 weight portions, is preferably 0.15～5 weight portions, is more preferably 0.2～4.5 weight portions, enters One step is preferably 0.5～4 weight portions.If the content in the range of Gai, then adhesive phase and optics structure The adaptation of part and durability time adhesive phase fits in optical component are good, it addition, can To obtain being capable of the adhesive composition of the shortening of the curing time of adhesive phase, and then also may be used To obtain the enhancing inhibition of peeling force.

(4) ionic compound (D)

Adhesive composition can contain ionic compound (D) further as binding agent Layer gives the antistatic additive of antistatic behaviour.Ionic compound (D) is for having inorganic cation or having Machine cation and inorganic anion or the compound of organic anion.Further, it is possible to use 2 kinds with On ionic compound (D).

As inorganic cation, can enumerate such as: lithium cation (Li⁺), sodium cation (Na⁺〕、 Potassium cationic (K⁺) etc alkali metal ion；Beryllium cation (Be²⁺), magnesium cation (Mg²⁺〕、 Calcium cation (Ca²⁺) etc alkaline-earth metal ions etc..

As organic cation, such as glyoxaline cation, pyridylium, pyrroles can be enumerated Alkane cation, ammonium cation, sulfonium cation, cation etc..

In above-mentioned cation constituent, from going out in terms of the excellent compatibility of adhesive composition Send out, organic cation composition is preferably used.In organic cation composition, it is arranged at bonding from stripping Be difficult to during stripping film in oxidant layer charged from the viewpoint of, pyridylium and imidazoles are preferably used Cation.

As inorganic anion, can enumerate such as: cl anion (Cl^-), bromine anions (Br^-〕、 Iodine anion (I^-), tetrachloro aluminic acid anion (AlCl₄ ^-), heptachlor two aluminic acid anion (Al₂Cl₇ ^-〕、 Tetrafluoroboric acid anion (BF₄ ^-), hexafluorophosphoric acid anion (PF₆ ^-), perchloric acid anion (ClO₄ ^-〕、 Nitric acid anions (NO₃ ^-), hexafluoroarsenate anion (AsF₆ ^-), hexafluoro-antimonic acid anion (SbF₆ ^-〕、 Hexafluoro niobic acid anion (NbF₆ ^-), hexafluoro tantalic acid anion (TaF₆ ^-), dicyanamide anion (dca) ((CN)₂N^-) etc..

As organic anion, can enumerate such as: acetate anion (CH₃COO^-), trifluoroacetic acid Anion (CF₃COO^-), methanesulfonic acid anion (CH₃SO₃ ^-), trifluoromethanesulfonic acid anion 〔CF₃SO₃ ^-), p-methyl benzenesulfonic acid anion (p-CH₃C₆H₄SO₃ ^-), double (fluorine sulphonyl) imines cloudy Ion ((FSO₂)₂N^-), double (fluoroform sulphonyl) imines anion ((CF₃SO₂)₂N^-), three (fluoroform sulphonyl) methane anion ((CF₃SO₂)₃C^-), dimethyl hypophosphorous acid anion ((CH₃)₂POO^-), (gathering) Fluohydric acid. fluoride anion (F (HF)_n ^-) (n is 1～about 3), sulfur cyanogen the moon Ion (SCN^-), perfluor fourth sulfonic acid anion (C₄F₉SO₃ ^-), double (five fluorine second sulphonyl) imines cloudy Ion ((C₂F₅SO₂)₂N^-), perfluorobutyric acid anion (C₃F₇COO^-), (fluoroform sulphonyl) (three Fluoromethane carbonyl) imide anion ((CF₃SO₂)(CF₃CO)N^-), perfluoropropane-1,3-bis- Sulfonic acid anion (^-O₃S(CF₂)₃SO₃ ^-), carbonate anion (CO₃ ^2-) etc..

In above-mentioned anion component, from the ionic compound (D) providing antistatic property excellence Aspect set out, particularly preferably use the anion component comprising fluorine atom.As comprising fluorine atom Anion component, specifically, can enumerate double (fluorine sulphonyl) imines anion, hexafluorophosphoric acid cloudy from Son or double (fluoroform sulphonyl) imines anion.

The concrete example of ionic compound (D) can be from above-mentioned cation constituent and anion component Combination suitably selects.If enumerate according to the structural classification of organic cation have organic cation from The example of sub-property compound (D), then can enumerate following compound.

Pyridiniujm:

N-hexyl pyridine hexafluorophosphate,

N-octylpyridinium hexafluorophosphate,

N-octyl group-4-picoline hexafluorophosphate,

N-butyl-4-picoline hexafluorophosphate,

Double (fluorine sulphonyl) imines of N-decyl pyridine,

Double (fluorine sulphonyl) imines of N-dococylpyridinium,

Double (fluorine sulphonyl) imines of N-tetradecylpyridinium,

Double (fluorine sulphonyl) imines of N-cetyl pyridinium,

Double (fluorine sulphonyl) imines of N-dodecyl-4-picoline,

Double (fluorine sulphonyl) imines of N-myristyl-4-picoline,

Double (fluorine sulphonyl) imines of N-cetyl-4-picoline,

Double (fluorine sulphonyl) imines of N-benzyl-2-picoline,

Double (fluorine sulphonyl) imines of N-benzyl-4-picoline,

Double (fluoroform sulphonyl) imines of N-hexyl pyridine,

Double (fluoroform sulphonyl) imines of N-octylpyridinium,

Double (fluoroform sulphonyl) imines of N-octyl group-4-picoline,

Double (fluoroform sulphonyl) imines of N-butyl-4-picoline.

Imidazole salts:

1-ethyl-3-methylimidazole hexafluorophosphate,

1-ethyl-3-methylimidazole tosilate,

Double (fluorine sulphonyl) imines of 1-ethyl-3-methylimidazole,

Double (fluoroform sulphonyl) imines of 1-ethyl-3-methylimidazole,

1-butyl-3-Methylimidazole. mesylate,

Double (fluorine sulphonyl) imines of 1-butyl-3-Methylimidazole..

Pyrrolidinium:

N-butyl-N-crassitude hexafluorophosphate,

Double (fluorine sulphonyl) imines of N-butyl-N-crassitude,

Double (fluoroform sulphonyl) imines of N-butyl-N-crassitude.

Quaternary ammonium salt:

TBuA hexafluorophosphate,

TBuA tosilate,

Double (fluoroform sulphonyl) imines of (2-hydroxyethyl) trimethyl ammonium,

(2-hydroxyethyl) trimethyl ammonium dimethyl hypophosphites.

If it addition, enumerate the example of the ionic compound (D) with inorganic cation, then including Following compound.

Lithium bromide,

Lithium iodide,

Lithium tetrafluoroborate,

Lithium hexafluorophosphate,

Lithium rhodanate,

Lithium perchlorate,

Lithium fluoroform sulphonate,

Double (fluorine sulphonyl) imines of lithium,

Double (fluoroform sulphonyl) imines of lithium,

Double (the five fluorine second sulphonyl) imines of lithium,

Lithium three (fluoroform sulphonyl) methane,

Lithium tosilate,

Sodium hexafluorophosphate,

Double (fluorine sulphonyl) imines of sodium,

Double (fluoroform sulphonyl) imines of sodium,

Sodium tosilate,

Potassium hexafluorophosphate,

Double (fluorine sulphonyl) imines of potassium,

Double (fluoroform sulphonyl) imines of potassium,

Potassium tosilate.

Ionic compound (D) is the most at room temperature solid.With use under room temperature be liquid from The situation of sub-property compound (D) is compared, and can keep antistatic property for a long time.If it is anti-quiet from this kind From the viewpoint of electrical long-time stability, then ionic compound (D) preferably have more than 30 DEG C, And then the fusing point of more than 35 DEG C.On the other hand, if this fusing point is too high, then with (methyl) acrylic acid Being the compatibility poor of resin (A), therefore fusing point is preferably less than 90 DEG C, more preferably 70 DEG C Below, more preferably less than 50 DEG C.

The content of the ionic compound (D) in adhesive composition is relative to (methyl) acrylic acid Be resin (A) 100 weight portion be preferably 0.2～8 weight portions, more preferably 0.2～5 weight portions, More preferably 0.3～5 weight portions, particularly preferably 0.5～3 weight portions.Ionic compound (D) to improving antistatic property favorably when content is more than 0.2 weight portion, ionic compound (D) when content is below 8 weight portions, the durability to maintenance adhesive phase is favourable.

(5) silane compound (E)

Adhesive composition can contain silane compound (E) further.Thus can improve bonding The adaptation of the optical components such as oxidant layer and glass substrate.

As silane compound (E), can enumerate such as: vinyltrimethoxy silane, vinyl Triethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3- Amino propyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-aminopropyl trimethoxy silicon Alkane, APTES, 3-glycidoxypropyltrime,hoxysilane, 3-epoxy Propoxypropyl methyl dimethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methacryloxy Propyl trimethoxy silicane, 3-mercaptopropyi trimethoxy silane, 3-glycidoxypropyl group trimethoxy Base silane, 3-glycidoxypropyl group triethoxysilane, 3-glycidoxypropyl group dimethoxy first Base silane, 3-glycidoxypropyl group ethyoxyl dimethylsilane etc..Silicon of more than two kinds can be used Hydride compounds.

Silane compound (E) can also be the compound of silicone oligomers type.If by silicone oligomers Represent with the form of (monomer) oligomer, then can enumerate such as following compound.

3-mercaptopropyi trimethoxy silane-tetramethoxy-silicane alkyl copolymer,

3-mercaptopropyi trimethoxy silane-tetraethoxy-silicane alkyl copolymer,

3-Mercaptopropyltriethoxysilane-tetramethoxy-silicane alkyl copolymer,

The copolymerization containing mercaptopropyi such as 3-Mercaptopropyltriethoxysilane-tetraethoxy-silicane alkyl copolymer Thing；

Mercapto methyl trimethoxy silane-tetramethoxy-silicane alkyl copolymer,

Mercapto methyl trimethoxy silane-tetraethoxy-silicane alkyl copolymer,

Mercapto methyl triethoxysilane-tetramethoxy-silicane alkyl copolymer,

The copolymerization containing mercapto methyl such as mercapto methyl triethoxysilane-tetraethoxy-silicane alkyl copolymer Thing；

3-glycidoxypropyltrime,hoxysilane-tetramethoxy-silicane alkyl copolymer,

3-glycidoxypropyltrime,hoxysilane-tetraethoxy-silicane alkyl copolymer,

3-glycidoxypropyl group triethoxysilane-tetramethoxy-silicane alkyl copolymer,

3-glycidoxypropyl group triethoxysilane-tetraethoxy-silicane alkyl copolymer,

3-glycidoxypropyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,

3-glycidoxypropyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,

3-glycidoxypropyl diethoxy silane-tetramethoxy-silicane alkyl copolymer,

3-glycidoxypropyl diethoxy silane-tetraethoxy-silicane alkyl copolymers etc. are containing 3-ring The copolymer of oxygen propoxypropyl；

3-methacryloxypropyl trimethoxy silane-tetramethoxy-silicane alkyl copolymer,

3-methacryloxypropyl trimethoxy silane-tetraethoxy-silicane alkyl copolymer,

3-methacryloxypropyl-tetramethoxy-silicane alkyl copolymer,

3-methacryloxypropyl-tetraethoxy-silicane alkyl copolymer,

3-methacryloyloxypropyl methyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,

3-methacryloyloxypropyl methyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,

3-methacryloyloxypropyl methyl diethoxy silane-tetramethoxy-silicane alkyl copolymer,

3-methacryloyloxypropyl methyl diethoxy silane-tetraethoxy-silicane alkyl copolymer etc. contains The copolymer of methacryloxypropyl；

3-acryloxypropyl trimethoxy silane-tetramethoxy-silicane alkyl copolymer,

3-acryloxypropyl trimethoxy silane-tetraethoxy-silicane alkyl copolymer,

3-acryloxypropyl triethoxysilane-tetramethoxy-silicane alkyl copolymer,

3-acryloxypropyl triethoxysilane-tetraethoxy-silicane alkyl copolymer,

3-acryloxypropyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,

3-acryloxypropyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,

3-acryloxypropyl diethoxy silane-tetramethoxy-silicane alkyl copolymer,

3-acryloxypropyl diethoxy silane-tetraethoxy-silicane alkyl copolymers etc. are containing propylene The copolymer of acryloxypropylethoxysilane；

Vinyltrimethoxy silane-tetramethoxy-silicane alkyl copolymer,

Vinyltrimethoxy silane-tetraethoxy-silicane alkyl copolymer,

VTES-tetramethoxy-silicane alkyl copolymer,

VTES-tetraethoxy-silicane alkyl copolymer,

Vinyl methyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,

Vinyl methyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,

Vinyl methyl diethoxy silane-tetramethoxy-silicane alkyl copolymer,

The copolymerization containing vinyl such as vinyl methyl diethoxy silane-tetraethoxy-silicane alkyl copolymer Thing；

3-TSL 8330-tetramethoxy-silicane alkyl copolymer,

3-TSL 8330-tetraethoxy-silicane alkyl copolymer,

APTES-tetramethoxy-silicane alkyl copolymer,

APTES-tetraethoxy-silicane alkyl copolymer,

3-amino propyl methyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,

3-amino propyl methyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,

3-amino propyl methyl diethoxy silane-tetramethoxy-silicane alkyl copolymer,

The copolymerization containing amino such as 3-amino propyl methyl diethoxy silane-tetraethoxy-silicane alkyl copolymer Thing etc..

The silane compound (E) more than illustrated is mostly liquid.Silanization in adhesive composition The content of compound (E) is relative to (methyl) acrylic resin (A) 100 weight portion usually 0.01～10 weight portions, preferably 0.05～5 weight portions, more preferably 0.2～0.4 weight portion.If The content of silane compound (E) is more than 0.01 weight portion, then be readily obtained raising adhesive phase with The effect of the adaptation of the optical components such as glass substrate.If it addition, content is below 10 weight portions, Silane compound (E) then can be suppressed to ooze out from adhesive phase.

(6) other compositions

Adhesive composition can contain crosslinking catalyst, weathering stabilizers, viscosifier, plasticizer, Softening agent, dyestuff, pigment, inorganic filler, light scattering microgranule, except (methyl) acrylic acid series tree The additives such as the resin beyond fat (A).In addition, it might be useful to: in adhesive composition Combined with ultraviolet radiation curable compound, and after forming adhesive phase, irradiation ultraviolet radiation makes it solidify, shape Become harder adhesive phase.As crosslinking catalyst, can enumerate such as hexamethylene diamine, ethylenediamine, Polyethylene imine, hexamethylenetetramine, diethylenetriamines, trien, isophorone The amine compounds such as diamidogen, trimethylene diamine, poly-amino resins and melmac.

The adhesive phase of the present invention is the adhesive phase comprising above-mentioned Invention adhesive compositions, For typical case, it is made up of the adhesive composition of the present invention.Adhesive phase can be above-mentioned by constituting Each composition of adhesive composition be dissolved or dispersed in solvent and make solvent-laden adhesive composition, Then this solvent-laden adhesive composition is coated on base material film and make it be dried and obtain.This The adaptation of bright adhesive phase and excellent in te pins of durability, and required curing time can be shortened.

Base material film is generally plastic foil, as its typical example, can enumerate and implement demoulding process Stripping film (barrier film).Stripping film can be such as to comprising polyethylene terephthalate, gathering The film of the various resins such as mutual-phenenyl two acid bromide two alcohol ester, Merlon, polyarylate will form bonding Film obtained by the demoulding process such as silicone-treated is implemented in the face of oxidant layer.For example, it is possible to by stripping film The demoulding processes face direct coating adhesive compositions and forms adhesive phase gluing this band stripping film Mixture layer is laminated in optical component to obtain the optical component of band adhesive phase.Alternatively, it is also possible at light Learn the surface direct coating adhesive compositions of component and form adhesive phase and as required in bonding The outer surface stacking stripping film of oxidant layer and make the optical component of band adhesive phase.Adhesive phase is being set When being placed in the surface of optical component, preferably binding face and/or the laminating of adhesive phase to optical component Surface activation process, such as Cement Composite Treated by Plasma, sided corona treatment etc. are implemented in face, more preferably implement electricity Dizzy process.

The thickness of adhesive phase is preferably 10～45 μm, more preferably 10～30 μm, further preferably It is 15～25 μm.If the thickness of adhesive phase is this scope, then to adhesive phase and optical component Adaptation and durability time adhesive phase fits in optical component are favourable.Based on same reason By, the gel fraction of adhesive phase is preferably the scope of 30～85%.

For the adhesive composition of the present invention,

By on the film by cyclic polyolefin hydrocarbon system resin formation with stratiform shape this adhesive composition, And by the adhesive composition of stratiform to be laminated in the state environment temperature 23 DEG C of alkali-free glass plate The adhesive composition of stratiform was gathered by ring-type with above-mentioned after 24 hours by lower keeping from this alkali-free glass plate The peeling force when film of olefin-based resin formation is peeled off together is set to P (CO) 23, and

By on the film by cyclic polyolefin hydrocarbon system resin formation with stratiform shape this adhesive composition, And by the adhesive composition of stratiform to be laminated in the state environment at temperature 50 C of alkali-free glass plate The adhesive composition of stratiform was gathered by ring-type with above-mentioned after 48 hours by lower keeping from this alkali-free glass plate When peeling force when the film of olefin-based resin formation is peeled off together is set to P (CO) 50,

The ratio (P (CO) 50/P (CO) 23) of above-mentioned P (CO) 50 and above-mentioned P (CO) 23 is preferably 3.2 Above, more preferably more than 3.5, more preferably more than 3.8.As long as gluing by comprising this kind The optical component of film that the adhesive phase of mixture composite will comprise by cyclic polyolefin hydrocarbon system resin formation Fit with unorganic glass liquid crystal cells with this film side, then peel off optical component after laminating immediately and transfer The so-called re-workability being attached at new optical component is good, and by carrying out heating after laminating Peeling force increases, therefore, it is possible to optical component more firmly fits in liquid crystal cells, therefore preferably.

It addition, for the adhesive composition of the present invention,

The combination of this binding agent will be shaped with stratiform on the film formed by (methyl) acrylic resin Thing and by the adhesive composition of stratiform to be laminated in the state of alkali-free glass plate temperature 23 DEG C Under environment keeping 24 hours after from this alkali-free glass plate by the adhesive composition of stratiform with above-mentioned by The peeling force when film that (methyl) acrylic resin is formed is peeled off together is set to P (AC) 23, and

The combination of this binding agent will be shaped with stratiform on the film formed by (methyl) acrylic resin Thing and by the adhesive composition of stratiform to be laminated in the state of alkali-free glass plate at temperature 50 C Under environment keeping 48 hours after from this alkali-free glass plate by the adhesive composition of stratiform with above-mentioned by The film that (methyl) acrylic resin is formed peels off the peeling force made when being set to P (AC) 50 together,

The ratio (P (AC) 50/P (AC) 23) of above-mentioned P (AC) 50 and above-mentioned P (AC) 23 is preferably 3.2 Above, more preferably more than 3.5, more preferably more than 3.8.As long as gluing by comprising this kind The adhesive phase of mixture composite will comprise the optics structure of the film formed by (methyl) acrylic resin Part is fitted with unorganic glass liquid crystal cells with this film side, then peel off optical component immediately after laminating and turn And be attached at the so-called re-workability of new optical component well, and by heating after laminating And peeling force increases, therefore, it is possible to optical component more firmly to be fitted in liquid crystal cells, therefore preferably.

Above-mentioned P (CO) 23 or P (AC) 23 be preferably 0.3～5N/25mm, more preferably 0.5～ 5N/25mm, more preferably 0.5～3N/25mm.If P (CO) 23 or P (AC) 23 is this kind Scope, then re-workability and good with the adaptation of liquid crystal cells.It addition, above-mentioned P (CO) 50 or P (AC) 50 is preferably 1～15N/25mm, more preferably 1.5～15N/25mm, further preferably It is 2～13N/25mm.If P (CO) 50 or P (AC) 50 is this kind of scope, then re-workability and with The adaptation of liquid crystal cells is good.

The adhesive composition of the present invention contains acylate (C-1) and compound (C-2), has The content of machine hydrochlorate (C-1) is excellent relative to (methyl) acrylic resin (A) 100 weight portions Elect 0.0001～0.1 weight portion, more preferably 0.0005～0.05 weight portion, particularly preferably as Being 0.001～0.02 weight portion, the content of compound (C-2) is relative to (methyl) acrylic acid series Resin (A) 100 weight portion is preferably 0.1～5 weight portions, more preferably 0.15～4 weight Part, particularly preferably 0.2～3 weight portions.

By containing acylate (C-1) and compound (C-2) with above-mentioned amount, thus easily The ratio (P (CO) 50/P (CO) 23) of above-mentioned P (CO) 50 and above-mentioned P (CO) 23 is adjusted to preferably 3.2 Above, more preferably more than 3.5, further preferred more than 3.8.

It addition, by containing acylate (C-1) and compound (C-2) with above-mentioned amount, from And easily the ratio (P (AC) 50/P (AC) 23) of above-mentioned P (AC) 50 and above-mentioned P (AC) 23 is adjusted to Preferably more than 3.2, more preferably more than 3.5, further preferred more than 3.8.

The adhesive phase of the present invention can be suitable as between by component, especially optical component Between laminating adhesive phase use.The optical component with adhesive phase of the present invention is the most permissible It is the component being laminated with adhesive phase on certain optical component, can also is that in addition at this adhesive phase Outer surface also stacking be fitted with the component of other optical components.

(1) first embodiment

1 of the optical component with adhesive phase of the present invention preferred embodiment comprises conduct The resin molding of optical component and the adhesive phase being laminated on its at least one face.Resin molding can be enumerated partially Shake the bloomings such as sheet, protecting film, phase retardation film；Or be fitted in as by blooming of protective etc. And for the surface protection film (protecting film) protecting its surface purpose from damage or pollution to use.

Polaroid is the film with the function taking out the inclined linear light of straight line from incident natural light, preferably Example be that gas absorption quantity has iodine or a dichromatic on the polyvinyl alcohol resin film by uniaxial tension The film of the dichromatic pigments such as dyestuff.The thickness of polaroid is not particularly limited, usually 0.5～35 μm.

Protecting film can be to comprise to have light transmission (the most transparent) resin, example Such as chain polyolefin-based resins (polypropylene-based resin etc.), cyclic polyolefin hydrocarbon system resin (norborene Be resin etc.) etc polyolefin-based resins；The fibre of triacetyl cellulose, diacetyl cellulose etc Dimension prime system resin；Polyester based resin；Polycarbonate-based resin；(methyl) acrylic resin；Poly- Phenylethylene resin series；Polyether-ether-ketone resin；The film of the thermoplastic resins such as polysulfone resin.

As chain polyolefin-based resins, the chain of polyvinyl resin, acrylic resin etc can be enumerated The homopolymer of shape alkene, additionally can enumerate the copolymer comprising chain olefin of more than two kinds.

Cyclic polyolefin hydrocarbon system resin is the general name of the resin being polymerized as polymerized unit using cyclic olefin. To enumerate the concrete example of cyclic polyolefin hydrocarbon system resin, then be cyclic olefin open loop (co) polymer, The copolymer of the chain olefin of the addition polymer of cyclic olefin, cyclic olefin and ethylene, propylene etc (representational is random copolymer) and they are modified with unsaturated carboxylic acid or derivatives thereofs Graft polymers and their hydride etc..Wherein, be preferably used make use of norborene or The norborneol alkene monomers such as multi-ring norborneol alkene monomer are as the norbornene resin of cyclic olefin.

Cellulose-based resin is the partially or completely carboxylate of cellulose, include, for example cellulose Acetas, propionic ester, butyrate, their mixed ester etc..Wherein, triacetyl cellulose is preferably used Element, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate etc..

Polyester based resin is to have ester bond, resin in addition to above-mentioned cellulose-based resin, typically Comprise the condensation polymer of polybasic carboxylic acid or derivatives thereof and polyhydric alcohol.As polybasic carboxylic acid or derivatives thereof, Dicarboxylic acids or derivatives thereof can be used, include, for example p-phthalic acid, M-phthalic acid, to benzene Dicarboxylic acid dimethyl ester, naphthalene diformic acid dimethyl ester etc..As polyhydric alcohol, it is possible to use glycol, such as may be used Enumerate ethylene glycol, propylene glycol, butanediol, neopentyl glycol, cyclohexanedimethanol etc..

The concrete example of polyester based resin includes polyethylene terephthalate, poly terephthalic acid fourth Diol ester, PEN, PBN, poly terephthalic acid the third two Alcohol ester, polytrimethylene naphthalate, polycyclohexylene's dimethyl ester, poly-naphthalenedicarboxylic acid ring Hexane dimethyl ester.

Polycarbonate-based resin comprises polymer obtained by monomeric unit bonding by carbonate group. Polycarbonate-based resin can also be the tree being referred to as modified polycarbonate having modified polymer backbone Fat or copolymerization polycarbonate etc..

(methyl) acrylic resin can be the polymerization using methacrylate as principal monomer Thing, is preferably the copolymer of other a small amount of comonomer components of copolymerization thereon.(methyl) third Olefin(e) acid system resin is more preferably the copolymer of methyl methacrylate and acrylic acid methyl ester., it is also possible to more altogether Poly-3rd monofunctional monomer.

As the 3rd monofunctional monomer, include, for example: ethyl methacrylate, methacrylic acid Butyl ester, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, metering system The first in addition to methyl methacrylate of acid 2-Octyl Nitrite, HEMA etc Base esters of acrylic acid；Ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, Benzyl acrylate, 2-EHA, acrylic acid 2-hydroxyl ethyl ester etc except acrylic acid methyl ester. Esters of acrylic acid in addition；2-(hydroxymethyl) acrylic acid methyl ester., 2-(1-hydroxyethyl) propylene Acid methyl ester, 2-(hydroxymethyl) ethyl acrylate, 2-(hydroxymethyl) butyl acrylate etc Hydroxy alkyl acrylate class；The unsaturated acids of methacrylic acid, acrylic acid etc；Chlorostyrene, The halogenated styrenes class of bromstyrol etc；The substituted benzene of vinyltoluene, α-methyl styrene etc Vinyl；The unsaturated nitrile of acrylonitrile, methacrylonitrile etc；Maleic anhydride, citraconic anhydride it The unsaturated acids anhydride of class；The unsaturated acyl of phenyl maleimide, N-cyclohexylmaleimide etc Imines etc..3rd monofunctional monomer may be used alone or in combination of two or more kinds.

Can also on (methyl) acrylic resin copolymerization polyfunctional monomer again.As multifunctional Monomer, include, for example: ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) third Olefin(e) acid ester, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, The second of nine ethylene glycol bisthioglycolates (methyl) acrylate, ten TEG two (methyl) acrylate etc The monomer that two terminal hydroxyl acrylic or methacrylics of glycol or its oligomer are Esterification；The third two The monomer that two terminal hydroxyl acrylic or methacrylics of alcohol or its oligomer are Esterification；New penta 2 Alcohol two (methyl) acrylate, hexanediol two (methyl) acrylate, butanediol two (methyl) Acrylate etc by Esterification for the hydroxyl acrylic or methacrylic of dihydroxylic alcohols monomer；Double Two terminal hydroxyls of phenol A, the alkylene oxide adducts of bisphenol-A or their halogen substituents are used The monomer that acrylic or methacrylic is Esterification；By many to trimethylolpropane, tetramethylolmethane etc Monomer that unit's alcohol acrylic or methacrylic is Esterification and on these terminal hydroxyls open loop add Become the monomer of the epoxy radicals of glycidyl acrylate or glycidyl methacrylate；In fourth two Acid, adipic acid, p-phthalic acid, phthalic acid, they the binary acid such as halogen substituents, with And the upper open loop addition such as their alkylene oxide addition product glycidyl acrylate or methacrylic acid The monomer of the epoxy radicals of ethylene oxidic ester；(methyl) benzyl acrylate；Divinylbenzene etc Divinyl aromatic compound etc..Wherein, ethylene glycol dimethacrylate, tetrem are preferably used Diol dimethacrylate, neopentylglycol dimethacrylate.

It is anti-that (methyl) acrylic resin can also also carry out between the functional group that copolymer is had Answer and be modified.As this reaction, include, for example carbomethoxy and the 2-(hydroxyl of acrylic acid methyl ester. Methyl) acrylic acid methyl ester. hydroxyl macromolecular chain in separating methanol condensation reaction, acrylic acid carboxyl with Dehydration condensation etc. in the macromolecular chain of the hydroxyl of 2-(hydroxymethyl) acrylic acid methyl ester..It addition, (methyl) acrylic resin can also have glutarimide derivant, glutaric anhydride derivant or The arbitrary structures of lactonic ring structure.

(methyl) acrylic resin can also contain additive as required.As additive, Include, for example lubricant, anti-blocking agent, heat stabilizer, antioxidant, antistatic additive, photostabilizer, Resistance to impact modifying agent, surfactant etc..

The viewpoints such as the resistance to impact from the masking making film and film, (methyl) acrylic acid series tree Fat can also contain acrylic rubber particle.So-called acrylic rubber particle is with by acrylate As the elastomeric polymer of main body as the particle of required composition, can enumerate only the most poly-by this elasticity The particle of the single layer structure that compound is constituted and using this elastomeric polymer as the multiple structure of 1 layer Particle.As the example of this elastomeric polymer, can enumerate using alkyl acrylate as main constituent and Copolymerization can be copolymerized therewith other vinyl monomers and the crosslinking elastocopolymer of cross-linkable monomer. As the alkyl acrylate of the main constituent becoming elastomeric polymer, include, for example acrylic acid methyl ester., The carbon number of the alkyl such as ethyl acrylate, n-butyl acrylate, 2-EHA is 1～8 left sides Right alkyl acrylate, particularly preferably uses the acrylic acid of the alkyl with carbon number more than 4.As Can be set forth in intramolecular have 1 with other vinyl monomers of this alkyl acrylate copolymer The compound of individual polymerism carbon-to-carbon double bond, more specifically, can enumerate methyl methacrylate etc Methacrylate, the aromatic ethenyl compound of styrene etc, the ethylene of acrylonitrile etc Base cyanogen compound etc..As cross-linkable monomer, intramolecular can be set forth in there are at least 2 polymerism carbon The compound of the bridging property of-carbon double bond, more specifically, can enumerate ethylene glycol bisthioglycolate (methyl) propylene (methyl) esters of acrylic acid of the polyhydric alcohol of acid esters, butanediol two (methyl) acrylate etc, (methyl) acrylic acid alkenyl esters of (methyl) allyl acrylate etc, divinylbenzene etc..

Film and the bag of (methyl) acrylic resin not containing rubber particles can also be comprised The sandwich of the film containing (methyl) acrylic resin containing rubber particles is as protecting film.

Phase retardation film is to demonstrate optically anisotropic blooming, can be by being drawn by resin molding Stretching is stretched film obtained by about 1.01～6 times, and described resin molding may be used for above-mentioned guarantor except comprising Beyond resin in cuticula, such as, can also comprise polyvinyl alcohol resin, polyarylate system resin, gather Imide series resin, polyether sulfone system resin, polyvinylidene fluoride/polymethyl methacrylate system resin, Liquid crystal polyester system resin, ethylene-acetidin copolymer saponification material, polyvinyl chloride resin etc.. Wherein, preferably by Merlon resin film, cyclic polyolefin resin film, (methyl) acrylic acid Resin film or cellulose-based resin molding be stretched uniaxially or biaxially obtained by stretched film.Additionally at this In description, zero-lag film be also contained in phase retardation film (but, zero-lag film can also be as guarantor Cuticula uses.).In addition, uniaxiality phase retardation film, wide viewing angle phase retardation film, low light it are referred to as The film of elastic modelling quantity phase retardation film etc. can also be suitable as phase retardation film and use.

So-called zero-lag film refers to phase difference value R in face_eAnd thickness direction phase difference value R_thIt is The film of-15～15nm.This phase retardation film can be suitable in the liquid crystal indicator of IPS pattern. Phase difference value R in face_eAnd thickness direction phase difference value R_thIt is preferably all-10～10nm, the most all For-5～5nm.Phase difference value R in face described herein_eAnd thickness direction phase difference value R_thIt it is wavelength Value under 590nm.

Phase difference value R in face_eAnd thickness direction phase difference value R_thDefine with following formula respectively.

R_e=(n_x-n_y)×d

R_th=((n_x+n_y)/2-n_z〕×d

In formula, n_xIt is the refractive index in slow axis direction (x-axis direction) in face, n_yIn being face The refractive index in leading phase shaft direction (y-axis direction orthogonal with x-axis in face), n_zIt it is film thickness side To the refractive index of (being perpendicular to the z-axis direction of face), d is the thickness of film.

As zero-lag film, such as, can use and comprise cellulose-based resin, chain polyolefin tree The polyolefin-based resins of fat and cyclic polyolefin hydrocarbon system resin etc, PET series tree Fat or the resin molding of (methyl) acrylic resin.From being easily controlled phase difference value and easily obtaining Aspect set out, particularly preferably use cellulose-based resin, polyolefin-based resins or (methyl) propylene Acid is resin.For example, it is also possible to the resin different from (methyl) acrylic resin will comprised Film conduct obtained by stacking on the one or both sides of phase contrast embodied layers (methyl) acrylic resin layer Phase retardation film.

It addition, utilize the coating of liquid crystal compounds, orientation embody optically anisotropic film, Or utilize the coated body of inorganic layered compounds to reveal optically anisotropic film can also be as phase place Difference film uses.In this kind of phase retardation film, there is the film being referred to as temperature compensating type phase retardation film, additionally The rod shaped liquid crystal sold with the trade name of " NH film " by JX day ore deposit day stone energy (strain) is also had to incline The film being tiltedly orientated, the disc-like liquid crystal sold with the trade name of " WV film " by Fujiphoto (strain) The film of tilted alignment, by Sumitomo Chemical (strain) with the trade name of " VAC film " sell the most double The film of axle orientating type, sold with the trade name of " new VAC film " by Sumitomo Chemical (strain) equally The film etc. of biaxially oriented version.

On the other hand, surface protection film is to exempt from using protection as by the surface of the blooming etc. of protective The film that the impaired purpose injuring pollution uses, such as optical component inclined of liquid crystal indicator Shake the various bloomings such as sheet, protecting film, phase retardation film, light diffusing sheet, reflector plate generally with at its table Face (in the case of one side has adhesive phase, be and the face of this adhesive phase opposite side) laminating The state having surface protection film circulates.The convention of surface protection film is that above-mentioned blooming is being fitted in liquid It is stripped removing after brilliant unit etc. are upper.

As the base material of surface protection film, include, for example: by polyethylene, polypropylene, poly-methyl The polyolefin-based resins of amylene etc；Polyvinyl fluoride, polyvinylidene fluoride, poly-ethylene fluoride etc Fluoro polyolefin-based resins；PEN, polyethylene terephthalate, poly-right Benzene dicarboxylic acid butanediol ester, polyethylene terephthalate/isophthalic copolymers etc Polyester based resin；The polyamide of nylon 6, nylon 6,6 etc；Polrvinyl chloride, vinyl chloride-acetic acid second Enoate copolymer, vinyl-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, The polyvinyl of vinylon etc；Triacetyl cellulose, diacetyl cellulose, celluloid etc Cellulose-based resin；Polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, (methyl) acrylic resin of butyl polyacrylate etc；And comprise polystyrene, poly-carbonic acid The film of the thermoplastic resins such as ester, polyarylate, polyimides.Resin molding is the present invention of surface protection film The optical component with adhesive phase be the component being provided with adhesive phase on the substrate.

In the optical component with adhesive phase of present embodiment, preferably at this adhesive phase table Attach above-mentioned stripping film on face, protected before using temporarily.It is pasted with this reality of stripping film The optical component with adhesive phase executing mode can utilize following method to manufacture, i.e. in stripping Coating adhesive compositions on film and form adhesive phase, stacking tree again on the adhesive phase of gained The method of adipose membrane；Coating adhesive compositions on resin molding and form adhesive phase, at its binding agent Fit on face the method for stripping film.

For the optical component of the band adhesive phase of present embodiment,

The adhesive phase that the optical component of this band adhesive phase is constituted it with utilization is being laminated in alkali-free The state of glass plate in the environment of temperature 23 DEG C keeping 24 hours after when this alkali-free glass plate is peeled off Peeling force be set to P23 and

The adhesive phase that the optical component of this band adhesive phase is constituted it with utilization is being laminated in alkali-free The state of glass plate in the environment of temperature 50 C keeping 48 hours after when this alkali-free glass plate is peeled off Peeling force when being set to P50,

The ratio (P50/P23) of P50 with P23 is more than 3.2, be more than 3.5 further, specifically for When more than 3.8, so-called good in processability, and heat and peeling force by carrying out after laminating Increase, therefore, it is possible to optical component more firmly to be fitted in liquid crystal cells, therefore preferably.

Above-mentioned P23 is preferably 0.3～5N/25mm, more preferably 0.5～5N/25mm, further It is preferably 0.5～3N/25mm.If P23 is this kind of scope, then re-workability and with liquid crystal cells Adaptation is good.It addition, above-mentioned P50 is preferably 1～15N/25mm, more preferably 1.5～ 15N/25mm, more preferably 2～13N/25mm.If P50 is this kind of scope, then reprocess Property and good with the adaptation of liquid crystal cells.

(2) second embodiments

Other preferred implementation of the optical component with adhesive phase of the present invention comprises resin The duplexer of film and the adhesive phase being laminated on its at least one face.The duplexer of resin molding is preferably The duplexer of the blooming in bloomings such as polaroid, protecting film, phase retardation film etc..Blooming The typical example of duplexer be polarization plates.The optical component with adhesive phase in present embodiment In, it is also preferred that attach stripping film in this adhesive layer surface, protected before using temporarily.

As polarization plates, can enumerate to have and absorb the vibration plane with certain direction injecting face The inclined linear light of straight line the straight line through the character of the inclined linear light of straight line with orthogonal vibration plane are inclined Vibration plate；There is the inclined linear light of straight line of the vibration plane with certain direction injecting face and pass through There is the polarized light separating plate of the character of the inclined linear light of straight line of orthogonal vibration plane；In linear polarization The elliptical polarization plate etc. of phase retardation film it is laminated with on plate.

Generally speaking linear polarization plate has and is fitted with on the one or both sides of above-mentioned polaroid The composition of the protecting film stated.In the case of the two sides of polaroid is fitted with protecting film, can be at this Adhesive phase is formed at least one surface of protecting film.When only laminating protection in the one side of polaroid In the case of film, binding agent can be formed on the surface (face of protecting film of not fitting) of polaroid Layer.Elliptical polarization plate is laminated with phase retardation film on linear polarization plate, and this linear polarization plate is general also There is composition same as described above.On elliptical polarization plate during stacking adhesive phase, generally at phase contrast Film side laminate adhesive oxidant layer.

Referring to the drawings, the tool of the optical component with adhesive phase when being polarization plates to optical component Style illustrates.In example shown in Fig. 1, will have the protecting film 3 of surface-treated layer 2 It is attached to the face with this surface-treated layer 2 opposite side and is constituted polarization plates in the one side of polaroid 1 10.The face with protecting film 3 opposite side of polaroid 1 arranges adhesive phase 20, constitutes band There is the polarization plates (with the optical component of adhesive phase) 25 of adhesive phase.This adhesive phase 20 can To be fitted on glass substrate 30 with the face with polarization plates 10 opposite side, for glass substrate 30 Will be described later.

The polarization plates 25 of the band adhesive phase shown in Fig. 2 is included in the polaroid 1 of polarization plates 10 The second protecting film 4 that another side is attached is in addition, identical with Fig. 1.Adhesive phase 20 layers It is laminated on the outer surface of the second protecting film 4.The polarization plates 25 of the band adhesive phase shown in Fig. 3 is included in The phase retardation film 7 that the another side of the polaroid 1 of polarization plates 10 is attached across interlayer adhesive 8, In addition, identical with Fig. 1.The polarization plates 25 of the band adhesive phase shown in Fig. 4 is included in polarization The phase retardation film 7 that the outer surface of the second protecting film 4 of plate 10 is attached across interlayer adhesive 8, In addition, identical with Fig. 2.In the example shown in Fig. 3 and Fig. 4, adhesive phase 20 is pasted Invest phase retardation film 7.

The surface-treated layer 2 being formed on the surface of protecting film 3 can be hard conating, antiglare layer, Anti-reflection layer, antistatic layer etc..Multiple layers in them can also be set.Such as Fig. 3 and Fig. 4 In the case of the such polarization plates of shown example 10 comprises phase retardation film 7, if middle-size and small-size liquid Crystal device, then as the example being suitable for of phase retardation film 7, can enumerate 1/4 wavelength plate.Now, In the way of typically the slow axis of the absorption axle of polaroid 1 with phase retardation film 7 being spent intersect by substantially 45 Configuration, but this angle the most also can be made relative to 45 degree of deviations one according to the characteristic of liquid crystal cells Determine degree.On the other hand, if the large-scale liquid crystal indicator such as TV, then for liquid crystal cells Phase difference compensation or the purpose of viewing angle compensation, with the characteristics match of this liquid crystal cells use have various The phase retardation film 7 of phase difference value.In the case of Gai, typically by absorption axle and the phase retardation film of polaroid 1 The slow axis of 7 is substantially orthogonal to be in or configures in the way of almost parallel relation.Using 1/4 wavelength In the case of plate constitutes phase retardation film 7, applicable use stretched film uniaxially or biaxially.It addition, going out In the case of the phase difference compensation of liquid crystal cells or the purpose of viewing angle compensation arrange phase retardation film 7, remove Uniaxially or biaxially beyond stretched film, it is also possible to will be also at thickness direction in addition to uniaxially or biaxially stretching On be orientated film, on support membrane, the phase contrast of coating of liquid crystalline etc. embodies material and to be allowed to orientation fixing Film etc. be referred to as the film of optical compensation films and use as phase retardation film 7.

Interlayer adhesive 8 as Fig. 3 and Fig. 4, it is common practice to use general (methyl) acrylic acid It is binding agent, but the adhesive phase of the present invention can certainly be used.As foregoing large-scale Liquid crystal indicator like that by the slow axis absorbing axle and phase retardation film 7 of polaroid 1 to be in substantially When the mode of orthogonal or almost parallel relation configures, it is also possible to replace interlayer adhesive 8 And use bonding agent.As bonding agent, include, for example and constituted by aqueous solution or aqueous dispersions, passed through Make to evaporate as the water of solvent and embody the water system bonding agent of bonding force, utilize ultraviolet irradiation to carry out Solidify and embody the ultraviolet hardening bonding agent etc. of bonding force.Polaroid 1 and protecting film 3,4 Laminating generally also use bonding agent to carry out.

The optical component of the band adhesive phase of present embodiment is that adhesive phase comprises the invention described above The component of adhesive composition, therefore adhesive phase is good with the adaptation of optical component and durability Good.According to the present invention, even if the surface of the optical component of adhesive phase of will fitting is at corona The surface activation process in the past carried out of reason, Cement Composite Treated by Plasma etc is not easy to the surface being activated, The band adhesive phase that adhesive phase is good with the adaptation of optical component and durability can also be obtained Optical component.Described herein process the surface being difficult to be activated for such as to enter through surface activation Contact angle rate of change during row sided corona treatment be less than 40% so that be less than 30% surface.Connect Feeler rate of change is usually more than 0.1%, is preferably more than 0.5%.

Contact angle rate of change is defined by following formula.After sided corona treatment, contact angle is at output After 0.3kW, line speed carried out 1 sided corona treatment to above-mentioned surface under conditions of 10m/ minute, 24 little contact angles constantly are placed in the environment of temperature 23 DEG C, relative humidity 60%.Contact angle is Contact angle to water, unit is " ° ".

Contact angle rate of change (%)=(contact angle after contact angle-sided corona treatment before sided corona treatment)/ Contact angle before sided corona treatment } × 100

Above-mentioned contact angle rate of change when carrying out sided corona treatment is according to the composition material on the surface of optical component Material difference and different.It is the thermoplastic resin of less than 40% as contact angle rate of change, for (methyl) Acrylic resin, cellulose-based resin, polyester based resin, polycarbonate-based resin etc..By these The surface of the optical component that thermoplastic resin is constituted can be the table of the blooming such as protecting film, phase retardation film Face.

(3) the 3rd embodiments

Other of the optical component with adhesive phase of the present invention are preferred embodiment above-mentioned The outer surface of the adhesive phase of the optical component with adhesive phase of the first or second embodiment is again Stacking is fitted the embodiment of other optical components.These other optical components are suitably for glass substrate, figure In 1～Fig. 4, represent in the lump and the polarization plates with adhesive phase of the second embodiment is fitted in Situation on glass substrate 30.

As glass substrate 30, include, for example the glass substrate of liquid crystal cells, anti-dazzle glass, Sunglasses glass etc..As the material of glass substrate 30, include, for example soda-lime glass, low alkali Glass, alkali-free glass etc..Wherein, glass substrate is preferably the glass substrate of liquid crystal cells.

In liquid crystal cells generally on its two sides across adhesive phase laminated polarizing plate, these polarization plates In the middle of, can be that the polarization plates of the front face side (observation side) being only configured at liquid crystal cells is the present invention Polarization plates with adhesive phase, it is also possible to be the rear side (backlight side) being only configured at liquid crystal cells The polarization plates with adhesive phase that polarization plates is the present invention, it is also possible to be both be the present invention The polarization plates with adhesive phase.The type of drive of liquid crystal cells can be known any side Formula.The polarization plates being configured at rear side (backlight side) does not the most have surface-treated layer 2.Also may be used Brightness is set with the outer surface in the polarization plates being configured at rear side and improves film, condensing film, diffusion barrier etc. Known configurations is in the various bloomings of the rear side of liquid crystal cells.

Polarization plates with adhesive phase etc. go for liquid crystal with the optical component of adhesive phase In display device.Liquid crystal indicator such as can be suitable as comprising notebook type, desk-top, PDA The PC of (Personal Digital Assistant) etc.；Smart mobile phone, panel type terminal etc. Various mobile devices；TV；Vehicle-mounted display；Electronic dictionary；Digital camera；DV； Electronic desktop computer；The liquid crystal indicator of clock and watch use etc. uses.

Embodiment

Below, it is shown that the present invention is further illustrated by embodiment and comparative example, but this Bright do not limited by these examples.Hereinafter, represent that usage amount or part of content and % are as long as no especially Illustrate to be weight basis.

Tool is added in the reaction vessel possessing condensing tube, nitrogen ingress pipe, thermometer and blender Formed (being weight % during 100 weight % with monomer total amount) by the monomer shown in table 2 and use second Monomer mixture after acetoacetic ester dilution, while make its most oxygen-containing limit incite somebody to action with the air in nitrogen replaceable equipment Interior temperature rise up to 55 DEG C.Afterwards, add whole amount by azobis isobutyronitrile (polymerization initiator) It is dissolved in the solution of ethyl acetate gained.This temperature holding 1 hour after interpolation initiator, then, Limit will keep internal temperature at 54～56 DEG C of limits and ethyl acetate will be added continuously in reaction vessel, in (first Base) concentration of acrylic resin reaches moment of 35 weight % and stops the interpolation of ethyl acetate, then From add ethyl acetate start to through 12 hours for being incubated at a temperature of terminating in this.Finally, add Add ethyl acetate, reach the mode of 20 weight % according to the concentration making (methyl) acrylic resin It is adjusted, is prepared as the ethyl acetate solution of (methyl) acrylic resin.

Weight average molecular weight (Mw) and glass transition to (methyl) acrylic resin of gained Temperature (Tg) is measured.Using make as eastern Cao (strain) of chromatographic column " TSKgel XL " 4 Root and manufactured by Showa electrician (strain) and sold by clear light trading (strain) " Shodex GPC KF-802 " 1 piece amount to 5 be connected in series after be configured at GPC device, use oxolane conduct Eluent, at sample solution concentration 5mg/mL, sample import volume 100 μ L, temperature 40 DEG C, flow velocity 1mL/ Under conditions of minute, determine Mw by polystyrene standard conversion.Use SII The differential scanning calorimetry (DSC) (DSC) of NanoTechnology Co., Ltd. " EXSTAR DSC6000 ", under nitrogen atmosphere, measure temperature range-80～50 DEG C, programming rate 10 DEG C/min Under conditions of determine Tg.By monomer composition (weight %) of the monomer mixture that used and Mw and Tg of (methyl) acrylic resin of gained is summarized in table 2.

[table 2]

Abbreviation in " monomer composition " hurdle of table 2 refers to following monomer.

BA: n-butyl acrylate,

EHA: 2-EHA,

MA: acrylic acid methyl ester.,

AA: acrylic acid,

HEA: acrylic acid 2-hydroxy methacrylate.

(1) preparation of adhesive composition

Relative to the solid constituent of (methyl) acrylic resin (A) of gained in above-mentioned manufacture example 100 weight portions, respectively with the cross-linking agent (B) shown in amount (weight portion) mixture table 3 shown in table 3, Compound (C) and silane compound (E), reach 14 weight % according still further to making solid component concentration Mode add ethyl acetate, prepare the solution of adhesive composition.At the commodity bundle used containing molten In the case of agent, the use level of each gradation composition shown in table 3 be included in it with effective ingredient The parts by weight of meter.

[table 3]

In table 3, the details with each gradation composition shown in abbreviation is as follows.

Ethyl acetate solution (the solid of the trimethylolpropane adduct of B1: toluene di-isocyanate(TDI) Constituent concentration 75%), purchased from Japanese polyurethane (strain) " CORONATE L ",

The isocyanuric acid ester body of B2: hexamethylene diisocyanate, the liquid of effective ingredient substantially 100% Body, purchased from Japanese polyurethane (strain) " CORONATE HXR ",

C1: sodium acetate: (be dissolved in ethanol purchased from Wako Pure Chemical Industries (strain) and make 0.5 Weight % solution, is then added in adhesive composition.)、

C2: purchased from " the AM-130G " (methoxy shown in following formula in Xin Zhong village chemical industry (strain) Base polyethylene glycol acrylate),

[changing 7]

S1:3-glycidoxypropyltrime,hoxysilane, purchased from SHIN-ETSU HANTOTAI's chemical industry (strain) “KBM403”。

(2) making of adhesive phase

By each adhesive composition glue spreader of preparation in above-mentioned (1) so that dried thickness is The mode of 20 μm is coated on being formed by polyethylene terephthalate film of implementing that the demoulding processes The demoulding of stripping film (purchased from " PLR-382051 " of Lintec (strain), referred to as barrier film) processes face On, it is dried 1 minute at 100 DEG C, produces adhesive phase (adhesive sheet).

(3) making of the polarization plates of band adhesive phase

On uniaxial tension polyvinyl alcohol film obtained by gas absorption quantity iodine the one of the polaroid of thick 23 μm Across the first protecting film formed by thermoplastic resin described in bonding agent laminating table 4 on individual face, Another face uses that bonding agent unlike those described above laminating is formed by (methyl) acrylic resin Two protecting film, thus make polarization plates.Then, the outer surface to the first protecting film, at output 0.3kW, line speed carry out 1 sided corona treatment under conditions of 10m/ minute.Then, at this electricity Adhesive phase that dizzy process face utilizes laminating machine to fit in above-mentioned (2) to make with barrier film opposite side Face (binding agent aspect) after, under conditions of temperature 23 DEG C, relative humidity 65%, carry out maintenance, Obtain the polarization plates of band adhesive phase.

The abbreviation described in " protecting film " hurdle of table 4 refers to following thermoplastic resin.

AC:(methyl) acrylic resin (based on contact angle rate of change defined above: 17.2%),

PE: polyester based resin (based on contact angle rate of change defined above: 14.7%),

CE: cellulose-based resin (based on contact angle rate of change defined above: 21.7%).

(4) evaluation of durability

After the polarization plates of the band adhesive phase made from above-mentioned (3) peels off barrier film, by this binding agent Aspect is attached to liquid crystal cells glass substrate (Corning in the way of forming Nicol crossed " the Eagle XG " of company) two sides, produce sample for evaluation.This sample is used to implement 3 kinds of following endurancings.

(endurancing)

Under the drying condition of temperature 80 DEG C keep 1000 hours heat resistant test,

In the environment of temperature 60 C, relative humidity 90% keep 1000 hours hot resistance test,

With holding 30 minutes under the drying condition of temperature 70 C, then doing temperature-40 DEG C Keep the operation of 30 minutes as 1 circulation under the conditions of dry, 500 circulations are repeated Heat shock resistance (HS) is tested.

Visualization respectively test after sample, have rated durability according to following metewand.Will Result is shown in Table 4.

A: can't see completely float, peel off, the cosmetic variation such as foaming,

B: be substantially not visible float, peel off, the cosmetic variation such as foaming,

C: see more float, peel off, the cosmetic variation such as foaming,

D: be clearly seen that float, peel off, the cosmetic variation such as foaming.

(5) evaluation during the adaptation of protecting film and adhesive phase and maintenance

The polarization plates of the band adhesive phase made from above-mentioned (3) cuts wide 25mm × long 150mm Test film.Then, after barrier film peeled off by this test film, it is fixed on (strain) Japanese system group system Closing force evaluate fixture, implement following disbonded test.Make test sheet rubber (material: neoprene Diene rubber, hardness: JIS A hardness 65) touch the surface of adhesive phase, and make this sheet rubber exist On test film reciprocal 20 times, thus with the surface of this sheet rubber frictional adhesion oxidant layer.Test rubber The moving direction of sheet is parallel with the width of test film.

The surface of the adhesive phase side of the test film after above-mentioned disbonded test is observed.In office In one embodiment comparative example, an end-to-side adhesion of the width of the test film after disbonded test Oxidant layer is peeling-off, remains in another end-to-side adhesion oxidant layer part.Obtain the adhesive phase of residual Position (position of the length direction of test film), measures the distance conduct from above-mentioned one end to this position Peel distance.Show the result in table 4.

In any embodiment comparative example, it is adhesive phase and the maintenance of 3 days during using maintenance Period is the adhesive phase of 7 days, makes the polarization plates of band adhesive phase, carries out disbonded test.If supporting Protect period be peel distance when 7 days be below 15mm, then protecting film and adhesive phase is closely sealed Property deserves to be called good.If it addition, be peel distance when 3 days during maintenance with maintenance during be 7 It time the difference of peel distance be below 5mm, then the face of the shortening during maintenance deserves to be called pole For favorably.Be explained, in comparative example 2, use contact angle rate of change be 56.3% ring-type In the case of polyolefin-based resins film replaces (methyl) acrylic resin film to be used as protecting film, support Protect period be 3 days, 7 days time peel distance be respectively 14mm, 11mm, it addition, based on upper The durability stating assay method is the best.

[table 4]

Tool is added in the reaction vessel possessing condensing tube, nitrogen ingress pipe, thermometer and blender Formed (being weight % during 100 weight % with monomer total amount) by the monomer shown in table 5 and use second Monomer mixture after acetoacetic ester dilution, while make its most oxygen-containing limit incite somebody to action with the air in nitrogen replaceable equipment Interior temperature rise up to 55 DEG C.Afterwards, add whole amount by azobis isobutyronitrile (polymerization initiator) It is dissolved in the solution of ethyl acetate gained.This temperature holding 1 hour after interpolation initiator, then, Limit will keep internal temperature at 54～56 DEG C of limits and ethyl acetate will be added continuously in reaction vessel, in (first Base) concentration of acrylic resin reaches moment of 35 weight % and stops the interpolation of ethyl acetate, then From add ethyl acetate start to through 12 hours for being incubated at a temperature of terminating in this.Finally, add Add ethyl acetate, reach the mode of 20 weight % according to the concentration making (methyl) acrylic resin It is adjusted, is prepared as the ethyl acetate solution of (methyl) acrylic resin.

Weight average molecular weight (Mw) and glass transition to (methyl) acrylic resin of gained Temperature (Tg) is measured.Using make as eastern Cao (strain) of chromatographic column " TSKgel XL " 4 Root and manufactured by Showa electrician (strain) and sold by clear light trading (strain) " Shodex GPC KF-802 " 1 piece amount to 5 be connected in series after be configured at GPC device, use oxolane conduct Eluent, at sample solution concentration 5mg/mL, sample import volume 100 μ L, temperature 40 DEG C, flow velocity 1mL/ Under conditions of minute, determine Mw by polystyrene standard conversion.Use SII The differential scanning calorimetry (DSC) (DSC) of NanoTechnology Co., Ltd. " EXSTAR DSC6000 ", under nitrogen atmosphere, measure temperature range-80～50 DEG C, programming rate 10 DEG C/min Under conditions of determine Tg.By monomer composition (weight %) of the monomer mixture that used and Mw, Mw/Mn and Tg of (methyl) acrylic resin of gained are summarized in table 5.

[table 5]

Abbreviation in table 5 " monomer composition " hurdle refers to following monomer.

BA: n-butyl acrylate,

EHA: 2-EHA,

MA: acrylic acid methyl ester.,

AA: acrylic acid,

HEA: acrylic acid 2-hydroxy methacrylate,

PEA: acrylic acid 2-phenoxy ethyl,

PEA2: acrylic acid 2-(2-phenoxy group) ethyl ester,

BMAM:N-(butoxymethyl) acrylamide.

(1) preparation of adhesive composition

Relative to the solid constituent of (methyl) acrylic resin (A) of gained in above-mentioned manufacture example 100 weight portions, respectively with the cross-linking agent (B) shown in amount (weight portion) mixture table 6 shown in table 6, Compound (C), ionic compound (D) and silane compound (E), according still further to making solid constituent Concentration reaches the mode of 14 weight % and adds ethyl acetate, prepares the solution of adhesive composition.? In the case of the commodity bundle that used is solvent-laden, the use level of each gradation composition shown in table 6 is wherein The parts by weight as active ingredients comprised.

[table 6]

In table 6, the details with each gradation composition shown in abbreviation is as follows.

C1: sodium acetate: (be dissolved in acetic acid purchased from Wako Pure Chemical Industries (strain) and make 3.3 Weight % solution, is then added in adhesive composition.)、

C2-1: purchased from " AM-130G " in Xin Zhong village chemical industry (strain) (shown in following formula Methoxylated polyethylene glycol acrylate),

[changing 8]

C2-2: purchased from " M-130G " in Xin Zhong village chemical industry (strain) (shown in following formula Methoxylated polyethylene glycol methacrylate),

[changing 9]

D1:N-octyl group-4-picoline hexafluorophosphoric acid ester,

(2) making of adhesive phase

(3) making of the polarization plates of band adhesive phase

On uniaxial tension polyvinyl alcohol film obtained by gas absorption quantity iodine the one of the polaroid of thick 23 μm Across the first protecting film formed by thermoplastic resin described in bonding agent laminating table 7 on individual face, Another face uses that bonding agent unlike those described above laminating is formed by (methyl) acrylic resin Two protecting film, thus make polarization plates.Then, the outer surface to the first protecting film, at output 0.3kW, line speed carry out 1 sided corona treatment under conditions of 10m/ minute.Then, at this electricity Adhesive phase that dizzy process face utilizes laminating machine to fit in above-mentioned (2) to make with barrier film opposite side Face (binding agent aspect) after, under conditions of temperature 23 DEG C, relative humidity 65%, carry out maintenance, Obtain the polarization plates of band adhesive phase.

The abbreviation described in " protecting film " hurdle of table 7 refers to following thermoplastic resin.

CO: cyclic polyolefin hydrocarbon system resin (based on contact angle rate of change defined above: 56.3%),

AC:(methyl) acrylic resin (based on contact angle rate of change defined above: 17.2%).

(4) evaluation of durability

(endurancing)

Visualization respectively test after sample, have rated durability according to following metewand.Will Result is shown in Table 7.

C: see more float, peel off, the cosmetic variation such as foaming,

(5) the peeling force evaluation of the optical component of band adhesive phase

The polarization plates of the band adhesive phase made from above-mentioned (3) cuts wide 25mm × long 150mm Test film.Then, after barrier film peeled off by this test film, this binding agent aspect is utilized and attaches dress Put (trade name " Lamipacker " that Fujipla (strain) makes) and be attached at liquid crystal cells glass base Plate (trade name " EAGLE XG ", purchased from Corning Incorporated, alkali-free glass plate).By the patch of gained Exist with the test film (being pasted with the optical component of the band adhesive phase of glass substrate) of glass substrate With temperature 50 C, pressure 5kgf/cm in autoclave²(490.3kPa) pressurize 20 minutes.Divide again Not in the atmosphere of temperature 23 DEG C in the condition of 24 hours and the atmosphere of temperature 50 C 48 hours Under the conditions of stand.Sample after standing is clamped in cupping machine ((strain) Shimadzu Seisakusho Ltd. system " AUTOGRAPH AGS-X "), in the environment of temperature 23 DEG C, relative humidity 55%, Peel off along 180 ° of directions with the draw speed condition of 300mm/ minute.By now measure Peel strength is evaluated as peeling force.Here, will take care of in the atmosphere of temperature 23 DEG C 24 hours Under the conditions of peeling force be set to P23, will in the atmosphere of temperature 50 C the keeping condition of 48 hours Under peeling force be set to P50.Show the result in table 7.

[table 7]

Symbol description

1 polaroid, 2 surface-treated layers, 3,4 protecting film, 7 phase retardation films, 8 interlayer adhesives, 10 polarization plates, 20 adhesive phases, the polarization plates of 25 band adhesive phases, 30 glass substrates.

Claims

1. an adhesive composition, it contains:

Containing Component units and its content from (methyl) acrylic monomer with hydroxyl is 3.5 Below weight % and (methyl) acrylic resin (A) that glass transition temperature is less than-25 DEG C 100 weight portions；

When containing described acylate (C-1), its content is relative to described (methyl) acrylic acid Be resin (A) 100 weight portion be 0.0001～5 weight portions,

When comprising compound (C-2) of alkylidene epoxide described in containing, its content is relative to described (methyl) acrylic resin (A) 100 weight portion is 0.1～5 weight portions.

Adhesive composition the most according to claim 1, wherein, described in comprise alkylidene epoxide Compound (C-2) for comprise at least 1 double bond and at least 1 alkylenedioxy group in intramolecular Compound.

Adhesive composition the most according to claim 1, wherein, described from having hydroxyl The content of the Component units of (methyl) acrylic monomer is more than 0.5 weight %.

Adhesive composition the most according to claim 1, it is possibly together with ionic compound (D).

Adhesive composition the most according to claim 1, it is possibly together with silane compound (E).

Adhesive composition the most according to claim 1, wherein, will be by cyclic polyolefin hydrocarbon system Described adhesive composition is shaped and by the adhesive composition of stratiform with stratiform on the film of resin formation To be laminated in after the state of alkali-free glass plate is taken care of 24 hours in the environment of temperature 23 DEG C from this alkali-free Peeling force when glass plate is peeled off is set to P (CO) 23, and

By on the film by cyclic polyolefin hydrocarbon system resin formation with stratiform shape described adhesive composition, And by the adhesive composition of stratiform to be laminated in the state environment at temperature 50 C of alkali-free glass plate When after lower keeping 48 hours, peeling force when this alkali-free glass plate is peeled off is set to P (CO) 50,

Ratio i.e. P (CO) 50/P (CO) 23 of described P (CO) 50 and described P (CO) 23 is more than 3.2.

Adhesive composition the most according to claim 1, wherein, will be by (methyl) propylene Acid is to shape described adhesive composition and by the binding agent group of stratiform with stratiform on the film of resin formation Compound be laminated in the state of alkali-free glass plate in the environment of temperature 23 DEG C after keeping 24 hours from this Peeling force when alkali-free glass plate is peeled off is set to P (AC) 23, and

The combination of described binding agent will be shaped with stratiform on the film formed by (methyl) acrylic resin Thing and by the adhesive composition of stratiform to be laminated in the state ring at temperature 50 C of alkali-free glass plate When under border, after keeping 48 hours, peeling force when this alkali-free glass plate is peeled off is set to P (AC) 50,

Ratio i.e. P (AC) 50/P (AC) 23 of described P (AC) 50 and described P (AC) 23 is more than 3.2.

Adhesive composition the most according to claim 1, it contains described acylate (C- 1) and described in comprise the compound (C-2) of alkylidene epoxide,

The content of described acylate (C-1) is relative to described (methyl) acrylic resin (A) 100 weight portions are 0.0001～0.1 weight portion,

The content of the described compound (C-2) comprising alkylidene epoxide is relative to described (methyl) third Olefin(e) acid system resin (A) 100 weight portion is 0.1～5 weight portions.

9. an adhesive phase, it comprises the binding agent combination according to any one of claim 1～8 Thing.

10. an optical component for band adhesive phase, it comprises optical component and the power being laminated thereon Profit requires the adhesive phase described in 9.

The optical component of 11. band adhesive phases according to claim 10, wherein, described in stacking The surface of the described optical component of the adhesive phase contact angle rate of change when carrying out sided corona treatment is Less than 40%.

The optical component of 12. band adhesive phases according to claim 11, wherein, described optics Component comprises polaroid and the protecting film being laminated thereon,

Described surface is the surface of described protecting film.

The optical component of 13. band adhesive phases according to claim 11, wherein, described surface For the surface through sided corona treatment.

14. according to the optical component of the band adhesive phase according to any one of claim 10～13, its Also comprise the glass substrate being layered on described adhesive phase.

The optics of 15. 1 kinds of band adhesive phases, it is to have resin molding and be laminated in this resin molding The optical component of band adhesive phase of adhesive phase at least one face,

Described adhesive phase comprises the adhesive composition according to any one of claim 1～8,

By the optics of this band adhesive phase to utilize described adhesive phase to be laminated in alkali-free glass The state of plate is stripping when this alkali-free glass plate is peeled off after keeping 24 hours in the environment of temperature 23 DEG C From power be set to P23 and

By the optics of this band adhesive phase to utilize described adhesive phase to be laminated in alkali-free glass plate State stripping when this alkali-free glass plate is peeled off after keeping 48 hours in the environment of temperature 50 C When power is set to P50,

The ratio i.e. P50/P23 of described P50 and described P23 is more than 3.2.