CN105969262B - Adhesive composition, adhesive phase and the optical component with adhesive phase - Google Patents

Abstract

The present invention provides a kind of adhesive composition, adhesive phase comprising the adhesive composition and the optical component with adhesive phase for having the adhesive phase, the content that described adhesive composition contains the Component units from (methyl) acrylic monomer with hydroxyl is 3.5 weight % or less and glass transition temperature is -25 DEG C of 100 parts by weight of (methyl) acrylic resin (A) below, aromatic isocyanate system crosslinking agent (B) 0.3~1 parts by weight, with at least one kind of compound (C) in the compound (C-2) selected from acylate (C-1) and comprising alkylidene oxygroup, when containing acylate (C-1), its content is 0.0001~5 parts by weight, when containing compound (C-2) comprising alkylidene oxygroup, its content is 0.1~5 weight Part.

Description

Adhesive composition, adhesive phase and the optical component with adhesive phase

Technical field

The present invention relates to adhesive composition, the adhesive phase comprising the adhesive composition and has the adhesive phase Optical component.

Background technique

The polarization plates made of the one or both sides stacking fitting protective film of polarizing film are in liquid crystal display device, Organic Electricity Image display devices, portable phone especially in recent years, smart phone, the plate ends such as photoluminescence (organic EL) display device Widely used optical component in the various mobile devices at end etc.The optical component of polarization plates etc is mostly by adhesive phase Other components (such as the optical components such as liquid crystal cells in liquid crystal display device) are fitted in use (referring for example to Japanese Unexamined Patent Publication 2010-229321 bulletin).Thus, for example polarization plates are in most cases to be previously provided with adhesive in one face The form of the polarization plates with adhesive phase of layer circulates on the market.

Summary of the invention

Adhesive composition requirement durability used in adhesive phase for optical component fitting.That is, fitting in Optical component and the adhesive phase for being assembled into image table showing device etc. be placed under high temperature or hot and humid environment sometimes or In the environment of being placed on high temperature and low temperature repeatedly, adhesive phase is required to inhibit under these circumstances with adjoining Optical component the issuable unfavorable condition of change in size.As the unfavorable condition, comprising: in adhesive phase and abut it Optical component interface on float or remove, the foaming of adhesive phase.

But durability of previous adhesive composition when fitting in optical component in the form of adhesive phase is sometimes not It sufficiently, is to be handled also not even across surface activations such as sided corona treatments on the surface that will be bonded the optical component of adhesive phase In the case where the surface easily effectively activated, durability is especially insufficient.

It is to be not easy to be had processing by surface activation the purpose of the present invention is to provide the surface even if optical component The surface of effect ground activation, durability when fitting in the surface in the form of adhesive phase also good adhesive composition, packet Adhesive phase containing the adhesive composition and the optical component with adhesive phase for having the adhesive phase.

The present invention provides adhesive composition as shown below, adhesive phase and the optical component with adhesive phase.

[1] a kind of adhesive composition, contains:

Containing the Component units from (methyl) acrylic monomer with hydroxyl and its content be 3.5 weight % with Under and glass transition temperature be -25 DEG C of 100 parts by weight of (methyl) acrylic resin (A) below；

Aromatic isocyanate system crosslinking agent (B) 0.3~1 parts by weight；With

At least one kind of compound (C) in compound (C-2) selected from acylate (C-1) and comprising alkylidene oxygroup,

When containing above-mentioned acylate (C-1), content is relative to above-mentioned 100 weight of (methyl) acrylic resin (A) Amount part is 0.0001~5 parts by weight,

When containing above-mentioned compound (C-2) comprising alkylidene oxygroup, content is relative to above-mentioned (methyl) acrylic acid Be 100 parts by weight of resin (A) be 0.1~5 parts by weight.

[2] adhesive composition according to [1], wherein the above-mentioned compound (C-2) comprising alkylidene oxygroup be Intramolecular includes the compound of at least one double bond and at least one alkylenedioxy group.

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

[4] adhesive composition according to any one of [1]~[3], also contains ionic compound (D).

[5] adhesive composition according to any one of [1]~[4], also contains silane compound (E).

[6] adhesive composition according to any one of [1]~[5] will be formed by cyclic polyolefin hydrocarbon system resin Film on above-mentioned adhesive composition is shaped with stratiform and the adhesive composition of stratiform is laminated in the shape of alkali-free glass plate Peeling force when state is removed after taking care of 24 hours in the environment of 23 DEG C of temperature from the alkali-free glass plate is set as P (CO) 23, and

Above-mentioned adhesive composition will be shaped with stratiform on the film formed by cyclic polyolefin hydrocarbon system resin and by stratiform Adhesive composition is to be laminated in after the state of alkali-free glass plate is taken care of 48 hours in the environment of temperature 50 C from the alkali-free glass When peeling force when glass plate is removed is set as P (CO) 50,

Above-mentioned P (CO) 50 is 3.2 or more with above-mentioned P (CO) the ratio between 23 (P (CO) 50/P (CO) 23).

[7] adhesive composition according to any one of [1]~[5], wherein will be by (methyl) acrylic acid series tree Rouge, which is formed on film, shapes above-mentioned adhesive composition and by the adhesive composition of stratiform with stratiform to be laminated in alkali-free glass plate State in the environment of 23 DEG C of temperature take care of 24 hours after from the alkali-free glass plate remove when peeling force be set as P (AC) 23, And

On the film formed by (methyl) acrylic resin above-mentioned adhesive composition will be shaped with stratiform and by stratiform Adhesive composition to be laminated in after the state of alkali-free glass plate is taken care of 48 hours in the environment of temperature 50 C from the alkali-free When peeling force when glass plate is removed is set as P (AC) 50,

Above-mentioned P (AC) 50 is 3.2 or more with above-mentioned P (AC) the ratio between 23 (P (AC) 50/P (AC) 23).

[8] adhesive composition according to any one of [1]~[7], containing above-mentioned acylate (C-1) and on The compound (C-2) comprising alkylidene oxygroup is stated,

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

The content of the above-mentioned compound (C-2) comprising alkylidene oxygroup is relative to above-mentioned (methyl) acrylic resin (A) 100 parts by weight are 0.1~5 parts by weight.

[9] a kind of adhesive phase, it includes the adhesive compositions described in any one of [1]~[8].

[10] a kind of optical component with adhesive phase, it includes glue described in optical component and [9] that are laminated thereon Mixture layer.

[11] optical component with adhesive phase according to [10], wherein the above-mentioned light of above-mentioned adhesive phase is laminated Learning contact angular rate of change of the surface of component when carrying out sided corona treatment is 40% or less.

[12] optical component with adhesive phase according to [11], wherein above-mentioned optical component include polarizing film and The protective film being laminated thereon,

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

[13] optical component with adhesive phase according to [11] or [12], wherein above-mentioned surface is by corona The surface of processing.

[14] optical component with adhesive phase according to any one of [10]~[13], also includes to be layered in State the glass substrate on adhesive phase.

[15] a kind of optical component with adhesive phase, be have resin film and be laminated in the resin film at least one The optical component with adhesive phase of the adhesive phase in face,

Above-mentioned adhesive phase includes adhesive composition described in any one of [1]~[8],

The optical component with adhesive phase is being existed with the state for being laminated in alkali-free glass plate using above-mentioned adhesive phase In the environment of 23 DEG C of temperature take care of 24 hours after from the alkali-free glass plate remove when peeling force be set as P23 and

By the optical component with adhesive phase with alkali-free glass plate is laminated in using above-mentioned adhesive phase state in temperature When peeling force when removing after taking care of 48 hours in the environment of 50 DEG C of degree from the alkali-free glass plate is set as P50,

The ratio between above-mentioned P50 and above-mentioned P23 (P50/P23) are 3.2 or more.

According to the present invention it is possible to provide the good adhesive composition of durability, the bonding comprising the adhesive composition Oxidant layer and the optical component with adhesive phase for having the adhesive phase.

Detailed description of the invention

Fig. 1 is the schematic sectional view for indicating an example of the optical component of the invention with adhesive phase.

Fig. 2 is another schematic sectional view for indicating the optical component of the invention with adhesive phase.

Fig. 3 is schematic sectional view that indicate the optical component of the invention with adhesive phase and another.

Fig. 4 is yet another schematic sectional view for indicating the optical component of the invention with adhesive phase.

Specific embodiment

<adhesive composition>

(1) (methyl) acrylic resin (A)

(methyl) acrylic resin (A) is to contain the Component units from (methyl) acrylic monomer with hydroxyl Polymer, the composition list preferably in addition to this composition unit also containing (methyl) acrylate shown in following formula (I)s Polymer of the member as principal component.In the present specification, " (methyl) acrylic acid " refers to acrylic acid and/or methacrylic acid, note " (methyl) " whens making (methyl) acrylate etc. is also identical meaning.

[changing 1]

In above-mentioned formula (I), R¹Indicate hydrogen atom or methyl, R²Indicate the carbon number that can be replaced by the alkoxy of carbon number 1~10 1~14 alkyl or can be by the aralkyl for the carbon number 7~21 that the alkoxy of carbon number 1~10 replaces.R²It preferably can be by The alkyl for the carbon number 1~14 that the alkoxy of carbon number 1~10 replaces.

As (methyl) acrylate shown in formula (I), (methyl) alkyl acrylate can be enumerated, concrete example includes: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) n-butyl acrylate, (first Base) n-octyl, (methyl) lauryl acrylate etc moieties be (methyl) alkyl acrylate of straight-chain； (methyl) isopropyl acrylate, (methyl) isobutyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid are different pungent The moieties of ester etc are (methyl) alkyl acrylate etc. of branched.Moieties in (methyl) alkyl acrylate Carbon number be preferably 1~8, more preferably 1~6.

In R²When for alkyl after being replaced by alkoxy, i.e. R²(methyl) propylene shown in formula (I) when for alkoxyalkyl The concrete example of acid esters includes (methyl) acrylic acid 2- methoxy acrylate, (methyl) ethioxy methyl esters etc..Above-mentioned alkoxy The carbon number of alkyl in alkyl is preferably 1~8, more preferably 1~6.The carbon number of alkoxy in above-mentioned alkoxyalkyl is preferred It is 1~8, more preferably 1~4.In R²For carbon number 7~21 aralkyl when formula (I) shown in (methyl) acrylate tool Body example 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 or two or more kinds may be used.Wherein, (first Base) acrylate preferably comprises (methyl) alkyl acrylate, more preferably comprising alkyl acrylate, further preferably comprising third Olefin(e) acid N-butyl.(methyl) acrylic resin (A) preferably comprises 50 weight % or more in the whole Component units for constituting it The Component units from n-butyl acrylate.It is of course also possible to also and in addition to it other than n-butyl acrylate (methyl) acrylate shown in formula (I).

The content of the Component units of (methyl) acrylate shown in formula (I) is in composition (methyl) acrylic resin It (A) is usually 60 weight % or more and less than 100 weight %, preferably 70~99.9 weight %, more in whole Component units Preferably 80~99.6 weight %.

(methyl) acrylic resin (A) contains the Component units from (methyl) acrylic monomer with hydroxyl. It improving the adaptation of adhesive phase and optical component containing this composition unit, be advantageous on the durability of adhesive phase.Tool (methyl) acrylic monomer for having hydroxyl is preferably (methyl) acrylate with hydroxyl.(methyl) propylene with hydroxyl The concrete example of acid esters includes: (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 3- hydroxy propyl ester, (methyl) acrylic acid 4- Hydroxybutyl, (methyl) acrylic acid 2- (2- hydroxyl-oxethyl) ethyl ester, (methyl) acrylic acid 2- or 3- chlorine-2-hydroxyl propyl ester etc (methyl) acrylic acid hydroxyl Arrcostab；The polyfunctional alcohol of diethylene glycol list (methyl) acrylate etc and (methyl) third Partial esterification object of olefin(e) acid etc..From the adaptation of adhesive phase and optical component, the durability (especially heat resistance) of adhesive phase From the perspective of, the monomer with hydroxyl is preferably (methyl) acrylate with hydroxyl, more preferably (methyl) acrylic acid Hydroxyl Arrcostab.The carbon number of moieties in the hydroxyl Arrcostab of (methyl) acrylic acid is preferably 1~8, more preferably It is 1~6.

The content of Component units from (methyl) acrylic monomer with hydroxyl is in composition (methyl) acrylic acid series In whole Component units of resin (A) for 3.5 weight % or less, preferably 3 weight % or less, more preferably 2.5 weight % with Under, further preferably 2 weight % or less.If the content of the Component units from (methyl) acrylic monomer with hydroxyl More than 3.5 weight %, then the durability of adhesive phase, especially heat resistance is insufficient.On the other hand, from (methyl) with hydroxyl The content of the Component units of acrylic monomer is usually 0.1 weight % or more, preferably 0.2 weight % or more, is more preferably 0.5 weight % or more.If the content of the Component units from (methyl) acrylic monomer with hydroxyl is less than 0.1 weight Measure %, then the adaptation of adhesive phase and optical component, adhesive phase durability the deficiencies of.

(methyl) acrylic resin (A) can be containing from addition to (methyl) acrylic monomer with hydroxyl The Component units of other monomers with polar functional group.The monomer with polar functional group preferably has polar functional group (methyl) acrylic monomer.As polar functional group possessed by the monomer, can enumerate carboxyl (free carboxy), amino, Heterocycle (such as epoxy group) etc..

The concrete example of other monomers with polar functional group includes: (methyl) acrylic acid, β-carboxy ethyl (methyl) third The monomer with carboxyl of olefin(e) acid ester etc；Acryloyl morpholine, caprolactam, n-vinyl-2-pyrrolidone, second Alkenyl pyridine, (methyl) tetrahydrofurfuryl acrylate, caprolactone modification tetrahydrofurfuryl acrylate, (methyl) acrylic acid 3,4- ring The monomer with heterocycle of oxygen cyclohexylmethyl, (methyl) glycidyl acrylate, 2,5-dihydrofuran etc；(methyl) The tool of acrylate, (methyl) acrylic acid N, N- dimethylaminoethyl, (methyl) dimethylaminoethyl methacrylate etc There is the monomer etc. of the amino different from heterocycle.Other monomers with polar functional group can be used alone only a kind, can also be simultaneously Use two or more.

Have in addition to (methyl) acrylic monomer with hydroxyl also and with other monomers with polar functional group, especially There is (methyl) acrylic monomer of carboxyl improving the adaptation of adhesive phase and optical component, the durability of adhesive phase It is advantageous in (especially heat resistance).

Composition list from other monomers with polar functional group, preferably (methyl) acrylic monomer with carboxyl The content of member is preferably 5 weight % or less in whole Component units of composition (methyl) acrylic resin (A), is more preferably 4 weight % or less.If the content of the Component units of the monomer from other with polar functional group is more than 5 weight %, exist The insufficient tendency of the durability of adhesive phase, especially heat resistance.On the other hand, from other monomers with polar functional group The content of Component units is usually 0.1 weight % or more in the case where containing its, is preferably 0.2 weight % or more, more preferable For 0.3 weight % or more.If the content of the Component units of the monomer from other with polar functional group less than 0.1 weight %, It is then difficult to confirm its using effect.It is all with polarity official including next self-contained (methyl) acrylic monomer with hydroxyl The Component units for the monomer that can be rolled into a ball are usually 0.1~8.5 in whole Component units of composition (methyl) acrylic resin (A) Weight %, preferably 0.2~7 weight %.

(methyl) acrylic resin (A) can be further included from having 1 olefinic double bond and extremely in the molecule The monomer of few 1 aromatic rings (wherein, does not include being equivalent to monomer shown in above-mentioned formula (I) or above-mentioned having polar functional group The monomer of monomer.) Component units.As suitable example, (methyl) acrylic monomer with aromatic rings can be enumerated.? This also includes neopentyl glycol benzoic ether (methyl) acrylate etc. in (methyl) acrylic monomer with aromatic rings, especially It is preferred that (the first with aromatic yloxy yl alkyl of (methyl) acrylate shown in following formula (II)s containing Phenoxyethyl etc Base) acrylate.(methyl) acrylate containing Phenoxyethyl etc. has 1 olefinic double bond and at least one in the molecule The monomer of aromatic rings can be used alone only a kind, and also two or more kinds may be used.

[changing 2]

In above-mentioned formula (II), R³Indicate that hydrogen atom or methyl, n indicate 1~8 integer, R⁴Indicate hydrogen atom, alkyl, aralkyl Base or aryl.In R⁴In the case where alkyl, carbon number can be 1~9 or so, in R⁴In the case where aralkyl, carbon number can 7~11 or so are thought, in addition, in R⁴In the case where aryl, carbon number can be 6~10 or so.

As the composition R in formula (II)⁴Carbon number 1~9 alkyl, methyl, butyl, nonyl etc. can be enumerated, as carbon number 7 ~11 aralkyl can enumerate benzyl, phenethyl, menaphthyl etc., as the aryl of carbon number 6~10, can enumerate phenyl, toluene Base, naphthalene etc..

The concrete example of (methyl) acrylate shown in formula (II) containing Phenoxyethyl includes (methyl) acrylic acid 2- benzene Oxygroup ethyl ester, (methyl) acrylic acid 2- (2- phenoxy group) ethyl ester, ethylene-oxide-modified nonyl phenol (methyl) propylene Acid esters, (methyl) acrylic acid 2- (adjacent phenylphenoxy) ethyl ester etc..Wherein, (methyl) acrylate containing Phenoxyethyl is preferred Include (methyl) acrylic acid 2- phenoxy ethyl, (methyl) acrylic acid 2- (adjacent phenylphenoxy) ethyl ester and/or (methyl) propylene Sour 2- (2- phenoxy group) ethyl ester.

Whole of the content of Component units from the monomer with aromatic rings in composition (methyl) acrylic resin (A) It is usually in Component units 0~20 weight % (such as 6~12 weight %).But in order to make (methyl) acrylic resin (A) Glass transition temperature be aftermentioned prescribed limit, it is sometimes preferred to without the Component units from the monomer with aromatic rings.

(methyl) acrylic resin (A) can be containing from except (methyl) acrylic acid shown in formula described above (I) It is the monomer other than monomer, the monomer with polar functional group and the monomer with aromatic rings (hereinafter, also referred to as " other lists Body ".) Component units.The concrete example of other monomers includes from (methyl) acrylic acid in the molecule with ester ring type construction It is the Component units of monomer ((methyl) acrylate preferably in the molecule with ester ring type construction), from styrenic monomers Component units, the Component units from vinyl monomer, from the molecule with multiple (methyl) acryloyl groups list The Component units of body, Component units from (methyl) acrylamide compound etc..Other monomers can be used alone only a kind, Also two or more kinds may be used.

In the molecule with ester ring type construction (methyl) acrylate in ester ring type be configured to carbon number be usually 5 with Upper, preferably 5~7 or so cycloalkane construct.The concrete example of (methyl) acrylate with ester ring type construction includes (first Base) isobornyl acrylate, (methyl) cyclohexyl acrylate, (methyl) dicyclopentyl acrylate, (methyl) acrylic acid ring ten Dialkyl ester, (methyl) acrylic methyl cyclohexyl, (methyl) acrylic acid 3-methyl cyclohexanol ester, (methyl) acrylic acid tert-butyl ring Own ester, (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, butylstyrene, hexyl styrene, heptyl benzene The ring-alkylated styrenes of ethylene, octyl styrene etc；Fluorobenzene ethene, chlorostyrene, bromstyrol, Dowspray 9, iodobenzene second The halogenated styrenes of alkene etc；Nitrostyrolene, acetylbenzene ethylene, methoxy styrene, divinylbenzene etc..

The concrete example of vinyl monomer includes: vinyl acetate, vinyl propionate, vinyl butyrate, 2 ethyl hexanoic acid The fatty acid vinyl ester of vinyl acetate, vinyl laurate etc；The vinyl halides of vinyl chloride, vinyl bromide etc；Vinylidene chloride Etc meta-halo ethylene；The nitrogenous aromatic vinyl of vinylpyridine, vinyl pyrrolidone, vinyl carbazole etc；Fourth The conjugate diene monomer of diene, isoprene, chlorobutadiene etc；Acrylonitrile, methacrylonitrile etc..

The concrete example of the monomer with multiple (methyl) acryloyl groups includes 1,4-butanediol two (methyl) third in the molecule Olefin(e) acid ester, 1,6- hexylene glycol two (methyl) acrylate, 1,9- nonanediol two (methyl) acrylate, ethylene glycol two (methyl) third Olefin(e) acid ester, diethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) propylene The monomer in the molecule with 2 (methyl) acryloyl groups of acid esters etc；Trimethylolpropane tris (methyl) acrylate it The monomer etc. in the molecule with 3 (methyl) acryloyl groups of class.

The concrete example of (methyl) acrylamide compound includes 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) propylene Amide, N, N- diethyl (methyl) acrylamide, N- isopropyl (methyl) acrylamide, N- (3- dimethylamino-propyl) (methyl) Acrylamide, N- (1,1- dimethyl -3- oxo butyl) (methyl) acrylamide, N- (2- (2- oxo -1- imidazolinyl) second Base) (methyl) acrylamide, 2- Acryloyl amino-2- methyl-1-propane sulfonic acid, N- (methoxy) acrylamide, N- (second Oxygroup methyl) (methyl) acrylamide, N- (propoxy methyl) (methyl) acrylamide, N- (1- methylethoxy ylmethyl) (first Base) acrylamide, N- (1- methyl propoxy methyl) (methyl) acrylamide, N- (2- methyl propoxy methyl) (methyl) propylene Amide (alias: N- (isobutoxymethyl) (methyl) acrylamide), N- (butoxymethyl) (methyl) acrylamide, N- (1, 1- dimethylethoxy ylmethyl) (methyl) acrylamide, N- (2- methoxy ethyl) (methyl) acrylamide, N- (2- ethyoxyl Ethyl) (methyl) acrylamide, N- (2- Among) (methyl) acrylamide, N- (2- (1- methyl ethoxy) ethyl) (methyl) acrylamide, N- (2- (1- methyl propoxyl group) ethyl) (methyl) acrylamide, N- (2- (2- methyl propoxyl group) second Base) (methyl) acrylamide (alias: N- (2- isobutoxyethy) (methyl) acrylamide), N- (2- butoxyethyl group) (first Base) acrylamide, N- (2- (1,1- dimethylethyloxy) ethyl) (methyl) acrylamide etc..Wherein, it is preferable to use N- (methoxy Ylmethyl) acrylamide, N- (ethoxyl methyl) acrylamide, N- (propoxy methyl) acrylamide, N- (butoxymethyl) Acrylamide, N- (2- methyl propoxy methyl) acrylamide.

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

Adhesive composition can belong to (methyl) acrylic acid series of (methyl) acrylic resin (A) containing two or more Resin.In addition, adhesive composition can contain other (methyl) acrylic acid series different from (methyl) acrylic resin (A) Resin.The example of other (methyl) acrylic resins is with the structure for coming from (methyl) acrylic monomer shown in formula (I) At unit and without (methyl) acrylic resin of polar functional group.Wherein, adhesive composition preferably comprises (methyl) third Olefin(e) acid system resin (A) is used as principal component, and the content of (methyl) acrylic resin (A) is in all (methyl) acrylic resins Summation in preferably 60 weight % or more, more preferably 80 weight % or more, further preferably 90 weight % or more.

(methyl) acrylic resin (A) utilizes the glass transition temperature (Tg) of differential scanning calorimetry (DSC) (DSC) measurement It is -25 DEG C or less, preferably -30 DEG C or less.According to the sheet for containing Tg being -25 DEG C of (methyl) acrylic resins (A) below The adaptation of adhesive phase and optical component, the durability of adhesive phase can be improved in the adhesive composition of invention.From durable Property from the perspective of, the Tg of (methyl) acrylic resin (A) is usually -55 DEG C or more, is preferably -50 DEG C or more.

In addition, being combined according to containing the adhesive of the invention that Tg is -25 DEG C of (methyl) acrylic resins (A) below Object can be realized the shortening of the curing time of adhesive phase.That is, generally for make cross-linking reaction to being obtained appropriate operation Property, the degree of processability and adhesive phase (adhesive sheet) is conserved, as a result: adhesive composition according to the present invention, The curing time of adhesive phase needed for sufficiently carrying out cross-linking reaction can be shortened.

What the standard polystyren that (methyl) acrylic resin (A) is based on gel permeation chromatography (GPC) converted divides equally again Son amount (Mw) is preferably in 500,000~2,000,000 range, is more preferably in 600,000~1,800,000 range.If Mw is 500,000 or more, Then the adaptation of the adhesive phase under hot and humid environment and optical component improves, between adhesive phase and optical component Generate the tendency that a possibility that floating, removing reduces, and the tendency that the re-workability in adhesive phase improves.In addition, if Even if Mw is 2,000,000 hereinafter, then when adhesive phase is fitted in optical component, the size of optical component changes, adhesive Layer is also easy to follow the change in size and change, therefore in the adaptation of adhesive phase and optical component, adhesive phase It is advantageous in terms of durability.In addition, the optical component with adhesive phase is applied to liquid crystal watch according to above-mentioned tracing ability When showing device, there is no difference between the brightness of the peripheral part of liquid crystal cells and the brightness of central part, there is the white (Bai order け of leakage), face The tendency that color unevenness is suppressed.Molecular weight shown in the ratio between weight average molecular weight (Mw) and number-average molecular weight (Mn) (Mw/Mn) point Cloth is usually 2~10 or so, preferably 3~7.

(methyl) acrylic resin (A), can any other (methyl) acrylic resins for example can benefit Well known to solution polymerization process, mass polymerization, suspension polymerization, emulsion polymerization etc. method manufactures.(methyl) acrylic acid It is in the manufacture of resin usually using polymerization initiator.Whole used in manufacture relative to (methyl) acrylic resin 100 parts by weight of total amount of monomer, use the polymerization initiator of 0.001~5 parts by weight or so.In addition, (methyl) acrylic acid series tree Rouge also can use to be manufactured in method that such as ultraviolet light isoreactivity energy-ray is polymerize.

As polymerization initiator, thermal polymerization, Photoepolymerizationinitiater initiater etc. are used.As Photoepolymerizationinitiater initiater, can arrange Citing such as 4- (2- hydroxyl-oxethyl) phenyl (2- hydroxyl -2- propyl) ketone.As thermal polymerization, it can be mentioned, for example 2, 2 '-azodiisobutyronitriles, 2,2 '-azos bis- (2- methylbutyronitriles), 1,1 '-azo bis- (hexamethylene -1- formonitrile HCNs), 2,2 '-azos Bis- (2,4- methyl pentane nitriles), 2,2 '-azos bis- (2,4- dimethyl -4- methoxyl-valeronitriles), 2, the 2 '-bis- (2- of azo of dimethyl - Methylpropionate), the azo compounds of 2,2 '-azos bis- (2- hydroxymethyl propionitrile) etc；Lauroyl peroxide, tert-butyl Hydrogen peroxide, benzoyl peroxide, tert butyl peroxy benzoate, cumyl hydroperoxide, dicetyl peroxydicarbonate diisopropyl Ester, dipropyl peroxydicarbonate, new peroxide tert-butyl caprate, the peroxidating pivalic acid tert-butyl ester, peroxidating (3,5,5- front threes Base hexanoyl) etc organic peroxide；The inorganic peroxide etc. of potassium peroxydisulfate, ammonium persulfate, hydrogen peroxide etc.Separately Outside, and the redox series initiators etc. of having used peroxide and reducing agent can also be used as polymerization initiator use.

As the manufacturing method of (methyl) acrylic resin, the preferred solution polymerization process in method illustrated above.It is molten An example of liquid polymerization is to mix used monomer and organic solvent, under nitrogen atmosphere, thermal polymerization is added, 40 ~90 DEG C or so, preferably 60~80 DEG C or so are stirred 3~15 hours or so.In order to control reaction, monomer, thermal polymerization can be drawn Hair agent is continuously or intermittently added in polymerization, or to be dissolved in the addition of the state of organic solvent.It, can be with as organic solvent Using for example: toluene, dimethylbenzene etc it is aromatic hydrocarbon；The esters of ethyl acetate, butyl acetate etc；Propyl alcohol, isopropanol Etc aliphatic alcohols；The ketone etc. of acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc.

(2) aromatic isocyanate system crosslinking agent (B)

Adhesive composition also contains aromatic isocyanate system crosslinking agent (B).Aromatic isocyanate system crosslinking agent (B) For with aromatic rings and in the molecule with the compound of 2 or more isocyanate group.By using aromatic isocyanate system Compound (B) is used as crosslinking agent, and the adaptation of adhesive phase and optical component, the durability of adhesive phase can be improved.

The concrete example of aromatic isocyanate system crosslinking agent (B) is toluene di-isocyanate(TDI), chlorophenylene diisocyanates, hexichol Dicyclohexylmethane diisocyanate, xylene diisocyanate, polymethylene polyphenyl isocyanate, naphthalene diisocyanate etc..In addition, Aromatic isocyanate system crosslinking agent (B) includes polyol compound adduct (such as three hydroxyls of these isocyanate compounds The adduct of methylpropane), isocyanuric acid carboxylate, biuret type compound and with polyether polyol, polyester polyol, Carbamate prepolymer obtained by the addition reactions such as acrylic polyol, polybutadiene polyol, polyisoprene polyol The derivative of the isocyanate compound of type etc..Aromatic isocyanate system crosslinking agent (B) can be used alone only a kind, can also To be used in combination of two or more.

In aromatic isocyanate system crosslinking agent (B), the adaptation for effectively improving adhesive phase and optical component, It is preferable to use the aromatic isocyanate systems that isocyanate group is combined on aromatic rings for the aspect of the durability of adhesive phase Crosslinking agent.The concrete example of aromatic isocyanate system crosslinking agent on aromatic rings in conjunction with isocyanate group includes toluene diisocyanate Acid esters, chlorophenylene diisocyanates, methyl diphenylene diisocyanate, polymethylene polyphenyl isocyanate, naphthalene diisocyanate Deng.

The content of aromatic isocyanate system crosslinking agent (B) is relative to 100 parts by weight of (methyl) acrylic resin (A) 0.3~1 parts by weight, preferably 0.35~0.9 parts by weight.If the content of aromatic isocyanate system crosslinking agent (B) is less than 0.3 weight Measure part, then even from the surface of the optical component of laminate adhesive oxidant layer material and apply sufficient curing time, adhesive Layer is also insufficient with the adaptation of optical component.In addition, not according to the material on the surface of the optical component of laminate adhesive oxidant layer Together, durability when adhesive phase to be fitted in optical component reduces.If the content of aromatic isocyanate system crosslinking agent (B) is super 1 parts by weight are crossed, even if then applying sufficient curing time, the adaptation of adhesive phase and optical component is also insufficient.In addition, will Durability, especially heat resistance when adhesive phase fits in optical component reduce.

(3) compound (C)

Adhesive composition also contains in the compound (C-2) selected from acylate (C-1) and comprising alkylidene oxygroup At least one kind of compound (C).According to the adhesive composition of the invention for containing compound (C), adhesive phase and light can be improved Learn the adaptation of component and durability when adhesive phase to be fitted in optical component, especially heat resistance.In addition, can be real The shortening of the curing time of existing adhesive phase.Adhesive composition can only contain acylate (C-1), can also be only containing packet The compound (C-2) of the oxygroup containing alkylidene, can also contain both.

Acylate (C-1) is preferably salt, the i.e. organic carboxylate formed by the organic acid with carboxylic acid terminal with alkali.? Use organic carboxylate as in the case where acylate (C-1), the counter cation of carboxylate anion is preferably trivalent or less Counter cation.Acylate (C-1) can be used only a kind, and also two or more kinds may be used.

As above-mentioned counter cation, metal ion, ammonium ion, cation with hetero ring type construction etc. can be enumerated. The preference of metal ion includes alkali metal ion and alkaline-earth metal ions.The preference packet of cation with hetero ring type construction Include pyrrolin ion, imidazol ion, triazole (triazolium) ion, pyrrolidinium ions, pyridinium ion and piperazine Pyridine ion.

As the carboxylate anion of acylate (C-1), it can be mentioned, for example: formate ion, acetate ion, propionic acid The linear saturation alkyl carboxylic acid radical ion of radical ion, enanthic acid radical ion, caprylate ion, laurate ion etc；(methyl) The straight chain unsaturated alkyl carboxylic acid ion of acrylic acid, oleic acid etc；The aromatic carboxylic acid root of benzoic acid, cinnamic acid etc from Son；The carboxylic acid ion with hetero ring type construction of niacin etc；The dicarboxylic acids of succinic acid, fumaric acid, phthalic acid etc Radical ion；The carboxylate anion etc. with oxygen ethylidene skeleton of 2- (2- ethyoxyl) ethoxy carboxylate radical ion etc.

The content of acylate (C-1) is 0.0001~5 weight relative to 100 parts by weight of (methyl) acrylic resin (A) Measure part, preferably 0.0005~5 parts by weight, more preferably 0.0007~3 parts by weight, further preferably 0.001~1 weight Part, particularly preferably 0.0015~0.5 parts by weight.If the content within the scope of this, then adhesive phase and optical component is closely sealed Property and durability when adhesive phase to be fitted in optical component are good, furthermore it is possible to obtain can be realized adhesive phase The adhesive composition of the shortening of curing time.

Compound (C-2) comprising alkylidene oxygroup preferably includes at least one double bond and at least one alkylene in the molecule The compound of base oxygroup.Alkylidene oxygroup is preferably contained in compound in the form of alkylenedioxy group (- O- alkylidene-O-) (C-2) in.The preference of above-mentioned double bond is double bond contained in (methyl) acryloyl group.Compound comprising alkylidene oxygroup (C-2) it can be used only a kind, also two or more kinds may be used.According to by containing the compound (C-2) comprising alkylidene oxygroup The adhesive phase that adhesive composition is formed, can also inhibit the stripping film for being laminated in adhesive layer surface relative to adhesive phase Peeling force it is heated and enhance.

Durability etc. when fitting in optical component from the adaptation of adhesive phase and optical component and by adhesive phase Viewpoint is set out, and the preference of above-mentioned alkylenedioxy group is the alkylenedioxy group of carbon number 1~4, more preferably carbon number 1~3 The alkylenedioxy group of linear chain or branched chain, further preferably ethylene oxygroup (- O-C₂H₄-O-).It is explained, is not sub- The example of the alkylidene oxygroup of two oxygroup of alkyl is also the same, and alkylidene oxygroup is preferably the alkylidene oxygroup, more excellent of carbon number 1~4 It is selected as the alkylidene oxygroup of the linear chain or branched chain of carbon number 1~3, is more preferably ethyleneoxy group (- O-C₂H₄-)。

Durability etc. when fitting in optical component from the adaptation of adhesive phase and optical component and by adhesive phase Viewpoint is set out, and compound (C-2) preferably comprises the compound (C- containing (methyl) acryloyl group shown in following formula (C-2a) 2a), it is more preferably made of compound (C-2a).In formula, h indicates 1~6 integer, Q¹Indicate hydrogen atom or methyl, Q⁰Indicate tool There is the group of the h valence of at least one alkylenedioxy group.Compound (C-2) may include compound of more than two kinds (C-2a).H is excellent It is selected as 1~3 integer.

[changing 3]

Q⁰Shown in the group of the h valence at least one alkylenedioxy group can be for at least one alkylidene dioxygen The alkyl of the h valence of base, it is however preferred to have the alkyl of 1~trivalent of at least one ethylene oxygroup.As the alkyl, can enumerate down The Q stated⁰¹、Q⁰²、Q⁰³And Q⁰⁴Shown in group.

[changing 4]

[changing 5]

Q⁰¹In, Q²Expression can be by alkyl, the aryl or aralkyl for the carbon number 1~4 that the alkoxy of carbon number 1~3 replaces, L Indicate that the alkylidene of singly-bound or carbon number 1~4, i indicate the integer of 1~50 (such as 1~30).It can be used as Q²Aryl carbon number it is excellent The carbon number for being selected as 6~20, aralkyl is preferably 7~20.Q⁰²In, j indicates the integer of 1~40 (such as 1~30).Q⁰³In, y and z Separately indicate that the integer of 1~40 (such as 1~30), y+z can be the integer of 1~40 (such as 1~30).Q⁰⁴In, e, f And g separately indicates that the integer of 1~20 (such as 1~10), e+f+g can be the integer of 1~30 (such as 1~25).

As it is preferable to use compound (C-2a), following formula (C-2a-1) compound represented (C-2a-1) can be enumerated. Compound (C-2) may include compound of more than two kinds (C-2a-1).Compound (C-2a-1) is the Q in above-mentioned formula (C-2a)⁰ For Q⁰¹Compound.Q in formula¹、L、i、Q²Indicate meaning same as described above.In compound (C-2a-1), L is preferably single Key, i are preferably 7~35 integer, more preferably 9~25 integer.Q²The preferably alkyl of carbon number 1~3 or carbon number 6~20 Aryl, as Q²Concrete example, methyl, ethyl, n-propyl, isopropyl, phenyl, xenyl can be illustrated.

[changing 6]

As the concrete example of compound (C-2a-1), Q can be enumerated¹、L、i、Q²Compound as described in Table 1.

[table 1]

It is preferable to use compound (C-2a) other examples be above-mentioned formula (C-2a) in Q⁰For Q⁰⁴Compound.At this point, H in above-mentioned formula (C-2a) is 3.Compound (C-2) may include Q of more than two kinds⁰For Q⁰⁴Compound.Q⁰⁴In, e+f+g is excellent It is selected as 5~25 integer.

It is preferable to use compound (C-2a) other examples be above-mentioned formula (C-2a) in Q⁰For Q⁰³Compound.At this point, H in above-mentioned formula (C-2a) is 2.Compound (C-2) may include Q of more than two kinds⁰For Q⁰³Compound.Q⁰³In, y+z is preferred For 5~25 integer.

The content of compound (C-2) relative to 100 parts by weight of (methyl) acrylic resin (A) be 0.1~5 parts by weight, Preferably 0.15~5 parts by weight, more preferably 0.2~4.5 parts by weight, further preferably 0.5~4 parts by weight.If the model Interior content is enclosed, then the adaptation of adhesive phase and optical component and durable when adhesive phase to be fitted in optical component Property is good, furthermore it is possible to obtain can be realized the adhesive composition of the shortening of the curing time of adhesive phase, and then may be used also To obtain the enhancing inhibitory effect of peeling force.

(4) ionic compound (D)

Adhesive composition can further contain ionic compound (D) as antistatic for assigning to adhesive phase The antistatic agent of property.Ionic compound (D) is with inorganic cation or organic cation and inorganic anion or organic yin The compound of ion.Further, it is possible to use ionic compound (D) of more than two kinds.

As inorganic cation, it can be mentioned, for example: 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, it can be mentioned, for example glyoxaline cation, pyridylium, pyrrolidines cations, ammonium Cation, sulfonium cation, phosphonium cation etc..

In above-mentioned cation constituent, from the aspect excellent in compatibility with adhesive composition, it is preferable to use Organic cation ingredient.In organic cation ingredient, it is not easy to charge when from the stripping film that removing is set on adhesive phase Viewpoint is set out, it is preferable to use pyridylium and glyoxaline cation.

As inorganic anion, it can be mentioned, for example: cl anion (Cl^-), bromine anions (Br^-), iodine anion (I^-), four Chlorine aluminic acid anion (AlCl₄ ^-), two aluminic acid anion (Al of heptachlor₂Cl₇ ^-), tetrafluoro boric acid anion (BF₄ ^-), hexafluorophosphoric acid yin Ion (PF₆ ^-), perchloric acid anion (ClO₄ ^-), nitric acid anions (NO₃ ^-), hexafluoroarsenate anion (AsF₆ ^-), hexafluoro-antimonic acid yin Ion (SbF₆ ^-), hexafluoro niobic acid anion (NbF₆ ^-), hexafluoro tantalic acid anion (TaF₆ ^-), dicyanamide anion (dca) ((CN)₂N^-) etc..

As organic anion, it can be mentioned, for example: acetate anion (CH₃COO^-), trifluoroacetic acid anion (CF₃COO^-〕、 Methylsulphur acid anion (CH₃SO₃ ^-), trifluoromethanesulfonic acid anion (CF₃SO₃ ^-), p-methyl benzenesulfonic acid anion (p-CH₃C₆H₄SO₃ ^-〕、 Bis- (fluorine sulphonyl) imines anion ((FSO₂)₂N^-), bis- (trifluoro methylsulfonyl) imines anion ((CF₃SO₂)₂N^-), three (fluoroforms Sulphonyl) methane anion ((CF₃SO₂)₃C^-), dimethyl hypophosphorous acid anion ((CH₃)₂POO^-), (poly-) hydrofluoric acid fluoride yin Ion (F (HF)_n ^-) (n is 1~3 or so), sulphur cyanogen anion (SCN^-), perfluor fourth sulfonic acid anion (C₄F₉SO₃ ^-), bis- (five fluorine Second sulphonyl) imines anion ((C₂F₅SO₂)₂N^-), perfluorobutyric acid anion (C₃F₇COO^-), (trifluoro methylsulfonyl) (fluoroform carbonyl Base) imide anion ((CF₃SO₂)(CF₃CO)N^-), perfluoropropane -1,3- disulfonic acid anion (^-O₃S(CF₂)₃SO₃ ^-), carbon Acid anion (CO₃ ^2-) etc..

In above-mentioned anion component, from providing antistatic property excellent ionic compound (D) aspect, Particularly preferably use the anion component comprising fluorine atom.As the anion component comprising fluorine atom, specifically, can enumerate Bis- (fluorine sulphonyl) imines anion, hexafluorophosphoric acid anion or bis- (trifluoro methylsulfonyl) imines anion.

The concrete example of ionic compound (D) can suitably be selected from the combination of above-mentioned cation constituent and anion component It selects.If enumerating the example of the ionic compound (D) with organic cation according to the structural classification of organic cation, can arrange Lift compound below.

Pyridiniujm:

N- hexyl pyridine hexafluorophosphate,

N- octylpyridinium hexafluorophosphate,

N- octyl -4- picoline hexafluorophosphate,

N- butyl -4- picoline hexafluorophosphate,

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

Bis- (fluorine sulphonyl) imines of N- dococylpyridinium,

Bis- (fluorine sulphonyl) imines of N- tetradecylpyridinium,

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

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

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

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

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

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

Bis- (trifluoro methylsulfonyl) imines of N- hexyl pyridine,

Bis- (trifluoro methylsulfonyl) imines of N- octylpyridinium,

Bis- (trifluoro methylsulfonyl) imines of N- octyl -4- picoline,

Bis- (trifluoro methylsulfonyl) imines of N- butyl -4- picoline.

Imidazole salts:

1- ethyl-3-methylimidazole hexafluorophosphate,

1- ethyl-3-methylimidazole tosilate,

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

Bis- (trifluoro methylsulfonyl) imines of 1- ethyl-3-methylimidazole,

1- butyl -3- methylimidazole mesylate,

Bis- (fluorine sulphonyl) imines of 1- butyl -3- methylimidazole.

Pyrrolidinium:

N- butyl-N- crassitude hexafluorophosphate,

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

Bis- (trifluoro methylsulfonyl) imines of N- butyl-N- crassitude.

Quaternary ammonium salt:

Tetrabutylammonium hexafluorophosphate,

Tetrabutylammonium tosilate,

Bis- (trifluoro methylsulfonyl) imines of (2- hydroxyethyl) trimethyl ammonium,

(2- hydroxyethyl) trimethyl ammonium dimethyl hypophosphites.

In addition, if enumerating the example of the ionic compound (D) with inorganic cation, including compound below.

Lithium bromide,

Lithium iodide,

Lithium tetrafluoroborate,

Lithium hexafluorophosphate,

Lithium rhodanate,

Lithium perchlorate,

Lithium fluoroform sulphonate,

Bis- (fluorine sulphonyl) imines of lithium,

Bis- (trifluoro methylsulfonyl) imines of lithium,

Bis- (the five fluorine second sulphonyl) imines of lithium,

Lithium three (trifluoro methylsulfonyl) methane,

Lithium tosilate,

Sodium hexafluorophosphate,

Bis- (fluorine sulphonyl) imines of sodium,

Bis- (trifluoro methylsulfonyl) imines of sodium,

Sodium tosilate,

Potassium hexafluorophosphate,

Bis- (fluorine sulphonyl) imines of potassium,

Bis- (trifluoro methylsulfonyl) imines of potassium,

Potassium tosilate.

Ionic compound (D) is preferably solid at room temperature.With use under room temperature be liquid ionic compound (D) The case where compare, antistatic property can be kept for a long time.If from the viewpoint of the long-time stability of such antistatic property, from Sub- property compound (D) the preferably fusing point with 30 DEG C or more and then 35 DEG C or more.On the other hand, if the fusing point is excessively high, with The compatibility poor of (methyl) acrylic resin (A), thus fusing point is preferably 90 DEG C or less, more preferably 70 DEG C or less, into One step is preferably less than 50 DEG C.

The content of ionic compound (D) in adhesive composition is relative to 100 weight of (methyl) acrylic resin (A) Amount part is preferably 0.2~8 parts by weight, more preferably 0.2~5 parts by weight, is more preferably 0.3~5 parts by weight, particularly preferred For 0.5~3 parts by weight.It is advantageous to antistatic property is improved when the content of ionic compound (D) is 0.2 parts by weight or more, from It is advantageous to the durability for maintaining adhesive phase when the content of sub- property compound (D) is 8 parts by weight or less.

(5) silane compound (E)

Adhesive composition can further contain silane compound (E).It is possible thereby to improve adhesive phase and glass base The adaptation of the optical components such as plate.

As silane compound (E), it can be mentioned, for example: vinyltrimethoxysilane, vinyltriethoxysilane, second Alkenyl three (2- methoxy ethoxy) silane, N- (2- amino-ethyl) -3- aminopropylmethyldimethoxysilane, N- (2- ammonia Base ethyl) -3- TSL 8330,3-aminopropyltriethoxysilane, 3- glycidoxypropyl group trimethoxy Base silane, 3- epoxy propoxy propyl methyl dimethoxysilane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, 3- Chloropropylmethyldimethoxysilane, 3- r-chloropropyl trimethoxyl silane, 3- methacryloxypropyl trimethoxy silane, 3-mercaptopropyi trimethoxy silane, 3- glycidoxypropyltrime,hoxysilane, 3- glycidoxypropyl group triethoxy Silane, 3- glycidoxypropyl group dimethoxymethylsilane, 3- glycidoxypropyl group ethyoxyl dimethylsilane etc..It can be with Use silane compound of more than two kinds.

Silane compound (E) is also possible to the compound of silicone oligomers type.If silicone oligomers are oligomeric with (monomer) The form of object indicates that then it can be mentioned, for example compounds below.

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

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

3- Mercaptopropyltriethoxysilane-tetramethoxy-silicane alkyl copolymer,

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

Mercapto methyl trimethoxy silane-tetramethoxy-silicane alkyl copolymer,

Mercapto methyl trimethoxy silane-tetraethoxy-silicane alkyl copolymer,

Mercapto methyl triethoxysilane-tetramethoxy-silicane alkyl copolymer,

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

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

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

3- epoxy propoxy propyl triethoxysilane-tetramethoxy-silicane alkyl copolymer,

3- epoxy propoxy propyl triethoxysilane-tetraethoxy-silicane alkyl copolymer,

3- epoxy propoxy propyl methyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,

3- epoxy propoxy propyl methyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,

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

The glycidoxies containing 3- third such as 3- glycidoxypropyl diethoxy silane-tetraethoxy-silicane alkyl copolymer The copolymer of base；

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- methacryloxypropylmethyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,

3- methacryloxypropylmethyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,

3- methacryloxypropyl methyl diethoxysilane-tetramethoxy-silicane alkyl copolymer,

3- methacryloxypropyl methyl diethoxysilane-tetraethoxy-silicane alkyl copolymer etc. contains methacryl The copolymer of oxygroup propyl；

3- acryloyloxypropyltrimethoxysilane-tetramethoxy-silicane alkyl copolymer,

3- acryloyloxypropyltrimethoxysilane-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- acryloyloxy propyl methyl diethoxysilane-tetramethoxy-silicane alkyl copolymer,

3- acryloyloxy propyl methyl diethoxysilane-tetraethoxy-silicane alkyl copolymer etc. contains acryloxypropyl Copolymer；

Vinyltrimethoxysilane-tetramethoxy-silicane alkyl copolymer,

Vinyltrimethoxysilane-tetraethoxy-silicane alkyl copolymer,

Vinyltriethoxysilane-tetramethoxy-silicane alkyl copolymer,

Vinyltriethoxysilane-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 copolymers containing vinyl such as vinyl methyl diethoxy silane-tetraethoxy-silicane alkyl copolymer；

3- TSL 8330-tetramethoxy-silicane alkyl copolymer,

3- TSL 8330-tetraethoxy-silicane alkyl copolymer,

3-aminopropyltriethoxysilane-tetramethoxy-silicane alkyl copolymer,

3-aminopropyltriethoxysilane-tetraethoxy-silicane alkyl copolymer,

3- aminopropylmethyldimethoxysilane-tetramethoxy-silicane alkyl copolymer,

3- aminopropylmethyldimethoxysilane-tetraethoxy-silicane alkyl copolymer,

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

Amino-containing copolymers such as 3-amino propyl methyl diethoxy silane-tetraethoxy-silicane alkyl copolymer etc..

The silane compound (E) illustrated above is mostly liquid.The content of silane compound (E) in adhesive composition Relative to 100 parts by weight of (methyl) acrylic resin (A) be usually 0.01~10 parts by weight, preferably 0.05~5 parts by weight, More preferably 0.2~0.4 parts by weight.If the content of silane compound (E) is 0.01 parts by weight or more, it is viscous to be easy to get raising The effect of the adaptation of the optical components such as mixture layer and glass substrate.In addition, if content be 10 parts by weight hereinafter, if can inhibit Silane compound (E) is oozed out from adhesive phase.

(6) other compositions

Adhesive composition can containing crosslinking catalyst, weathering stabilizers, tackifier, plasticizer, softening agent, dyestuff, The additives such as pigment, inorganic filler, light scattering particle, resin in addition to (methyl) acrylic resin (A).Except this with Outside, it might be useful to: cooperate ultra-violet solidified compound in adhesive composition, and irradiates after forming adhesive phase ultraviolet Line makes its solidification, forms harder adhesive phase.As crosslinking catalyst, it can be mentioned, for example hexamethylene diamine, ethylenediamine, gather Ethylenimine, hexa, diethylenetriamines, trien, isophorone diamine, trimethylene diamine, The amine compounds such as poly- amino resins and melamine resin.

<adhesive phase>

Adhesive phase of the invention is the adhesive phase comprising above-mentioned Invention adhesive compositions, for typical, by Adhesive composition of the invention is constituted.Adhesive phase can by will constitute above-mentioned adhesive composition each ingredient dissolve or It is scattered in solvent and solvent-laden adhesive composition is made and then the solvent-laden adhesive composition is coated on base material film It goes up and makes it dry to obtain.The adaptation and excellent in te pins of durability of adhesive phase of the invention, and required support can be shortened Protect the time.

Base material film is generally plastic foil, as its typical example, can enumerate implement demoulding processing stripping film (every Film).Stripping film for example can be to comprising polyethylene terephthalate, polybutylene terephthalate (PBT), polycarbonate, Implement film obtained by the demouldings such as silicone-treated processing in the face that will form adhesive phase of the film of the various resins such as polyarylate.Example Such as, adhesive phase can be formed by the direct coating adhesive composition of the demoulding process face in stripping film and shells the band Adhesive phase from film is laminated in optical component to obtain the optical component with adhesive phase.Alternatively, it is also possible in optical component The direct coating adhesive composition in surface and formed adhesive phase and as needed adhesive phase outer surface stacking removing Film and the optical component with adhesive phase is made.When adhesive phase to be set to the surface of optical component, preferably to optics structure The binding face of part and/or the binding face of adhesive phase implement surface activation processing, such as corona treatment, sided corona treatment Deng, more preferably implementation sided corona treatment.

The thickness of adhesive phase is preferably 10~45 μm, more preferably 10~30 μm, further preferably 15~25 μm.If Adhesive phase with a thickness of the range, then the adaptation to adhesive phase and optical component and adhesive phase is fitted in into light Durability when learning component is advantageous.For the same reason, the gel fraction of adhesive phase is preferably 30~85% range.

For adhesive composition of the invention,

The adhesive composition and gluing stratiform will be shaped with stratiform on the film formed by cyclic polyolefin hydrocarbon system resin Mixture composite is to be laminated in after the state of alkali-free glass plate is taken care of 24 hours in the environment of 23 DEG C of temperature from the alkali-free glass Peeling force when plate is peeled off together the adhesive composition of stratiform and the above-mentioned film formed by cyclic polyolefin hydrocarbon system resin is set as P (CO) 23, and

The adhesive composition and gluing stratiform will be shaped with stratiform on the film formed by cyclic polyolefin hydrocarbon system resin Mixture composite is to be laminated in after the state of alkali-free glass plate is taken care of 48 hours in the environment of temperature 50 C from the alkali-free glass Peeling force when plate is peeled off together the adhesive composition of stratiform and the above-mentioned film formed by cyclic polyolefin hydrocarbon system resin is set as P (CO) 50 when,

Above-mentioned P (CO) 50 and above-mentioned P (CO) the ratio between 23 (P (CO) 50/P (CO) 23) are preferably 3.2 or more, are more preferably It 3.5 or more, is more preferably 3.8 or more.As long as will be comprising by ring by the adhesive phase comprising such adhesive composition The optical component for the film that shape polyolefin-based resins are formed is bonded with the film side with unorganic glass liquid crystal cells, then after being bonded immediately The removing optical component and so-called re-workability for transferring to be attached at new optical component is good, and by being added after fitting Heat and peeling force increases, therefore optical component can more firmly be fitted in liquid crystal cells, therefore it is preferred that.

In addition, for adhesive composition of the invention,

The adhesive composition will be shaped with stratiform on the film formed by (methyl) acrylic resin and by stratiform Adhesive composition is to be laminated in after the state of alkali-free glass plate is taken care of 24 hours in the environment of 23 DEG C of temperature from the alkali-free glass Peeling force when glass plate is peeled off together the adhesive composition of stratiform and the above-mentioned film formed by (methyl) acrylic resin It is set as P (AC) 23, and

The adhesive composition will be shaped with stratiform on the film formed by (methyl) acrylic resin and by stratiform Adhesive composition is to be laminated in after the state of alkali-free glass plate is taken care of 48 hours in the environment of temperature 50 C from the alkali-free glass The adhesive composition of stratiform and the above-mentioned film formed by (methyl) acrylic resin are peeled off together the peeling force made by glass plate When being set as P (AC) 50,

Above-mentioned P (AC) 50 and above-mentioned P (AC) the ratio between 23 (P (AC) 50/P (AC) 23) are preferably 3.2 or more, are more preferably It 3.5 or more, is more preferably 3.8 or more.As long as will be comprising by (first by the adhesive phase comprising such adhesive composition Base) optical component of film that is formed of acrylic resin be bonded with the film side with unorganic glass liquid crystal cells, then and it is vertical after fitting The so-called re-workability removed optical component and transfer to be attached at new optical component is good, and by carrying out after fitting It heats and peeling force increase, therefore optical component can more firmly be fitted in liquid crystal cells, therefore it is preferred that.

Above-mentioned P (CO) 23 or P (AC) 23 are preferably 0.3~5N/25mm, are more preferably 0.5~5N/25mm, are further excellent It is selected as 0.5~3N/25mm.If P (CO) 23 or P (AC) 23 is such range, re-workability and the adaptation with liquid crystal cells Well.In addition, above-mentioned P (CO) 50 or P (AC) 50 are preferably 1~15N/25mm, are more preferably 1.5~15N/25mm, are further Preferably 2~13N/25mm.If P (CO) 50 or P (AC) 50 is such range, re-workability and the adaptation with liquid crystal cells Well.

Adhesive composition of the invention contains acylate (C-1) and compound (C-2), and acylate (C-1's) contains Amount relative to 100 parts by weight of (methyl) acrylic resin (A) be preferably 0.0001~0.1 parts by weight, further preferably 0.0005~0.05 parts by weight, particularly preferably 0.001~0.02 parts by weight, the content of compound (C-2) is relative to (methyl) 100 parts by weight of acrylic resin (A) are preferably 0.1~5 parts by weight, are more preferably 0.15~4 parts by weight, particularly preferred For 0.2~3 parts by weight.

By containing acylate (C-1) and compound (C-2) with above-mentioned amount, thus be easy by above-mentioned P (CO) 50 with Above-mentioned P (CO) the ratio between 23 (P (CO) 50/P (CO) 23) is adjusted to preferably 3.2 or more, more preferable 3.5 or more, further preferred 3.8 More than.

In addition, by containing acylate (C-1) and compound (C-2) with above-mentioned amount, to be easy above-mentioned P (AC) 50 preferably 3.2 or more are adjusted to above-mentioned P (AC) the ratio between 23 (P (AC) 50/P (AC) 23), are more preferable 3.5 or more, further excellent Select 3.8 or more.

<optical component with adhesive phase>

Adhesive phase of the invention can be suitable as viscous by what is be bonded between component, especially between optical component Mixture layer come using.Optical component with adhesive phase of the invention for example can be laminated on some optical component it is viscous The component of mixture layer, furthermore can also be also to be laminated in the outer surface of the adhesive phase and is fitted with the components of other optical components.

(1) first embodiment

1 preferred embodiment of the optical component with adhesive phase of the invention includes the tree as optical component Adipose membrane and the adhesive phase being laminated on its at least one face.Resin film can enumerate the optics such as polarizing film, protective film, phase difference film Film；Or be fitted in as upper by optical film of protective etc. and for protecting purpose of its surface from damaging or polluting to use Surface protection film (protecting film).

Polarizing film is with the film for the function of taking out the inclined linear light of straight line from incident natural light, and preferred example is in quilt Gas absorption quantity has the film of the dichroism pigments such as iodine or dichroic dye on the polyvinyl alcohol resin film being uniaxially stretched.Polarizing film Thickness be not particularly limited, usually 0.5~35 μm.

Protective film can be comprising (preferably optically transparent) resin, such as chain polyolefin with translucency The polyolefin-based resins of resin (polypropylene-based resin etc.), cyclic polyolefin hydrocarbon system resin (norbornene resin etc.) etc；Three The cellulose-based resin of acetylcellulose, diacetyl cellulose etc；Polyester based resin；Polycarbonate-based resin；(methyl) third Olefin(e) acid system resin；Polystyrene resin；Polyether-ether-ketone resin；The film of the thermoplastic resins such as polysulfone resin.

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

Cyclic polyolefin hydrocarbon system resin is the general name for the resin being polymerize using cyclic olefin as polymerized unit.To enumerate ring-type The concrete example of polyolefin-based resins is then the open loop (co) polymer of cyclic olefin, the addition polymer of cyclic olefin, cyclic annular alkene Hydrocarbon is used unsaturated with the copolymer (representative is random copolymer) of the chain olefin of ethylene, propylene etc and by them Graft polymers and their hydride that carboxylic acid or derivatives thereof has been modified etc..Wherein, it is preferable to use norborneol is utilized Norbornene resin of the orbornene-baseds monomer such as alkene or polycyclic orbornene-based monomer as cyclic olefin.

Cellulose-based resin is the partially or completely carboxylate of cellulose, such as can enumerate the acetic acid esters of cellulose, propionic acid Ester, butyrate, their mixed ester etc..Wherein, it is preferable to use triacetyl cellulose, diacetyl cellulose, cellulose ethanoate Propionic ester, cellulose acetate butyrate etc..

Polyester based resin is that have ester bond, the resin in addition to above-mentioned cellulose-based resin, generally comprises polybasic carboxylic acid Or derivatives thereof condensation polymer with polyalcohol.As polybasic carboxylic acid or derivatives thereof, dicarboxylic acids or derivatives thereof, example can be used Terephthalic acid (TPA), M-phthalic acid, dimethyl terephthalate (DMT), naphthalene diformic acid dimethyl ester can such as be enumerated.It, can as polyalcohol To use glycol, such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, cyclohexanedimethanol can be enumerated etc..

The concrete example of polyester based resin includes polyethylene terephthalate, polybutylene terephthalate (PBT), poly- naphthalene Naphthalate, polypropylene terephthalate, polytrimethylene naphthalate, gathers at polybutylene naphthalate Terephthalic acid (TPA) cyclohexane dicarboxylates, poly- naphthalenedicarboxylic acid cyclohexane dicarboxylates.

Polycarbonate-based resin includes polymer obtained by being bonded monomeric unit by carbonate group.Polycarbonate-based tree Rouge is also possible to have modified resin referred to as modified polycarbonate or copolymerization polycarbonate of polymer backbone etc..

(methyl) acrylic resin can be the polymer using methacrylate as principal monomer, preferably at it On be copolymerized the copolymers of other a small amount of comonomer components.(methyl) acrylic resin is more preferably methyl methacrylate The copolymer of ester and methyl acrylate can also be copolymerized third monofunctional monomer again.

It as third monofunctional monomer, such as can enumerate: ethyl methacrylate, butyl methacrylate, metering system Sour cyclohexyl, phenyl methacrylate, benzyl methacrylate, 2-Ethylhexyl Methacrylate, methacrylic acid 2- hydroxyl second The methyl acrylic ester in addition to methyl methacrylate of ester etc；Ethyl acrylate, butyl acrylate, acrylate Ester, phenyl acrylate, benzyl acrylate, 2-EHA, acrylic acid 2- hydroxyl ethyl ester etc except methyl acrylate with Outer esters of acrylic acid；2- (hydroxymethyl) methyl acrylate, 2- (1- hydroxyethyl) methyl acrylate, 2- (hydroxymethyl) third The hydroxy alkyl acrylate class of olefin(e) acid ethyl ester, 2- (hydroxymethyl) butyl acrylate etc；Methacrylic acid, acrylic acid etc Unsaturated acids；The halogenated styrenes class of chlorostyrene, bromstyrol etc；Vinyltoluene, α-methylstyrene etc Substituted phenylethylene class；The unsaturated nitrile of acrylonitrile, methacrylonitrile etc；The insatiable hunger of maleic anhydride, citraconic anhydride etc And anhydride；Unsaturated acyl imines of phenyl maleimide, N-cyclohexylmaleimide etc etc..Third monofunctional monomer It may be used alone or in combination of two or more kinds.

It can also be copolymerized polyfunctional monomer again on (methyl) acrylic resin.As polyfunctional monomer, such as can arrange Lift: ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, Tetraethylene glycol two (methyl) acrylate, nine ethylene glycol two (methyl) acrylate, ten tetraethylene glycol two (methyl) acrylate Etc ethylene glycol or its oligomer the monomer that has been esterified with acrylic or methacrylic acid of two terminal hydroxyls；Propylene glycol or its The monomer that two terminal hydroxyls of oligomer have been esterified with acrylic or methacrylic acid；Neopentyl glycol two (methyl) acrylate, The hydroxyl acrylic acid or first by dihydric alcohol of hexylene glycol two (methyl) acrylate, butanediol two (methyl) acrylate etc The monomer of base acroleic acid esterification；Two end hydroxyls of bisphenol-A, the alkylene oxide adducts of bisphenol-A or their halogen substituents The monomer that base has been esterified with acrylic or methacrylic acid；By the polyalcohol propylene of trimethylolpropane, pentaerythrite etc The monomer of acid or methacrylated and open loop addition glycidyl acrylate or first on these terminal hydroxyls The monomer of the epoxy group of base glycidyl acrylate；Succinic acid, adipic acid, terephthalic acid (TPA), phthalic acid, they The binary acid such as halogen substituents and their alkylene oxide addition product etc. go up open loop addition glycidyl acrylate or methyl The monomer of the epoxy group of glycidyl acrylate；(methyl) benzyl acrylate；The aromatic series diethyl of divinylbenzene etc Alkenyl compound etc..Wherein, it is preferable to use ethylene glycol dimethacrylate, tetraethylene glycol dimethylacrylate, new penta 2 Alcohol dimethylacrylate.

(methyl) acrylic resin can also also carry out the reaction between functional group possessed by copolymer and be modified.Make For the reaction, such as the macromolecular chain of the carbomethoxy of methyl acrylate and the hydroxyl of 2- (hydroxymethyl) methyl acrylate can be enumerated Dehydration is contracted in the macromolecular chain of the hydroxyl of interior separating methanol condensation reaction, the carboxyl of acrylic acid and 2- (hydroxymethyl) methyl acrylate Close reaction etc..In addition, (methyl) acrylic resin also can have glutarimide derivative, glutaric anhydride derivative or interior The arbitrary structures of ester ring structure.

(methyl) acrylic resin also can according to need containing additive.As additive, such as lubrication can be enumerated Agent, anti-blocking agent, heat stabilizer, antioxidant, antistatic agent, photostabilizer, impact resistance modifying agent, surfactant etc..

From viewpoints such as the impact resistances of film formation property and film that film is made, (methyl) acrylic resin can also contain Acrylic rubber particle.So-called acrylic rubber particle be using by acrylate as main body elastomeric polymer as must The particle of ingredient is needed, the particle for the single layer structure being substantially only made of the elastomeric polymer can be enumerated and is gathered with the elasticity Close particle of the object as 1 layer of multilayered structure.As the example of the elastomeric polymer, can enumerate using alkyl acrylate as master Ingredient and the crosslinking elastocopolymer for being copolymerized other vinyl monomers and cross-linkable monomer that can be copolymerized therewith.As at For the alkyl acrylate of the principal component of elastomeric polymer, such as the positive fourth of methyl acrylate, ethyl acrylate, acrylic acid can be enumerated The alkyl acrylate that the carbon number of the alkyl such as ester, 2-EHA is 1~8 or so, particularly preferably using with carbon number 4 The acrylic acid of above alkyl.As can enumerate with other vinyl monomers of the alkyl acrylate copolymer in molecule Inside there is the compound of 1 polymerism carbon-to-carbon double bond, more specifically, the methyl-prop of methyl methacrylate etc can be enumerated The vinyl cyanide compound etc. of the aromatic ethenyl compound of olefin(e) acid ester, styrene etc, acrylonitrile etc.As bridging property More specifically monomer, the compound that can enumerate the bridging property at least two polymerism carbon-to-carbon double bond in the molecule can arrange Lift (methyl) acrylate of the polyalcohol of ethylene glycol two (methyl) acrylate, butanediol two (methyl) acrylate etc The alkenyl esters, divinylbenzene of (methyl) acrylic acid etc. of class, (methyl) allyl acrylate etc.

It can also be by the film comprising (methyl) acrylic resin without containing rubber particles and comprising containing rubber particles (methyl) acrylic resin film sandwich as protective film.

Phase difference film is to show optically anisotropic optical film, be can be by the way that resin film is stretched as 1.01~6 Times or so obtained by stretched film, the resin film is other than comprising can be used for the resin in said protection film, such as may be used also To include polyvinyl alcohol resin, polyarylate system resin, polyimides system resins, polyether sulfone system resin, polyvinylidene fluoride/poly- Methyl methacrylate system resin, liquid crystal polyester system resin, ethylene-acetidin copolymer saponification material, polyvinyl chloride tree Rouge etc..Wherein, preferably by polycarbonate-based resin film, cyclic polyolefin resin film, (methyl) acrylic resin film or fibre Stretched film obtained by dimension prime system resin film is stretched uniaxially or biaxially.In addition in the present specification, zero-lag film is also contained in (still, zero-lag film can also be used as protective film use in phase difference film.).In addition to this, be referred to as uniaxiality phase difference film, The film of wide viewing angle phase difference film, low modulus of photoelasticity phase difference film etc. can also be suitable as phase difference film 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. The phase difference film can be suitable in the liquid crystal display device of IPS mode.Phase difference value R in face_eAnd thickness direction phase difference Value R_thIt is preferably all -10~10nm, is more preferably -5~5nm.Phase difference value R in face described herein_eAnd thickness direction phase Potential difference value R_thIt is the value under wavelength 590nm.

Phase difference value R in face_eAnd thickness direction phase difference value R_thFollowing formula definition 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 the slow axis direction (x-axis direction) in film surface, n_yBe in film surface leading phase shaft direction ( The y-axis direction orthogonal with x-axis in face) refractive index, n_zIt is the refractive index in film thickness direction (perpendicular to the z-axis direction of film surface), d It is the thickness of film.

As zero-lag film, can be used for example comprising cellulose-based resin, chain polyolefin-based resins and cyclic polyolefin The tree of the polyolefin-based resins of hydrocarbon system resin etc, PET series resin or (methyl) acrylic resin Adipose membrane.From being easy to control phase difference value and being easy the aspect obtained, cellulose-based resin, polyolefin are particularly preferably used It is resin or (methyl) acrylic resin.For example, it is also possible to which the resin different from (methyl) acrylic resin will be being included Phase difference embodied layers one or both sides on be laminated (methyl) acrylic resin layer obtained by film as phase difference film.

In addition, embodying optically anisotropic film using the coating of liquid crystal compounds, orientation or utilizing inorganic laminated The coating of compound, which embodies optically anisotropic film, can also be used as phase difference film use.In such phase difference film, have Film referred to as temperature compensating type phase difference film, in addition there are also sold by JX days mine days Shi Nengliang (strain) with the trade name of " NH film " The film of rod shaped liquid crystal tilted alignment, the disc-like liquid crystal tilted alignment sold by Fujiphoto (strain) with the trade name of " WV film " Film, the complete biaxially oriented version sold by Sumitomo Chemical (strain) with the trade name of " VAC film " film, equally by Sumitomo Chemical The film etc. for the biaxially oriented version that (strain) is sold with the trade name of " new VAC film ".

On the other hand, surface protection film be using protect as by the surface of the optical film of protective etc. from damaging and polluting The film that uses of purpose, such as polarizing film, protective film, phase difference film, the light of the optical component as liquid crystal display device expands The various optical films such as discrete piece, reflector plate usually (in the case where one side has adhesive phase, to be and the adhesive on its surface The face of layer opposite side) it is fitted with the state circulation of surface protection film.The convention of surface protection film is pasted by above-mentioned optical film It closes and is stripped removing after liquid crystal cells etc. are upper.

It as the substrate of surface protection film, such as can enumerate: by the polyene of polyethylene, polypropylene, polymethylpentene etc Hydrocarbon system resin；The fluoro polyolefin-based resins of polyvinyl fluoride, polyvinylidene fluoride, poly- ethylene fluoride etc；Poly- naphthalenedicarboxylic acid second Diol ester, polyethylene terephthalate, polybutylene terephthalate (PBT), polyethylene terephthalate/isophthalic two The polyester based resin of fumarate copolymers etc；The polyamide of nylon 6, nylon 6,6 etc；Polyvinyl chloride, vinyl chloride-acetic acid second The ethylene of enoate copolymer, vinyl-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, vinylon etc Based polyalcohol；The cellulose-based resin of triacetyl cellulose, diacetyl cellulose, celluloid etc；Polymethyl methacrylate, (methyl) acrylic resin of polyethyl methacrylate, polyethyl acrylate, butyl polyacrylate etc；And comprising poly- The film of the thermoplastic resins such as styrene, polycarbonate, polyarylate, polyimides.Resin film is the of the invention of surface protection film Optical component with adhesive phase is the component for being equipped with adhesive phase on the substrate.

In the optical component with adhesive phase of present embodiment, preferably attached in the adhesive layer surface above-mentioned Stripping film, temporarily protected before use.It is pasted with the optics with adhesive phase of the present embodiment of stripping film Component can use following method to manufacture, that is, the coating adhesive composition on stripping film and form adhesive phase, in institute Adhesive phase on laminated resin film again method；The coating adhesive composition on resin film and form adhesive phase, The method of stripping film is bonded on its adhesive face.

For the optical component with adhesive phase of present embodiment,

By the shape of the optical component with adhesive phase to be laminated in alkali-free glass plate using the adhesive phase for being constituted it State in the environment of 23 DEG C of temperature take care of 24 hours after from the alkali-free glass plate remove when peeling force be set as P23 and

By the shape of the optical component with adhesive phase to be laminated in alkali-free glass plate using the adhesive phase for being constituted it When peeling force when state is removed after taking care of 48 hours in the environment of temperature 50 C from the alkali-free glass plate is set as P50,

The ratio between P50 and P23 (P50/P23) they are 3.2 or more, be further 3.5 or more, specifically for 3.8 or more when, it is so-called It is good in processability, and peeling force increases and being heated after fitting, therefore can be by optical component more firmly Fit in liquid crystal cells, therefore it is preferred that.

Above-mentioned P23 is preferably 0.3~5N/25mm, more preferably 0.5~5N/25mm, further preferably 0.5~3N/ 25mm.If P23 is such range, re-workability and good with the adaptation of liquid crystal cells.In addition, above-mentioned P50 be preferably 1~ 15N/25mm, more preferably 1.5~15N/25mm, further preferably 2~13N/25mm.If P50 is such range, then is added Work and good with the adaptation of liquid crystal cells.

(2) second embodiment

Other preferred embodiments of optical component with adhesive phase of the invention include the laminated body of resin film With the adhesive phase being laminated on its at least one face.The laminated body of resin film is preferably selected from polarizing film, protective film, phase difference The laminated body of optical film in optical films such as film etc..The typical example of the laminated body of optical film is polarization plates.In present embodiment In optical component with adhesive phase, it is also preferred that attaching stripping film in the adhesive layer surface, faced before use When protect.

As polarization plates, can enumerate with absorb inject film surface the vibration plane with some direction the inclined linear light of straight line, And the linear polarization plate of the property through the inclined linear light of straight line with orthogonal vibration plane；The tool of film surface is injected with reflection There is the inclined linear light of the straight line of the vibration plane in some direction and through the property of the inclined linear light of straight line with orthogonal vibration plane Polarised light separating plate；The elliptical polarization plate etc. of phase difference film is laminated on linear polarization plate.

In general linear polarization plate has is fitted with above-mentioned protective film on the one or both sides of above-mentioned polarizing film Composition.In the case where being fitted with protective film on the two sides of polarizing film, can at least one surface of the protective film shape Composite adhesives layer.In the case where being only bonded protective film in the one side of polarizing film, (it can be bonded on the surface of polarizing film The face of protective film) on form adhesive phase.Elliptical polarization plate is laminated with phase difference film on linear polarization plate, and the linear polarization Plate generally also has composition same as described above.When adhesive phase is laminated on elliptical polarization plate, usually in phase difference film side layer Folded adhesive phase.

Referring to attached drawing, the concrete example of the optical component with adhesive phase when being polarization plates to optical component is said It is bright.In example shown in Fig. 1, by the protective film 3 with surface-treated layer 2 with the face with 2 opposite side of surface-treated layer It is attached in the one side of polarizing film 1 and constitutes polarization plates 10.It is arranged on the face with 3 opposite side of protective film of polarizing film 1 viscous Mixture layer 20 constitutes the polarization plates (optical component with adhesive phase) 25 for having adhesive phase.The adhesive phase 20 can be with It is fitted on glass substrate 30 with the face with 10 opposite side of polarization plates, glass substrate 30 will be described later.

What the another side that the polarization plates 25 shown in Fig. 2 with adhesive phase are included in the polarizing film 1 of polarization plates 10 was attached Second protective film 4 is in addition to this, identical as Fig. 1.Adhesive phase 20 is laminated in the outer surface of the second protective film 4.It is shown in Fig. 3 Polarization plates 25 with adhesive phase are included in the phase that the another side of the polarizing film 1 of polarization plates 10 is attached across interlayer adhesive 8 Potential difference film 7 is in addition to this, identical as Fig. 1.Polarization plates 25 shown in Fig. 4 with adhesive phase are included in the second of polarization plates 10 The phase difference film 7 that the outer surface of protective film 4 is attached across interlayer adhesive 8 is in addition to this, identical as Fig. 2.In Fig. 3 and Fig. 4 Shown in example, adhesive phase 20 is attached at phase difference film 7.

The surface-treated layer 2 being formed on the surface of protective film 3 can be hard conating, antiglare layer, anti-reflection layer, antistatic Layer etc..Also multiple layers in them can be set.It include phase difference film 7 in the such polarization plates 10 of example as shown in Figures 3 and 4 In the case where, if it is middle-size and small-size liquid crystal display device, then as the suitable example of phase difference film 7,1/4 wavelength can be enumerated Plate.At this point, generally the absorption axiss of polarizing film 1 and the slow axis of phase difference film 7 are configured in such a way that substantially 45 degree intersect, still It so that the angle is deviateed to a certain degree relative to 45 degree according to the characteristic of liquid crystal cells sometimes.On the other hand, if it is electricity Depending on etc. large-scale liquid crystal display device, then for the purpose of the phase difference compensation of liquid crystal cells or viewing angle compensation, with the liquid crystal cells Characteristics match using have various phase difference values phase difference film 7.In this case, generally by the absorption axiss of polarizing film 1 with The slow axis of phase difference film 7 configures in a manner of in substantially orthogonal or substantially parallel relationship.Phase is being constituted with 1/4 wavelength plate In the case where potential difference film 7, it is suitble to using stretched film uniaxially or biaxially.In addition, for liquid crystal cells phase difference compensation or In the case where the purpose setting phase difference film 7 of viewing angle compensation, other than uniaxial or biaxial stretching film, can also will except uniaxial or The biaxial stretch-formed film being also orientated in a thickness direction in addition, the phase difference of coating of liquid crystalline etc. embodies substance and makes on support membrane The film of orientation fixation etc. be referred to as the film of optical compensation films as the use of phase difference film 7.

Interlayer adhesive 8 as Fig. 3 and Fig. 4, it is common practice to use general (methyl) acrylic adhesive, but work as Adhesive phase of the invention so also can be used.As mentioned-above large-scale liquid crystal display device by the suction of polarizing film 1 It, can also when the slow axis of receipts axis and phase difference film 7 configures in a manner of in substantially orthogonal or substantially parallel relationship Bonding agent is used to replace interlayer adhesive 8.As bonding agent, such as it can enumerate and be made of aqueous solution or aqueous dispersions, be led to Cross make the water evaporation as solvent and embody bonding force water system bonding agent, using ultraviolet light irradiation solidified and embodied Ultraviolet hardening bonding agent of bonding force etc..Polarizing film 1 is generally also carried out using bonding agent with being bonded for protective film 3,4.

The optical component with adhesive phase of present embodiment is the adhesive combination that adhesive phase includes aforementioned present invention The component of object, therefore the adaptation and durability of adhesive phase and optical component are good.According to the present invention, even if will paste The surface of the optical component of conjunction adhesive phase is the surface active carried out in the past by sided corona treatment, corona treatment etc Processing is also not easy the surface being activated, and also the adaptation and durability of available adhesive phase and optical component are good Optical component with adhesive phase.The surface described herein that be not easy to be activated that handles by surface activation is for example to carry out electricity Contact angular rate of change when dizzy processing is 40% or less and then is 30% surface below.Contacting angular rate of change is usually 0.1% It above, is preferably 0.5% or more.

Contact angular rate of change is defined by following formula.Contact angle is in output power 0.3kW, production linear speed after sided corona treatment After degree carried out 1 sided corona treatment to above-mentioned surface under conditions of 10m/ minutes, in the environment of 23 DEG C of temperature, relative humidity 60% Contact angle when placing 24 hours.Contact angle is the contact angle to water, and unit is " ° ".

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

Contact angular rate of change when above-mentioned carry out sided corona treatment according to the difference of the constituent material on the surface of optical component and It is different.As contact angular rate of change be 40% thermoplastic resin below, be (methyl) acrylic resin, cellulose-based resin, Polyester based resin, polycarbonate-based resin etc..The surface for the optical component being made of these thermoplastic resins can for protective film, The surface of the optical films such as phase difference film.

(3) third embodiment

Other preferred embodiments of optical component with adhesive phase of the invention are in the above-mentioned first or second The reality for being bonded other optical components is laminated in the outer surface of the adhesive phase of the optical component with adhesive phase of embodiment again Apply mode.Other optical components are suitably for glass substrate, in FIG. 1 to FIG. 4, represent having second embodiment together The polarization plates of adhesive phase are fitted in the situation on glass substrate 30.

As glass substrate 30, such as the glass substrate, anti-dazzle with glass, sunglasses glass of liquid crystal cells can be enumerated Deng.As the material of glass substrate 30, such as soda-lime glass, glass with lower alkali content, alkali-free glass can be enumerated etc..Wherein, glass substrate The preferably glass substrate of liquid crystal cells.

Usually on its two sides in adhesive phase laminated polarizing plate, these polarization plates in liquid crystal cells, can be The polarization plates for being only configured at the front side (observation side) of liquid crystal cells are the polarization plates with adhesive phase of the invention, can also be with The polarization plates for being the back side (backlight side) for being only configured at liquid crystal cells are the polarization plates with adhesive phase of the invention, also Both be can be as the polarization plates with adhesive phase of the invention.The driving method of liquid crystal cells can be previous known Any way.The polarization plates for being configured at back side (backlight side) do not have surface-treated layer 2 usually.It can also be configured at The outer surface setting brightness of the polarization plates of back side improves the known configurations such as film, condensing film, diffusion barrier in the back side of liquid crystal cells The various optical films of side.

Polarization plates with adhesive phase etc. can be adapted in liquid crystal display device with the optical component of adhesive phase. Liquid crystal display device can for example be suitable as including notebook type, desk-top, PDA (Personal Digital Assistant) Deng PC；The various mobile devices such as smart phone, panel type terminal；TV；Vehicle-mounted display；Electronic dictionary；Number Code camera；DV；Electronic desktop computer；Clock and watch with etc. liquid crystal display device come using.

Embodiment

The present invention is further illustrated hereinafter, showing Examples and Comparative Examples, but the present invention is not by these Example limits.Hereinafter, part and % of expression usage amount or content are weight basis unless otherwise specified.

<Production Example 1~7: the manufacture of adhesive phase (methyl) acrylic resin>

Being added into the reaction vessel for having condenser pipe, nitrogen ingress pipe, thermometer and blender has list shown in table 2 Body composition while being 100 weight % (weight %) with monomer total amount and the monomer mixture after being diluted with ethyl acetate, while using nitrogen Air in gas displacement apparatus makes its not oxygen-containing side by up to 55 DEG C of interior temperature rise.Later, add whole amount by azobisisobutylonitrile Nitrile (polymerization initiator) is dissolved in the resulting solution of ethyl acetate.1 hour, then, side are kept in the temperature after addition initiator 54~56 DEG C of sides will be kept internal temperature at ethyl acetate is added continuously in reaction vessel, in (methyl) acrylic resin Concentration stops the addition of ethyl acetate at the time of reaching 35 weight %, then since adding ethyl acetate until by 12 hours In being kept the temperature at this temperature.Finally, addition ethyl acetate, according to making the concentration of (methyl) acrylic resin reach 20 weights The mode of amount % is adjusted, and is prepared into the ethyl acetate solution of (methyl) acrylic resin.

The weight average molecular weight (Mw) and glass transition temperature (Tg) of resulting (methyl) acrylic resin are surveyed It is fixed.By what is made as the Tosoh of chromatographic column (strain) " TSKgel XL " 4 and by Showa electrician (strain) manufacture and had trade relations by clear light (strain) sale " Shodex GPC KF-802 " 1 total 5 be connected in series after be configured at GPC device, made using tetrahydrofuran Pass through under conditions of sample solution concentration 5mg/mL, 100 μ L of sample import volume, 40 DEG C of temperature, flow velocity 1mL/ minutes for eluent Standard polystyren conversion determines Mw.Use the differential scanning calorimetry (DSC) of SII NanoTechnology Co. Ltd. system (DSC) " EXSTAR DSC6000 ", under nitrogen atmosphere, the item of -80~50 DEG C of measuring temperature range, 10 DEG C/min of heating rate Tg is determined under part.By the monomer composition (weight %) of used monomer mixture and resulting (methyl) acrylic acid series tree The Mw and Tg of rouge are summarized in table 2.

[table 2]

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

BA: n-butyl acrylate,

EHA: 2-EHA,

MA: methyl acrylate,

AA: acrylic acid,

HEA: acrylic acid 2- hydroxy methacrylate.

<Examples 1 to 10, comparative example 1~8>

(1) preparation of adhesive composition

Relative to 100 parts by weight of solid component of (methyl) acrylic resin (A) obtained in above-mentioned Production Example, respectively With crosslinking agent (B), compound (C) and silane compound (E) shown in amount (parts by weight) mixture table 3 shown in table 3, according still further to making The mode that solid component concentration reaches 14 weight % adds ethyl acetate, prepares the solution of adhesive composition.Used In the solvent-laden situation of commodity bundle, the use level of each gradation composition shown in table 3 be included in it as active ingredients Parts by weight.

[table 3]

It is as follows with the details of each gradation composition shown in abbreviation in table 3.

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

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

C1: it sodium acetate: (is dissolved in ethyl alcohol purchased from Wako Pure Chemical Industries (strain) and 0.5 weight % solution is made, then add It is added in adhesive composition.),

C2: it is purchased from " AM-130G " (methoxylated polyethylene glycol propylene shown in following formula of the village Xin Zhong chemical industry (strain) Acid esters),

[changing 7]

S1:3- glycidoxypropyltrime,hoxysilane, " KBM403 " for being purchased from SHIN-ETSU HANTOTAI's chemical industry (strain).

(2) production of adhesive phase

By each adhesive composition prepared in above-mentioned (1) with glue spreader by make it is dry after with a thickness of 20 μm in a manner of apply Cloth is in the stripping film formed by polyethylene terephthalate film for implementing demoulding processing (purchased from Lintec (strain) " PLR-382051 ", be referred to as diaphragm) demoulding process face on, it is 1 minute dry at 100 DEG C, produce adhesive phase (adhesive Piece).

(3) production of the polarization plates with adhesive phase

Across viscous on a face of 23 μm of thickness of polarizing film obtained by gas absorption quantity iodine on being uniaxially stretched polyvinyl alcohol film The first protective film formed by thermoplastic resin recorded in agent fitting table 4 is connect, is used in another face unlike those described above viscous It connects agent and is bonded the second protective film formed by (methyl) acrylic resin, thus make polarization plates.Then, to the first protective film Outer surface, under conditions of output power 0.3kW, line speed 10m/ minutes carry out 1 sided corona treatment.Then, at this Sided corona treatment face is bonded the face (adhesive phase with diaphragm opposite side of the adhesive phase made in above-mentioned (2) using laminating machine Face) after, it is conserved under conditions of 23 DEG C of temperature, relative humidity 65%, obtains the polarization plates with adhesive phase.

The abbreviation recorded in " protective film " column of table 4 refers to thermoplastic resin below.

AC:(methyl) acrylic resin (contact angular rate of change based on above-mentioned definition: 17.2%),

PE: polyester based resin (contact angular rate of change based on above-mentioned definition: 14.7%),

CE: cellulose-based resin (contact angular rate of change based on above-mentioned definition: 21.7%).

(4) evaluation of durability

After the polarization plates removing diaphragm with adhesive phase made in above-mentioned (3), by the adhesive level to be formed just The mode of Nicol is handed over to be attached to the two sides of liquid crystal cells glass substrate (" the Eagle XG " of Corning corporation), Produce sample for evaluation.Implement 3 kinds of following durability tests using the sample.

(durability test)

Kept under 80 DEG C of temperature of drying condition 1000 hours heat resistant test,

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

To keep 30 minutes under the drying condition of temperature 70 C, then be kept under -40 DEG C of temperature of drying condition Operation in 30 minutes is recycled as 1, and heat shock resistance (HS) test of 500 circulations is repeated.

Sample after visually observing each test has rated durability according to following evaluation criteria.Show the result in table 4 In.

A: can't see completely float, remove, foaming etc. cosmetic variations,

B: be substantially not visible float, remove, foaming etc. cosmetic variations,

C: see it is more float, remove, foaming etc. cosmetic variations,

D: it is clearly seen that and the cosmetic variations such as floats, removes, foaming.

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

Wide 25mm × long 150mm test film is cut from the polarization plates with adhesive phase made in above-mentioned (3).Then, After test film removing diaphragm, it is fixed on the closing force evaluation fixture of (strain) Japanese system group, implements removing below Test.Test is set to touch the surface of adhesive phase with sheet rubber (material: chloroprene rubber, hardness: JIS A hardness 65), and Make the sheet rubber reciprocal 20 times on test film, thus with the surface of sheet rubber friction adhesive phase.Test sheet rubber Moving direction is parallel with the width direction of test film.

The surface of the adhesive phase side of test film after above-mentioned disbonded test is observed.In any embodiment ratio Compared in example, an end-to-side adhesion oxidant layer of the width direction of the test film after disbonded test is peeling-off, in another end side Adhesive phase part residual.The position (position of the length direction of test film) of remaining adhesive phase is found out, is measured from above-mentioned One end to the position distance as peel distance.It shows the result in table 4.

In any embodiment comparative example, use during maintenance to be 7 days viscous during 3 days adhesive phases and maintenance Mixture layer makes the polarization plates with adhesive phase, carries out disbonded test.If peel distance when being 7 days during maintenance is 15mm Hereinafter, then the adaptation of protective film and adhesive phase deserves to be called good.In addition, if maintenance during be 3 days when peel distance with The difference of peel distance when being 7 days during maintenance is 5mm hereinafter, then the face of the shortening during maintenance deserves to be called and extremely has Benefit.It is explained, in comparative example 2, (first is being replaced by 56.3% cyclic polyolefin resin film using contact angular rate of change Base) acrylic resin film as protective film in the case where, during maintenance be 3 days, 7 days when peel distance be respectively 14mm, 11mm, in addition, the durability based on said determination method is also better.

[table 4]

<Production Example 8~10: the manufacture of adhesive phase (methyl) acrylic resin>

Being added into the reaction vessel for having condenser pipe, nitrogen ingress pipe, thermometer and blender has list shown in table 5 Body composition while being 100 weight % (weight %) with monomer total amount and the monomer mixture after being diluted with ethyl acetate, while using nitrogen Air in gas displacement apparatus makes its not oxygen-containing side by up to 55 DEG C of interior temperature rise.Later, add whole amount by azobisisobutylonitrile Nitrile (polymerization initiator) is dissolved in the resulting solution of ethyl acetate.1 hour, then, side are kept in the temperature after addition initiator 54~56 DEG C of sides will be kept internal temperature at ethyl acetate is added continuously in reaction vessel, in (methyl) acrylic resin Concentration stops the addition of ethyl acetate at the time of reaching 35 weight %, then since adding ethyl acetate until by 12 hours In being kept the temperature at this temperature.Finally, addition ethyl acetate, according to making the concentration of (methyl) acrylic resin reach 20 weights The mode of amount % is adjusted, and is prepared into the ethyl acetate solution of (methyl) acrylic resin.

The weight average molecular weight (Mw) and glass transition temperature (Tg) of resulting (methyl) acrylic resin are surveyed It is fixed.By what is made as the Tosoh of chromatographic column (strain) " TSKgel XL " 4 and by Showa electrician (strain) manufacture and had trade relations by clear light (strain) sale " Shodex GPC KF-802 " 1 total 5 be connected in series after be configured at GPC device, made using tetrahydrofuran Pass through under conditions of sample solution concentration 5mg/mL, 100 μ L of sample import volume, 40 DEG C of temperature, flow velocity 1mL/ minutes for eluent Standard polystyren conversion determines Mw.Use the differential scanning calorimetry (DSC) of SII NanoTechnology Co. Ltd. system (DSC) " EXSTAR DSC6000 ", under nitrogen atmosphere, the item of -80~50 DEG C of measuring temperature range, 10 DEG C/min of heating rate Tg is determined under part.By the monomer composition (weight %) of used monomer mixture and resulting (methyl) acrylic acid series tree Mw, Mw/Mn and Tg of rouge are summarized in table 5.

[table 5]

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

BA: n-butyl acrylate,

EHA: 2-EHA,

MA: methyl acrylate,

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.

<embodiment 11~26>

(1) preparation of adhesive composition

Relative to 100 parts by weight of solid component of (methyl) acrylic resin (A) obtained in above-mentioned Production Example, respectively With crosslinking agent (B), compound (C), ionic compound (D) and silanization shown in amount (parts by weight) mixture table 6 shown in table 6 It closes object (E), adds ethyl acetate according still further to the mode for making solid component concentration reach 14 weight %, prepare adhesive composition Solution.In the solvent-laden situation of used commodity bundle, the use level of each gradation composition shown in table 6 is included in it Parts by weight as active ingredients.

[table 6]

It is as follows with the details of each gradation composition shown in abbreviation in table 6.

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

C1: it sodium acetate: (is dissolved in acetic acid purchased from Wako Pure Chemical Industries (strain) and 3.3 weight % solution is made, then add It is added in adhesive composition.),

C2-1: it is purchased from " AM-130G " (methoxylated polyethylene glycol third shown in following formula of the village Xin Zhong chemical industry (strain) Olefin(e) acid ester),

[changing 8]

C2-2: it is purchased from " M-130G " (methoxylated polyethylene glycol first shown in following formula of the village Xin Zhong chemical industry (strain) Base acrylate),

[changing 9]

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

S1:3- glycidoxypropyltrime,hoxysilane, " KBM403 " for being purchased from SHIN-ETSU HANTOTAI's chemical industry (strain).

(2) production of adhesive phase

By each adhesive composition prepared in above-mentioned (1) with glue spreader by make it is dry after with a thickness of 20 μm in a manner of apply Cloth is in the stripping film formed by polyethylene terephthalate film for implementing demoulding processing (purchased from Lintec (strain) " PLR-382051 ", be referred to as diaphragm) demoulding process face on, it is 1 minute dry at 100 DEG C, produce adhesive phase (adhesive Piece).

(3) production of the polarization plates with adhesive phase

Across viscous on a face of 23 μm of thickness of polarizing film obtained by gas absorption quantity iodine on being uniaxially stretched polyvinyl alcohol film The first protective film formed by thermoplastic resin recorded in agent fitting table 7 is connect, is used in another face unlike those described above viscous It connects agent and is bonded the second protective film formed by (methyl) acrylic resin, thus make polarization plates.Then, to the first protective film Outer surface, under conditions of output power 0.3kW, line speed 10m/ minutes carry out 1 sided corona treatment.Then, at this Sided corona treatment face is bonded the face (adhesive phase with diaphragm opposite side of the adhesive phase made in above-mentioned (2) using laminating machine Face) after, it is conserved under conditions of 23 DEG C of temperature, relative humidity 65%, obtains the polarization plates with adhesive phase.

The abbreviation recorded in " protective film " column of table 7 refers to thermoplastic resin below.

CO: cyclic polyolefin hydrocarbon system resin (contact angular rate of change based on above-mentioned definition: 56.3%),

AC:(methyl) acrylic resin (contact angular rate of change based on above-mentioned definition: 17.2%).

(4) evaluation of durability

After the polarization plates removing diaphragm with adhesive phase made in above-mentioned (3), by the adhesive level to be formed just The mode of Nicol is handed over to be attached to the two sides of liquid crystal cells glass substrate (" the Eagle XG " of Corning corporation), Produce sample for evaluation.Implement 3 kinds of following durability tests using the sample.

(durability test)

Kept under 80 DEG C of temperature of drying condition 1000 hours heat resistant test,

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

To keep 30 minutes under the drying condition of temperature 70 C, then be kept under -40 DEG C of temperature of drying condition Operation in 30 minutes is recycled as 1, and heat shock resistance (HS) test of 500 circulations is repeated.

Sample after visually observing each test has rated durability according to following evaluation criteria.Show the result in table 7 In.

A: can't see completely float, remove, foaming etc. cosmetic variations,

B: be substantially not visible float, remove, foaming etc. cosmetic variations,

C: see it is more float, remove, foaming etc. cosmetic variations,

D: it is clearly seen that and the cosmetic variations such as floats, removes, foaming.

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

Wide 25mm × long 150mm test film is cut from the polarization plates with adhesive phase made in above-mentioned (3).Then, After test film removing diaphragm, which is utilized into the adhering device (trade name of Fujipla (strain) system " Lamipacker ") being attached at liquid crystal cells glass substrate, (trade name " EAGLE XG " is purchased from Corning Incorporated, alkali-free glass Plate).By the resulting test film (optical component with adhesive phase for being pasted with glass substrate) for being pasted with glass substrate in height It presses in kettle with temperature 50 C, pressure 5kgf/cm²(490.3kPa) pressurizes 20 minutes.Again respectively 24 in 23 DEG C of temperature of atmosphere It is stood under conditions of 48 hours in the condition of hour and the atmosphere of temperature 50 C.Sample after standing is clamped in cupping machine (" the AUTOGRAPH AGS-X " of (strain) Shimadzu Seisakusho Ltd.), in the environment of 23 DEG C of temperature, relative humidity 55%, to stretch 300mm/ minutes conditions of speed are removed along 180 ° of directions.The peel strength measured at this time is evaluated as peeling force.Here, Peeling force under conditions of taking care of 24 hours in 23 DEG C of temperature of atmosphere is set as P23, will be protected in the atmosphere of temperature 50 C Peeling force under conditions of pipe 48 hours is set as P50.It shows the result in table 7.

[table 7]

Symbol description

1 polarizing film, 2 surface-treated layers, 3,4 protective films, 7 phase difference films, 8 interlayer adhesives, 10 polarization plates, 20 adhesives Layer, 25 polarization plates with adhesive phase, 30 glass substrates.

Claims (15)

1. a kind of adhesive composition, contains:

Containing the Component units from (methyl) acrylic monomer with hydroxyl and its content is 3.5 weight % or less, simultaneously And glass transition temperature is -25 DEG C of 100 parts by weight of (methyl) acrylic resin (A) below；

Aromatic isocyanate system crosslinking agent (B) 0.3 parts by weight~1 parts by weight；With

At least one kind of compound (C) in compound (C-2) selected from acylate (C-1) and comprising alkylidene oxygroup,

The compound (C-2) comprising alkylidene oxygroup is the compound for containing 1 (methyl) acryloyl group in the molecule,

When containing the acylate (C-1), content is relative to 100 parts by weight of (methyl) acrylic resin (A) For 0.0001 parts by weight~5 parts by weight,

When containing compound (C-2) comprising alkylidene oxygroup, content is relative to (methyl) the acrylic acid series tree 100 parts by weight of rouge (A) are 0.1 parts by weight~5 parts by weight.

2. adhesive composition according to claim 1, wherein the compound (C-2) comprising alkylidene oxygroup is It in the molecule include the compound of at least one double bond and at least one alkylenedioxy group.

3. adhesive composition according to claim 1, wherein described from (methyl) acrylic acid series list with hydroxyl The content of the Component units of body is 0.5 weight % or more.

4. adhesive composition according to claim 1 also contains ionic compound (D).

5. adhesive composition according to claim 1 also contains silane compound (E).

6. adhesive composition according to claim 1, wherein by the film formed by cyclic polyolefin hydrocarbon system resin with Stratiform shapes described adhesive composition and by the adhesive composition of stratiform to be laminated in the state of alkali-free glass plate in temperature Peeling force when removing after taking care of 24 hours in the environment of 23 DEG C from the alkali-free glass plate is set as P (CO) 23, and

Described adhesive composition will be shaped with stratiform on the film formed by cyclic polyolefin hydrocarbon system resin and by the bonding of stratiform Agent composition is to be laminated in after the state of alkali-free glass plate is taken care of 48 hours in the environment of temperature 50 C from the alkali-free glass plate When peeling force when removing is set as P (CO) 50,

P (CO) the 50 and P (CO) the ratio between 23 is that P (CO) 50/P (CO) 23 is 3.2 or more.

7. adhesive composition according to claim 1, wherein will be on the film formed by (methyl) acrylic resin Shape described adhesive composition and by the adhesive composition of stratiform with stratiform to be laminated in the state of alkali-free glass plate in temperature Peeling force when removing after taking care of 24 hours in the environment of 23 DEG C of degree from the alkali-free glass plate is set as P (AC) 23, and

Described adhesive composition and gluing stratiform will be shaped with stratiform on the film formed by (methyl) acrylic resin Mixture composite is to be laminated in after the state of alkali-free glass plate is taken care of 48 hours in the environment of temperature 50 C from the alkali-free glass When peeling force when plate is removed is set as P (AC) 50,

P (AC) the 50 and P (AC) the ratio between 23 is that P (AC) 50/P (AC) 23 is 3.2 or more.

8. adhesive composition according to claim 1, containing the acylate (C-1) and it is described include alkylene The compound (C-2) of base oxygroup,

The content of the acylate (C-1) is 0.0001 relative to 100 parts by weight of (methyl) acrylic resin (A) Parts by weight~0.1 parts by weight,

The content of the compound (C-2) comprising alkylidene oxygroup is relative to (methyl) acrylic resin (A) 100 Parts by weight are 0.1 parts by weight~5 parts by weight.

9. a kind of adhesive phase, it includes adhesive compositions according to any one of claims 1 to 8.

10. a kind of optical component with adhesive phase it includes optical component and is laminated thereon as claimed in claim 9 viscous Mixture layer.

11. the optical component according to claim 10 with adhesive phase, wherein the light of stacking described adhesive layer Learning contact angular rate of change of the surface of component when carrying out sided corona treatment is 40% or less.

12. the optical component according to claim 11 with adhesive phase, wherein the optical component include polarizing film and The protective film being laminated thereon,

The surface is the surface of the protective film.

13. the optical component according to claim 11 with adhesive phase, wherein the surface is by sided corona treatment Surface.

14. also including to be layered in institute according to claim 1 with the optical component of adhesive phase described in any one of 0~13 State the glass substrate on adhesive phase.

15. a kind of optical component with adhesive phase is that have resin film and be laminated at least one face of the resin film The optical component with adhesive phase of adhesive phase,

Described adhesive layer includes adhesive composition according to any one of claims 1 to 8,

By the optical component with adhesive phase be laminated on alkali-free glass plate layer by layer using described adhesive state in temperature In the environment of 23 DEG C take care of 24 hours after from the alkali-free glass plate remove when peeling force be set as P23 and

By the optical component with adhesive phase to be laminated on the state of alkali-free glass plate layer by layer using described adhesive in temperature 50 When peeling force when removing after taking care of 48 hours in the environment of DEG C from the alkali-free glass plate is set as P50,

The ratio between the P50 and the P23 are that P50/P23 is 3.2 or more.