CN107434960A

CN107434960A - Light absorption composition

Info

Publication number: CN107434960A
Application number: CN201710367875.9A
Authority: CN
Inventors: 小泽昭; 小泽昭一; 宫崎胜旭; 飞田宪之
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2016-05-25
Filing date: 2017-05-23
Publication date: 2017-12-05
Anticipated expiration: 2037-05-23
Also published as: KR20170133266A; JP2017210552A; TW201815936A; TWI738783B; CN107434960B; KR102297237B1; JP6705699B2

Abstract

It is an object of the present invention to provide a kind of light absorption composition, the visible ray of its short wavelength near to 400nm shows that light extraction selection is absorbefacient simultaneously, and the dissolubility with the compatibility of the material of the member of formation of display device and/or in various solvents is high.The present invention provides a kind of light absorption composition, and it includes at least two kinds of light selection absorbing compounds, wherein, there is at least two kinds of light selection absorbing compounds identical to be conjugated architecture.

Description

Light absorption composition

Technical field

Polymer composition the present invention relates to light absorption composition and comprising the light absorption composition, optics Film and display device.

Background technology

In the panel display apparatus such as organic EL display, liquid crystal display device (FPD), used organic EL element or The various components of the optical film such as the display elements such as liquid crystal cells and polarization plates or polarizer etc.Due in these components The material such as organic EL compounds used and liquid-crystal compounds is organic matter, therefore deteriorates and can turn into as caused by ultraviolet (UV) Problem.In order to solve such a problem, employ and UV absorbents etc. are added in the diaphragm of the polarization plates used into display device Countermeasure.Such as in patent document 1, by adding UV absorbents in the diaphragm of the polarization plates used into these display devices And realize preventing for the deterioration to component.

In addition, also requiring the slimming of optical film during the slimming of display device in recent years promotes, also develop The optical film of diaphragm is gone out not possess., it is necessary to which the components matching being added in existing diaphragm arrives in such a optical film In other components, such as assign UV absorption functions to the adhesive phase being laminated on optical film sometimes.In patent document 2, record There is the bonding sheet for the one side that the UV absorbents synthesized by the monomer mixture comprising UV absorbability monomers are coated on to its base material.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2006-308936 publications

Patent document 2：Japanese Unexamined Patent Publication 2008-56859 publications

The content of the invention

Invent problem to be solved

Above-mentioned UV absorbents need to select absorbability with light, i.e. absorb the light of ultraviolet range, playing prevents component The effect of deterioration, on the other hand, absorption characteristic is not shown to blue light (visible region for being greater than 430nm).

In addition, the UV absorbents are in order to be fitted into the member of formation of the display devices such as adhesive, optical film, it is necessary to have and structure High-affinity into component, highly dissoluble in a solvent.If the compatibility of UV absorbents is insufficient, such as to bonding In the case of adding UV absorbents in agent, UV absorbents can ooze out, and hinder adhesive function, in addition, if to adhesive coating fluid In solvent in dissolubility it is low, then UV absorbents will not be evenly dispersed in member of formation, are had light absorbs function and are not filled Situation about dividing.

In addition, when heating and stretching after the addition UV absorbents into optical films such as phase retardation films, UV absorbents can be to film Surface is oozed out, and can not fully embody light absorbs function.Thus, in order to be used as UV absorbents, the structure with display device Compatibility into the material of component, the dissolubility in various solvents need excellent.

Thus, it is an object of the present invention to provide a kind of light absorption composition, and it is to the short wavelength's near 400nm Visible ray shows light extraction selection absorbability, while with the compatibility of the material of the member of formation of display device and/or various molten Dissolubility in agent is high.

For solving the method for problem

The present invention provides following suitable mode.

[1] a kind of light absorption composition, it is the light absorption combination for including at least two kinds of light selection absorbing compounds There is identical to be conjugated architecture for thing, at least two kinds of light selection absorbing compounds.

[2] the light absorption composition according to described in [1], wherein, at least two kinds of has identical conjugation tying The difference of the maxima and minima of the maximum absorption wavelength of the light selection absorbing compounds of structure is below 5nm.

[3] the light absorption composition according to described in [1] or [2], wherein, the selection of at least two kinds of light is inhaled The property received compound is to select absorbing compounds by the light of formula (I) or formula (II) expression,

Change 1

[in formula,

R¹The alkyl of hydrogen atom or carbon number 1~10 is represented, in the case where the alkyl has at least one methylene, At least one of the methylene can be substituted by oxygen atom or sulphur atom,

R²And R³The alkyl of hydrogen atom or carbon number 1~12 is represented independently of one another,

A represents methylene, secondary amino group, oxygen atom or sulphur atom,

X¹And X²Electron-withdrawing group, X are represented independently of one another¹And X²It can be interconnected and form ring structure]；

Change 2

[in formula,

R¹、X¹、X²With above-mentioned synonymous,

A²Hydrogen atom, the alkyl of carbon number 1~6, aromatic hydrocarbyl or aromatic heterocycle are represented, is had in the alkyl In the case of at least one methylene, at least one of the methylene can be substituted by secondary amino group, oxygen atom, sulphur atom, the fragrance Race's alkyl and aromatic heterocycle can have substituent].

[4] the light absorption composition according to described in [3], wherein, the light represented with the formula (I) selects to absorb Property compound be that the light represented with formula (I-2) selects absorbing compounds,

Change 3

[in formula,

R¹With above-mentioned synonymous,

R⁴The alkyl of hydrogen atom or carbon number 2~50 is represented, in the case where the alkyl has at least one methylene, At least one of the methylene can be substituted by oxygen atom],

The light selection absorbing compounds represented with the formula (II) are that the light represented with formula (II-2) selects absorbability Compound,

Change 4

[in formula, R¹And R⁴With it is above-mentioned synonymous].

[5] the light absorption composition that any one of [1]~[4] according to are recorded, wherein, in the light absorption group Contained at least two kinds of light with identical conjugation architecture are selected in absorbing compounds in compound, light absorption composition In the maximum light selection absorbing compounds of content content and the total amount of the content of other light selection absorbing compounds Ratio is 1：10~10：1.

[6] the light absorption composition that any one of [1]~[5] according to are recorded, it meets formula (1), formula (2) and formula (3)：

ε(420)/ε(400)≤0.3 (1)

λmax≤420nm (2)

ε(400)≥20 (3)

[in formula,

ε (420) represents gram absorptivity under wavelength 420nm,

ε (400) represents gram absorptivity under wavelength 400nm,

λ max represent maximum absorption wavelength].

[7] a kind of polymer composition, its contain any one of described [1]~[6] record light absorption composition and Polymer.

[8] polymer composition according to described in [7], wherein, for the mass parts of polymer 100 The content of the light absorption composition be 1~15 mass parts.

[9] a kind of optical film, it includes the polymer composition described in [7] or [8].

[10] optical film according to described in [9], its thickness are 0.1~18 μm.

[11] a kind of laminated polarizing film, it includes the optical film and polarizing coating described in [9] or [10].

[12] the laminated polarizing film according to described in [11], it meets following formula (4) and formula (5)：

Ap(400)≥0.4 (4)

Ap(420)/Ap(400)≤0.3 (5)

[in formula,

Ap (400) represents the absorbance of the optical film on the transmission direction of principal axis of the polarizing coating under wavelength 400nm,

Ap (420) represents the absorbance of the optical film on the transmission direction of principal axis of the polarizing coating under wavelength 420nm].

[13] a kind of laminated phase-difference film, it includes the optical film and phase retardation film described in [9] or [10].

[14] a kind of elliptical polarization film, it includes optical film, polarizing coating and the phase difference described in [9] or [10] Film.

[15] a kind of display device, it includes the film that any one of described [9]~[14] are recorded.

Invention effect

According to the present invention it is possible to provide a kind of light absorption composition, the visible ray of its short wavelength near to 400nm Show that light extraction selection is absorbefacient simultaneously, with the compatibility of the material of the member of formation of display device and/or in various solvents Dissolubility it is high.

Brief description of the drawings

Fig. 1 is the constructed profile of the example of the Rotating fields for the optical laminate for representing an embodiment of the invention.

Fig. 2 is the constructed profile of the example of the Rotating fields for the optical laminate for representing an embodiment of the invention.

Embodiment

Hereinafter, embodiments of the present invention are described in detail.Moreover, the scope of the present invention is not by reality described herein as The mode of applying is limited, and various changes can be carried out in the scope for not damaging spirit of the invention.

The light absorption composition of the present invention is to include the composition that at least two kinds of light selects absorbing compounds, at least 2 There is the above-mentioned light selection absorbing compounds of kind identical to be conjugated architecture.Moreover, in the present invention, so-called conjugation architecture, Represent molecular structure of the pi-electron system along strand non-localized.So-called conjugation architecture, such as can enumerate following by four The structure of the angular scope enclosed.Moreover, in following chemical formulas, with the conjugation architecture (model enclosed by quadrangle The structure enclosed) bonding part be methylene, as long as but be conjugated architecture do not extend, the part is not limited to methylene Base, such as methine etc. can be enumerated.

Change 5

Carbon number possessed by being conjugated architecture is preferably 1~20, more preferably 2~15, more preferably 3~ 10.If being conjugated carbon number possessed by architecture, within the above range, light absorption composition of the invention will be in distress To absorb blue light, the visible ray to the short wavelength near 400nm shows that light extraction selects absorbefacient trend.

In the light absorption composition of the present invention, contained at least two kinds of light selection absorbing compounds in said composition Architecture is conjugated with identical.Thus, in the case where with the addition of the light absorption composition of the present invention into adhesive sheet, Oozing out for the selection absorbing compounds of the light in adhesive can be suppressed, while the adhesive function of adhesive is difficult to be hindered. Further, since light oozing out for absorbing compounds of selection is inhibited, therefore the light of high concentration can be coordinated to select into adhesive Absorbing compounds are selected, thinness and light absorption while excellent adhesive sheet can be obtained.With the slimming of display device, It is also required to each component being thinned, but if carrying out the slimming of component, it is necessary to improve and coordinate the light in the component to inhale Receive the concentration of agent.According to the light absorption composition of the present invention, it is inhibited due to oozing out, therefore the slim of component can be tackled Requirement.In addition, in the case where with the addition of the light absorption composition of the present invention into optical film, light selection can be suppressed and inhaled The property received compound is oozed out, while can be suppressed optical function and be hindered.Moreover, in the present invention, as long as above-mentioned light absorption There is contained at least two kinds of light selection absorbing compounds identical to be conjugated architecture in composition, then can also contain tool There are other light selection absorbing compounds of the conjugation architecture different from the conjugation architecture.

In the suitable embodiment of the present invention, conjugated system possessed by any a kind of light selection absorbing compounds Structure is identical with conjugation architecture possessed by other at least one kind of light selection absorbing compounds.That is, wrap in the composition In the case of containing the light selection absorbing compounds A with conjugation architecture a, also include has identical conjugation in the composition Architecture a other light selection absorbing compounds B.In addition, the light choosing with conjugation architecture b is also included in the composition In the case of selecting absorbing compounds C, the light selection with conjugation architecture b is preferably further also included in the composition and is absorbed Property compound D.That is, for example comprising 4 kinds of light selection absorbing compounds A~D's in the light absorption composition of the present invention In the case of, the light selection absorbing compounds for preferably not having only a kind have a case that other conjugation architecture.The situation Under, it can further suppress light and select absorbing compounds from the member of formation (optical film, adhesive etc.) of display device Ooze out, can further suppress the obstruction to the optical function of optical film and/or the adhesive function of adhesive.

Contained, at least two kinds of light choosing with identical conjugation architecture in the light absorption composition of the present invention Select in absorbing compounds, the difference of the maxima and minima of maximum absorption wavelength (also referred to as following " λ max ") is preferably 5nm Hereinafter, more preferably below 4nm, more preferably below 3nm, particularly preferably below 2nm, for example, below 1nm.It is above-mentioned The difference of λ max maxima and minima is that each light that below 5nm means that there is identical to be conjugated architecture selects absorbability The structure of compound is close to (having similar structure).If the λ max of light selection absorbing compounds maxima and minima Difference select absorbing compounds from the member of formation of display device below above-mentioned higher limit, then can further to suppress light Ooze out, furthermore it is possible to obtain the more excellent light absorption composition of light selection absorbability.Moreover, light selects absorbability The poor lower limit of the λ max of compound maxima and minima is, for example, more than 0nm.

In an embodiment of the invention, from the viewpoint of high light selection absorbability is embodied, above-mentioned light choosing It is preferably that the light represented with formula (I) or formula (II) selects absorbing compounds to select absorbing compounds,

Change 6

[in formula,

A¹Methylene, secondary amino group, oxygen atom or sulphur atom are represented,

X¹And X²Electron-withdrawing group, X are represented independently of one another¹And X²Can be interconnected and form ring structure],

Change 7

[in formula,

R¹、X¹、X²With above-mentioned synonymous,

A²Hydrogen atom, the alkyl of carbon number 1~6, aromatic hydrocarbyl or aromatic heterocycle are represented, is had in the alkyl In the case of at least one methylene, at least one of the methylene can be substituted by secondary amino group, oxygen atom, sulphur atom, the fragrance Race's alkyl and aromatic heterocycle can have substituent].Moreover, the light absorption composition in the present invention is included with above-mentioned formula (I) in the case of the compound represented and the compound both sides represented with above-mentioned formula (II), the X in formula¹、X²And R¹Respectively can be with Difference can also be identical.

In formula (I) and (II), R¹The alkyl of hydrogen atom or carbon number 1~10 is represented, selects to inhale from high light is embodied From the viewpoint of the property received, carbon number 1~8 is preferably represented, carbon number 1~5 is more preferably represented, further preferably represents that carbon is former The alkyl of subnumber 1~3.Herein, in the case where the alkyl has at least one methylene, at least one of the methylene can be by Oxygen atom or sulphur atom substitution.As the alkyl, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, tertiary fourth can be enumerated Base, n-hexyl, n-octyl, positive decyl, methoxyl group, ethyoxyl, isopropoxy and polypropylene glycol base etc..

In formula (I) and (II), X¹And X²Electron-withdrawing group is represented independently of one another.As electron-withdrawing group, such as can To enumerate-CN (cyano group) ,-NO₂(nitro), halogen atom, the alkyl ,-Y that instead of by halogen atom¹- R⁴(in formula, R⁴ Hydrogen atom, the alkyl of carbon number 2~50 are represented, in the case where the alkyl has at least one methylene, the methylene is extremely Few 1 can be substituted by oxygen atom, and substituent, Y can also be bonded with the carbon atom on the alkyl¹Expression-CO- ,- COO- ,-OCO- ,-NR⁶CO- or-CONR⁷- (R⁶And R⁷Hydrogen atom, the alkane of carbon number 1~6 are represented independently of one another Base or phenyl)).X¹And X²It can be interconnected and form ring structure, as the ring structure, such as 4~8 yuan of rings can be enumerated Ring structure, the preferably ring structure of 5 yuan of rings or 6 yuan of rings, as its example, can enumerate Michaelis acid structure, barbiturates structure, Dimetone structure etc..

For R⁴In carbon number 2~50 alkyl, from the compatibility of the material of the member of formation with display device and/ Or from the viewpoint of the dissolubility in various solvents, carbon number is preferably more than 3, more preferably more than 6.Additionally, it is preferred that For less than 40, more preferably less than 30, more preferably less than 12.Additionally, it is preferred that for carbon number 2~40 (such as 2~ 20), more preferably carbon number 3~40 (such as 3~18), more preferably 3~30 (such as 3~16), particularly preferably 6 ~12 (such as 6~14).

In R⁴In, in the case where the alkyl of carbon number 2~50 has at least one methylene, at least one methylene can To be substituted by oxygen atom, as the alkyl, such as ethyoxyl, propoxyl group, 2- methoxvethoxvmethvls can be enumerated.In addition, The polyethylene glycol groups such as diethylene glycol base, triethylene glycol base and DPG base, tripropylene glycol base etc. poly- the third two can also be enumerated Alcohol etc..

Alternatively, it is also possible in R⁴Alkyl on carbon atom on be bonded with substituent.As substituent, such as can enumerate Halogen atom, the alkyl of carbon number 1~6, cyano group, nitro, the alkyl sulphinyl of carbon number 1~6, carbon number 1~6 Alkyl sulphonyl, carboxyl, the fluoroalkyl of carbon number 1~6, the alkoxy of carbon number 1~6, the alkane of carbon number 1~6 Sulfenyl, the N- alkyl aminos of carbon number 1~6, the N of carbon number 2~12, N- dialkyl amidos, carbon number 1~6 The N of N- alkylsulfamoyl groups, carbon number 2~12, N- dialkyl sulfamine etc..

In R⁴In the case of alkyl for carbon number 2~50, from the compatibility with lyophobic dust and in hydrophobicity From the viewpoint of dissolubility in solvent, R⁴More preferably there is the alkyl of branched structure.

Herein, the so-called alkyl with branched structure, refer to that at least one of carbon atom possessed by the alkyl is tertiary carbon Or the alkyl of quaternary carbon.As the concrete example of the alkyl with branched structure of carbon number 3~12, can enumerate with following knots The alkyl of structure.

Change 8

For X¹And X², from light select absorbability and with the compatibility of the material of the member of formation of display device and/or From the viewpoint of dissolubility in various solvents ,-CN (cyano group) ,-NO are preferably each independently₂(nitro), halogen atom, Or-Y¹- R⁴In Y¹For-CO- ,-COO- or-OCO-, more preferably-CN (cyano group) or-Y¹- R⁴In Y¹ For-COO-.

In above-mentioned formula (I), R²And R³The alkyl of hydrogen atom or carbon number 1~12 is represented independently of one another, from embodying height Light selection absorbability from the viewpoint of, preferably represent the alkyl of hydrogen atom or carbon number 1~10, more preferably represent hydrogen atom Or the alkyl of carbon number 1~8, the alkyl of hydrogen atom or carbon number 1~5 is further preferably represented, particularly preferably represents hydrogen The alkyl of atom or carbon number 1~3, very preferably represents hydrogen atom.

In formula (I), A¹Represent methylene, secondary amino group, oxygen atom or sulphur atom.Secondary amino group is with formula-NR⁵- represent Substituent, R⁵Such as represent the aliphatic hydrocarbon of carbon number 1~15, preferably carbon number 1~10, more preferably carbon number 1~5 Base, alicyclic type hydrocarbon or aromatic hydrocarbyl.From the viewpoint of high light selection absorbability is embodied, A¹It is preferred that represent methylene Or oxygen atom.

In formula (II), A²Represent hydrogen atom, the alkyl of carbon number 1~6, aromatic hydrocarbyl or aromatic heterocycle. In the case that the alkyl has at least one methylene, at least one of the methylene can be by secondary amino group, oxygen atom or sulphur atom Substitution, the aromatic hydrocarbyl and aromatic heterocycle can have substituent.As being expressed as A²Alkyl, such as can enumerate Methyl, ethyl, n-propyl, isopropyl, normal-butyl, the tert-butyl group, n-hexyl, methoxyl group, ethyoxyl, isopropoxy etc..In addition, make To be expressed as A²Aromatic hydrocarbyl and the substituent that can have of aromatic heterocycle, such as halogen atom, carbon can be enumerated Alkyl, cyano group, the nitro of atomicity 1~6.As the aromatic hydrocarbyl of such a aromatic hydrocarbyl, preferably carbon number 6~12, Such as phenyl, naphthyl etc. can be enumerated.In addition, the aromatic heterocycle as aromatic heterocycle, preferably carbon number 3~9, Such as pyridine radicals, quinolyl, thienyl, imidazole radicals, oxazolyls, pyrrole radicals, thiazolyl and furyl etc. can be enumerated.From From the viewpoint of easness in manufacture, A²Preferably phenyl or naphthyl, more preferably phenyl.

The feelings of the compound represented with above-mentioned formula (I) more than at least two kinds of are included in the light absorption composition of the present invention Under condition, the R in the formula (I) of each compound is represented¹~R³、X¹、X²And A¹Respectively can difference can also be identical, but R¹~R³、 X¹、X²And A¹In at least one it is different.In the preferred embodiment of the present invention, in the light absorption composition bag of the present invention Containing in the case of at least two kinds of compounds represented with above-mentioned formula (I) above, light absorption group of the invention is improved from further From the viewpoint of the light selection absorbability of compound, the R in the formula (I) of each compound is represented¹~R³、X¹And A¹Identical, X respectively²No Together.In the case where the light absorption composition of the present invention includes the compound represented with above-mentioned formula (II) more than at least two kinds of, Represent the R in the formula (II) of each compound¹、X¹、X²And A²Respectively can difference can also be identical, but at least one is different. The present invention preferred embodiment in, the present invention light absorption composition include it is at least two kinds of more than with above-mentioned formula (II) in the case of the compound represented, absorbefacient sight is selected from the light of the further light absorption composition for improving the present invention Point considers, represents the R in the formula (II) of each compound¹、X¹And A²Identical, X respectively²It is different.

Absorbing compounds are selected as the light represented with formula (I), such as compound represented with following formula etc. can be enumerated.

Change 9

Change 10

In formula (I-1-2), A¹、R¹~R⁴、X¹And Y¹Meaning same as described above is represented respectively.

Select absorbing compounds for the light that is represented with formula (I), due to light selection absorbability, with display device The compatibility of the material of member of formation and/or dissolubility in various solvents are excellent, therefore preferably with following formula (I-2) table The light selection absorbing compounds shown.

Change 11

In formula (I-2), R¹And R⁴With it is above-mentioned synonymous.

As the compound represented with formula (I-2), specifically, compound as follows can be enumerated.

Change 12

Change 13

Change 14

Change 15

Absorbing compounds are selected for the light represented with formula (II), the easness in absorbability and manufacture is selected from light Viewpoint considers that the light preferably represented with following formula (II-2) selects absorbing compounds.

Change 16

In formula, R¹And R⁴With it is above-mentioned synonymous.

As the compound represented with formula (II-2), specifically, compound as follows can be enumerated.

Change 17

Change 18

Change 19

Change 20

Change 21

In addition, selecting absorbing compounds as the light represented with formula (II), the chemical combination represented with following formula can also be enumerated Thing etc..

Change 22

The compound represented with the formula (I-2) for example can be by the way that 2- methylpyrrolines be made using methylating agent 1,2- dimethyl pyrrole quinoline salt, next, be allowed to and N, N '-amitraz diphenylurea react.Finally, in acetic anhydride and amine In the presence of catalyst, activity methene compound is set to react and manufacture.The compound represented with the formula (I) and (I-1-2) It can utilize and be manufactured with the compound identical method represented with the formula (I-2).The change represented with formula (II) and (II-2) Compound can be by making 3- formyls indoles react (Knoevenagel reactions) with activity methene compound to obtain, can also In reaction and use amine catalyst.R in formula (II) and (II-2)¹, can in the case of alkyl for carbon number 1~10 By making haloalkyl and 3- formyl indole reactions in the presence of base catalyst, to be allowed to thereafter and activity methene compound React and manufacture required light selection absorbing compounds.In addition, commercially available product can also be used as these compounds.

Contained, at least two kinds of light choosing with identical conjugation architecture in the light absorption composition of the present invention Select in absorbing compounds, the maximum light selection absorbing compounds of the content in light absorption composition are being set to compound In the case of cmax, the content of the compound cmax in light absorption composition and containing for other light selection absorbing compounds The ratio ([compound cmax content] of the total amount of amount：[total amount of the content of other light selection absorbing compounds]) preferably For 1：10~10：1, more preferably 1：8~8：1, more preferably 1：6~6：1, particularly preferably 1：5~5：1, it is especially excellent Elect 1 as：4~4：1, particularly preferably 1：3~3：1, for example, 1：2~2：1.If above-mentioned ratio is within the above range, can To suppress oozing out for light selection absorbing compounds, can be allowed to be difficult to hinder as the adhesive function of adhesive, as optics The optical function of film.

The compatibility of above-mentioned light absorption composition and the member of formation of display device (such as adhesive, optical film etc.) And/or the dissolubility in various solvents is excellent.If the dissolubility in the solvent for forming adhesive coating fluid is excellent, can So that light selection absorbing compounds are homogeneously dispersed in adhesive sheet, therefore can obtain with excellent light absorption Adhesive.As the solvent, for example, can enumerate methanol, ethanol, ethylene glycol, isopropanol, n-butyl alcohol, 2- butanol, propane diols, The alcoholic solvents such as methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether；Ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetic acid The ester solvents such as ester, gamma-butyrolacton, propylene glycol methyl ether acetate, ethyl lactate；Acetone, 2- butanone, cyclopentanone, cyclohexanone, The ketone solvents such as methyl amyl ketone, methyl iso-butyl ketone (MIBK)；The aliphatic hydrocarbon solvents such as pentane, hexane, heptane；Toluene, dimethylbenzene, equal three The aromatic hydrocarbon solvents such as toluene；The nitrile solvent such as acetonitrile；The ether solvents such as tetrahydrofuran, dimethoxy-ethane, the dioxane of Isosorbide-5-Nitrae-；With And the chlorinated hydrocarbon solvent such as dichloromethane, chloroform, chlorobenzene.

In the solvent, there are hydrophilic solvent and hydrophobic solvent.Although such as alcoholic solvent also will according to carbon number and It is fixed, but it is typically hydrophilic solvent.On the other hand, the aliphatic hydrocarbon solvent such as pentane, hexane, heptane is typically Hydrophobic solvent.From the viewpoint of the selectivity that can widen solvent, preferably above-mentioned light absorption composition dissolves in parent In aqueous solvent or hydrophobic solvent, more preferably the light absorption composition is dissolved in hydrophilic solvent and hydrophobic solvent, More preferably have amphipathic.

The compatibility of the light absorption composition and adhesive, optical film etc. of the present invention is especially excellent.It is if viscous with forming The compatibility of the polymer (particularly acrylic resin) of mixture is excellent, then can suppress light and select absorbing compounds from viscous Oozing out in mixture piece, it is difficult to hinder adhesive function possessed by adhesive sheet.In addition, if the light absorption combination of the present invention Thing and polymer (the particularly polyvinyl alcohol, makrolon, polyester, polyarylate, polyimides, polyolefin, poly- for forming optical film Cycloolefin, polystyrene, polysulfones, polyether sulfone, polyvinylidene fluoride/polymethyl methacrylate, acetylcellulose, ethene-second Vinyl acetate copolymer is saponified, polyvinyl chloride) compatibility it is excellent, then can suppress light and select absorbing compounds from optics Oozing out in film, therefore, it is difficult to hinder optical function possessed by optical film.In addition, if the polymer with forming diaphragm The compatibility of (particularly triacetyl cellulose, cyclic olefin polymer) is excellent, then can suppress light select absorbing compounds from Oozing out in diaphragm.

Above-mentioned light absorption composition preferably meets following formula (1).

ε(420)/ε(400)≤0.3 (1)

In formula (1), ε (420) represents gram absorptivity of the light absorption composition under wavelength 420nm, and ε (400) is represented Gram absorptivity of light absorption composition under wavelength 400nm.ε (420)/ε (400) value is represented relative to wavelength 420nm Under absorption intensity (gram absorptivity) for wavelength 400nm under absorption intensity (gram absorptivity), the value is smaller, Then more there can be specificity to absorb in the wavelength region near 400nm compared with the absorption of the wavelength region near 420nm, it is more aobvious Show to select absorbability with light.The value is smaller, and jaundice is fewer, more as transparent compound.

In the case where above-mentioned light absorption composition meets above-mentioned formula (1), absorbing wavelength 400nm light, on the other hand, It is difficult to absorbing wavelength 420nm light, it is difficult to absorb the visible ray of blueness, therefore the light absorption composition of the present invention can be made To be difficult to hinder the light absorber of good color representation to provide.In addition, in the optics stacking comprising the light absorption composition In the case of body, it can suppress to form component (such as the optical film such as phase retardation film, organic EL element or the liquid crystal of optical laminate The display elements such as display element) because of the visible ray of short wavelength (light i.e. near wavelength 400nm) performance degradation occurs.Above-mentioned light The ε (420) of absorbing composition/ε (400) value is preferably less than 0.3, more preferably less than 0.25, more preferably 0.2 Hereinafter, particularly preferably less than 0.15, especially preferably less than 0.1, very preferably less than 0.05, for example, less than 0.03. Its lower limit is not particularly limited, but from the absorbability maintained near the 400nm that is brought by above-mentioned light absorption composition From the viewpoint of, it is often preferred that more than 0.005.In the suitable embodiment of the present invention, ε (420)/ε's (400) It is worth for 0.01~0.17.

In addition, above-mentioned light absorption composition preferably in addition to meeting above-mentioned formula (1), also meet following formula (2) and (3)。

λmax≤420nm (2)

ε(400)≥20 (3)

In formula (2), λ max represent the maximum absorption wavelength of light absorption composition.In formula (3), ε (400) represents wavelength Gram absorptivity of light absorption composition under 400nm, the unit of gram absorptivity are defined by L/ (gcm).

In the case where meeting above-mentioned formula (2) and (3), it may be said that be that the maximum absorption of light absorption composition is present in 420nm short wavelength side, and the composition of high-selenium corn is nearby shown to wavelength 400nm.By making above-mentioned light absorption group Compound meets such a formula, and the component such as optical film comprising said composition is difficult to impact display characteristic, can have High-light-fastness.In the present invention, the maximum absorption λ max of light absorption composition are more preferably below 410nm, more preferably Below 400nm.The maximum absorption λ max of light absorption composition are, for example, more than 370nm.

In addition, in the case where above-mentioned light absorption composition meets above-mentioned formula (3), due to high light absorption, Even if it is a small amount of therefore to form light absorption composition contained in the component of optical laminate, inhaled in adhesive containing the light It also is difficult to hinder its adhesive function in the case of the property received composition, in addition the feelings containing the light absorption composition in diaphragm Under condition, it is difficult to hinder the optical function as diaphragm.ε (400) value is preferably more than 20 [L/ (gcm)], more preferably More than 30 [L/ (gcm)], more than more preferably 40 [L/ (gcm)], still more preferably for 50 [L/ (gcm)] with On, more than particularly preferably 80 [L/ (gcm)], more than very preferably 90 [L/ (gcm)].Moreover, ε (400) value is led to Often for 300 [L/ (gcm)] below.

In other embodiments of the present invention, there is provided the polymer containing above-mentioned light absorption composition and polymer Composition (below also referred to as " polymer composition of the invention ").By using the polymer composition, can be formed The various components (such as adhesive sheet, diaphragm, polarizing coating, phase retardation film and front panel etc.) of optical laminate.The optical layer Stack is because containing the excellent above-mentioned light absorption composition of light selection absorbability, therefore, it is difficult to absorb the visible ray of blueness, institute To be difficult to hinder good color representation.In addition, the performance of display element, optical film as the member of formation of display device is not It can only deteriorate because of ultraviolet, can also be deteriorated because of the visible ray in short wavelength region, the light i.e. near wavelength 400nm, but this Caused by invention can suppress the visible ray as short wavelength of the component of composition optical laminate contained in image display device Deterioration.

The thickness of the optical film of the present invention is not particularly limited, but preferably generally less than 18 μm, more preferably 13 μm Hereinafter, more preferably less than 8 μm.If the thickness of optical film is below above-mentioned higher limit, even if contained in optical film Light absorption composition concentration it is high, it is also difficult to generation is oozed out, and is readily available slim optical laminate, while can play Function possessed by stabilized light absorption and optical film (such as phase difference function, adhesive sheet possessed by phase retardation film Possessed adhesive function).In addition, the lower limit of the thickness of the optical film of the present invention is not particularly limited, but preferably 0.1 More than μm, more preferably more than 1 μm, more preferably more than 2 μm.If the thickness of optical film is below above-mentioned higher limit, Then from the viewpoint of slimming preferably.Moreover, the thickness of optical film is such as can utilize laser microscope, ellipsometer Measure.

In other embodiments of the present invention, the adhesive and optical film for including above-mentioned polymer composition are also provided (also referred to as " optical film of the invention ").In the present invention, as optical film, can enumerate polarizing coating, phase retardation film, diaphragm, Adhesive sheet and front panel etc..These optical films and adhesive can be enumerated as the component for forming optical laminate.And And in the present invention, so-called optical laminate, refer to the layered product of the optical film comprising the present invention, include laminated polarizing described later Film, laminated phase-difference film and elliptical polarization film.

Herein, for optical laminate, several suitable Rotating fields are represented with constructed profile in Fig. 1 and Fig. 2 Example.In example shown in Fig. 1, there can be the first diaphragm 4 of surface-treated layer 2 in the one side fitting of polarizing coating 1, the One diaphragm 4 is bonded with the face with its opposite side of surface-treated layer 2, in the protection of another side fitting second of polarizing coating 1 Film 3, so as to form polarization plates 10.In the outside for the second diaphragm 3 for forming polarization plates 10, adhesive sheet 20 is set, forms band There are the polarization plates 15 of adhesive.Hereafter, the face of the adhesive sheet 20 and polarization plates 10 opposite side is fitted in into image to show Element 30, form optical laminate 40.The optical laminate can be used for image display device.Moreover, include the light of the present invention The component preferred disposition of absorbing composition is in image-displaying members such as the optical films or organic EL element easily deteriorated Observation side.Using the configuration, the reduction of the function of the component easily deteriorated can be suppressed.

In addition, in example shown in Fig. 2, there can be the first protection of surface-treated layer 2 in the one side fitting of polarizing coating 1 Film 4, the first diaphragm 4 are bonded with the face with its opposite side of surface-treated layer 2, are protected in the another side fitting second of polarizing coating 1 Cuticula 3, then phase retardation film 7 is bonded across interlayer adhesive 6 in the outside of the second diaphragm 3 folder, form polarization plates 10.Forming The outside of the phase retardation film 7 of polarization plates 10 sets adhesive sheet 20, so as to form the polarization plates 15 with adhesive.In addition, will The adhesive sheet 20 fits in image-displaying member 30 with the face of the opposite side of phase retardation film 7, forms optical laminate 40.

In these examples, it is however generally that the first diaphragm 4 and the second diaphragm 3 include tri acetyl cellulose membrane or polycyclic Alkene, but can also be formed with following transparent resin films.Furthermore it is possible to it is formed at the surface on the surface of the first diaphragm 4 Process layer can also be hard conating, antiglare layer, anti-reflection layer, anti-static electricity interference layer etc..It can also set multiple among them Layer.

In the case where example as shown in Figure 2 is laminated phase retardation film 7 like that in polarization plates 10, if middle-size and small-size Liquid crystal display device, then the suitable example as the phase retardation film 7 can enumerate 1/4 wavelength plate.In this case, in general, with The absorption axiss of polarizing coating 1 are made generally to be configured with the slow axis of the phase retardation film 7 as 1/4 wavelength plate in a manner of 45 degree intersect, But according to the characteristic of image-displaying member 30 angle can also be made to deviate 45 degree to a certain extent.On the other hand, such as Fruit is the large-scale liquid crystal display device such as television set, then the mesh of the phase difference compensation for image-displaying member 30 or viewing angle compensation , the phase retardation film with various phase difference values using the characteristics match with the image-displaying member 30.It is in this case, general For in a manner of making the absorption axiss of polarizing coating 1 be generally orthogonal or generally parallel relation with the slow axis of phase retardation film 7 Configuration., can be suitably using stretched film uniaxially or biaxially in the case where forming phase retardation film 7 with 1/4 wavelength plate.Separately Outside, in the case where setting phase retardation film 7 for the purpose of the phase difference compensation of image-displaying member 30 or viewing angle compensation, except Uniaxially or biaxially beyond stretched film, will can also be gone back beyond uniaxially or biaxially stretching film that through-thickness is allowed to be orientated, Coating of liquid crystalline equiphase difference embodies material and is allowed to the film that film that orientation secures etc. is referred to as optical compensation films on support membrane Used as phase retardation film 7.

Phase retardation film 7 is pressed from both sides in the composition of polarization plates 10 like that in example similarly as shown in Figure 2 and glued across interlayer In the case that mixture 6 is bonded, as the interlayer adhesive 6, it is common practice to using in general acrylic adhesive, but herein The adhesive or adhesive sheet of the polymer composition comprising the present invention can be used.In large-scale liquid crystal display as elucidated before Device is such, so that the absorption axiss of polarizing coating 1 are generally orthogonal or generally parallel relation with the slow axis of phase retardation film 7 In the case that mode configures, when making polarization plates 10, it can be pressed from both sides by polarizing coating 1 and phase retardation film 7 across interlayer adhesive 6 Volume to volume fitting is carried out during fitting.

The phase retardation film with adhesive formed with adhesive sheet is except can be by its adhesive sheet on phase retardation film Fit in image-displaying member and be made beyond optical laminate, polarization plates can also be bonded in its phase retardation film side.

Herein, so-called polarizing coating (" polarizer "), it is with the function that polarised light is projected relative to incident lights such as natural lights Optical film.In polarization plates, there are linear polarization plate, polarization separating film, elliptical polarization plate etc., the linear polarization plate, which has, to be inhaled Receive the rectilinearly polarized light for the vibration plane with some direction for injecting polarization plate face, transmit with the straight of orthogonal vibration plane The property of linearly polarized light, the polarization separating film inject the linear polarization of the vibration plane with some direction of film surface with reflection Light, transmission with orthogonal vibration plane rectilinearly polarized light property, the elliptical polarization plate be by polarization plates with it is aftermentioned Phase retardation film stacking and obtain.As polarization plates, particularly linear polarization plate (sometimes referred to as polarizer or polarizer membrane) Suitable concrete example, can enumerate by uniaxial tension polyvinyl alcohol resin film on be adsorbed with iodine or dichroic dye Etc. dichroism pigment and it is allowed to the material being orientated.Alternatively, it is also possible to use the film polarizing coating of application type.As application type Film polarizing coating, such as Japanese Unexamined Patent Publication 2012-58381, Japanese Unexamined Patent Publication 2013-37115, International Publication No. can be used 2012/147633rd, the material illustrated in International Publication No. 2014/091921.The thickness of polarizer is not particularly limited, but logical Often use 0.5~35 μm of polarizer.

So-called phase retardation film, it is to show optically anisotropic optical film, such as can enumerates by the way that poly- second will be included Enol, makrolon, polyester, polyarylate, polymethacrylates, polyimides, polyolefin, polycyclic alkene (ENB, four The polymer of cyclododecene or their derivative), polystyrene, polysulfones, polyether sulfone, polyvinylidene fluoride/polymethyl The polymer such as sour methyl esters, liquid crystal polyester, acetylcellulose, ethylene-acetidin copolymer saponification material, polyvinyl chloride gather Compound film is stretched as stretched film etc. obtained by 1.01~6 times or so.Wherein, preferably by polycarbonate membrane, polycyclic alkene film single shaft Stretching or it is biaxial stretch-formed obtained by polymer film.In an embodiment of the invention, to including above-mentioned polymer and this hair The composition of bright light absorption composition carries out membranization, and the film of gained is stretched uniaxially or biaxially, it is hereby achieved that Phase retardation film.Alternatively, it is also possible to which optically anisotropic film will be embodied because the coating of polymerizable liquid crystal compound is orientated Used as phase retardation film.

In addition it is also possible to the film that diaphragm has been bonded on these optical films is used as optical film.As diaphragm, Transparent resin film can be used, as the transparent resin, such as can enumerate using triacetyl cellulose, diacetyl cellulose as The acetyl fibre prime system resin that represents, using polymethyl methacrylate as the methacrylic resin of representative, polyester resin, poly- Olefin-based resin, polycarbonate resin, polyether-ether-ketone resin, polysulfone resin etc..In the resin for forming diaphragm, it can also match somebody with somebody Close salicylate based compound, benzophenone based compound, BTA based compound, triazine based compound, alpha-cyanoacrylate The ultra-violet absorbers such as ester based compound, nickel complex based compound, in this case, being combined using the light absorption with the present invention The cooperative effect of the effect of thing, it can rightly suppress the deterioration of display device.As diaphragm, three second can be suitably used The acetylcellulose resin film such as acyl cellulose membrane.

Among the optical film being described above, linear polarization plate be often with formed it polarizing coating, for example comprising The state that the one or both sides of the polarization plates of polyvinyl alcohol resin are fitted with diaphragm uses.In addition, foregoing elliptical polarization Plate is to be laminated linear polarization plate and phase retardation film and obtain, and the polarization plates are also often with the one or both sides of polarization plates patch The state that closing has diaphragm uses.

In addition, so-called diaphragm, be in order at protect as by the surface of the optical film of protective etc. from damaging or polluting The film that uses of purpose.As the base material of diaphragm, such as the polyolefin such as polyethylene, polypropylene, polymethylpentene can be enumerated； The fluoro polyolefin such as polyethylene fluorine, polyvinylidene fluoride, polyvinyl fluoride；PEN, poly terephthalic acid second Diol ester, polybutylene terephthalate (PBT), polyethylene terephthalate/ethylene isophthalate copolymer etc. is poly- Ester；Nylon 6, the grade polyamide of nylon 6,6；Polyvinyl chloride, vinyl chloride vinyl acetate copolymer, ethane-acetic acid ethyenyl ester are common The polyvinyls such as polymers, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, vinylon；Cellulose triacetate, oxalic acid fiber The cellulosic polymers such as element, glassine paper, triacetyl cellulose；Polymethyl methacrylate, polyethyl methacrylate, polypropylene The acrylic polymers such as acetoacetic ester, butyl polyacrylate；It is and polystyrene, makrolon, polyarylate, polyimides, poly- Urethane etc..

So-called adhesive sheet, it is the piece for including adhesive.Adhesive is to be used to make the components such as above-mentioned optical film and other structures The reagent of part engagement.The polymer for forming adhesive is not particularly limited, such as can enumerate poly- (methyl) acrylate (propylene Acid resin), siloxane polymer, polyurethane and rubber etc..Above-mentioned polymer can be used alone or in combination.Wherein, From can by select import polymer in monomer species and easily to adhesive assign it is functional from the aspect of, make It is adapted to use acrylic resin for above-mentioned polymer.Moreover, so-called (methyl) acrylate, refers to acrylate and/or first Base acrylate.

By using the present invention polymer composition, can obtain form optical laminate each component.For example, at this In one embodiment of invention, the combination of polymers by the light absorption composition comprising the present invention and polymer can be provided Adhesive sheet, diaphragm, phase retardation film, polarizing coating and front panel that thing is formed etc..

For polymer contained in above-mentioned polymer composition, from the structure that can rightly manufacture composition optical laminate From the viewpoint of part, above-mentioned acrylic resin [poly- (methyl) acrylate], polyurethane, polyester, poly- carbon are preferably selected from It is at least one kind of in acid esters, polycyclic alkene and triacetyl cellulose.

(in the case of particularly coordinating in high concentration), bonded in the case of having coordinated UV absorbents into adhesive sheet The adhesive function of agent piece can be hindered, but the adhesive sheet of the polymer composition comprising the present invention is keeping adhesive function While, light selection absorbability is excellent, furthermore, it is possible to suppress from oozing out in adhesive sheet, therefore can play for a long time steady Surely the light absorption changed.In the display device of the adhesive sheet has been used, it is not necessary to which configuration has other of light absorbs function Component, therefore the slimming and lightweight of display device can be realized.

In an embodiment of the invention, above-mentioned polymer composition can also be inhaled in above-mentioned polymer and above-mentioned light Beyond the property received composition, also contain crosslinking agent as needed.Crosslinking agent being particularly for example, and in poly- (methyl) acrylate Come from the Component units reaction of the monomer containing hydroxyl, polar functional group, make poly- (methyl) acrylate cross linked compound. Specifically, isocyanates based compound, epoxy based compound, aziridine based compound, metal-chelating materialization can be exemplified Compound etc..

Among them, isocyanates based compound, epoxy based compound and aziridine based compound have extremely in intramolecular Few 2 functional groups that can be reacted with the hydroxyl in poly- (methyl) acrylate (A) and the polar functional group according to circumstances having.

In above-mentioned polymer composition, light for the mass parts of above-mentioned polymer (solid constituent) 100, above-mentioned The content of absorbing composition (being preferably the total amount of light selection absorbing compounds contained in light absorption composition) is preferred For 1~15 mass parts, more preferably 1.5~12 mass parts, more preferably 2~10 mass parts, particularly preferably 2.2~8 Mass parts.If the content of above-mentioned light absorption composition is more than above-mentioned lower limit, the light quantity absorbed becomes more, can press down System form optical laminate component (such as the image-displaying member such as the optical film such as phase retardation film, organic EL element) by shortwave Deterioration caused by long visible ray.If the content of above-mentioned light absorption composition is below above-mentioned higher limit, will polymerize Compositions can fully play adhesive function when being used in adhesive, be more difficult to hinder conduct to use combination of polymers in addition The optical function for the optical film that thing obtains.Moreover, above-mentioned light absorption composition is because the dissolubility in various solvents is excellent, Therefore even if above-mentioned content is high (such as the mass parts of above-mentioned polymer (solid constituent) 100, above-mentioned light absorption The content of composition (being preferably the total amount of light selection absorbing compounds contained in light absorption composition) is preferably 1 mass Part more than, more preferably more than 1.5 mass parts, more preferably more than 2 mass parts, particularly preferably 2.2 mass parts with On), it can also suppress to ooze out, can be allowed to be difficult to hinder the adhesive function as adhesive, the optical function as optical film.

In the case where the polymer composition of the present invention is to form the adhesive composition of adhesive sheet, the present invention's In preferred embodiment, polymer composition of the invention contains：

(A) acrylic resin, its on the basis of the overall amount of the solid constituent of acrylic resin (polymer), be with (A-1) the mass % of (methyl) acrylate monomer 50~99.9 and (A-2) represented with following formula (A-1) has polarity official Copolymers of the mass % of unsaturated monomer 0.1~50 that can be rolled into a ball as constituent, weight average molecular weight are 500,000~2,000,000；

Change 23

And

(B) relative to the crosslinking agent that the mass parts of acrylic resin 100 are 0.01~10 mass parts.

In the formula (A-1), R^pFor hydrogen atom or methyl.R^qThe alkyl or aralkyl of carbon number 1~20 are represented, it is excellent Elect the alkyl or aralkyl of carbon number 1~10 as, the hydrogen atom for forming the alkyl or the aralkyl can also be by-O- (C₂H₄O)_n- R^rSubstitution.Herein, n preferably represents 0~4, integer of more preferably expression 0~3, R^rRepresent to be preferably carbon number 1 ~12 alkyl, the more preferably alkyl of carbon number 1~5, the preferably aryl of carbon number 1~12, more preferably carbon are former The aryl of subnumber 1~10.

As (methyl) acrylate monomer (A-1) (hereinafter sometimes referred to as " monomer represented with the formula (A-1) (A-1) methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, third can "), specifically, be exemplified The alkyl acrylate of the straight-chains such as olefin(e) acid n-octyl, lauryl acrylate；Isobutyl acrylate, 2-EHA, The alkyl acrylate of the branched such as Isooctyl acrylate monomer；Methyl methacrylate, EMA, methacrylic acid third The methacrylate of the straight-chains such as ester, n-BMA, n octyl methacrylate, lauryl methacrylate Ester；The metering system of the branched such as Isobutyl methacrylate, 2-Ethylhexyl Methacrylate, EHMA Acid alkyl ester；Phenyl acrylate, benzyl acrylate etc. have the acrylate of aromatic group；Acrylic acid 2- phenoxy groups Ethyl ester, methacrylic acid 2- phenoxy ethyls, acrylic acid phenoxy group ester, phenyl methacrylate, benzyl methacrylate Deng methacrylate with aromatic group etc..They may be used alone, can also be used in combination a variety of.Wherein, from From the viewpoint of embodying cohesive, preferred n-butyl acrylate.

In the unsaturated monomer (A-2) (hereinafter sometimes referred to as " monomer (A-2) ") with polar functional group, as pole Property functional group, free carboxy, hydroxyl, amino, heterocyclic radical headed by epoxide ring etc. can be enumerated.Monomer (A-2) is preferably to have (methyl) acrylic compounds of polarized functional group.As its example, can enumerate acrylic acid, methacrylic acid and P-carboxy ethyl acrylates etc. have the unsaturated monomer of free carboxy；(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) third Olefin(e) acid 2- hydroxy propyl esters, (methyl) acrylic acid 2- or 3- chlorine-2-hydroxyl propyl ester and diethylene glycol list (methyl) propylene Acid esters etc. has the unsaturated monomer of hydroxyl；Acryloyl morpholine, caprolactam, N- vinyl -2- pyrrolidines Ketone, tetrahydrofurfuryl (methyl) acrylate, caprolactone modification tetrahydrofurfuryl acrylate, 3,4- epoxycyclohexyl-methyl (first Base) acrylate, (methyl) glycidyl acrylate and DHF etc. have the unsaturated monomer of heterocyclic radical； (methyl) acrylic acid N, N- dimethylamino ethyl ester etc. has unsaturated monomer of the amino different from heterocycle etc..These monomers (A-2) it can individually use, can also use different a variety of.

Among them, from the viewpoint of improving the adhesive tension of adhesive composition, further improving durability, preferably make The unsaturated monomer with hydroxyl is included to form one of monomer (A-2) of acrylic resin (A).

Acrylic resin (hereinafter sometimes referred to as " the propylene of Component units is used as using monomer (A-1) and monomer (A-2) Acid resin (A) ") on the basis of the overall amount of its solid constituent, preferably with 50~99.9 mass %, more preferably with 70~99.9 Quality % ratio includes the Component units for coming from monomer (A-1).Additionally, it is preferred that with 0.1~50 mass %, more preferably with 0.1~30 mass % ratio includes the Component units for coming from monomer (A-2).If monomer (A-1) and monomer (A-2) Ratio in the scope, then can provide processability more excellent adhesive composition.

In addition, can also be used as in acrylic resin (A) constituent include monomer (A-1) and monomer (A-2) with Outer other monomers (hereinafter sometimes referred to as " monomer (A-3) ").As other monomers, such as it can enumerate and have in intramolecular There are (methyl) acrylate of ester ring type structure, styrenic monomers, vinyl monomer, have multiple (methyl) in intramolecular The monomer of acryloyl group, (methyl) acrylamide derivative etc..

So-called ester ring type structure, it is that carbon number is usually more than 5, is preferably 5~7 or so cycloalkane structure.As tool There is the concrete example of the acrylate of ester ring type structure, isobornyl acrylate, cyclohexyl acrylate, the ring of acrylic acid two can be enumerated Pentyl ester, acrylic acid cyclododecane base ester, acrylic methyl cyclohexyl, acrylic acid 3-methyl cyclohexanol ester, t-butylcyclohexyl Ester, α-ethoxy-c olefin(e) acid cyclohexyl, acrylate base phenylester etc., as the methacrylic acid with ester ring type structure The concrete example of ester, isobornyl methacrylate, cyclohexyl methacrylate, the ring pentyl ester of methacrylic acid two, first can be enumerated Base acrylic acid cyclododecane base ester, methyl methacrylate base cyclohexyl, methacrylic acid 3-methyl cyclohexanol ester, methacrylic acid uncle Butylcyclohexyl ester, methacrylic acid cyclohexyl benzene base ester etc..

As styrenic monomers, in addition to styrene, methyl styrene, dimethyl styrene, three can also be enumerated Methyl styrene, ethyl styrene, diethyl, triethylbenzene ethene, propylstyrene, butylstyrene, hexyl benzene The ring-alkylated styrenes such as ethene, heptyl styrene, octyl styrene；Fluorobenzene ethene, chlorostyrene, bromstyrol, Dowspray 9, The halogenated styrenes such as iodobenzene ethene；And nitrostyrolene, acetylbenzene ethene, methoxy styrene, divinylbenzene etc..

As vinyl monomer, vinyl acetate, propionate, vinyl butyrate, 2 ethyl hexanoic acid can be enumerated The fatty acid ethylene base ester such as vinyl acetate, vinyl laurate；The vinyl halides such as vinyl chloride, bromine ethene；Vinylidene chloride etc. inclined two Halogen ethene；The nitrogenous aromatic ethenyl such as vinylpyridine, vinyl pyrrolidone, vinyl carbazole；Butadiene, isoamyl two Alkene, chlorobutadiene equiconjugate diene monomers；And acrylonitrile, methacrylonitrile etc..

As the monomer in intramolecular with multiple (methyl) acryloyl groups, BDO two (methyl) can be enumerated Acrylate, 1,6- hexylene glycols two (methyl) acrylate, 1,9- nonanediols two (methyl) acrylate, (first of ethylene glycol two Base) acrylate, diethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, (the first of tripropylene glycol two Base) acrylate etc. has the monomer of 2 (methyl) acryloyl groups in intramolecular；Trimethylolpropane tris (methyl) acrylate Deng in the monomer of intramolecular with 3 (methyl) acryloyl groups etc..

As (methyl) acrylamide derivative, N- methylols (methyl) acrylamide, 2- hydroxyethyls can be enumerated (methyl) acrylamide, 3- hydroxypropyls (methyl) acrylamide, 4- hydroxybutyls (methyl) acrylamide, 5- hydroxyls penta Base (methyl) acrylamide, 6- hydroxyls hexyl (methyl) acrylamide, N- methoxies (methyl) acrylamide, N- second Epoxide methyl (methyl) acrylamide, N- propoxy methyls (methyl) acrylamide, N- butoxymethyls (methyl) acryloyl Amine, N, N- dimethyl (methyl) acrylamide, N, N- diethyl (methyl) acrylamide, N- isopropyls (methyl) acryloyl Amine, N- dimethylaminopropyls (methyl) acrylamide, N- (1,1- dimethyl -3- oxa-s butyl) (methyl) acryloyl Amine, N- (2- (2- oxa- -1- imidazolidinyls) ethyl) (methyl) acrylamide, 2- Acryloyl amino -2- first Base -1- propane sulfonic acid etc..

The monomer (A-1), monomer (A-2) and monomer (A-3) can be used individually, or are applied in combination more Kind.In the present invention, in the acrylic resin (A) that can be used in adhesive composition, with consolidating for acrylic resin (A) On the basis of the overall amount of body composition, generally with 0~20 mass parts, preferably contained with the ratio of 0~10 mass parts come from it is described The Component units of monomer (A-3).

In an embodiment of the invention, adhesive composition can also contain the one kind or two or more propylene Acid resin (A).

The conversion of the polystyrene standard based on gel permeation chromatography (GPC) of the acrylic resin (A) is divided equally again Son amount (Mw) is preferably 500,000~2,000,000, more preferably 600,000~1,800,000, more preferably 700,000~1,700,000.If should Polystyrene standard conversion weight average molecular weight is more than 500,000, then hot and humid lower adhesivity raising, in glass substrate (image Display element) generation is tilted between adhesive sheet or the possibility of peeling has the trend of reduction, and re-workability is improved Trend, therefore preferably.In addition, if the weight average molecular weight is less than 2,000,000, then the adhesive sheet is being fitted in into optical film Deng when, even if the size of optical film changes, adhesive sheet also can follow the change in size and change, therefore in liquid crystal cells Deng there is no difference between the lightness of the peripheral part of image-displaying member and the lightness of central part, show money or valuables one carries unintentionally or irregular colour have by To the trend of suppression, therefore preferably.The molecular weight represented with the ratio (Mw/Mn) of weight average molecular weight (Mw) and number-average molecular weight (Mn) Distribution is generally in 2~10 or so scope.

The acrylic resin (A) can for example utilize solution polymerization process, emulsion polymerization, mass polymerization, suspension Various methods manufacture respectively known to polymerization etc..In the manufacture of the acrylic resin, usually using polymerization initiator.Phase For total 100 mass parts of whole monomers used in the manufacture of acrylic resin, made with 0.001~5 mass parts or so Use polymerization initiator.

As polymerization initiator, thermal polymerization or Photoepolymerizationinitiater initiater etc. can be used.As Photoepolymerizationinitiater initiater, Such as 4- (2- hydroxyl-oxethyls) phenyl (2- hydroxyl -2- propyl group) ketone etc. can be enumerated.As thermal polymerization, example It can such as enumerate 2,2 '-azodiisobutyronitrile, 2,2 '-azo two (2- methylbutyronitriles), 1,1 '-azo two (hexamethylene- 1- formonitrile HCNs), 2,2 '-azo two (2,4- methyl pentane nitrile), 2, (2, the 4- dimethyl -4- methoxyl groups penta of 2 '-azo two Nitrile), dimethyl -2,2 '-azo two (2 Methylpropionic acid ester), 2, the azo system such as 2 '-azo two (2- hydroxymethyls propionitrile) Compound；Lauroyl peroxide, TBHP, benzoyl peroxide, peroxidized t-butyl perbenzoate, hydroperoxidation are withered Alkene, di-isopropyl peroxydicarbonate, dipropyl peroxydicarbonate, new peroxide tert-butyl caprate, peroxidating neopentanoic acid uncle The organic peroxides such as butyl ester, (3,5,5- trimethyl acetyl base) peroxide；Potassium peroxydisulfate, ammonium persulfate, hydrogen peroxide etc. Inorganic peroxide etc..Alternatively, it is also possible to using and by the use of peroxide and reducing agent redox series initiators etc. as poly- Initiator is closed to use.

As acrylic resin (A) manufacture method, among method indicated above, preferred solution polymerization process.Such as The concrete example that fruit enumerates solution polymerization process illustrates, then can enumerate and mix desired monomer and organic solvent, in nitrogen Added under gas atmosphere thermal polymerization, at 40~90 DEG C or so, preferably in 50~80 DEG C or so stirrings 3~15 hours or so Method etc..In addition, in order to control reaction, can also continually or intermittently be added in polymerization monomer or thermal polymerization, Or the addition monomer of the state to be dissolved in organic solvent or thermal polymerization.Herein, as organic solvent, such as can make It is aromatic hydrocarbon with toluene, dimethylbenzene etc.；The esters such as ethyl acetate, butyl acetate；The aliphatic alcohols such as propyl alcohol, isopropanol；Third Ketones such as ketone, 2- butanone, methyl iso-butyl ketone (MIBK) etc..

Adhesive composition can also be beyond the acrylic resin (A), also containing different acrylic compounds Resin.As such a acrylic resin, such as it can enumerate using the Component units for coming from (methyl) acrylate and be used as master Composition (such as poly- (methyl) methyl acrylate) and for lower molecular weight of the weight average molecular weight in 50,000~300,000 scope Acrylic resin.

In the case of containing the acrylic resin different from acrylic resin (A) in adhesive composition, with propylene The content of the different acrylic resin of acid resin (A) is relative to the mass parts of acrylic resin (A) 100, it is often preferred that Below 50 mass parts, more preferably below 30 mass parts.

For acrylic resin contained in adhesive composition (be combined with it is of more than two kinds in the case of be them Mixture), the solution for being dissolved in that solid component concentration is adjusted to 20 mass % in ethyl acetate is aobvious preferably at 25 DEG C Below 20Pas is shown, more preferably shows 0.1~7Pas viscosity.If viscosity now is below 20Pas, Adhesivity under hot and humid improves, and the possibility for tilting or peeling off is produced between display element and adhesive sheet step-down Trend, and the trend that re-workability is improved, therefore preferably.Viscosity can utilize Brookfield viscosimeters to determine.

In adhesive composition, as crosslinking agent, such as it can use with particularly coming in acrylic resin (A) The compound reacted from the Component units in the unsaturated monomer with polar functional group, be crosslinked acrylic resin (A).Tool For body, isocyanates based compound, epoxy based compound, aziridine based compound, metallo-chelate chemical combination can be exemplified Thing etc..Among them, isocyanates based compound, epoxy based compound and aziridine based compound have at least 2 in intramolecular The individual functional group that can be reacted with the polar functional group in acrylic resin (A).

Isocyanates based compound is the compound for having at least two NCO (- NCO) in intramolecular, such as can With enumerate toluene di-isocyanate(TDI), hexamethylene diisocyanate, IPDI, XDI, Hydrogenated xylene diisocyanate, methyl diphenylene diisocyanate, hydrogenated diphenyl methane diisocyanate, the isocyanic acid of naphthalene two Ester, triphenylmethane triisocyanate etc..In addition, make the polyalcohols such as glycerine, trimethylolpropane and these isocyanates systems Compound reaction obtained by adduct, by isocyanates based compound dimer, trimer etc. is made obtained by material can also As crosslinking agent used in adhesive.The isocyanates based compound that can also be mixed with two or more.

Epoxy based compound is the compound for having at least two epoxy radicals in intramolecular, such as can enumerate bisphenol A-type Epoxy resin, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, glycerin diglycidyl ether, glycerine three shrink Glyceryl ether, 1,6- hexanediol diglycidyl ethers, trimethylolpropane tris glycidyl ether, N, N- diglycidyls Aniline, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1,3- pairs (N, N '-diglycidyl amino first Base) hexamethylene etc..The epoxy based compound that can also be mixed with two or more.

Aziridine based compound be intramolecular have at least two be also referred to as Ethylenimine by 1 nitrogen-atoms and 2 The compound of the skeleton for 3 yuan of rings that carbon atom is formed, such as can enumerate diphenyl methane -4,4 '-bis- (1- aziridine first Acid amides), Toluene-2,4-diisocyanate, double -1- (the 2- methyl of 4- double (1- aziridine formamide), three ethylene melamines, a phenyl-diformyl Aziridine), three -1- '-aziridinos phosphine oxides, hexa-methylene -1,6- double (1- aziridine formamide), trihydroxy methyls third - the β of alkane-three-'-aziridino the propionic ester ,-β of tetramethylol methane-three-'-aziridino propionic ester etc..

As meal chelate compounds, for example, can enumerate aluminium, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and Compound of acetylacetone,2,4-pentanedione or ethyl acetoacetate etc. is coordinated on the high-valency metals such as zirconium.

Among these crosslinking agents, preferably using isocyanates based compound, especially XDI, toluene two Isocyanates or hexamethylene diisocyanate make these isocyanates based compounds and glycerine or trimethylolpropane etc. The mixed of material obtained by dimer, trimer etc. is made in isocyanates based compound by adduct obtained by polyol reaction Compound, the material for being obtained by mixing these isocyanates based compounds etc..As suitable isocyanates based compound, Ke Yiju Go out toluene di-isocyanate(TDI), make toluene di-isocyanate(TDI) and adduct, the two of toluene di-isocyanate(TDI) obtained by polyol reaction The trimer and hexamethylene diisocyanate of polymers and toluene di-isocyanate(TDI), make hexamethylene diisocyanate with The three of adduct obtained by polyol reaction, the dimer of hexamethylene diisocyanate and hexamethylene diisocyanate Polymers.They can be used alone, can also composition use two or more.

In the present invention, adhesive composition relative to the acrylic resin the mass parts of solid constituent 100 (containing It is its total 100 mass parts in the case of acrylic resin of more than two kinds), preferably comprise 0.01~10 mass parts, more preferably Comprising 0.01~0.08 mass parts, further preferably include the crosslinking agents of 0.01~0.06 mass parts.If the amount of crosslinking agent is More than 0.01 mass parts, then the trend that the durability of adhesive sheet improves is had, therefore preferably, in addition, if being 10 mass parts Hereinafter, then the adhesive obtained by the adhesive composition is applied into showing money or valuables one carries unintentionally when in liquid crystal display device will not be eye-catching.

In addition, adhesive composition preferably comprises silane based compound in the present invention, especially preferably coordinating crosslinking agent Contain silane based compound in preceding acrylic resin.Silane based compound can improve the bonding force to glass, therefore pass through Containing silane based compound, can make to be improved by the display element of glass substrate clamping and the adaptation of adhesive sheet.

As silane based compound, such as vinyltrimethoxy silane, VTES, second can be enumerated Alkenyl three (2- methoxy ethoxies) silane, N- (2- amino-ethyls) -3- amino propyl methyls dimethoxysilane, N- (2- amino-ethyls) -3- TSL 8330s, APTES, 3- glycidoxies Propyl trimethoxy silicane, 3- glycidoxypropyls dimethoxysilane, 2- (3,4- epoxycyclohexyl) ethyl three Methoxy silane, 3- chloropropylmethyldimethoxysilanes, 3- r-chloropropyl trimethoxyl silanes, 3- methacryloxies Propyl trimethoxy silicane, 3-mercaptopropyi trimethoxy silane, 3- glycidoxypropyltrime,hoxysilanes, 3- rings Oxygen propoxypropyl triethoxysilane, 3- glycidoxypropyl groups dimethoxymethylsilane, 3- glycidoxypropyl groups Ethyoxyl dimethylsilane etc..They can be used alone, can also composition use two or more.

Silane based compound can also be the compound of siloxane oligomer type.If the table in the form of (monomer) oligomer Show siloxane oligomer, such as oligomer as follows can be enumerated.

3-mercaptopropyi trimethoxy silane-tetramethoxy-silicane alkyl copolymer, 3-mercaptopropyi trimethoxy silane- Tetraethoxy-silicane alkyl copolymer, 3- Mercaptopropyltriethoxysilanes-tetramethoxy-silicane alkyl copolymer, 3- mercaptopropyis three The copolymers containing mercaptopropyi such as Ethoxysilane-tetraethoxy-silicane alkyl copolymer；

Mercapto methyl trimethoxy silane-tetramethoxy-silicane alkyl copolymer, the ethoxy of mercapto methyl trimethoxy silane-four Base silane copolymer, mercapto methyl triethoxysilane-tetramethoxy-silicane alkyl copolymer, mercapto methyl triethoxysilane- The copolymer containing mercapto methyl such as tetraethoxy-silicane alkyl copolymer；

3- methacryloxypropyl trimethoxy silanes-tetramethoxy-silicane alkyl copolymer, 3- methacryloxypropyls Base propyl trimethoxy silicane-tetraethoxy-silicane alkyl copolymer, 3- methacryloxypropyls-four Trimethoxysilane copolymer, 3- methacryloxypropyls-tetraethoxy-silicane alkyl copolymer, 3- first Base acryloxypropyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer, 3- methacryloxypropyl first Base dimethoxysilane-tetraethoxy-silicane alkyl copolymer, 3- methacryloyloxypropyl methyls diethoxy silane-four Trimethoxysilane copolymer, 3- methacryloyloxypropyl methyls diethoxy silane-tetraethoxy-silicane alkyl copolymer etc. Copolymer containing methacryloxypropyl；

3- acryloxypropyls trimethoxy silane-tetramethoxy-silicane alkyl copolymer, 3- acryloxypropyls three Methoxy silane-tetraethoxy-silicane alkyl copolymer, 3- acryloxypropyls triethoxysilane-tetramethoxy-silicane are common Polymers, 3- acryloxypropyls triethoxysilane-tetraethoxy-silicane alkyl copolymer, 3- acryloxypropyls Dimethoxysilane-tetramethoxy-silicane alkyl copolymer, 3- acryloxypropyls dimethoxysilane-tetraethoxy Silane copolymer, 3- acryloxypropyls diethoxy silane-tetramethoxy-silicane alkyl copolymer, 3- acryloyl-oxies The copolymers containing acryloxypropyl such as base hydroxypropyl methyl diethoxy silane-tetraethoxy-silicane alkyl copolymer；

Vinyltrimethoxy silane-tetramethoxy-silicane alkyl copolymer, vinyltrimethoxy silane-tetraethoxy-silicane Alkyl copolymer, VTES-tetramethoxy-silicane alkyl copolymer, VTES-tetraethoxy Silane copolymer,

Vinyl methyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer, vinyl methyl dimethoxysilane-four Ethoxysilane copolymer, vinyl methyl diethoxy silane-tetramethoxy-silicane alkyl copolymer, vinyl methyl diethoxy The copolymers containing vinyl such as base silane-tetraethoxy-silicane alkyl copolymer；

3- TSL 8330s-tetramethoxy-silicane alkyl copolymer, 3- TSL 8330s- Tetraethoxy-silicane alkyl copolymer, APTES-tetramethoxy-silicane alkyl copolymer, 3- aminopropyls three Ethoxysilane-tetraethoxy-silicane alkyl copolymer, 3- amino propyl methyls dimethoxysilane-tetramethoxy-silicane copolymerization Thing, 3- amino propyl methyls dimethoxysilane-tetraethoxy-silicane alkyl copolymer, 3- amino propyl methyl diethoxy silicon Alkane-tetramethoxy-silicane alkyl copolymer, 3-amino propyl methyl diethoxy silane-tetraethoxy-silicane alkyl copolymer etc. contains Copolymer of amino etc..

For the use level of the silane based compound in adhesive composition, relative to the solid constituent of acrylic resin 100 mass parts (using being their total 100 mass parts in the case of of more than two kinds), it is generally left with 0.01~10 mass parts The right side, preferably used with the ratio of 0.01~5 mass parts.If relative to the mass parts of solid constituent 100 of acrylic resin The amount of the silane based compound of speech is more than 0.01 mass parts, then the adaptation of adhesive sheet and display element improves, therefore excellent Choosing.In addition, if below in an amount of from 10 mass parts, then becoming of can suppressing that silane based compound oozes out from adhesive sheet is had Gesture, therefore preferably.

Adhesive composition can also contain crosslinking catalyst, anti-static electricity interference agent, antioxidant, weathering stabilizers, increasing Resin beyond stick, plasticizer, softening agent, dyestuff, pigment, inorganic filler, acrylic resin etc..As antioxidant, Hydroquinones, dibutyl hydroxy toluene, 2,2 '-di-2-ethylhexylphosphine oxide (6- tert-butyl-4-methyl-Phenols), 3,9- can be enumerated Double [2- [3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyloxy] -1,1- dimethyl ethyls] -2,4, 8,10- tetra- oxaspiro [5,5] hendecanes, 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) -1,3,5- tri- The phenol antioxidants such as piperazine -2,4,6 (1H, 3H, 5H)-triketones, 6,6 '-di-t-butyl -4,4 '-fourth, two m-cresols of fork, The isodecyl base ester of phosphorous acid three, phosphorous acid three (4- nonyls phenyl) ester, phosphorous acid 2,2 '-di-2-ethylhexylphosphine oxide (4,6- di-tert-butyls Base) phosphorous antioxidant, 3 such as 2- ethylhexyls, phosphorous acid three (2,4- di-tert-butyl-phenyl) ester, 3 '-thiobis propionic acid is double Double [[3- (the dodecylthio) -1- propionyloxies] first of tridecane base ester, double [3- (dodecylthio) propionic acid] 2,2- Base] -1,3-PD ester, double [[3- (the dodecylthio) -1- oxos third of double [3- (dodecylthio) propionic acid] 2,2- Base epoxide] methyl] sulphur system antioxidant, the tetramethyl -4- piperidines of methacrylic acid 2,2,6,6- such as -1,3-PD ester Alcohol ester, the pentamethyl -4- piperidines alcohol ester of methacrylic acid 1,2,2,6,6-, carbonic acid=bis- (2,2,6,6- tetramethyl -1- ten One alkoxypiperidin -4- bases) ester, four (1,2,2,6,6- pentamethyl -4- piperidyls) 1,2,3,4- butane tetracarboxylic acid esters Etc. amine system antioxidant.

In addition, following operation and useful way, i.e. coordinate ultra-violet solidified chemical combination into adhesive composition Thing, irradiate ultraviolet after adhesive sheet is formed and be allowed to solidify, harder adhesive sheet is made.Wherein, if crosslinking urged Agent is coupled in adhesive composition together with crosslinking agent, then can prepare adhesive sheet using the curing of short time, In the optical laminate of gained, can suppress polarization plates or diaphragm etc. produced between adhesive sheet tilting or peel off or Foaming is produced in adhesive sheet, re-workability can also become good in addition.As crosslinking catalyst, such as six Asias can be enumerated Methanediamine, ethylene diamine, poly- Ethylenimine, hexa, diethylenetriamines, trien, different Fo Er Amine compounds such as ketone diamines, trimethylene diamine, poly- amino resins, melmac etc..Make in adhesive composition In the case of coordinating amine compound for crosslinking catalyst, isocyanates based compound is suitably for as crosslinking agent.

Adhesive composition can also be formed in the state of being dissolved in solvent by forming each composition of adhesive.Make For the solvent, such as methanol, ethanol, ethylene glycol, isopropanol, propane diols, methyl cellosolve, butyl cellosolve, third can be enumerated The alcoholic solvents such as glycol monomethyl ether；Ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, gamma-butyrolacton, propylene glycol monomethyl ether The ester solvents such as acetic acid esters, ethyl lactate；Acetone, 2- butanone, methyl iso-butyl ketone (MIBK), cyclopentanone, cyclohexanone, methyl amyl ketone, first The ketone solvents such as base isobutyl ketone；The aliphatic hydrocarbon solvents such as pentane, hexane, heptane；The aromatic hydrocarbon solvents such as toluene, dimethylbenzene；Second The nitrile solvent such as nitrile；The ether solvents such as tetrahydrofuran, dimethoxy-ethane；And the chlorinated hydrocarbon solvent such as chloroform, chlorobenzene.Wherein, from each The dissolubility of composition and from the viewpoint of mitigating environmental pressure, preferably 2- butanone, methyl iso-butyl ketone (MIBK) etc..

Adhesive sheet can for example utilize following method to set, i.e. be formed with adhesive composition as described above Solvent solution, it is coated on using die coating machine or gravure coater etc. and is intended to its film of stacking or layer (such as polarization plates, diaphragm Deng) on, it is allowed to drying.Alternatively, it is also possible to be set using following method, i.e. will be formed in being carried out the modeling of demoulding processing Expect that the sheet adhesive on film (being referred to as barrier film) transfers to the film or layer for being intended to stacking.

In other embodiments of the present invention, there is provided the laminated polarizing of optical film and polarizing coating comprising the present invention Film (also referred to as " laminated polarizing film of the invention ").Herein, so-called polarizing coating, it is to have to project relative to incident lights such as natural lights The optical film of the function of polarised light.In polarizing coating, there are linear polarization film, polarization separating film, elliptical polarization plate etc., the straight line Rectilinearly polarized light of the polarizing coating with the vibration plane with some direction for absorbing injection film surface, transmission are shaken with orthogonal The property of the rectilinearly polarized light in dynamic face, the polarization separating film inject the vibration plane with some direction of film surface with reflection The property of the rectilinearly polarized light of rectilinearly polarized light, transmission with orthogonal vibration plane, the elliptical polarization plate is to polarize Film is laminated and obtained with phase retardation film described later.As polarizing coating, particularly linear polarization film (sometimes referred to as polarizer) Suitable concrete example, the polymerization in polyvinyl alcohol resin film, polymerizable liquid crystal compound by uniaxial tension can be enumerated The dichroism pigments such as iodine or dichroic dye are adsorbed with thing and are allowed to the film being orientated.Laminated polarizing film be comprising polarizing coating, Optical film with the present invention, the laminated optical film such as adhesive sheet, diaphragm, phase retardation film.Also will include polarizing coating and The laminated optical film of adhesive sheet, particularly be laminated with polarizing coating adhesive sheet laminated optical film be referred to as carry adhesive Polarization plates.

The laminated polarizing film of the present invention preferably meets following formula (4).

Ap(400)≥0.4 (4)

In formula (4), Ap (400) represents the absorbance on the transmission direction of principal axis of the polarizing coating under wavelength 400nm.Ap(400) Value it is bigger, then it represents that the absorption under wavelength 400nm is higher, if the value is less than 0.4, the absorption under wavelength 400nm is weak, difficult To ensure the sufficiently high light resistance to the visible ray of the short wavelength near 400nm.Thus, the Ap of laminated polarizing film of the invention (400) value is preferably more than 0.4, more preferably more than 0.6, more preferably more than 0.8, still more preferably for 1 with On, particularly preferably more than 1.2, especially preferably more than 1.5, very preferably more than 1.8, for example, more than 2.Ap(400) The upper limit of value be not particularly limited, but from the viewpoint of the oozing out of the light absorption composition for suppressing stacking polarizing coating, Preferably generally less than 5.

In addition, the laminated polarizing film of the present invention preferably meets following formula (5).

Ap(420)/Ap(400)≤0.3 (5)

In formula (5), Ap (400) represents the absorbance on the transmission direction of principal axis of the polarizing coating under wavelength 400nm, Ap (420) Represent the absorbance on the transmission direction of principal axis of the polarizing coating under wavelength 420nm.Ap (420)/Ap (400) value is represented relative to ripple The intensity of the absorption under wavelength 400nm for the intensity of absorption under long 420nm, the value are smaller, then it represents that near 420nm The absorption of wavelength region more have specific absorption compared to wavelength region near 400nm.The value is smaller, then jaundice is got over It is few, more there is the trend that can obtain transparent laminated polarizing film.

In the case where above-mentioned laminated polarizing film meets above-mentioned formula (5), meeting absorbing wavelength 400nm light is on the other hand, difficult With absorbing wavelength 420nm light, while it is difficult to the visible ray for absorbing blueness, therefore, it is difficult to hinder good color representation, in addition Anti- blue light function (ブルーライトカット Machine energy can also be embodied).The laminated polarizing film is being included into optical laminate In the case of, it can suppress to form component (such as the optical film such as phase retardation film, organic EL element or the liquid crystal display of optical laminate The display elements such as element) because of the visible ray of short wavelength (light i.e. near wavelength 400nm) and performance deteriorates.Above-mentioned stacking is inclined The Ap (420) of vibrating diaphragm/Ap (400) value is preferably less than 0.25, more preferably less than 0.2, more preferably less than 0.15, For example, less than 0.1.Its lower limit is not particularly limited, but from the absorption near the 400nm for maintaining above-mentioned laminated polarizing film From the viewpoint of ability, it is often preferred that more than 0.01.In the suitable embodiment of the present invention, Ap (420)/Ap (400) value is 0.05~0.15.

In other embodiments of the present invention, there is provided the stacking phase of optical film and phase retardation film comprising the present invention Potential difference film (also referred to as " laminated phase-difference film of the invention ").Herein, so-called phase retardation film, be show it is optically anisotropic Optical film, such as can enumerate by the way that polyvinyl alcohol, makrolon, polyester, polyarylate, polyimides, polyolefin, poly- will be included Cycloolefin, polystyrene, polysulfones, polyether sulfone, polyvinylidene fluoride/polymethyl methacrylate, acetylcellulose, ethene-second Vinyl acetate copolymer is saponified, the polymeric membrane of polyvinyl chloride etc. is stretched as stretched film etc. obtained by 1.01~6 times or so.Its In, preferred pair polycarbonate membrane or cyclic olefine resin film be stretched uniaxially or biaxially obtained by polymeric membrane.In addition, In the case where the optical laminate of the present invention includes phase retardation film, from the viewpoint of slimming, preferably comprise because of polymerism Coating and the orientation of liquid-crystal compounds and embody optically anisotropic phase retardation film.

Laminated phase-difference film is optical film such as adhesive sheet, diaphragm, polarizing coating comprising phase retardation film and the present invention Deng laminated optical film.In addition, also provide the optical film comprising the present invention, polarizing coating and phase retardation film elliptical polarization film ( Referred to as " elliptical polarization film of the invention ").Elliptical polarization film is the layer of the optical film comprising phase retardation film, polarizing coating and the present invention Folded optical film.Moreover, also it is laminated with by the laminated optical film comprising phase retardation film and adhesive sheet, particularly on phase retardation film The laminated optical film of adhesive sheet is referred to as the phase retardation film with adhesive.

In the laminated phase-difference film of the present invention, preferably meet following formula (6).

100nm≤Re(550)≤170nm (6)

By the way that 1/4 wavelength can be used as with the optical characteristics represented with above-mentioned formula (6), laminated phase-difference film of the invention Plate plays a role.Moreover, laminated phase-difference film Re (550)=137.5nm preferred in theory of the present invention, but be used as can be with The scope of good display characteristic is obtained, preferably meets following formula (6-1).

130nm≤Re (550)≤150nm (6-1)

In the laminated phase-difference film of the present invention, phase retardation film preferably has inverse wave length dispersiveness.So-called inverse wave length is disperseed Property, it is the optical characteristics that phase difference value is more than phase difference value in the face under long wavelength in the face under short wavelength, phase retardation film is preferred Meet following formula (7) and formula (8).Moreover, Re (λ) is represented for phase difference value in the face of wavelength X nm light.

Re(450)/Re(550)≤1 (7)

1≤Re(630)/Re(550) (8)

In the laminated phase-difference film of the present invention, in the case where phase retardation film has inverse wave length dispersiveness, display device In black display when coloring reduce, therefore preferably, if 0.82≤Re (450)/Re (550)≤0.93 in the formula (7), then More preferably.

In the laminated phase-difference film of the present invention, phase retardation film is preferably the state of orientation for including polymerizable liquid crystal compound Under polymer layer (hereinafter sometimes referred to as " optical anisotropic layer ").So-called polymerizable liquid crystal compound, it is that there is polymerization Property functional group, particularly optical polymerism functional group liquid-crystal compounds.So-called optical polymerism functional group, refers to utilize by light Living radical, acid etc. caused by polymerization initiator participate in the group of polymerisation.As optical polymerism functional group, can enumerate Vinyl, ethyleneoxy, 1- chlorovinyls, isopropenyl, 4- ethenylphenyls, acryloxy, methacryloxy, Epoxy ethyl (oxiranyl), oxetanyl etc..Wherein, preferably acryloxy, methacryloxy, ethylene oxy Base, epoxy ethyl and oxetanyl, more preferably acryloxy.Liquid crystal liquid crystal property can be thermotropic liquid crystal or molten Cause property liquid crystal, from the aspect of the film thickness monitoring that can realize densification, preferred thermotropic liquid crystal.In addition, as thermotropic liquid Brilliant phase order structure, can be nematic crystal or smectic crystal.

In the present invention, as the polymerizable liquid crystal compound, from embody foregoing inverse wave length dispersiveness in terms of examine Consider, the structure of particularly preferred following formula (III)s.

Change 24

In formula (III), Ar represents the aromatic group of divalent, former comprising nitrogen-atoms, oxygen in the aromatic group of the divalent It is more than at least one in son, sulphur atom.

G¹And G²The aromatic group of divalent or the alicyclic type hydrocarbon of divalent are represented independently of one another.Herein, the fragrance of the divalent Contained hydrogen atom can be by halogen atom, the alkyl of carbon number 1~4, carbon atom in the alicyclic type hydrocarbon of race's group or divalent The fluoroalkyl of number 1~4, the alkoxy of carbon number 1~4, cyano group or nitro substitution, form the aromatic group or divalent of the divalent The carbon atom of alicyclic type hydrocarbon can be substituted by oxygen atom, sulphur atom or nitrogen-atoms.

L¹、L²、B¹And B²It is each independently singly-bound or the linking group of divalence.

K and l represents 0~3 integer independently of one another, meets 1≤k+l relation.Herein, in the case of 2≤k+l, B¹And B²、G¹And G²Respectively can be with identical, can also be different.

E¹And E²The alkane diyl of carbon number 1~17 is represented independently of one another, and herein, contained hydrogen atom can in alkane diyl To be substituted by halogen atom, contained-CH in the alkane diyl₂- can be substituted by-O- ,-Si-.

P¹And P²Represent that polymerizable group or hydrogen atom, at least one are polymerizable group independently of one another.

G¹And G²It is each independent, preferably can be by least one in the alkyl selected from halogen atom and carbon number 1~4 Substituent substitution Isosorbide-5-Nitrae-phenyl, can be by least one substituent in the alkyl selected from halogen atom and carbon number 1~4 Substituted Isosorbide-5-Nitrae-cyclohexyl, more preferably by methyl substituted Isosorbide-5-Nitrae-phenyl, unsubstituted Isosorbide-5-Nitrae-phenyl or unsubstituted Isosorbide-5-Nitrae-trans-cyclohexyl, particularly preferably unsubstituted Isosorbide-5-Nitrae-phenyl or unsubstituted Isosorbide-5-Nitrae-trans-cyclohexyl.

Additionally, it is preferred that it there are multiple G¹And G²In at least one be divalent alicyclic type hydrocarbon, in addition, more preferably with L¹Or L²The G of bonding¹And G²In at least one be divalent alicyclic type hydrocarbon.

L¹And L²Each independence, preferably singly-bound ,-O- ,-CH₂CH₂- ,-CH₂O- ,-COO- ,-OCO- ,-N =N- ,-CR^a=CR^b- or-C ≡ C-.R herein^aAnd R^bRepresent the alkyl or hydrogen atom of carbon number 1~4.

L¹And L²Each independence, more preferably singly-bound ,-O- ,-CH₂CH₂- ,-COO- or-OCO-.

B¹And B²Each independence, preferably singly-bound ,-O- ,-S- ,-CH₂O- ,-COO- or-OCO-, it is more excellent Elect singly-bound ,-O- ,-COO- or-OCO- as.

For k and l, from the viewpoint of inverse wave length dispersiveness is embodied, the preferably scope of 2≤k+l≤6, more preferably k + l=4, more preferably k=2 and l=2.If k=2 and l=2, symmetrical structure can be turned into, therefore preferably.

E¹And E²Each independence, the preferably alkane two of the alkane diyl of carbon number 1~17, more preferably carbon number 4~12 Base.

As with P¹Or P²The polymerizable group of expression, epoxy radicals, vinyl, ethyleneoxy, 1- vinyl chloride can be enumerated Base, isopropenyl, 4- ethenylphenyls, acryloxy, methacryloxy, epoxy ethyl and oxetanyl Deng.Wherein, preferably acryloxy, methacryloxy, ethyleneoxy, epoxy ethyl and oxetanyl, more preferably Acryloxy.

Ar preferably has heteroaromatic.As the heteroaromatic, furan nucleus, benzofuran ring, pyrroles can be enumerated Ring, thiphene ring, pyridine ring, thiazole ring, benzothiazole ring, thieno thiazole ring, oxazole rings, benzoxazole ring and phenanthroline Ring etc..Wherein, preferably with thiazole ring, benzothiazole ring or benzofuran ring, more preferably with benzothiazolyl.In addition, In the case of including nitrogen-atoms in Ar, the nitrogen-atoms preferably has pi-electron.

In formula (III), with the total number N of pi-electron contained in the aromatic group of the Ar divalents represented_πPreferably 10 with On, more preferably more than 14, more preferably more than 18.Additionally, it is preferred that it is less than 30, more preferably less than 26, further Preferably less than 24.

As the aromatic group represented with Ar, such as following group can be enumerated.

Change 25

In formula (Ar-1)~formula (Ar-20), * marks represent connecting portion, Z⁰、Z¹And Z²Represent that hydrogen is former independently of one another Son, halogen atom, the alkyl of carbon number 1~12, cyano group, nitro, the alkyl sulphinyl of carbon number 1~12, carbon atom Alkyl sulphonyl, carboxyl, the fluoroalkyl of carbon number 1~12, the alkoxy of carbon number 1~6, the carbon number 1 of number 1~12 ~12 alkylthio group, the N- alkyl aminos of carbon number 1~12, the N of carbon number 2~12, N- dialkyl amidos, carbon atom The N- alkylsulfamoyl groups of number 1~12 or the N of carbon number 2~12, N- dialkyl sulfamines.

Q¹、Q²And Q³Expression-CR independently of one another^2’R^3’- ,-S- ,-NH- ,-NR^2’- ,-CO- or-O-, R^2’And R^3’The alkyl of hydrogen atom or carbon number 1~4 is represented independently of one another.

Y¹、Y²And Y³The aromatic hydrocarbyl or aromatic heterocycle that can be substituted are represented independently of one another.

W¹And W²Hydrogen atom, cyano group, methyl or halogen atom are represented independently of one another, and m represents 0~6 integer.

As Y¹、Y²And Y³In aromatic hydrocarbyl, the carbon atoms such as phenyl, naphthyl, anthryl, phenanthryl, xenyl can be enumerated The aromatic hydrocarbyl of number 6~20, preferably phenyl, naphthyl, more preferably phenyl.As aromatic heterocycle, furan can be enumerated Mutter base, pyrrole radicals, thienyl, pyridine radicals, thiazolyl, benzothiazolyl etc. include at least one nitrogen-atoms, oxygen atom, sulphur atom Etc. the aromatic heterocycle of heteroatomic carbon number 4~20, preferably furyl, thienyl, pyridine radicals, thiazolyl, benzo Thiazolyl.

Y¹、Y²And Y³The polycyclic system aromatic hydrocarbyl or polycyclic system aromatic series that can be substituted can also be each independently Heterocyclic radical.Polycyclic system aromatic hydrocarbyl refers to fused polycyclic system aromatic hydrocarbyl or comes from the group of aromatic rings set.It is polycyclic It is that aromatic heterocycle refers to fused polycyclic system aromatic heterocycle or comes from the group of aromatic rings set.

Z⁰、Z¹And Z²It is preferred that be each independently hydrogen atom, halogen atom, the alkyl of carbon number 1~6, cyano group, nitro, The alkoxy of carbon number 1~12, Z⁰More preferably hydrogen atom, the alkyl of carbon number 1~12, cyano group, Z¹And Z²More preferably Hydrogen atom, fluorine atom, chlorine atom, methyl, cyano group.

Q¹、Q²And Q³Preferably-NH- ,-S- ,-NR^2’- ,-O-, R^2’Preferably hydrogen atom.It is wherein particularly preferred For-S- ,-O- ,-NH-.

In formula (Ar-1)~(Ar-20), from the viewpoint of the stability of molecule, preferred formula (Ar-6) and formula (Ar-7).

In formula (Ar-14)~(Ar-20), Y¹The nitrogen-atoms and Z that can also be bonded with it⁰Aromatic series is formed together Heterocyclic radical.For example, pyrrole ring, imidazole ring, pyrrolin ring, pyridine ring, pyrazine ring, pyrimidine ring, indole ring, quinoline can be enumerated Ring, isoquinolin ring, purine ring, pyrrolidine ring etc..The aromatic heterocycle can also have substituent.In addition, Y¹Can also be with Its nitrogen-atoms and Z for being bonded⁰It is miscellaneous for the foregoing polycyclic system aromatic hydrocarbyl that can be substituted or polycyclic system aromatic series together Ring group.

Optical anisotropic layer is by using the combination for making to include above-mentioned polymerizable liquid crystal compound such as light irradiation Thing (also referred to as " optical anisotropic layer is formed with composition ") is solidified to form.Optical anisotropic layer formation composition can So that comprising various additives, as additive, above-mentioned polymerization initiator, polymerization inhibitor, photosensitizer and levelling agent can be enumerated. The conjunction of shared polymerizable liquid crystal compound in the mass parts of solid constituent 100 of above-mentioned optical anisotropic layer formation composition The content of meter is usually the mass parts of 70 mass parts~99.5, the mass parts of preferably 80 mass parts~99, more preferably 80 mass parts The mass parts of~94 mass parts, more preferably 80 mass parts~90.If above-mentioned total content is within the above range, institute The trend that the orientation of the optical anisotropic layer obtained is improved.Herein, so-called solid constituent, refer to remove from composition molten The total amount of composition after agent.

In other embodiments of the present invention, also provide and possess above-mentioned optical film, laminated polarizing film, laminated phase-difference The display device of any one of film or elliptical polarization film.The display device is due to possessing containing above-mentioned light absorption composition Component, therefore the deterioration of the optical films such as phase retardation film, display element can be suppressed, furthermore, it is possible to embody anti-blue light function. In addition, above-mentioned light absorption composition is due to selecting the light of the light near wavelength 400nm, absorbability is excellent, and therefore, it is difficult to absorb As the light near the wavelength 430nm of blue light, image display device can embody good color representation.

[embodiment]

Hereinafter, using embodiment and comparative example, the present invention will be described in more detail.In embodiment and comparative example " % " and " part " is exactly " quality % " and " mass parts " as long as no particularly pointing out.

＜ gel permeation chromatographies determine ＞

In addition, in the following examples, the measure of weight average molecular weight and number-average molecular weight is (following in gel permeation chromatography It is denoted as GPC.) configure 4 " TSK gel XL the middle conduct Coupled columns of device (GPC-8120, Tosoh (strain) make) (Tosoh (strain) systems) " and 1 " Shodex GPC KF-802 (Showa electrician (strain) system) " amount to 5, make as eluent With tetrahydrofuran, enter in sample solution concentration 5mg/mL, μ L of sample import volume 100,40 DEG C of temperature, flow velocity under conditions of 1mL/ minutes OK, calculated using polystyrene standard.

The preparation ＞ of ＜ acrylic resins

According to the composition shown in table 1, using following method, acrylic resin (a) and acrylic resin are prepared (b)。

The preparation of [polymerization example 1] acrylic resin (a)

Into the reaction vessel for possessing cooling tube, nitrogen ingress pipe, thermometer and mixer, the acetic acid second as solvent is added 81.8 parts of ester, 20.0 parts of 70.4 parts of butyl acrylate, methyl acrylate as monomer (A-1) and acrylic acid 2- benzene oxygen The mixed solution of 0.6 part of 8.0 parts of base ethyl ester, 1.0 parts of the acrylic acid 2- hydroxy methacrylates as monomer (A-2) and acrylic acid, While not oxygen-containing one side is set to the air in nitrogen replaceable equipment by interior temperature rise to 55 DEG C.Thereafter, add in acetic acid second The whole amount of solution dissolved with 0.14 part of azodiisobutyronitrile (polymerization initiator) in 10 parts of ester.After polymerization initiator is added Kept with the temperature within 1 hour, then held while interior temperature is remained into 54~56 DEG C with 17.3 parts/hr of adding speed to reaction Ethyl acetate is added continuously in device, stops the addition of ethyl acetate at the time of the concentration of acrylic resin reaches 35%, In addition, it is incubated since the addition of ethyl acetate until by 12 hours with the temperature.It is eventually adding ethyl acetate and incites somebody to action The concentration of acrylic resin is adjusted to 20%, prepares the ethyl acetate solution of acrylic resin.The acrylic compounds of gained The weight average molecular weight Mw of the conversion of the polystyrene based on GPC of resin is 1,420,000, Mw/Mn 5.2.It is set to acrylic compounds Resin (a).

The preparation of [polymerization example 2] acrylic resin (b)

Into the reaction vessel for possessing cooling tube, nitrogen ingress pipe, thermometer and mixer, the acetic acid second as solvent is added The mixing of 81.8 parts of ester, 96.0 parts of the butyl acrylate as monomer (A-1) and 4.0 parts of the acrylic acid as monomer (A-2) Solution, while being set to not oxygen-containing one side with the air in nitrogen replaceable equipment by interior temperature rise to 55 DEG C.Thereafter, add in second The whole amount of solution dissolved with 0.14 part of azodiisobutyronitrile (polymerization initiator) in 10 parts of acetoacetic ester.Trigger in addition polymerization Kept with the temperature within 1 hour after agent, then while interior temperature is remained into 54~56 DEG C with 17.3 parts/hr of adding speed to anti- Answer and ethyl acetate is added continuously in container, stop adding for ethyl acetate at the time of the concentration of acrylic resin reaches 35% Add, in addition, being incubated since the addition of ethyl acetate until by 12 hours with the temperature.Be eventually adding ethyl acetate and The concentration of acrylic resin is adjusted to 20%, prepares the ethyl acetate solution of acrylic resin.The acrylic acid of gained The weight average molecular weight Mw of the conversion of the polystyrene based on GPC of resinoid is 750,000 6000, Mw/Mn 4.1.It is set to propylene Acid resin (b).

【Table 1】

·BA：Butyl acrylate

·MA：Methyl acrylate

·PEA：Acrylic acid 2- phenoxy ethyls

·HEA：Acrylic acid 2- hydroxy methacrylates

·AA：Acrylic acid

(a) preparation of adhesive composition

It is as follows, by acrylic resin (a), light select absorbing compounds (ultra-violet absorber), crosslinking agent and Silane based compound mixes, and prepares adhesive composition respectively.

Moreover, crosslinking agent and silane based compound are as follows.By light select absorbing compounds (compound (1)~ (9) structure transitivity) is shown in table 2.In addition, light is selected to the addition of absorbing compounds (compound (1)~(9)) It is shown in table 3 and 5, the addition is the mass parts for the mass parts of solid constituent 100 in acrylic resin. It is added to after crosslinking agent and light selection absorbing compounds are mixed with 2- butanone respectively in acrylic resin.

[crosslinking agent]

·CORONATE L：The trimethylolpropane adduct of toluene di-isocyanate(TDI) ethyl acetate solution (solid into Point concentration 75%), Japanese polyurethane Co. Ltd. system

·TAKENATE D-110N：The ethyl acetate solution of the trimethylolpropane addition product of XDI (solid component concentration 75%), Mitsui Chemicals, Inc's system (hereinafter referred to as " D110N ")

[silane based compound]

KBM-403: 3- glycidoxypropyltrime,hoxysilane, liquid, Shin-Etsu Chemial Co., Ltd's system

[light selection absorbing compounds]

【Table 2】

(synthesis example 1)

Change 26

To being provided with the 200mL- four-hole boiling flasks of enlightening nurse rood cooling tube and thermometer, in a nitrogen atmosphere, add with Patent document (Japanese Unexamined Patent Publication 2011-184414) is the powder 10g of intermediate 1 with reference to synthesis, acetic anhydride (and Wako Pure Chemical Industries (strain) makes) 3.7g, morpholine (and the pure medicine of light (strain) system) 2.5g and 2- propyl group alcohol (and Wako Pure Chemical Industries (strain) system) 15g, are used Magnetic stirrer stirs.By interior temperature rise to 72 DEG C, stir 3 hours.After reaction terminates, room temperature is cooled to, uses vaporising device Solvent is distilled off.Into the concentrate of gained, methanol 17g and water 3g mixed liquor is added, obtains crystal.To the crystal 40 DEG C it is dried under reduced pressure, thus obtains compound (1) 2.0g as yellow powder.Yield is 70%.

Very big wavelength (λ is absorbed in addition, being determined using spectrophotometer UV-3150 ((strain) Shimadzu Seisakusho Ltd. system) Max), its result is λ max=389nm (in 2- butanone), and ε (400) is 171L/ (gcm), and ε (420)/ε (400) is 0.0251。

Compound (1) is carried out¹H-NMR is determined.Its result is as follows.

¹H-NMR (CDCl₃)δ：1.55 (s, 6H), 3.55-3.73 (m, 8H), 6.83 (q, 1H), 7.87 (d, 1H), 8.00 (d、1H)

(synthesis example 2)

Change 27

To being provided with the 200mL- four-hole boiling flasks of enlightening nurse rood cooling tube and thermometer, in a nitrogen atmosphere, in addition The powder of mesosome 2 (and Wako Pure Chemical Industries (strain) system) 3g, cyanoacetic acid 2- ethoxy ethyl esters (Tokyo chemical conversion industry (strain) system) 2.2g and acetonitrile (and Wako Pure Chemical Industries (strain) system) 12g, is stirred with magnetic stirrer.By interior temperature rise to 75 DEG C, pyrrole is added dropwise Pyridine (and Wako Pure Chemical Industries (strain) system) 1.1g, is stirred 6 hours.After reaction terminates, room temperature is cooled to, is removed using vaporising device distillation Remove solvent.Into the concentrate of gained, toluene 20g, 4.1 mass % aqueous hydrochloric acid solution 30g are added, liquid separation is carried out to toluene solution Cleaning.Then, water 40g is added into toluene solution, has carried out liquid separation cleaning.Toluene is distilled off using vaporising device, obtains Crystal.The crystal is dried under reduced pressure at 40 DEG C, thus obtains compound (2) 3.5g as yellow powder.Yield is 73%.

Very big wavelength (λ is absorbed in addition, being determined using spectrophotometer UV-3150 ((strain) Shimadzu Seisakusho Ltd. system) Max), its result is λ max=386nm (in 2- butanone), and ε (400) is 51L/ (gcm), and ε (420)/ε (400) is 0.165.

Compound (2) is carried out¹H-NMR is determined.Its result is as follows.

¹H-NMR (CDCl₃)δ：1.21 (t, 3H), 3.56 (q, 2H), 3.69-3.73 (m, 5H), 4.37 (m, 2H), 7.36-7.44 (m, 5H), 7.56-7.58 (m, 3H), 8.42-8.46 (m, 1H)

(synthesis example 3)

Change 28

To being provided with the 200mL- four-hole boiling flasks of enlightening nurse rood cooling tube and thermometer, in a nitrogen atmosphere, add with Patent document (Japanese Unexamined Patent Publication 2014-194508) is the powder 10g of intermediate 3 with reference to synthesis, acetic anhydride (and Wako Pure Chemical Industries (strain) makes) 3.7g, cyanoacetic acid 2- ethoxy ethyl esters (Tokyo chemical conversion industry (strain) system) 5.8g and acetonitrile (and the pure medicine work of light Industry (strain) is made) 60g, is stirred with magnetic stirrer.N, N- diisopropyls is added dropwise from dropping funel with 1 hour at 25 DEG C of temperature inside Ethylamine (hereinafter referred to as DIPEA.Tokyo chemical conversion industry (strain) make) 4.7g, after completion of dropwise addition inside temperature 25 DEG C at be incubated 2 again Hour.After reaction terminates, acetonitrile is removed using device is evaporated under reduced pressure, toluene is added into the grease of gained, filters off except institute The insoluble component of generation.Reduction vaporization device is reused to filtrate to concentrate, and the solution after concentration is supplied to column chromatography (silica gel) is purified, and is recrystallized from toluene, thus obtains purpose thing.60 DEG C are carried out to the crystal to be dried under reduced pressure, and are thus made Compound (3) 5.2g is obtained for yellow powder.Yield is 65%.

Very big wavelength (λ is absorbed in addition, being determined using spectrophotometer UV-3150 ((strain) Shimadzu Seisakusho Ltd. system) Max), its result is λ max=389nm (in 2- butanone), and ε (400) is 125L/ (gcm), and ε (420)/ε (400) is 0.0153。

Compound (3) is carried out¹H-NMR is determined.Its result is as follows.

¹H-NMR (CDCl₃)δ：1.21 (t, 3H), 2.10 (quin.2H), 2.98-3.04 (m, 5H), 3.54-3.72 (m、6H)、4.31(t、2H)、5.53(d、2H)、7.93(d、2H)

(synthesis example 4)

Change 29

To provided with enlightening nurse rood cooling tube, thermometer 200mL- four-hole boiling flasks in, in a nitrogen atmosphere, add with special Sharp document (Japanese Unexamined Patent Publication 2014-194508) is the powder 10g of intermediate 3 with reference to synthesis, acetic anhydride (and Wako Pure Chemical Industries strain Formula commercial firm system) 3.6g, cyanoacetic acid 2- ethylhexyls (Tokyo HuaCheng Industry Co., Ltd's system) 6.9g and acetonitrile (and light is pure Medicine Industrial Co., Ltd system) 60g, is stirred with magnetic stirrer.DIPEA is added dropwise from dropping funel with 1 hour at 25 DEG C of temperature inside (Tokyo HuaCheng Industry Co., Ltd's system) 4.5g, after completion of dropwise addition inside temperature 25 DEG C at be incubated 2 hours again.After reaction terminates, make Acetonitrile is removed with device is evaporated under reduced pressure, there is provided is purified to column chromatography (silica gel), the efflux containing compound (4) is used Device is evaporated under reduced pressure and removes solvent, obtains yellow crystals.The crystal is dried under reduced pressure at 60 DEG C, thus as yellow powder Obtain compound (4) 4.6g.Yield is 50%.

Determined using spectrophotometer UV-3150 (Shimadzu Scisakusho Ltd's system) and absorb very big wavelength (λ max), Its result is λ max=389nm (in 2- butanone), and ε (400) value is 108L/ (gcm), and ε (420)/ε (400) value is 0.013。

Compound (4) is carried out¹H-NMR is determined.Its result is as follows.

¹H-NMR (CDCl₃)δ：0.87-0.94 (m, 6H), 1.32-1.67 (m, 8H), 1.59-1.66 (m, 2H), 2.09(quin、2H)、3.00(m、5H)、3.64(t、2H)、4.10(dd、2H)、5.52(d、2H)、7.87(d、2H)

(synthesis example 5)

Change 30

To being provided with the 200mL- four-hole boiling flasks of enlightening nurse rood cooling tube and thermometer, in a nitrogen atmosphere, cyanogen is added Guanidine-acetic acid (Tokyo chemical conversion industry (strain) system) 2.0g, triethylene glycol monomethyl ether (Tokyo chemical conversion industry (strain) system) 4.3g, to toluene Sulfonic acid monohydrate (and Wako Pure Chemical Industries (strain) system) 0.2g, toluene (and Wako Pure Chemical Industries (strain) system) 20g, use magnetic stirrer Stirring.By interior temperature rise to 110 DEG C, stir 3 hours.After reaction terminates, water 40g is added into toluene solution, has carried out liquid separation Cleaning.Toluene is distilled off from obtained toluene solution using vaporising device, the liquid as oily obtains 4.7g centre Body 4.Yield is 86%.

Change 31

To being provided with the 200mL- four-hole boiling flasks of enlightening nurse rood cooling tube and thermometer, in a nitrogen atmosphere, in addition The powder of mesosome 2 (and Wako Pure Chemical Industries (strain) system) 2.0g, intermediate 42.6g and acetonitrile (and Wako Pure Chemical Industries (strain) system) 8.0g, stirred with magnetic stirrer.By interior temperature rise to 75 DEG C, piperidines (and Wako Pure Chemical Industries are added dropwise from dropping funel with 1 hour (strain) make) 0.7g, after completion of dropwise addition inside temperature 75 DEG C at be incubated 6 hours again.

After reaction terminates, room temperature is cooled to, solvent is distilled off using vaporising device.Second is added into the concentrate of gained Acetoacetic ester (and Wako Pure Chemical Industries (strain) system) 10g, water 20g, liquid separation cleaning has been carried out to ethyl acetate solution.Use vaporising device Ethyl acetate is distilled off from obtained ethyl acetate solution, the liquid as oily obtains compound (5) 3.6g.Yield is 93%.

Compound (5) is carried out¹H-NMR is determined.Its result is as follows.

¹H-NMR (CDCl₃)δ：1.26 (t, 1H), 2.04 (s, 1H), 3.37 (s, 3H), 3.64-3.71 (m, 12H), 4.37 (dd, 2H), 7.35-7.46 (m, 5H), 7.54-7.59 (m, 3H), 8.42-8.46 (m, 1H)

(synthesis example 6)

Change 32

To being provided with the 200mL- four-hole boiling flasks of enlightening nurse rood cooling tube and thermometer, in a nitrogen atmosphere, in addition The powder of mesosome 2 (and Wako Pure Chemical Industries (strain) system) 3.0g, cyanoacetic acid 2- ethylhexyls (Tokyo chemical conversion industry (strain) system) 2.7g, pyridine (and Wako Pure Chemical Industries (strain) system) 1.0g and acetonitrile (and Wako Pure Chemical Industries (strain) system) 12g, are stirred with magnetic stirrer Mix.By interior temperature rise to 75 DEG C, 6 hours are incubated.After reaction terminates, room temperature is cooled to, filters the crystal of precipitation.The crystal is used Acetonitrile (and Wako Pure Chemical Industries (strain) system) 10g cleanings, then the crystal is dried under reduced pressure at 40 DEG C, thus as yellow powder Obtain compound (6) 4.3g.Yield is 81%.

Compound (6) is carried out¹H-NMR is determined.Its result is as follows.

¹H-NMR (CDCl₃)δ：0.90 (t, 6H), 1.03-1.62 (m, 10H), 2.35 (s, 1H), 3.72 (s, 3H), 4.13 (q, 2H), 7.16-7.26 (m, 1H), 7.36-7.44 (m, 4H), 7.56-7.58 (m, 2H), 8.44-8.49 (m, 1H)

(synthesis example 7)

Change 33

To being provided with the 200mL- four-hole boiling flasks of enlightening nurse rood cooling tube and thermometer, in a nitrogen atmosphere, in addition The powder 10g of mesosome 3, acetic anhydride (and Wako Pure Chemical Industries (strain) system) 2.9g, cyanoacetic acid isobutyl ester (Tokyo chemical conversion industry (strain) System) 4.4g and acetonitrile (and Wako Pure Chemical Industries (strain) system) 30g, is stirred with magnetic stirrer.Leaked inside at 25 DEG C of temperature from dropping liquid DIPEA (Tokyo chemical conversion industry (strain) system) 3.7g was added dropwise with 1 hour in bucket, after completion of dropwise addition including be incubated 2 hours again at warm 25 DEG C. After reaction terminates, acetonitrile solution is added dropwise into cold water 150g, filters the crystal of precipitation.By crystal water 2g, acetonitrile 10g it is mixed Solution cleaning is closed, then the crystal is cleaned with heptane 10g.The crystal cleaned is dried under reduced pressure at 70 DEG C, thus as yellow Powder obtains compound (7) 5.2g.Yield is 84%.

Very big wavelength (λ is absorbed in addition, being determined using spectrophotometer UV-3150 ((strain) Shimadzu Seisakusho Ltd. system) Max), its result is λ max=389nm (in 2- butanone), and ε (400) is 130L/ (gcm), and ε (420)/ε (400) is 0.0092。

Compound (7) is carried out¹H-NMR is determined.Its result is as follows.

¹H-NMR (CDCl₃)δ：0.97 (d, 6H), 1.95-2.15 (m, 3H), 3.00 (t, 5H), 3.64 (t, 2H), 3.95 (d、2H)、5.53(d、1H)、7.92(d、1H)

(synthesis example 8)

Change 34

To being provided with the 200mL- four-hole boiling flasks of enlightening nurse rood cooling tube and thermometer, in a nitrogen atmosphere, cyanogen is added Guanidine-acetic acid (Tokyo chemical conversion industry (strain) system) 6.3g, 2- n-octylcyclam-lauryl alcohol (Tokyo chemical conversion industry (strain) system) 20.0g, P-methyl benzenesulfonic acid monohydrate (and Wako Pure Chemical Industries (strain) system) 0.6g, toluene (and Wako Pure Chemical Industries (strain) system) 100g, use magnetic Property agitator stirring.By interior temperature rise to 110 DEG C, stir 3 hours.After reaction terminates, water 100g is added into toluene solution, is entered Liquid separation cleaning is gone.Toluene is distilled off from obtained toluene solution using vaporising device, 22g centre is obtained as liquid Body 5.Yield is 90%.

Change 35

To being provided with the 200mL- four-hole boiling flasks of enlightening nurse rood cooling tube and thermometer, in a nitrogen atmosphere, in addition The powder 6g of mesosome 3, acetic anhydride (and Wako Pure Chemical Industries (strain) system) 1.8g, the 6.3g of intermediate 5 and acetonitrile (and Wako Pure Chemical Industries (strain) makes) 18g, is stirred with magnetic stirrer.DIPEA (Tokyo chemical conversion works are added dropwise from dropping funel with 1 hour at 25 DEG C of temperature inside Industry (strain) make) 3.7g, after completion of dropwise addition inside temperature 25 DEG C at be incubated 2 hours again.After reaction terminates, second is added dropwise into cold water 90g Nitrile solution, filter the crystal of precipitation.The crystal is cleaned with water 2g, acetonitrile 10g mixed solution, then this is cleaned with heptane 10g Crystal.The crystal cleaned is dried under reduced pressure at 70 DEG C, thus obtains compound (8) 6.5g as yellow powder.Yield is 92%.

Very big wavelength (λ is absorbed in addition, being determined using spectrophotometer UV-3150 ((strain) Shimadzu Seisakusho Ltd. system) Max), its result is λ max=389nm (in 2- butanone), and ε (400) is 52L/ (gcm), and ε (420)/ε (400) is 0.0121。

Compound (8) is carried out¹H-NMR is determined.Its result is as follows.

¹H-NMR (CDCl₃)δ：0.88 (t, 6H), 1.68 (s, 1H), 2.09 (q, 2H), 2.97-3.03 (t, 5H), 3.64 (t、2H)、4.07(d、2H)、5.52(d、1H)、7.90(d、1H)

(synthesis example 9)

Change 36

To being provided with the 200mL- four-hole boiling flasks of enlightening nurse rood cooling tube and thermometer, in a nitrogen atmosphere, cyanogen is added Guanidine-acetic acid (Tokyo chemical conversion industry (strain) system) 14g, 2- ethyl-n-butyl alcohol (Tokyo chemical conversion industry (strain) system) 15g, to toluene Sulfonic acid monohydrate (and Wako Pure Chemical Industries (strain) system) 1.4g, toluene (and Wako Pure Chemical Industries (strain) system) 75g, use magnetic stirrer Stirring.By interior temperature rise to 110 DEG C, stir 3 hours.After reaction terminates, water 100g is added into toluene solution, has carried out liquid separation Cleaning.Toluene is distilled off from obtained toluene solution using vaporising device, 22g intermediate 6 is obtained as liquid.Yield For 90%.

Change 37

To being provided with the 200mL- four-hole boiling flasks of enlightening nurse rood cooling tube and thermometer, in a nitrogen atmosphere, in addition The powder 10g of mesosome 3, acetic anhydride (and Wako Pure Chemical Industries (strain) system) 2.9g, the 4.8g of intermediate 6 and acetonitrile (and the pure medicine work of light Industry (strain) is made) 30g, is stirred with magnetic stirrer.DIPEA (Tokyo chemical conversions are added dropwise from dropping funel with 1 hour at 25 DEG C of temperature inside Industrial (strain) system) 3.7g, 2 hours are incubated again at 25 DEG C of temperature inside after completion of dropwise addition.After reaction terminates, it is added dropwise into cold water 150g Acetonitrile solution, filter the crystal of precipitation.The crystal is cleaned with water 2g, acetonitrile 10g mixed solution, then cleaned with heptane 10g The crystal.The crystal cleaned is dried under reduced pressure at 70 DEG C, thus obtains compound (9) 5.7g as yellow powder.Yield For 84%.

Very big wavelength (λ is absorbed in addition, being determined using spectrophotometer UV-3150 ((strain) Shimadzu Seisakusho Ltd. system) Max), its result is λ max=389nm (in 2- butanone), and ε (400) is 118L/ (gcm), and ε (420)/ε (400) is 0.0090。

Compound (9) is carried out¹H-NMR is determined.Its result is as follows.

¹H-NMR (CDCl₃)δ：0.91 (t, 6H), 1.41 (q, 4H), 1.58 (q, 2H), 2.98-3.04 (m, 5H), 3.64 (t、2H)、4.10(d、2H)、5.52(d、1H)、7.92(d、1H)

(a-1) Production Example 1：The preparation of adhesive composition (1)

Relative to the mass parts of solid constituent 100 of acrylic resin (a), crosslinking agent (CORONATE L) is respectively cooperating with 0.50 mass parts, the mass parts of silane based compound (KBM-403) 0.50.Added again in a manner of making solid component concentration be 14% Add 2- butanone, using mixer (motor of YAMATO science Co. Ltd. system 3 1), be stirred 30 minutes with 300rpm, Prepare adhesive composition (1).

(a-2) Production Example 2~27：The preparation of adhesive composition (2)~(27)

Relative to the mass parts of solid constituent 100 of acrylic resin (a), crosslinking agent is coordinated with the amount shown in table 3 Light selection shown in (CORONATE L) 0.50 mass parts and the mass parts of silane based compound (KBM-403) 0.50 and table 3 Absorbing compounds (compound (1)~(9)).2- butanone is added in a manner of making solid component concentration be 14 mass % again, is made With mixer (motor of YAMATO science Co. Ltd. system 3 1), it is stirred 30 minutes, is prepared respectively viscous with 300rpm Mixture composite (2)~(27).

【Table 3】

To adhesive composition (2)~(27) obtained in Production Example 2~27, spectrophotometer UV-3150 is used ((strain) Shimadzu Seisakusho Ltd. system), determines maximum absorption wavelength X max.In addition, also determining ε (400) and ε (420), ε is calculated (420)/ε(400).It the results are shown in table 4.

【Table 4】

(a-3) Production Example 28：The preparation of adhesive composition (28)

Relative to the mass parts of solid constituent 100 of acrylic resin (b), crosslinking agent (CORONATE L) is respectively cooperating with 0.50 mass parts, the mass parts of silane based compound (KBM-403) 0.50.Added again in a manner of making solid component concentration be 14% Add 2- butanone, using mixer (motor of YAMATO science Co. Ltd. system 3 1), be stirred 30 minutes with 300rpm, Prepare adhesive composition (28).

(a-4) Production Example 29~52：The preparation of adhesive composition (29)~(52)

Relative to the mass parts of solid constituent 100 of acrylic resin (b), coordinate crosslinking agent (CORONATE L) 0.50 matter Light selection described in the table 5 measured shown in amount part and the mass parts of silane based compound (KBM-403) 0.50 and table 5 absorbs Property compound.2- butanone is added in a manner of making solid component concentration be 14% again, uses mixer (YAMATO science strain formulas The motor of commercial firm's system 3 1), it is stirred 30 minutes with 300rpm, prepares adhesive composition (29)~(52) respectively.

【Table 5】

To adhesive composition (29)~(52) obtained in Production Example 29~52, spectrophotometer UV-3150 is used ((strain) Shimadzu Seisakusho Ltd. system), determines maximum absorption wavelength X max.In addition, also determining ε (400) and ε (420), ε is calculated (420)/ε(400)。

It the results are shown in table 6.

【Table 6】

(b-1) reference example 1

To implement the demoulding processing polyethylene terephthalate film (LINTEC company systems SP-PLR382050, with Under be abbreviated as " barrier film ") demoulding process face, by make dried adhesive phase thickness be 10 μm in a manner of use gluer The adhesive composition (1) prepared in coating Production Example 1, dried 1 minute at 100 DEG C and produce adhesive sheet (R1).

Utilize spectrophotometer (UV-3150；(strain) Shimadzu Seisakusho Ltd. system) determine gained adhesive sheet (R1) light Learn characteristic.It the results are shown in Table 7.T (400) in table represents the transmissivity (%) under wavelength 400nm, and T (420) represents ripple Transmissivity (%) under long 420nm.

(b-2) reference example 2

Demoulding process face to barrier film, applied in a manner of the thickness for making dried adhesive phase is 5 μm using gluer The adhesive composition (1) prepared in cloth Production Example 1, dried 1 minute at 100 DEG C and produce adhesive sheet (R2).Using with The identical method of reference example 1 determines the optical characteristics of the adhesive sheet (R2) of gained.It the results are shown in Table 7.

(b-3) comparative example 1~17

Substitute adhesive composition (1), and respectively use Production Example 2~18 in prepare adhesive composition (2)~ (18), using with the identical method of reference example 1, produce adhesive sheet (C1)~(C17) of comparative example 1~17 respectively.Utilize Adhesive sheet (C1)~(C17) of gained optical characteristics is determined with the identical method of reference example 1.It the results are shown in table 7 In.

(b-4) embodiment 1~9

Substitute adhesive composition (1), and respectively use Production Example 19~27 in prepare adhesive composition (19)~ (27), using with the identical method of reference example 1, produce adhesive sheet (E1)~(E9) of embodiment 1~9 respectively.Using with The identical method of reference example 1 determines adhesive sheet (E1)~(E9) of gained optical characteristics.It the results are shown in Table 7.

(b-5) embodiment 10~14

Substitute adhesive composition (1), and using adhesive composition (19)~(23) prepared in Production Example 19~23, Using with the identical method of reference example 2, produce adhesive sheet (E10)~(E14) of embodiment 10~14 respectively.Using with ginseng Examine the optical characteristics that the identical method of example 1 determines adhesive sheet (E10)~(E14) of gained.It the results are shown in Table 7.

(b-6) reference example 3

Using the adhesive composition (28) prepared in Production Example 28, using with the identical method of reference example 1, produce ginseng Examine the adhesive sheet (R3) of example 3.Optics using the adhesive sheet (R3) that gained is determined with the identical method of reference example 1 is special Property.It the results are shown in Table 8.

(b-7) comparative example 18~34

Using adhesive composition (29)~(45) prepared in Production Example 29~45, using with the identical side of reference example 1 Method, adhesive sheet (C18)~(C34) of comparative example 18~34 is produced respectively.Determined using with the identical method of reference example 1 Adhesive sheet (C18)~(C34) of gained optical characteristics.It the results are shown in Table 8.

(b-8) embodiment 15~21

Using adhesive composition (46)~(52) prepared in Production Example 46~52, using with the identical side of reference example 1 Method, adhesive sheet (E15)~(E21) of embodiment 15~21 is produced respectively.Determined using with the identical method of reference example 1 Adhesive sheet (E15)~(E21) of gained optical characteristics.It the results are shown in Table 8.

The crystal of ＜ adhesive sheets separates out evaluation ＞

[40 DEG C of heating experiments (being expressed as " heating " in table 7 and 8)]

To thermostat (ESPEC Co. Ltd. systems：Model PL-3KT) in, above-mentioned adhesive sheet is put into respectively, in temperature 40 DEG C drying condition under, after placing 7 days and 30 days respectively, the apparent condition of adhesive sheet is visually observed, according to following Metewand evaluated.It the results are shown in table 7 and 8.

(metewand of 40 DEG C of heating experiments)

A：The cosmetic variations such as crystal precipitation are substantially not visible in sample after 30 days.

B：The cosmetic variations such as crystal precipitation are substantially not visible in sample after 7 days.

C：The cosmetic variations such as crystal precipitation are clearly seen that in sample after 7 days.

[- 15 DEG C of cooling tests (being expressed as " cooling down " in table 7 and 8)]

Above-mentioned adhesive sheet is put into thermostat, under the drying condition of -15 DEG C of temperature, after placing 7 days and 30 days respectively, profit With the apparent condition for visually observing adhesive sheet, evaluated according to following metewand.It the results are shown in table 7 and 8.

(metewand of -15 DEG C of cooling tests)

【Table 7】

【Table 8】

Then, laminated optical film is produced as shown below.In the making of laminated optical film, following polymerization has been used Thing film.In addition, for processing unit, measure device and assay method also shown below.

Cyclic olefin polymer (COP) film：The ZF-14 of Japanese ZEON Co. Ltd. systems

Corona treatment plant：The AGF-B10 of Kasuga Electric K. K.

The condition of sided corona treatment：Using above-mentioned corona treatment plant, in power output 0.3kW, processing speed 3m/ minutes Under conditions of implement 1 time

Polarised light UV irradiation units：The SPOT CURE with polarizer unit of USHINO Electric Co., Ltd SP-7

Laser microscope：The LEXT of OLYMPAS Co. Ltd. systems

High-pressure mercury-vapor lamp：The UNICURE VB-15201BY-A of USHINO Electric Co., Ltd

The measure of phase difference value in face：Using double refraction detection device, (prince measures machine Co. Ltd. system KOBRA-WR) determine

The measure of the thickness of alignment films：Determined using the ellipsometer M-220 of Japan Spectroscopy Corporation

In the manufacture of optical anisotropic layer and layered product etc., " optical alignment film formation group as shown below has been used Compound ", " friction orientation polymer composition ", " composition for including polymerizable liquid crystal compound A " and " polarization plates ".

The preparation ＞ of ＜ optical alignment film formation compositions

5 parts of the light orientation material of following structures is mixed for 95 parts with cyclopentanone (solvent), by the mixture of gained 80 DEG C stirring 1 hour, thus obtain optical alignment film formation composition.

Change 38

＜ includes the preparation ＞ of polymerizable liquid crystal compound A composition

Using the polymerizable liquid crystal compound A of following structures, following polymerization initiators and levelling agent and solvent as composition Mixed, obtain including polymerizable liquid crystal compound A composition.Moreover, polymerizable liquid crystal compound A is special using Japan Open the method synthesis described in 2010-31223 publications.Polymerizable liquid crystal compound A maximum absorption wavelength X max (LC) is 350nm。

Polymerizable liquid crystal compound A (12.0 parts)：

Change 39

Polymerization initiator (0.72 part)：2- dimethylamino -2- benzyls -1- (4- morpholinyl phenyls) -1- fourths Ketone (IRGACURE 369；Ciba Specialty Chemicals company systems)

Levelling agent (0.12 part)：Polyacrylic acid ester compounds (BYK-361N；BYK-Chemie company systems)

Solvent (100 parts)：Cyclopentanone

The manufacture ＞ of ＜ polarization plates

Thick 30 μm polyvinyl alcohol film (99.9 moles of average degree of polymerization about 2400, saponification degree more than %) is drawn using dry type It is about 4 times to stretch uniaxial tension, then after keeping tense situation unchangeably to be impregnated 40 seconds in 40 DEG C of pure water, in iodine/KI/water Weight than having carried out dyeing processing within 30 seconds in 28 DEG C of dippings in the dyeing aqueous solution for 0.044/5.7/100.Thereafter, in iodine Change the weight of potassium/boric acid/water than being impregnated 120 seconds at 70 DEG C in the boric acid aqueous solution for 11.0/6.2/100.Next, with 8 DEG C Pure water clean 15 seconds after, with 300N tension force keep in the state of, 60 DEG C dry 50 seconds, then 75 DEG C dry 20 Second, obtain the polarizer of 12 μm of thickness that iodine is adsorbed with polyvinyl alcohol film and has been orientated.

To gained polarizer and cyclo-olefin-polymer films (COP, Japanese ZEON Co. Ltd. systems ZF-4, absorb without UV it is special Property, 30 μm) between inject water system adhesive, be bonded with niproll.The tension force of the fitting thing of gained is being remained 430N/m's Meanwhile dried 2 minutes at 60 DEG C, obtain 42 μm of the polarization plates as diaphragm in one side with cycloolefin film.It is moreover, above-mentioned Water system adhesive is to add carboxy-modified polyvinyl alcohol (Co., Ltd.'s Kuraray systems into 100 parts of water；Kuraray POVAL KL318) 3 parts, water soluble polyamide epoxy resin (firmly change Chemtex Co. Ltd. systems；Sumirez Resin 650；Solid into The aqueous solution of point concentration 30%) 1.5 parts and prepare.

The degree of polarization Py and monomer transmissivity Ty of the polarization plates of gained are determined as shown below.

Using in spectrophotometer (UV-3150；Shimadzu Scisakusho Ltd's system) in the folder with polarizer is installed The device of tool, the monomer for determining transmission direction of principal axis in 380~680nm wave-length coverage with 2nm step-lengths using reference beam method are saturating Penetrate rate (T1) and absorb the monomer transmissivity (T2) of direction of principal axis.Using following formula (p) and (q), the monomer calculated under each wavelength is saturating Rate, degree of polarization are penetrated, recycles JIS Z8701 2 degree of visual angles (illuminant-C) to carry out visibility amendment, calculates visibility amendment monomer Transmissivity (Ty) and visibility amendment degree of polarization (Py).As a result, obtain visibility amendment monomer transmissivity Ty for 43.0%, Visibility amendment degree of polarization Py is 99.99% absorption-type polarization plates.

Monomer transmissivity Ty (%)={ (T1+T2)/2 } × 100 (p)

Degree of polarization Py (%)={ (T1-T2)/(T1+T2) } × 100 (q)

The manufacture ＞ of ＜ optical anisotropic layers

Using corona treatment plant (AGF-B10, Kasuga Electric K. K.'s system) in power output 0.3kW, processing speed Under conditions of 3m/ minutes, cyclo-olefin-polymer films (COP, Japanese ZEON Co. Ltd. system ZF-14) have been carried out with 1 processing. To the surface for implementing sided corona treatment, optical alignment film formation composition is coated with using bar coater, dries 1 minute, makes at 80 DEG C With polarised light UV irradiation units (SPOT CURE SP-7；USHINO Electric Co., Ltd system), with 100mJ/cm²Accumulation light Amount implements polarised light UV exposures.The thickness of the alignment films of gained is determined using ellipsometer, its result is 100nm.

Next, to the group by including polymerizable liquid crystal compound A in alignment films, previously prepared using bar coater coating Compound form coating fluid, 120 DEG C dry 1 minute after, using high-pressure mercury-vapor lamp (UNICURE VB-15201BY-A, USHINO Electric Co., Ltd system), ultraviolet is irradiated (in a nitrogen atmosphere, under wavelength 313nm from the surface side for being coated with coating fluid Accumulated light：500mJ/cm²), thus obtain including the optical film of optical anisotropic layer (phase retardation film).Shown using laser Micro mirror determines the thickness of the optical anisotropic layer of gained, and its result is 2 μm.

(c-1) embodiment 22：The manufacture of laminated optical film (1)

To the optical anisotropic layer side of above-mentioned optical film, the adhesive sheet (E1) made in embodiment 1 is bonded, removes institute After the barrier film for stating adhesive sheet (E1), polarization plates are stated the superficial layer of the adhesive composition (19) shown is stacked on.Thereafter, make With corona treatment plant (AGF-B10, Kasuga Electric K. K.'s system) in power output 0.3kW, processing speed 3m/ minutes Under the conditions of carry out 1 processing, thus above-mentioned polarization plates and above-mentioned optical anisotropic layer are pressed from both sides across adhesive composition (19) Fitting.Now, it is laminated in a manner of the slow axis for making optical anisotropic layer is 45 ° relative to the relation of the absorption axiss of polarization plates, Form circularly polarizing plate.Thereafter, the COP films of the base material as above-mentioned optical film are peeled off, thus obtain having transferred light in polarization plates Learn the laminated optical film (circularly polarizing plate) 1 of anisotropic band.The thickness of the laminated optical film 1 of gained is 64 μm.

In order to determine the optical characteristics of laminated optical film 1, by transferring to produce test sample on glass.Utilize Double refraction detection device (KOBRA-WR；Prince measures machine Co. Ltd. system) determine wavelength 450nm, the wavelength of the sample 550nm and wavelength 630nm phase difference value, utilize spectrophotometer (UV-3150；Shimadzu Scisakusho Ltd's system) measure Go out wavelength 400nm and wavelength 420nm transmissivity.It is moreover, inclined complete straight line is made by configuring devating prism in light source side Shake light, by the way that the rectilinearly polarized light is irradiated to determine to test sample.Now, by with (the circularly polarizing plate of laminated optical film 1 1) axis of homology of polarization plates side abreast injects rectilinearly polarized light, and determines the wavelength of the transmission direction of principal axis of polarization plates Stacking under the wavelength 420nm of the absorbance A p (400) of laminated optical film under 400nm and the transmission direction of principal axis of polarization plates The absorbance A p (420) of optical film.It the results are shown in table 9.Moreover, laminated optical film 1 have with following formula (4)~ (8) complete characteristic of the optical characteristics represented.

Ap(400)≥0.4 (4)

Ap(420)/Ap(400)≤0.3 (5)

100nm≤Re(550)≤170nm (6)

Re(450)/Re(550)≤1 (7)

1≤Re(630)/Re(550) (8)

(c-2) reference example 4~6, comparative example 35~39 and embodiment 23~42：Respectively using described in table 9 below Adhesive sheet, using with the identical method of embodiment 22, produce laminated optical film (circularly polarizing plate).Using with embodiment 22 Identical method determines the optical characteristics of the laminated optical film (circularly polarizing plate) of gained.

【Table 9】

The evaluation ＞ of ＜ laminated optical films

To the laminated optical film made using aforesaid operations, optical durability experiment, heat resistant test, moisture-proof heat examination have been carried out Test and heatproof impact test.Moreover, each experiment is carried out according to following method.

[optical durability experiment]

To sunshine weather meter (Suga testing machine Co. Ltd. systems：Model SUNSHINE WEATHER METER S80 input laminated optical film in), after irradiating 100 hours, wavelength 450nm, wavelength 550nm and wavelength 630nm phase are determined Difference Re (λ).According to the change of the front and rear phase difference value of optical durability experiment, evaluated according to following benchmark.Will As a result it is shown in table 10.

(metewand of optical durability experiment)

A：The changes delta Re (λ) of the front and rear phase difference value of optical durability experiment is less than 5

B：The changes delta Re (λ) of the front and rear phase difference value of optical durability experiment is for 5 less than 10

C：The changes delta Re (λ) of the front and rear phase difference value of optical durability experiment is more than 10

[heat resistant test]

To thermostat (ESPEC Co. Ltd. systems：Model PL-3KT) in input laminated optical film, in the dry of 85 DEG C of temperature After placing 250 hours, 500 hours under the conditions of dry respectively, the apparent condition of laminated optical film is visually observed, according to following Metewand is evaluated.It the results are shown in Table 10.

(metewand of heat resistant test)

A：The cosmetic variations such as tilting, peeling, foaming, crystal precipitation are substantially not visible in sample after 500 hours.

B：The cosmetic variations such as tilting, peeling, foaming, crystal precipitation are substantially not visible in sample after 250 hours.

C：The cosmetic variations such as tilting, peeling, foaming, crystal precipitation are clearly seen that in sample after 250 hours.

[hot resistance test]

To thermostat (ESPEC Co. Ltd. systems：Model PH-4KT) in input laminated optical film, in temperature 60 C, relative After humidity 90% places 250 hours, 500 hours respectively, the apparent condition of laminated optical film is visually observed, according to following Metewand is evaluated.It the results are shown in Table 10.

(metewand of hot resistance test)

[heat shock resistance (HS) experiment]

To thermal shock device (ESPEC Co. Ltd. systems：Model TSA-71L-A) in input laminated optical film, from adding Heat to 70 DEG C of state cools to -40 DEG C, is then warming up to 70 DEG C, the process is set into 1 circulation (30 minutes), by this After process repeats 50 circulations, 100 circulations respectively, the apparent condition of laminated optical film is visually observed.According to Following metewand is evaluated.It the results are shown in Table 10.

(metewand of heatproof impact test)

A：The cosmetic variations such as tilting, peeling, foaming, crystal precipitation are substantially not visible in sample after 100 circulations.

B：The cosmetic variations such as tilting, peeling, foaming, crystal precipitation are substantially not visible in sample after 50 circulations.

C：The cosmetic variations such as tilting, peeling, foaming, crystal precipitation are clearly seen that in sample after 50 circulations.

【Table 10】

The optical film of embodiment 22~42 is understood due to the high-selenium corn characteristic under wavelength 400nm, thus with reference example 4 ~6 compared to the Δ Re (450) and Δ Re (550) that can suppress phase retardation film.

The explanation of symbol

1 polarizing coating,

2 surface-treated layers,

3 second diaphragms,

4 first diaphragms,

6 interlayer adhesives,

7 phase retardation films,

10 polarization plates,

15 carry the polarization plates of adhesive,

20 adhesive sheets,

30 image-displaying members (glass substrate),

40 optical laminates

Claims

1. a kind of light absorption composition, it includes at least two kinds of light selection absorbing compounds, wherein, at least two kinds of is described There is light selection absorbing compounds identical to be conjugated architecture.

2. light absorption composition according to claim 1, wherein,

The maximum of the maximum absorption wavelength of at least two kinds of light selection absorbing compounds with identical conjugation architecture The difference of value and minimum value is below 5nm.

3. light absorption composition according to claim 1 or 2, wherein,

At least two kinds of light selection absorbing compounds are that the light represented with formula (I) or formula (II) selects absorbing compounds,

In formula,

R¹Represent the alkyl of hydrogen atom or carbon number 1~10, in the case where the alkyl has at least one methylene, the methylene At least one of base can be substituted by oxygen atom or sulphur atom,

A represents methylene, secondary amino group, oxygen atom or sulphur atom,

X¹And X²Electron-withdrawing group, X are represented independently of one another¹And X²It can be interconnected and form ring structure,

In formula,

R¹、X¹、X²With above-mentioned synonymous,

A²Hydrogen atom, the alkyl of carbon number 1~6, aromatic hydrocarbyl or aromatic heterocycle are represented, has at least 1 in the alkyl In the case of individual methylene, at least one of the methylene can be substituted by secondary amino group, oxygen atom, sulphur atom, the aromatic hydrocarbyl And aromatic heterocycle can have substituent.

4. light absorption composition according to claim 3, wherein,

The light selection absorbing compounds represented with the formula (I) are that the light represented with formula (I-2) selects absorbing compounds,

In formula,

R¹With above-mentioned synonymous,

R⁴Represent the alkyl of hydrogen atom or carbon number 2~50, in the case where the alkyl has at least one methylene, the methylene At least one of base can be substituted by oxygen atom,

The light selection absorbing compounds represented with the formula (II) are that the light represented with formula (II-2) selects absorbability chemical combination Thing,

In formula, R¹And R⁴With it is above-mentioned synonymous.

5. according to light absorption composition according to any one of claims 1 to 4, wherein,

Contained at least two kinds of light selection absorbability chemical combination with identical conjugation architecture in the light absorption composition In thing, content and other light selection absorbability of the light selection absorbing compounds of the content maximum in light absorption composition The ratio of the total amount of the content of compound is 1：10~10：1.

6. according to light absorption composition according to any one of claims 1 to 5, it meets formula (1), formula (2) and formula (3)：

ε(420)/ε(400)≤0.3 (1)

λmax≤420nm (2)

ε(400)≥20 (3)

In formula,

ε (420) represents gram absorptivity under wavelength 420nm,

ε (400) represents gram absorptivity under wavelength 400nm,

λ max represent maximum absorption wavelength.

7. a kind of polymer composition, it contains light absorption composition according to any one of claims 1 to 6 and polymerization Thing.

8. polymer composition according to claim 7, wherein,

The content of the light absorption composition for the mass parts of polymer 100 is 1~15 mass parts.

9. a kind of optical film, it includes the polymer composition described in claim 7 or 8.

10. optical film according to claim 9, its thickness is 0.1~18 μm.

11. a kind of laminated polarizing film, it includes the optical film and polarizing coating described in claim 9 or 10.

12. laminated polarizing film according to claim 11, it meets following formula (4) and formula (5)：

Ap(400)≥0.4 (4)

Ap(420)/Ap(400)≤0.3 (5)

In formula,

Ap (420) represents the absorbance of the optical film on the transmission direction of principal axis of the polarizing coating under wavelength 420nm.

13. a kind of laminated phase-difference film, it includes the optical film and phase retardation film described in claim 9 or 10.

14. a kind of elliptical polarization film, it includes optical film, polarizing coating and the phase retardation film described in claim 9 or 10.

15. a kind of display device, it includes the film any one of claim 9~14.